Pd Thin Films Research Articles

Influence of magnetron sputtering process parameters on the morphology of palladium thin films: An empirical study

Abstract The heightened initial energy of deposited atoms during the magnetron sputtering process alters the conventional rules of structure zone transformation for film morphology, posing challenges in fabricating Pd films with specific morphologies. This study aims to elucidate the impacts of substrate temperature and sputtering power on the morphology of Pd films and to determine the magnetron sputtering process parameters for preparing Pd films within a typical structure zone. Pd thin films were fabricated by using magnetron sputtering under varying substrate temperatures and sputtering powers. The morphologies of the films were examined through Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). With increasing substrate temperature, the structure zone of Pd films transitions from Zone T to Zone 2, and subsequently to Zone 3. Given that initial energy enhances the diffusion capability of deposited atoms, the threshold temperature for structural zone transformation of Pd films prepared by magnetron sputtering is lower than the critical value suggested by the Structure Zone Model (SZM). While sputtering power does not critically affect the structure zone of Pd films, it influences grain size and preferred orientation. The substrate temperature is the decisive factor affecting the structural zone of thin films, with the critical temperature for structure zone transformation in magnetron sputtering being lower than that proposed by the Structural Zone Model (SZM). Furthermore, the research has determined the magnetron sputtering process parameters necessary for fabricating Pd thin films with specific structure zones. This study paves the way for subsequent enhancements in the hydrogen sensitivity of palladium thin film sensors through morphology control.

Impact of laser interaction on morphological and mechanical properties of palladium thin film

This research work investigates surface morphology, plasma plume intensity and the hardness of palladium thin film deposited on silicon substrates under the action of laser light. For this purpose, a pulsed Nd:YAG laser (1064 nm, 10 mJ, 12 ns) was used to irradiate the specimen with repetitive laser pulses. The experiment was repeated under the illumination with UV light. The surface morphology of the specimens was examined through an Optical and Field-Emission Scanning Electron Microscopy showing thermal conduction, exfoliation, crater formation, re-deposition of the material, ripples formation, debris, heat-affected zone, holes formation and the formation of nanoparticles. The diameter and the depth of the crater formed on non-UV illuminated Pd thin film were greater than the crater formed on UV illuminated Pd thin film, because of its higher absorption. The photographs of the plasma plume were captured with a computer-controlled image capture system and examined by image processing software. The intensity of UV-illuminated Pd thin film was higher than non-UV illuminated Pd thin film because UV illumination induces defects in the specimen that have additional electronic states. These defects cause higher absorption and more ionization of the target material and emerge a more luminous plasma plume. A nanoindentation test was applied on the material surface to investigate the mechanical properties such as hardness and elastic modulus of the target specimen. The hardness and elastic modulus of the material were increased by cumulative laser shots.

Structural pathways for ultrafast melting of optically excited thin polycrystalline Palladium films

Due to its extremely short timescale, the non-equilibrium melting of metals is exceptionally difficult to probe experimentally. The knowledge of melting mechanisms is thus based mainly on the results of theoretical predictions. This work reports on the investigation of ultrafast melting of thin polycrystalline Pd films studied by optical laser pump – X-ray free-electron laser probe experiments and molecular-dynamics simulations. By acquiring X-ray diffraction snapshots with sub-picosecond resolution, we capture the sample's atomic structure during its transition from the crystalline to the liquid state. Bridging the timescales of experiments and simulations allows us to formulate a realistic microscopic picture of the crystal-liquid transition. According to the experimental data, the melting process gradually accelerates with the increasing density of deposited energy. The molecular dynamics simulations reveal that the transition mechanism progressively varies from heterogeneous, initiated inside the material at structurally disordered grain boundaries, to homogenous, proceeding catastrophically in the crystal volume on a picosecond timescale comparable to that of electron-phonon coupling. We demonstrate that the existing models of strongly non-equilibrium melting, developed for systems with relatively weak electron-phonon coupling, remain valid even for ultrafast heating rates achieved in femtosecond laser-excited Pd. Furthermore, we highlight the role of pre-existing and transiently generated crystal defects in the transition to the liquid state.

