Decomposition Characteristics of the TTIP (Tetraisopropyl Orthotitanate) Precursor for Atomic Layer Deposition

The decomposition of tetraisopropyl orthotitanate (TTIP), a representative precursor used in the atomic layer deposition (ALD) of titanium dioxide (TiO₂) film, and the resulting changes in the thin film properties of the TiO₂ film were investigated. TTIP was evaluated after exposure to thermal stress in an enclosed container. The vapor pressure results provide reasonable evidence that impurities are generated by the decomposition of TTIP under thermal stress. These impurities led to changes in the thermal properties of TTIP and changes in the growth rate, morphology, and composition of the thin film; in particular, these impurities increased the unstable oxidation states of Ti²⁺ (TiO) content in the TiO₂ film. The changes in the properties of the TiO₂ film resulting from the changes in the physical properties of TTIP led to a change in the properties of the device. We proved that the thermal stability of the precursor is a factor that can determine the reliability of the ALD process and the resulting thin film. Additionally, systematic evaluation of the precursor can provide useful information that can improve the development of the precursor and the consistency of the process.     

Structure and Electrical Behavior of Hafnium-Praseodymium Oxide Thin Films Grown by Atomic Layer Deposition

Crystal structure and electrical properties of hafnium-praseodymium oxide thin films grown by atomic layer deposition on ruthenium substrate electrodes were characterized and compared with those of undoped HfO₂ films. The HfO₂ reference films crystallized in the stable monoclinic phase of HfO₂. Mixing HfO₂ and PrO_x resulted in the growth of nanocrystalline metastable tetragonal HfO₂. The highest relative permittivities reaching 37–40 were measured for the films with tetragonal structures that were grown using HfO₂:PrO_x cycle ratio of 5:1 and possessed Pr/(Pr + Hf) atomic ratios of 0.09–0.10. All the HfO₂:PrO_x films exhibited resistive switching behavior. Lower commutation voltages and current values, promising in terms of reduced power consumption, were achieved for the films grown with HfO₂:PrO_x cycle ratios of 3:1 and 2:1 and showing Pr/(Pr + Hf) atomic ratios of 0.16–0.23. Differently from the undoped HfO₂ films, the Pr-doped films showed low variability of resistance state currents and stable endurance behavior, extending over 10⁴ switching cycles.     

Microstructures of HfOx Films Prepared via Atomic Layer Deposition Using La(NO3)3·6H2O Oxidants

Hafnium oxide (HfO_x) films have a wide range of applications in solid-state devices, including metal–oxide–semiconductor field-effect transistors (MOSFETs). The growth of HfO_x films from the metal precursor tetrakis(ethylmethylamino) hafnium with La(NO₃)₃·6H₂O solution (LNS) as an oxidant was investigated. The atomic layer deposition (ALD) conditions were optimized, and the chemical state, surface morphology, and microstructure of the prepared films were characterized. Furthermore, to better understand the effects of LNS on the deposition process, HfO_x films deposited using a conventional oxidant (H₂O) were also prepared. The ALD process using LNS was observed to be self-limiting, with an ALD temperature window of 200–350 °C and a growth rate of 1.6 Å per cycle, two times faster than that with H₂O. HfO_x films deposited using the LNS oxidant had smaller crystallites than those deposited using H₂O, as well as more suboxides or defects because of the higher number of grain boundaries. In addition, there was a difference in the preferred orientations of the HfO_x films deposited using LNS and H₂O, and consequently, a difference in surface energy. Finally, a film growth model based on the surface energy difference was proposed to explain the observed growth rate and crystallite size trends.     

Inhibition of Crystal Growth during Plasma Enhanced Atomic Layer Deposition by Applying BIAS

In this study, the influence of direct current (DC) biasing on the growth of titanium dioxide (TiO₂) layers and their nucleation behavior has been investigated. Titania films were prepared by plasma enhanced atomic layer deposition (PEALD) using Ti(OiPr)₄ as metal organic precursor. Oxygen plasma, provided by remote inductively coupled plasma, was used as an oxygen source. The TiO₂ films were deposited with and without DC biasing. A strong dependence of the applied voltage on the formation of crystallites in the TiO₂ layer is shown. These crystallites form spherical hillocks on the surface which causes high surface roughness. By applying a higher voltage than the plasma potential no hillock appears on the surface. Based on these results, it seems likely, that ions are responsible for the nucleation and hillock growth. Hence, the hillock formation can be controlled by controlling the ion energy and ion flux. The growth per cycle remains unchanged, whereas the refractive index slightly decreases in the absence of energetic oxygen ions.     

