Elastic Recoil Detection Analysis Research Articles

Patterning of COC Polymers by Middle‐Energy Ion Beams for Selective Cell Adhesion in Microfluidic Devices

AbstractMicrofluidic devices play a crucial role in advanced cell biology applications, including cell separations, cultivations, migration and interaction studies, diagnostic devices, and organ‐on‐chips. One of the frequent purposes of such devices is the ability to selectively address the attachment of cells at defined locations on the surface. This study explores the application of middle‐energy carbon, oxygen, and nitrogen ions to locally modify the surface of cyclic olefin copolymer (COC) thermoplastic material, allowing selective cell growth on patterned polymer surfaces. The investigation considers ion element type, ion beam energy, and ion irradiation fluence, analyzing their influence on the modification effect. Characterization of the modified surfaces involves various surface‐analytical methods such as contact angle, energy dispersive spectroscopy (SEM‐EDX), atomic force microscopy (AFM), x‐ray photoelectron spectroscopy (XPS), rutherford backscattering spectrometry (RBS), and elastic recoil detection analysis (ERDA). The study extends to practical aspects, with a representative cancer cell line, MCF‐7, grown on the patterned surface to evaluate the degree of selective attachment. Additionally, the stability of the irradiated patterns is tested under elevated temperatures beyond the glass transition temperature (Tg), demonstrating the compatibility of the approach with hot embossing technology. The findings underscore the potential of ion beam treatment for COC in cell‐biology‐related applications, offering insights into surface modification techniques for enhanced functionality in microfluidic devices.

Li concentration change around Cu/LiPON interface measured by TOF-ERDA

AbstractLithium metal is a promising anode material for the development of advanced all-solid-state batteries (ASSBs) with high energy density. Among the various solid electrolytes, lithium phosphorus oxynitride glass electrolyte (LiPON) is notable for facilitating stable Li plating-stripping reactions in ASSBs employing Li metal. The aim of this study is to examine the Li/LiPON interface, with a specific emphasis on the reductive decomposition of LiPON near this interface. We employed time-of-flight elastic recoil detection analysis (TOF-ERDA) to assess changes in Li concentration around the Cu/LiPON interface immediately prior to the Li plating reaction. Our electrochemical measurements indicate that critical decomposition of LiPON occurs when the voltage at the Cu electrode is reduced to 0.1 V vs. Li/Li+ at 25 °C, resulting in the in situ formation of Li3P operating at 0.7 V vs. Li/Li+ as an anode material. The TOF-ERDA findings reveal that this decomposition reaction results in a layer with partial decomposition (ranging from 5 to 25% on average) extending up to approximately 30 nm from the Cu/LiPON interface. This insight is vital for enhancing the design and performance of ASSBs. Graphical abstract

Comparison of three titanium-precursors for atomic-layer-deposited TiO2 for passivating contacts on silicon

Atomic layer-deposited (ALD) TiO2 thin films on silicon were deposited using titanium tetrachloride (TiCl4), titanium tetraisopropoxide (TTIP), and tetrakis(dimethylamino)titanium (TDMAT) together with water vapor as the oxidant at temperatures ranging between 75 and 250 °C. The Si surface passivation quality of as-deposited and isothermally annealed samples was compared using photoconductance lifetime measurements in order to calculate their effective surface recombination velocities Seff. A low Seff of 3.9 cm/s (J0s=24fA/cm2) is achieved for as-deposited TiCl4-TiO2 at 75 °C when a chemically grown (i.e., from RCA cleaning) SiOx interface layer is present. Depositing TTIP-TiO2 at 200 °C on a chemically grown SiOx interface layer yields equivalent Seff values; however, in this case, TTIP-TiO2 requires a 5–15 min postdeposition forming gas anneal at 250 °C. In contrast, TDMAT-TiO2 was not found to provide a similar level of passivation with/without a chemically grown SiOx interface layer and postdeposition anneal. Modeling of the effective lifetime curves was used to determine the magnitude of the effective charge densities Qf in the TiO2 films. In all cases, Qf was found to be of the order of ∼1011 q cm−2, meaning field-effect passivation arising from ALD TiO2 is relatively weak. By comparing the material properties of the various TiO2 films using ellipsometry, photothermal deflection spectroscopy, Raman spectroscopy, elastic recoil detection analysis, x-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy, we find experimental support for the role of Cl (in conjunction with hydrogen) playing a beneficial role in passivating dangling bond defects at the Si surface. It is concluded that low deposition temperature TiCl4 processes are advantageous, by providing the lowest Seff without any postanneal and a comparatively high growth per cycle (GPC).