Palladium effect on electrochemical hydrogen storage properties of nanoporous silicon

Coating porous silicon with metal catalysts such as palladium is considered a reliable method to improve the hydrogen storage performance of electrodes. Here, in order to evaluate the most effective use of Pd nanoparticle or Pd thin film, Pd nanoparticles with a size of 36 nm obtained by electroless method, and a Pd thin film with a thickness of 30 nm deposited by thermal evaporation were coated onto nanoporous silicon sample” and studied. The Pd deposits were confirmed by Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The obtained electrode materials: PS and Pd/PS were characterized by different electrochemical characterization techniques: cyclic voltammetry (CV) and galvanostatic charge/discharge. The results showed that Pd NPs/PS achieved the highest hydrogen storage capacity with a value of 425.9 mA h g-1. These results confirm that using Pd nanoparticles as catalyst metal is more suitable to improving the hydrogen storage capacity of electrode materials.

Polarization Property Associated with Surface Plasmon Resonance in a Palladium Thin-Film Coated Aluminum Grating in a Conical Mounting and Its Application to Hydrogen Gas Detection.

We have investigated a polarization property of the (specularly) reflected light from an aluminum grating, coated with a palladium (Pd) thin-film on its surface. The polarization property, which is associated with surface plasmon resonance (SPR), and occurs in the Pd thin-film on the aluminum grating in a conical mounting, is observed as a rapid change in the normalized Stokes parameter s3, around the resonance angle, θsp, at which point, SPR occurs. The sensing technique used the rapid change in s3 to allow us to successfully detect a small change in the complex refractive index of the Pd thin-film layer upon exposure to hydrogen gas, with a concentration near the lower explosion level. Experimental results showed that the sensing technique provided a sensitive and stable response when the Pd thin-film layer was exposed to gas mixtures containing hydrogen at concentrations of 1 to 4% (by volume) in nitrogen.

Ultrathin damage-tolerant flexible metal interconnects reinforced by in-situ graphene synthesis

Conductive patterned metal films bonded to compliant elastomeric substrates form meshes which enable flexible electronic interconnects for various applications. However, while bottom-up deposition of thin films by sputtering or growth is well-developed for rigid electronics, maintaining good electrical conductivity in sub-micron thin metal films upon large deformations or cyclic loading remains a significant challenge. Here, we propose a strategy to improve the electromechanical performance of nanometer-thin palladium films by in-situ synthesis of a conformal graphene coating using chemical vapor deposition (CVD). The uniform graphene coverage improves the thin film’s damage tolerance, electro-mechanical fatigue, and fracture toughness owing to the high stiffness of graphene and the conformal CVD-grown graphene-metal interface. Graphene-coated Pd thin film interconnects exhibit stable increase in electrical resistance even when strained beyond 60% and longer fatigue life up to a strain range of 20%. The effect of graphene is more significant for thinner films of < 300 nm, particularly at high strains. The experimental observations are well described by the thin film electro-fragmentation model and the Coffin-Manson relationship. These findings demonstrate the potential of CVD-grown graphene nanocomposite materials in improving the damage tolerance and electromechanical robustness of flexible electronics. The proposed approach offers opportunities for the development of reliable and high-performance ultra-conformable flexible electronic devices.

In situ cell for grazing-incidence x-ray diffraction on thin films in thermal catalysis.

A cell for synchrotron-based grazing-incidence x-ray diffraction at ambient pressures and moderate temperatures in a controlled gas atmosphere is presented. The cell is suited for the in situ study of thin film samples under catalytically relevant conditions. To some extent, in addition to diffraction, the cell can be simultaneously applied for x-ray reflectometry and fluorescence studies. Different domes enclosing the sample have been studied and selected to ensure minimum contribution to the diffraction patterns. The applicability of the cell is demonstrated using synchrotron radiation by monitoring structural changes of a 3nm Pd thin film upon interaction with gas-phase hydrogen and during acetylene semihydrogenation at 150 °C. The cell allows investigation of very thin films under catalytically relevant conditions.