Single-Crystal Y2O3 Epitaxially on GaAs(001) and (111) Using Atomic Layer Deposition

Single-crystal atomic-layer-deposited (ALD) Y₂O₃ films 2 nm thick were epitaxially grown on molecular beam epitaxy (MBE) GaAs(001)-4 × 6 and GaAs(111)A-2 × 2 reconstructed surfaces. The in-plane epitaxy between the ALD-oxide films and GaAs was observed using in-situ reflection high-energy electron diffraction in our uniquely designed MBE/ALD multi-chamber system. More detailed studies on the crystallography of the hetero-structures were carried out using high-resolution synchrotron radiation X-ray diffraction. When deposited on GaAs(001), the Y₂O₃ films are of a cubic phase and have (110) as the film normal, with the orientation relationship being determined: Y₂O₃(110)[001][1¯10]//GaAs(001)[110][11¯0]. On GaAs(111)A, the Y₂O₃ films are also of a cubic phase with (111) as the film normal, having the orientation relationship of Y₂O₃(111)[21¯1¯][011¯]//GaAs(111)[2¯11][01¯1]. The relevant orientation for the present/future integrated circuit platform is (001). The ALD-Y₂O₃/GaAs(001)-4 × 6 has shown excellent electrical properties. These include small frequency dispersion in the capacitance-voltage (CV) curves at accumulation of ~7% and ~14% for the respective p- and n-type samples with the measured frequencies of 1 MHz to 100 Hz. The interfacial trap density (D_it) is low of ~10¹² cm⁻²eV⁻¹ as extracted from measured quasi-static CVs. The frequency dispersion at accumulation and the D_it are the lowest ever achieved among all the ALD-oxides on GaAs(001).     

Tuning of Emission Wavelength of CaS:Eu by Addition of Oxygen Using Atomic Layer Deposition

Atomic layer deposition (ALD) technology has unlocked new ways of manipulating the growth of inorganic materials. The fine control at the atomic level allowed by ALD technology creates the perfect conditions for the inclusion of new cationic or anionic elements of the already-known materials. Consequently, novel material characteristics may arise with new functions for applications. This is especially relevant for inorganic luminescent materials where slight changes in the vicinity of the luminescent centers may originate new emission properties. Here, we studied the luminescent properties of CaS:Eu by introducing europium with oxygen ions by ALD, resulting in a novel CaS:EuO thin film. We study structural and photoluminescent properties of two different ALD deposited Eu doped CaS thin films: Eu(thd)₃ which reacted with H₂S forming CaS:Eu phosphor, or with O₃ originating a CaS:EuO phosphor. It was found that the emission wavelength of CaS:EuO was 625.8 nm whereas CaS:Eu was 647 nm. Thus, the inclusion of O²⁻ ions by ALD in a CaS:Eu phosphor results in the blue-shift of 21.2 nm. Our results show that ALD can be an effective way to introduce additional elements (e.g., anionic elements) to engineer the physical properties (e.g., inorganic phosphor emissions) for photonics and optoelectronics.     

Surface Modification of Nanoporous Anodic Alumina during Self-Catalytic Atomic Layer Deposition of Silicon Dioxide from (3-Aminopropyl)Triethoxysilane

Changes associated to atomic layer deposition (ALD) of SiO₂ from 3-aminopropyl triethoxysilane (APTES) and O₃, on a nanoporous alumina structure, obtained by two-step electrochemical anodization in oxalic acid electrolyte (Ox sample) are analysed. A reduction of 16% in pore size for the Ox sample, used as support, was determined by SEM analysis after its coverage by a SiO₂ layer (Ox+SiO₂ sample), independently of APTES or O₃ modification (Ox+SiO₂/APTES and Ox+SiO₂/APTES/O₃ samples). Chemical surface modification was determined by X-ray photoelectron spectroscopy (XPS) technique during the different stages of the ALD process, and differences induced at the surface level on the Ox nanoporous alumina substrate seem to affect interfacial effects of both samples when they are in contact with an electrolyte solution according to electrochemical impedance spectroscopy (EIS) measurements, or their refraction index as determined by spectroscopic ellipsometry (SE) technique. However, no substantial differences in properties related to the nanoporous structure of anodic alumina (photoluminescent (PL) character or geometrical parameters) were observed between Ox+SiO₂/APTES and Ox+SiO₂/APTES/O₃ samples.     