Mechanical properties of VC/ZrC and VC/HfC superlattices

Face-centered cubic transition metal carbides exhibit high melting points and hardness, making them prominent candidates for protective coating applications. Vanadium carbide (VC) has typical characteristics of transition metal carbides. It serves as model material in this study, in which we showcase the effect of superlattice architecture on mechanical properties and fracture toughness. While beneficial effects of superlattice arrangement have been demonstrated for a series of nitride-based coatings, transition metal carbides remain largely unexplored territory. Following density functional theory based ab initio predictions on lattice and shear modulus mismatch, we develop VC/ZrC and VC/HfC superlattice coatings synthesized via pulsed DC sputter deposition. The bilayer periods (Λ) of our fully fcc-structured polycrystalline coatings range between 2–50 nm (indicated by X-ray diffraction, transmission and scanning electron microscopy). The chemical composition is close to 1:1 stoichiometry (from X-ray fluorescence, elastic back-scattering spectrometry and elastic recoil detection analysis). Both superlattice series exhibit a strong dependence of hardness, elastic modulus, and fracture toughness on their bilayer periods, which can only be correlated with the in-plane stress variations for VC/ZrC. The VC/HfC superlattices provide their peak-hardness of 36.0 ± 1.6 GPa for Λ = 6 nm and their peak in fracture toughness of 3.5 ± 0.5 MPa√m for Λ = 10 nm.

NbC thin films via reactive DC sputtering in a CH4/Ar atmosphere

We have demonstrated the growth of NbC-Amorphous C films that manifest a well-known nanocomposite structure (Klages and Memming, 1990; Nedfors et al., 2011; Sala et al., 2021). The films were deposited using reactive DC sputtering in a CH4/Ar atmosphere using an insulating substrate near room temperature. A metallic Nb sputtering target was sputtered in an argon/CH4 atmosphere with a pressure range of 5.9 to 8.5 mTorr as the CH4 flow was also varied. Crystalline NbC films were deposited at room temperature at the lowest CH4 flow rate. The films exhibited ohmic electrical response at room temperature. The DC electrical resistivity scaled almost 4 orders of magnitude from 4.39 × 10−4 Ω-cm to 1.08 × 10−1 Ω-cm through changes in CH4 flow rates and the resultant C content of the films. The large variation in resistivity cannot be attributed to the changes in sample composition, e.g. volumetric mixing. It is postulated from XRD and TEM results that the large change in resistivity is due to the decreasing NbC crystallite size with increasing CH4. This leads to additional three-dimensional nanoscale intragranular interfaces and results in increased resistivity. X-ray reflectivity measurements were conducted, and the modelled film density was found to match the expected density for the film compositions as measured using X-ray photoelectron spectroscopy. Elastic recoil detection analysis (ERDA) was used to quantify H content of the films. The H content increased from 5.5 to 22 atomic percent with corresponding increase in CH4 flow. Transmission electron microscopy utilizing precession electron diffraction (PED) was conducted and showed a strong dependence of crystallinity on CH4 flow. A multilayer layer sample with varying CH4 flowrates was examined with TEM and showed that films were amorphous in nature for flow rates above 10 SCCM CH4; in agreement with XRD results.