Pd-H as an irreplaceable model system for the study of hydrogen electrosorption in aqueous and non-aqueous electrolytes

Even though Pd-H system has been known since the nineteenth century, it is still of interest to scientists. Pd thin film electrode (called as a Limited Volume Electrode – LVE) is able to electrosorb hydrogen form aqueous (acid, base) and non-aqueous electrolytes (e.g. ionic liquids). Therefore Pd-H is an irreplaceable model system for the study of hydrogen electrosorption in different media. The paper presents: (1) short overview of the study of hydrogen sorption in Pd, (2) the detailed description of the electrochemical measurement methods and (3) the equations for the determination of hydrogen electrosorption charges needed to hydrogen electrosorption isotherms creation. The presented approach can be applied for laboratory work. The results show that Pd-LVE can be effectively used as a model system before the studies of multicomponent hydrogen storage alloys (e.g. AB5 alloys).Graphical abstract

Sulfonic acid (-HSO3) functionalization effect on graphene oxide membrane by (3 mercaptopropyl) trimethoxysilane and their applications in hydrogen membrane fuel cells

Conventional proton exchange membrane fuel cells (PEMFCs) use a perfluorinated ionomer membrane, e.g., Nafion®, which is expensive and subject to a rigorous synthesis process. Graphene oxide membrane (GOM) is acknowledged as a promising alternative electrolyte due to its hydrophilic nature and attractive proton conductivity in wet conditions. However, GOM loses its negative surface functional groups by hydrogen gas at the anode during operation in PEMFCs, resulting in increased electronic conductivity. In addition, two-dimensional graphene oxide (GO) nanosheets exhibited a larger anisotropy difference in proton conductivity compared to Nafion®. In this study, (3-mercaptopropyl)trimethoxysilane (MPTS, HS(CH2)3Si(OCH3)3) was reacted with the surface of GO nanosheet (M-GOM) by vigorous stirring, where unreacted MPTS was partially removed by a rinsing cycle except the M-GOM powder. Reactive MPTS has two essential reactions which were carried out by forming a hydrolysis reaction (Si-OCH3 to Si-OH) and a condensation reaction (Si-OH to Si-O-Si). The thiol groups of MPTS were oxidized to sulfonic acid groups (-HSO3) to provide high proton conducting stations with GO functional groups (M-GOM/oxid) and compared with non-oxidized thiol groups in a GO matrix (M-GOM/unoxid). The superior –HSO3 effect on M-GOM have reported for proton conductivity, physicochemical properties, ion exchange capacity, thermal stability, gas permeability and fuel cell performance. Furthermore, a hydrogen-permeable metal layer was deposited by a DC magnetron sputter to increase mechanical strength and reduce fuel crossover. A dual-layer membrane composed of M-GOM/unoxid or M-GOM/oxid and Pd thin film was analyzed as an electrolyte for a hydrogen membrane fuel cell (HMFC), which simultaneously performs two roles, an anode catalyst and an electrolyte.

An In Situ Fabricated Hydrogel Polymer - Palladium Nanocomposite Electrocatalyst for the HER: Critical Role of the Polymer in Realizing High Efficiency and Stability.

Development of general and simple designs of catalytic electrodes for the hydrogen evolution reaction (HER) is critical. The present work demonstrates the multiple roles played by a hydrogel polymer in the fabrication and activity enhancement of the nanoelectrocatalyst. A nanocomposite thin film of Pd with the insulating hydrogel, poly(2-hydroxyethyl methacrylate) (PHEMA), is fabricated through a facile in situ process, the polymer itself functioning as the reducing/stabilizing agent in the formation of Pd nanoparticles. Pd-PHEMA on Ni foam enables efficient HER in alkaline medium with a low overpotential; the polymer enables the electrocatalysis by its swelling and confinement of the electrolyte. Most significantly, when the electrode is subjected to an optimized cycling protocol, the overpotential decreases steadily, reaching an impressively low value of 36 mV (@10 mA cm-2 ). A low Tafel slope (68 mV dec-1 ), high exchange current density, Faradaic efficiency and TOF (3.27 mA cm-2 , 99 %, 122.7 h-1 ), and extended stability are achieved. Detailed investigations reveal the active role of the polymer in the evolution of the nanocatalyst, itself undergoing favorable morphological changes. The study illustrates the widened scope for developing efficient and stable catalytic electrodes with hydrogel polymers and unique features that promote the generation of green hydrogen.