Gas-Phase Deposition of Ultrathin Aluminium Oxide Films on Nanoparticles at Ambient Conditions

We have deposited aluminium oxide films by atomic layer deposition on titanium oxide nanoparticles in a fluidized bed reactor at 27 ± 3 °C and atmospheric pressure. Working at room temperature allows the coating of heat-sensitive materials, while working at atmospheric pressure would simplify the scale-up of this process. We performed 4, 7 and 15 cycles by dosing a predefined amount of precursors, i.e., trimethyl aluminium and water. We obtained a growth per cycle of 0.14–0.15 nm determined by transmission electron microscopy (TEM), similar to atomic layer deposition (ALD) experiments at a few millibars and ~180 °C. We also increased the amount of precursors dosed by a factor of 2, 4 and 6 compared to the base case, maintaining the same purging time. The growth per cycle (GPC) increased, although not linearly, with the dosing time. In addition, we performed an experiment at 170 °C and 1 bar using the dosing times increased by factor 6, and obtained a growth per cycle of 0.16 nm. These results were verified with elemental analysis, which showed a good agreement with the results from TEM pictures. Thermal gravimetric analysis (TGA) showed a negligible amount of unreacted molecules inside the alumina films. Overall, the dosage of the precursors is crucial to control precisely the growth of the alumina films at atmospheric pressure and room temperature. Dosing excess precursor induces a chemical vapour deposition type of growth due to the physisorption of molecules on the particles, but this can be avoided by working at high temperatures.     

The Influence of ZnO Oxide Layer on the Physicochemical Behavior of Ti6Al4V Titanium Alloy

Titanium and its alloys are characterized by high biocompatibility and good corrosion resistance as a result of the ability to form a TiO₂ oxide layer. However, based on literature data it can be concluded that titanium degradation products, in the form of titanium particles, metal-protein groups, oxides and ions, may cause allergic, inflammatory reactions and bone resorption. The corrosion process of Ti6Al4V in the human body environment may be intensified by a decreased pH and concentration of chloride compounds. The purpose of this article was to analyze the corrosion resistance of the Ti6Al4V alloy, obtained by the selective laser melting method in a corrosion solution of neutral pH and in a solution simulating peri-implant inflammatory conditions. Additionally, the influence of zinc oxide deposited by the atomic layer deposition method on the improvement of the physicochemical behavior of the Ti6Al4V alloy was analyzed. In order to characterize the ZnO layer, tests of chemical and phase composition as well as surface morphology investigation were performed. As part of the assessment of the physicochemical properties of the uncoated samples and those with the ZnO layer, tests of wetting angle, pitting corrosion and impedance corrosion were carried out. The number of ions released after the potentiodynamic test were measured using the inductively coupled plasma atomic emission spectrometry (ICP–AES) method. It can be concluded that samples after surface modification (with the ZnO layer) were characterized by favorable physicochemical properties and had higher corrosion resistance.     

The Effects of Zr Doping on the Optical,Electrical and Microstructural Properties of Thin ZnO Films Deposited by Atomic Layer Deposition