Tribological behavior of DLC film models in base oils: Analysis of influence of sp3/sp2 ratio and hydrogen content

DLC coatings have been proven in formulated oils used in the automotive industry. The development of electric cars and its consequences on the future of the internal combustion engine makes it increasingly necessary that these coatings take their place in other applications where lubrication is generally of lower quality such as for example strips cold rolling where DLC shows significant potential both for production and finishing cold rolling. As a result, the interest of the behavior of these coatings in base oils takes on a new dimension. In this study, we explore the influence of the composition and the sp3/sp2 ratio on tribological behavior of DLC coatings in mineral and synthetic base oils. Hydrogenated DLC films deposited by conventional PECVD with various levels of hydrogen measured by Elastic Recoil Detection Analysis (ERDA) and non-hydrogenated DLC films deposited by PLD in the nanosecond mode (ns-PLD) and by cathodic arc evaporation, thus allowing to have different sp3/sp2 ratios confirmed by Multiwavelength Raman spectrometry, are tested and compared. The tests are performed on a ball-on-flat device with coated balls to better evaluate wear level. The behavior of highly hydrogenated DLC is of particular interest; with a very high level of durability in both base oils and friction level which comparatively varies between low and very low depending on the base oil.

Effect of hydrogen on the chemical state, stoichiometry and density of amorphous Al2O3 films grown by thermal atomic layer deposition

Amorphous oxide thin films grown by thermal atomic layer deposition (ALD) typically contain high impurity concentrations of hydrogen, which affects both chemistry and structure and thereby the functional properties, such as the barrier properties in, for example, microelectronic and photovoltaic devices. This study discloses the effect of H incorporation in amorphous Al2O3 ALD oxide films on the local chemical binding states of Al, O and H, as well as the oxide density and stoichiometry, by a combined analytical approach using elastic recoil detection analysis, Rutherford backscattering spectroscopy and full chemical state analysis by dual‐source X‐ray photoelectron spectroscopy (XPS)/hard X‐ray photoelectron spectroscopy (HAXPES). The experimental findings are compared with crystalline anhydrous α‐Al2O3 and hydroxide α‐Al (OH)3 reference phases and further supported by molecular dynamic simulations. It is shown that H preferably forms covalent –OH hydroxyl bonds with O in the nearest‐neighbour coordination spheres of interstitial Al cations, which affects both the ligand electronic polarizability and the bond length of the randomly interconnected [AlOn] polyhedral building blocks in the amorphous ALD oxide films.

Enhancing electrocatalytic activity in metallic thin films through surface segregation of carbon.

Thin layers of commonly used adhesion metals i.e., Cr and Ti were annealed to investigate and estimate their impact on the electrochemical properties of the carbon nanomaterials grown on top of them. The microstructure, surface chemistry, and electrochemical activities of these materials were evaluated and compared with those of as-deposited thin films. The results from X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, grazing incidence X-ray diffraction (GIXRD), time-of-flight elastic recoil detection analysis (TOF-ERDA), and conductive atomic force microscopy (C-AFM) indicated the formation of a catalytic graphite layer on Cr following annealing, while no such layer was formed on Ti. This is attributed to the formation of the Cr2O3 layer on annealed Cr, which acts as a barrier to carbon diffusion into the underlying Cr. Conversely, Ti exhibits a high solubility for both carbon and oxygen, preventing the formation of the graphite layer. Cyclic voltammetry results showed that annealed Cr electrodes are electrochemically active towards both dopamine (DA) and ascorbic acid (AA) while no electrochemical activity is exhibited by annealed Ti. Quantum chemical calculations suggested that the presence of carbon as graphene or an amorphous form is critical for the oxidation reaction of probes. These results are significant for comprehending how the distinct solubilities of typical interstitial solutes influence the microstructure of adhesion metal layers and consequently yield diverse electrochemical properties.

Characterization of solar cell passivating contacts using time-of-flight elastic recoil detection analysis

The unambiguous detection of hydrogen in solar cell contact structures is critical to understanding passivation and degradation phenomena. Deuterium is often used to depict the distribution of hydrogen more clearly. However, experimental noise and artifacts can hinder the clear identification of species. This work provides a report of time-of-flight elastic recoil detection (ToF-ERD) analysis to identify H/D contents in a thin poly-Si/SiOx passivating contact. The structure contained a 1.3 nm interfacial SiOx and an n+ doped poly-Si layer with a partly deuterated SiNx coating. The samples were annealed to release H/D, and ToF-ERD was used to detect H/D in monatomic, singly charged forms, without the detection artifacts associated with conventional secondary ion mass spectroscopy. Chlorine ions were used to recoil surface species, which were analyzed to clearly and unambiguously resolve H and D. Depth profiles for the recoiled Si, N, O, D, and H atoms were calculated from the energy and velocity information registered after scattering events, which enabled the analysis of the structure of the multilayer stack. Even though the surface roughness and experimental limitations cause visible broadening of the profiles, which can hinder clear detection at the interfacial oxide, the ability to resolve hydrogen-related species makes ToF-ERD a significant and promising tool for studying the role of hydrogen in the performance and degradation of solar cell passivating contacts.