Impact of gaseous interferents on palladium expansion for hydrogen optical sensing: A time stability study

Continuous monitoring of hydrogen (H2) concentration is critical for safer use, which can be done using optical sensors. Palladium (Pd) is the most commonly used transducer material for this monitoring. This material absorbs H2 leading to an isotropic expansion. This process is reversible but is affected by the interaction with interferents, and the lifetime of Pd thin films is a recurring issue. Fiber Bragg Grating (FBG) sensors are used to follow the strain induced by H2 on Pd thin films. In this work, it is studied the stability of Pd-coated FBGs, protected with a thin Polytetrafluoroethylene (PTFE) layer, 10 years after their deposition to assess their viability to be used as H2 sensors for long periods of time. It was found that Pd coatings that were PTFE-protected after deposition had a longer lifetime than unprotected films, with the same sensitivities that they had immediately after their deposition, namely 23 and 10 pm/vol% for the sensors with 150 and 100 nm of Pd, respectively, and a saturation point around 2 kPa. Furthermore, the Pd expansion was analyzed in the presence of H2, nitrogen (N2), carbon dioxide (CO2), methane (CH4) and water vapor (H2O), finding that H2O is the main interferent. Finally, an exhaustive test for 90 h is also done to analyze the long-term stability of Pd films in dry and humid environments, with only the protected sensor maintaining the long-term response. As a result, this study emphasizes the importance of using protective polymeric layers in Pd films to achieve the five-year lifetime required for a real H2 monitoring application.

Effect of ceria particle size as intermediate layer for preparation of composite Pd-membranes by electroless pore-plating onto porous stainless-steel supports

The use of H2-selective membranes for ultra-pure H2 production has been assigned as an attractive technology, particularly those based on Pd-films deposited onto porous stainless-steel (PSS) supports. The ability to incorporate thin Pd-films with enough adherence on any internal or external surfaces becomes essential to minimize their complexity and cost while improving their performance. The modification of original PSS substrates with diverse intermediate layers, especially those made of ceria, is presented as a promising alternative. In this context, the current study addresses for the first time the use of different CeO2 particle sizes to generate an intermediate layer and facilitate the subsequent generation of a thin Pd-film by electroless pore-plating (ELP-PP). The membrane containing the smallest CeO2 particle size (membrane S) demonstrated the lowest performance, which was assigned to the high compaction of the material and generation of cracks on its surface during calcination that consequently led to the deposition of a greater amount of Pd. On the other hand, the morphology of membranes M (medium CeO2 particle size) and L (large CeO2 particle size) were very similar, although the first one demonstrated a slightly smaller interparticle porosity, which led to the deposition of a more homogeneous and thinner Pd-film. Therefore, an outstanding performance in terms of H2 permeance (5.98 × 10−4 mol·m−2·s−1·Pa−0.5 at 400 °C) was obtained for this membrane. Permeation tests with binary mixtures (H2-N2, H2-CO2, or H2-CO) revealed a concentration-polarization effect in all cases, as well as a certain inhibition effect in the presence of CO. Finally, it should be highlighted the high stability of the membranes during the entire set of experiments, independently of the considered particle size. Thus, enough mechanical and thermal resistances can be assured for future applications.

Deposition and characterization of α-Fe2O3/Pd thin films for neutron reflectometry studies

We report deposition of hematite/Pd thin films on silicon wafers via radio frequency (RF) magnetron sputtering and subsequent characterization for future in situ neutron reflectometry studies. Following deposition, the hematite/Pd thin films were characterized as prepared and after annealing in air for 2h at 400, 500, and 600 °C, respectively. Raman spectroscopy, grazing incidence x-ray diffraction, and neutron reflectometry (NR) were used to characterize the structure and chemical compositions of the thin films. The results indicate that pure α-Fe2O3 (hematite) films were produced, free from other iron oxide phases and impurities. NR data reveal that one intermediate layer between the Pd layer and the hematite layer was formed during sputtering deposition processes. The fitted scattering length density (SLD) of the as-deposited hematite layer is 70% of the theoretical SLD value, indicating that the grains are loosely packed in the RF-deposited hematite films. After annealing at elevated temperatures, the hematite films show increased SLD values but remain comparable to that of preannealed.