Electrosynthesis and Performance of Homogeneously Mesoporous Ni-Rich Ni-Pt Thin Films for Efficient Hydrogen Evolution Reaction in Acidic Media

The development of green hydrogen technology requires abundant electrocatalyst materials to (partially) replace costly platinum while maintaining the catalytic efficiency and durability. Nickel is an excellent choice for the partial replacement of Pt for water splitting, and is widely used for electrocatalysis in alkaline media. Although Ni cannot provide an activity identical to Pt, specific nanostructures aimed at a high surface-to-volume ratio, such as nanoporous structures, can significantly improve catalytic efficiency. However, in acidic media, the use of non-noble metals for electrocatalysis requires extensive durability tests to confirm the stability of the alloy. Additionally, the impact of hydrogen itself is often overlooked, as hydrogen is known to cause hydrogen embrittlement in Ni and its alloys.This contribution deals with the synthesis of a homogeneously mesoporous Ni-Pt alloy with high catalytic efficiency (Fig. 1). By electrodeposition from aqueous media, Ni-rich Ni-Pt alloy thin films are synthesised in a wide compositional range (between 60 and 99 at% Ni), depending on the deposition potential. The addition of the amphiphilic block copolymer Pluronic P-123 to the electrolyte formulation enables a micelle-assisted deposition process, resulting in films with homogeneous porosity with an approximate pore size of 10 nm irrespective of composition. Moreover, all thin films are single-phase and nanocrystalline [1], and show excellent performance under hydrogen evolution reaction (HER) in acidic media [2].As determined by Rutherford backscattering (RBS), the as-deposited Ni-Pt thin films with film thickness between 180 nm and 260 nm exhibit Pt enrichment at the surface of 1-2 nm in depth, after which Ni and Pt exhibit constant composition over depth. After hydrogen evolution in 0.5 M H2SO4, a gradient in Ni/Pt ratio over the film thickness is established, indicating preferential leaching of Ni into the electrolyte, and resulting in higher Pt content at the surface. Due to the porosity of the thin films, this leaching affects the entire film thickness. A chronopotentiometric durability test (24 h) reveals that the overpotential stabilises over time, indicating that the leaching of Ni is suppressed once a certain Pt/Ni ratio is attained in the thin films. In addition, the HER electrocatalysis is accompanied by a significant hydrogen uptake, determined by elastic recoil detection analysis (ERDA). Depending on the electrodeposition parameters, the as-deposited thin films already exhibit significant hydrogen concentrations between 2 and 10 at%. After the HER durability test, local cracking is observed by SEM, related to an excess of hydrogen in the thin films. Despite the cracking, no significant detachment of the films from the substrate is observed. The hydrogen contained in the films is assumed to be interstitial and does not affect the metallic nature of the Ni-Pt films. An X-ray photoelectron spectroscopy (XPS) post-analysis shows that the fraction of metallic Ni with respect to Ni in higher oxidation states is higher after exposure to the HER than for the as-prepared surface. Acknowledgement: Financed by the European Union – NextGenerationEU.[1] K. Eiler, J. Fornell, C. Navarro-Senent, E. Pellicer, J. Sort, Nanoscale, 2020, 12, 7749[2] K. Eiler, S. Suriñach, J. Sort, E. Pellicer, Appl. Catal. B, 2020, 265, 118597Figure 1: SEM micrograph of a mesoporous Ni93Pt7 thin film. Figure 1

Evaluating the Ge: C ratio on the bonding structure, hardness, and residual stress of Ge1-x-Cx coatings fabricated by the PE-CVD method

In the present research, the effect of the Ge: C ratio was evaluated and explained on the bonding structure, the hardness, and residual stress of germanium-carbon (Ge1-x-Cx) coatings fabricated by plasma-enhanced chemical vapor deposition (PECVD) method. For characterizing the coatings, a field emission scanning electron microscope (FE-SEM) equipped with an energy dispersive spectrometer (EDS), transmission electron microscope (TEM), Raman spectrometer, Rutherford backscattering spectrometer (RBS), elastic recoil detection (ERD) analysis, X-ray photoelectron spectrometer (XPS), nanoindentation test, and cohesion test were used. by increasing the flow rate ratio of CH4:GeH4 and as a result of decreasing the ratio of Ge: C, the fraction of sp2 C-C and sp3 Ge-C bonds were increased and the fraction of Ge-Ge bonds was decreased. The hardness of the Ge1-x-Cx coatings was heavily reliant on changes in the Ge: C ratio and, consequently, the fraction of the bonds incorporated within the coating structure. To achieve a hard coating, the selection of a moderate carbon content is very important such that it would lead to the formation of maximum sp3 Ge-C bonds alongside slight amounts of sp2 C-C and hydrogen bonds. For very low carbon concentrations, the existence of dominant Ge-Ge bonds would create the coating structure as germanium-like; the excessive rise of the carbon concentration promotes the undesirable graphite-like structures. In the optimum conditions, the hardness of the coating was obtained at 10.1 GPa. The coatings presented a very low residual stress (∼98-240 MPa) despite having suitable hardness.

Cryogenic heavy ion RBS-ERDA depth profiling of ion implanted PET films

The analysis of thin films using heavy ions offers some specific advantages over traditional light ion beam analysis techniques. In this work, polyethylene terephthalate (PET) substrate was implanted with 150 keV Ag+-ions at low temperature at fluences of 1.00 x 1016 and 5.00 x 1016 ions/cm2. A newly constructed low temperature chamber equipped with heavy ion Rutherford Backscattering Spectrometry (HI-RBS) and Elastic Recoil Detection Analysis (HI-ERDA) detectors was used for sample characterisation, using 14 MeV 28Si4+-ions at an irradiation fluence of about 2.40 x 1013 ions/cm2. The analyses were carried out at room temperature and with the sample holder cooled to liquid nitrogen temperature. Silicon beam irradiation effects on the PET were then compared at room- and low-temperature measurements. Significant hydrogen loss of about 64 % relative to pristine PET was observed for room-temperature measurements, whereas for low-temperature analyses the hydrogen loss was about 12 %. The significant release of hydrogen atoms from the surface region of the PET was accompanied by a drastic change in the surface layer composition. For room-temperature measurements, there was surface enhancement of the carbon content by about 31 %, while for low-temperature measurements the accumulation was about 9 % compared to the nominal 45 % content in pristine PET.

Pathway to high performance, low temperature thin-film solid oxide cells grown on porous anodised aluminium oxide

Reversible solid oxide cells (rSOCs) present a promising solution to future energy challenges through the efficient conversion between electrical and chemical energy. To date, the benefits of rSOC technology have been off-limits to portable power and electrolysis applications due to the excessive polarisation resistance of the oxygen electrode at low temperatures, characterised by high area specific resistance (ASR) values below 500 °C. In this work we demonstrate growth of symmetric and complete rSOC structures based on state-of-the-art vertically aligned nanocomposite (VAN) films grown by pulsed laser deposition (PLD) on porous Pt-coated anodised aluminium oxide (AAO) substrates. The symmetric rSOC structures give the first demonstration of an rSOC oxygen electrode with ASR below 0.1 Ωcm2 at temperatures less than 450 °C. This is achieved through oxygen vacancy tuning by annealing, as confirmed by Time-of-Flight Elastic Recoil Detection Analysis (ToF-ERDA) and Rutherford Backscattering Spectrometry (RBS) measurements. Thus, the present work describes a promising route towards future high-performance rSOC devices for portable power applications.