Porous Thin Films with Large Specific Surface Area on the Basis of Spray-Coated Metal Aerogels

The preparation of aerogels in the form of thin films deposited on a substrate (e.g., as an electrode material) is an attractive but challenging task. Such thin films are expected to combine the highly porous gel nanostructure, good mechanical stability, and a remarkably high specific surface area with efficient charge-carrier transport via the interconnected nanoparticle chains. All together, they make them attractive for the fabrication of (electro)catalysts or sensors for microfluidics, flexible electrodes for microelectronics, soft electrodes compatible with a stress-sensitive bioenvironment, etc. In this work, thin aerogel films of colloidal Pd and PtNi building blocks were prepared from the corresponding wet gels using a spray technique. The films were fabricated on substrates of around 1.5 cm2. During the modification of the substrates, the film thickness can be adjusted by controlling the ink content (flow rate, gas pressure, and temperature) and the number of spray cycles. In this way, both the electrical (down to Rs = ∼0.2 kOhm/sq) and optical parameters of the thin porous films can be tuned. Comparative studies of the pore and surface structures of the films have confirmed their integrity and the highly porous structure typical for aerogels. In perspective, spray-coated aerogels can be easily adapted to industrial applications because upscaling is possible and expensive equipment such as supercritical or freeze-dryers is not required. It is important to note that the spray-coating technique is applicable through a mask or can be converted to inkjet printing, which allows for the desired micropatterning of aerogel thin films.

Pulsed laser-induced dewetting to fabricate Au-Pd nanoparticles supported on ZnO films and its application for the photocatalytic degradation of indigo carmine

Gold-palladium (Au-Pd) bimetallic alloy nanoparticles (NPs) were obtained by the interaction of a laser pulse with a stack of Au and Pd thin films, these films were previously and sequentially deposited on a zinc oxide (ZnO) thin films grown on a glass substrate. This method can produce, with a single laser pulse, spherical NPs of different compositions which remain attached to the surface of the ZnO film. X-ray diffraction analysis showed that the NPs are composed of a solid solution of the metals whose relative content was modified by varying the deposition time of the starting metal films. The higher amount of Pd in the NPs, the smaller particle size being the minimum around 50 nm. To demonstrate the usefulness of this method to produce Au-Pd NPs directly on surfaces, the decorated ZnO layers were tested as photocatalysts material for the decomposition of indigo carmine dye. The bimetallic NPs supported on ZnO showed to have a better photocatalytic performance to decompose the dye than their mono-metallic counterpart and bare ZnO thin film. The bimetallic NPs richer in Pd achieved a degradation of 99% of the dye while bare ZnO film reached just 32%.

A self-driving laboratory optimizes a scalable process for making functional coatings

Functional coatings are used in a wide range of high surface-area technologies, such as low-E windows and photovoltaics. Solution-based coatings are typically less expensive to produce than vacuum-based coatings; however, it is generally more difficult to produce high-quality coatings using solution-based methods due to lower control over the physical and chemical processes involved. Here, we show how a self-driving laboratory can be used to optimize spray coating parameters. For this demonstration, we optimized the combustion synthesis of spray-cast conductive palladium (Pd) films. The closed-loop optimization yielded films with conductivities of >4 MS/m, which compares favorably with the conductivities of 2–6 MS/m reported for thin Pd films obtained by vacuum-based sputtering processes. The champion coating conditions were scaled up to an 8× larger area using the same spray-coating apparatus while preserving coating quality and conductivity. This work shows how self-driving laboratories can optimize solution-based coatings at scale.

The spin polarization of palladium on magneto-electric Cr2O3

While induced spin polarization of a palladium (Pd) overlayer on antiferromagnetic and magneto-electric Cr2O3(0001) is possible because of the boundary polarization at the Cr2O3(0001), in the single domain state, the Pd thin film appears to be ferromagnetic on its own, likely as a result of strain. In the conduction band, we find the experimental evidence of ferromagnetic spin polarized in Pd thin films on a Cr2O3(0001) single crystal, especially in the thin limit, Pd thickness of around 1–4 nm. Indeed there is significant spin polarization in 10 Å thick Pd films on Cr2O3(0001) at 310 K, i.e. above the Néel temperature of bulk Cr2O3. While Cr2O3(0001) has surface moments that tend to align along the surface normal, for Pd on Cr2O3, the spin polarization contains an in-plane component. Strain in the Pd adlayer on Cr2O3(0001) appears correlated to the spin polarization measured in spin polarized inverse photoemission spectroscopy. Further evidence for magnetization of Pd on Cr2O3 is provided by measurement of the exchange bias fields in Cr2O3/Pd(buffer)/[Co/Pd] n exchange bias systems. The magnitude of the exchange bias field is, over a wide temperature range, virtually unaffected by the Pd thickness variation between 1 and 2 nm.

Pd quantum dot induced changes in the photocatalytic, electrocatalytic, photoelectrochemical and thermoelectric performances of galvanically synthesized Sb2Se3 thin films

We present a novel solution-based galvanic (electrochemical) synthesis of antimony selenide light absorber thin films on FTO (Fluorine doped tin oxide) coated glass substrates. The structural, surface morphological, compositional, optical and electrical properties of the samples were characterized using X-Ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy (TEM), Fast Fourier Transform (FFT), Energy Dispersive X-ray spectroscopy (EDS), UV–Vis and Photoluminescence (PL) spectroscopy and Electrochemical Impedance spectroscopy (EIS). X-ray Photoelectron Spectroscopy (XPS) was employed to determine the elemental state composition of as-deposited and annealed Sb2Se3 films containing Pd. The annealed Sb2Se3:Pd films exhibited hydrogen evolution in neutral buffer medium with small potential of 164 mV and a Tafel slope of 39 mV/decade. Pd incorporation enhances the efficiency towards HER performance, which shows the 10 mAcm−2 current density at a low overpotential of 244 mV with reasonable durability. Photoelectrochemical (PEC) water splitting was observed at a potential of 0.41 V versus a reversible hydrogen electrode (RHE) with 3.2 mA cm−2 at 0 V versus RHE, under air mass 1.5 global illumination in a neutral electrolyte. To check the performance of this material for waste water treatment photodegradation of hazardous dyes and metal ion reduction experiments were performed. The photodegradation percentages of MG, MB and RhB dyes with annealed Sb2Se3:Pd thin film catalysts and H2O2 were 99.32% in 10 min, 98.95% in 20 min and 99.16% in 30 min, respectively. Cu2+ ions were photocatalytically reduced with the same catalyst to an extent of 98.9% in 20 min. Thermoelectric measurements on annealed Sb2Se3:Pd yielded the best Figure of merit and power factor values of 39.8 μW/cmK2 and 10.81 × 10−3, respectively at 373 K.

Sensors for anaerobic hydrogen measurement: A comparative study between a resistive PdAu based sensor and a commercial thermal conductivity sensor

Hydrogen sensors able to perform measurements in real time in anaerobic environment such as natural gas (NG) will greatly help the development of power to gas technology. For now, thermal conductivity (TC) gas sensors and Pd thin film based sensors have demonstrated their capability to measure H2 in air and N2 but there is still lack of testing in natural gas environment. In this study, the sensing performances (response, hysteresis, response time and selectivity) of two sensors were assessed in three anaerobic environments: N2, CH4, and NG. The first one is a homemade resistive sensor based on a PdAu thin film and the second one is a commercial thermal conductivity sensor. While most performances are equivalent for both technologies, only the PdAu sensor is able to detect selectively H2, without any interfering effect with NG components. Thus, Pd based thin film sensors are promising for H2 detection in anaerobic environments.

Rapid Fabrication of Fe and Pd Thin Films as SERS-Active Substrates via Dynamic Hydrogen Bubble Template Method

Fe and Pd thin film samples have been fabricated in a rapid fashion utilizing the versatile technique of dynamic hydrogen bubble template (DHBT) method via potentiostatic electrodeposition over a copper substrate. The morphology of the samples is dendritic, with the composition being directly proportional to the deposition time. All the samples have been tested as SERS substrates for the detection of Rhodamine 6G (R6G) dye. The samples perform very well, with the best performance shown by the Pd samples. The lowest detectable R6G concentration was found to be 10-6 M (479 μgL-1) by one of the Pd samples with the deposition time of 180 s. The highest enhancement of signals noticed in this sample can be attributed to its morphology, which is more nanostructured compared to other samples, which is extremely conducive to the phenomenon of localized surface plasmon resonance (LSPR). Overall, these samples are cheaper, easy to prepare with a rapid fabrication method, and show appreciable SERS performance.