Molecular layer deposition of hybrid silphenylene-based dielectric film

Molecular layer deposition (MLD) offers molecular level control in deposition of organic and hybrid thin films. This article describes a new type of inorganic–organic silicon-based MLD process where Aluminium chloride (AlCl3) and 1,4-bis(triethoxysilyl)benzene (BTEB) were used as precursors. Hybrid films were deposited at a temperature range of 300 to 500 °C and high growth per cycle (GPC) up to 1.94 Å was obtained. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) were used to analyze the appearance of the film surface. The hybrid film was amorphous in low-magnification FESEM images but some particulates appeared in high-magnification FESEM images (200 k). Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), Time-of-flight elastic recoil detection analysis (ToF-ERDA), and X-ray photoelectron spectroscopy (XPS) were employed to analyze the structure and composition of the hybrid film. The ratio of Al/Si in the hybrid film was 0.8. The storage environment of the films affected their capacitance, dielectric constant, leakage performance, and breakdown voltage. A film stored in a high vacuum (10–6 mbar) environment had low leakage current density (< 10–6 A × cm−2 at an applied voltage of 28 V) and a dielectric constant of 4.94, which was much smaller than after storing in a humid ambient environment.Graphical abstract

Substrate bias effects on cathodic arc deposited Cr coatings

We investigate the effects of substrate bias on cathodic arc deposition of Cr coatings without external substrate heating at four different substrate bias levels, floating, −30, −50, and −70 V. After 10 min of deposition, the substrate temperature reaches 180, 210, 230, and 260 °C for floating potential, −30, −50, and −70 V, respectively. Time-of-flight energy elastic recoil detection analysis shows that all grown coatings are of high purity, with no coating containing more than 0.2 at.% of C and/or O. Increasing the substrate bias also reduces the number of macroparticles, steers the texture from preferred [110]- to [100]-orientation and induces a residual compressive stress of ∼450 MPa in the coatings. The hardness of the coatings remains at a constant 7.5 GPa irrespective of the substrate bias. The four-point probe resistivity of the grown coatings is 15–17 μΩcm regardless of substrate bias, close to the 12.9 μΩcm of bulk Cr.

A systematical investigation of layer growth rate, impurity level and morphology evolution in TiO2 thin films grown by ALD between 100 and 300 °C

TiO2 thin films prepared by atomic layer deposition (ALD) have attracted great attention due to the widespread application of the oxide as a promising charge storage material for lithium or proton batteries. In this work, we study TiO2 film grown on Si substrates by atomic layer deposition with tetrakis (dimethylamino) titanium as metal precursor (TDMAT) and water vapour as an oxidant. The chemical composition and impurity content of the film as a function of growth temperature is studied by Ion Beam Analysis (IBA). D2O (99.8%) was used as oxidant to study the film growth to distinguish between hydrogen atoms originating from the water oxidant or the metal precursor. Combining ellipsometry with Rutherford Backscattering Spectrometry (RBS), Nuclear Reaction Analysis (NRA) and Elastic Recoil Detection Analysis (ERDA) reveals film density as a function of growth temperature. Atomic force microscopy (AFM) was used to characterize the film surface structure. By investigating the structural and compositional range of ALD TiO2 films will open the new opportunities of application.

Positron annihilation spectroscopy of thermally annealed hydrogenated amorphous carbon films

Hydrogenated amorphous carbon (a-C:H) films are prepared using a bipolar-type plasma-based ion implantation and deposition system, followed by thermal annealing of the films at 200 °C-800 °C. The structural and compositional changes are examined by Raman spectroscopy, Rutherford backscattering spectrometry, and elastic recoil detection analysis (ERDA). Positron annihilation spectroscopy (PAS) is also conducted to investigate the behavior of voids in the films. The results of Raman and ERDA measurement clearly show that the sp2 ring clusters increase, and hydrogen content apparently decreases at temperatures between 400 °C and 800 °C. Uncorrelated behaviors between positron lifetimes and line-shape parameters are observed in the PAS results, which can be attributed to several competing effects, such as hydrogen release, bond reconstruction, and electronic-state change of voids. Furthermore, it is suggested that the graphitization of the films begins from the surface to the inside, accompanied by the hydrogen release that is related to the void behavior.

Combination of ERDA, FTIR spectroscopy and NanoSIMS for the characterization of hydrogen incorporation in natural diamonds

Hydrogen is a volatile element involved in several geological processes ranging from rock weakening to the initiation of tectonic plates. Because it is present in diamond, the investigation of hydrogen content in natural diamonds could provide valuable information. Such studies are scarce despite hydrogen being among the main impurities in their structure. Using Elastic Recoil Detection Analysis, Fourier Transform Infrared spectroscopy and Nanoscale Secondary Ions Mass Spectrometry, we analyzed the incorporation of hydrogen in three diamonds growth habits: octahedral, cuboid and fibrous. Up to 25 wt. ppm of hydrogen was measured in some samples, placing hydrogen as the second most abundant impurity in natural diamonds after nitrogen and before boron. Comparison between the three methods indicates a difference in the main mode of hydrogen incorporation depending on the growth habit. Hydrogen is more readily incorporated in the fibrous and cuboid habits compared to the octahedral one. We also show that the incorporation of hydrogen is not correlated with the incorporation of nitrogen. Results suggest no chemical equilibration of hydrogen by diffusion through geological times and also confirm that not all hydrogen may be infrared active.

Atomic Layer Deposition of Boron‐Doped Al2O3 Dielectric Films

AbstractThis paper presents preparation of boron‐doped Al2O3 thin films by atomic layer deposition (ALD) using phenylboronic acid (PBA) and trimethylaluminum (TMA) as precursors. Deposition temperatures of 160–300 °C are studied, giving a maximum growth per cycle (GPC) of 0.77 Å at 200 °C. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) are used to study the surface morphology and roughness of the films. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR), Time‐of‐flight elastic recoil detection analysis (ToF‐ERDA), and X‐ray photoelectron spectroscopy (XPS) are used to study the composition of the films. An annealing process is carried out at 450 °C for 1 h to investigate its effect on the elemental composition and electrical properties of the boron‐doped Al2O3 thin films. The boron‐doped Al2O3 70 nm thick film deposited at 200 °C has a boron content of 3.7 at.% with low leakage current density (10−9 to 10−6 A cm−2) when the film thickness is 70 nm. The dielectric constant of this boron doped Al2O3 film is 5.18.

The sensory and photo-catalytic properties of graphene oxide and polyimide thin films implanted by 1500 keV Cu ions

Thin films of polyimide (PI) and graphene oxide (GO) were exposed to the accelerated Cu-ions with an energy of 1500 keV at different ion fluences (3.75 × 1012; 3.75 × 1014; 1 × 1016) cm−2. The reason for Cu-ion irradiation lies in the modification of thin PI and GO layers and their subsequent use in electronics, photo-catalysis and humidity sensing. It was expected that three ways would primarily carry out modification: i) interaction of the accelerated ions with atoms and electrons of the irradiated films, ii) implantation of Cu ions inside the matrices and their attachment to the structures in the form of CuO, and iii) formation of C and Cu aggregates and Cu nanoparticles in the subsurface layer to form an electrically conductive network. The effects of the interactions of energetic Cu-ions on the PI and GO matrices, including the prediction of the depth of Cu ion penetration, were simulated by SRIM software. Elemental changes, including the depth profiles of implanted Cu-ions, were investigated by Rutherford backscattering spectrometry (RBS) and Elastic recoil detection analysis (ERDA). Changes in the chemical bonding on the PI and GO surfaces were studied by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The effect of energetic Cu-ions on the surface morphology was analyzed by Atomic force microscopy (AFM). For the possible application of PI and GO composites in electronics and sensory, the sheet resistivity were measured by the two- point method and the effect of air humidity on electrical properties was studied. Furthermore, the degradation of Rhodamine B solution in the presence of prepared composites under UV-light irradiation was measured for possible use in photo-catalysis. It was found that the interaction of Cu- ions with the matrix leads to the release of oxygen and hydrogen, resulting in an increase in carbon concentration. The increase in carbon concentration leads to an increase in the electrical conductivity of both materials. The irradiation with Cu ion fluence of 1 × 1016 cm−2 probably formed in PI a subsurface conducting network that reduced the sheet resistivity by almost eleven orders of magnitude. The ion irradiation by Cu ion with fluences below 1 × 1016 cm−2 enhances the photo- catalytic properties of both used materials and the best result was achieved in the case of PI irradiated by the ion fluence of 3.75 × 1014 cm−2.