Transparent conducting oxides (TCOs), with high optical transparency (≥85%) and low electrical resistivity (10⁻⁴ Ω·cm) are used in a wide variety of commercial devices. There is growing interest in replacing conventional TCOs such as indium tin oxide with lower cost, earth abundant materials. In the current study, we dope Zr into thin ZnO films grown by atomic layer deposition (ALD) to target properties of an efficient TCO. The effects of doping (0–10 at.% Zr) were investigated for ~100 nm thick films and the effect of thickness on the properties was investigated for 50–250 nm thick films. The addition of Zr⁴⁺ ions acting as electron donors showed reduced resistivity (1.44 × 10⁻³ Ω·cm), increased carrier density (3.81 × 10²⁰ cm⁻³), and increased optical gap (3.5 eV) with 4.8 at.% doping. The increase of film thickness to 250 nm reduced the electron carrier/photon scattering leading to a further reduction of resistivity to 7.5 × 10⁻⁴ Ω·cm and an average optical transparency in the visible/near infrared (IR) range up to 91%. The improved n-type properties of ZnO: Zr films are promising for TCO applications after reaching the targets for high carrier density (>10²⁰ cm⁻³), low resistivity in the order of 10⁻⁴ Ω·cm and high optical transparency (≥85%).     

Critical Role of Etching Parameters in the Evolution of Nano Micro SLA Surface on the Ti6Al4V Alloy Dental Implants

The surface of dental implants plays a vital role in early and more predictable osseointegration. SLA (sandblasted large grit and acid-etched) represents the most widely accepted, long-term clinically proven surface. Primarily, dental implants are manufactured by either commercially pure titanium (CP-Ti) or Ti6Al4V ELI alloy. The acid etch behavior of CP-Ti is well known and its effects on the surface microstructure and physicochemical properties have been studied by various researchers in the past. However, there is a lack of studies showing the effect of acid etching parameters on the Ti6Al4V alloy surface. The requirement of the narrow diameter implants necessitates implant manufacturing from alloys due to their high mechanical properties. Hence, it is necessary to have an insight on the behavior of acid etching of the alloy surface as it might be different due to changed compositions and microstructure, which can further influence the osseointegration process. The present research was carried out to study the effect of acid etching parameters on Ti6Al4V ELI alloy surface properties and the optimization of process parameters to produce micro- and nanotopography on the dental implant surface. This study shows that the Ti6Al4V ELI alloy depicts an entirely different surface topography compared to CP-Ti. Moreover, the surface topography of the Ti6Al4V ELI alloy was also different when etching was done at room temperature compared to high temperature, which in turn affected the behavior of the cell on these surfaces. Both microns and nano-level topography were achieved through the optimized parameters of acid etching on Ti6Al4V ELI alloy dental implant surface along with improved roughness, hydrophilicity, and enhanced cytocompatibility.     

Evaluation of Bacterial Adhesion to the ZrO2 Atomic Layer Deposited on the Surface of Cobalt-Chromium Dental Alloy Produced by DMLS Method

The main purpose of the research was to analyze the influence of surface modification of the cobalt-based alloy used in dental prosthetics by applying zirconium oxide (ZrO₂) layers using the ALD (Atomic Layer Deposition) method. The samples were made using the DMLS (Direct Metal Laser Sintering) technique, and their surfaces were prepared in accordance with the principles of removable partial dentures (RPDs). A 50 nm-thick zirconium oxide coating was applied to the prepared substrates. This paper deals with the issues of prosthetic stomatopathy, which is a complex of pathological changes occurring in approx. 40% of the Polish population using removable dentures. Often, these changes, occurring on the mucosa, are related to improper performance, allergic reactions or the multiplication of bacteria on the surface of partial dentures. An innovative method of surface modification was proposed, together with the analysis of its influence on the physicochemical properties of the alloy and the adhesion of bacteria to the surface.     

Comparison of Chemical and Mechanical Surface Treatments on Metallic Precision Spheres for Using as Optical Reference Artifacts

The improvement of industrial manufacturing processes requires measurement procedures and part inspection tasks to be faster and faster while remaining effective. In this sense, the capabilities of noncontact measuring systems are of great help, not only because of the great amount of data they provide but also for the ease of the integration of these systems as well as their automation, minimising the impact on the industry. This work presents a comparative study on the influence of two surface treatments performed on low-cost, high-precision metallic spheres on the suitability of these spheres to be used as artefacts for the calibration of optical sensors, specifically laser triangulation sensors. The first surface treatment is sandblasting (a mechanical process), whose effect has been studied and presented in previous work. The second treatment focused on in this paper is acid etching (a chemical process). The comparison has been performed by evaluating the same metrological characteristics on two identical groups of spheres of similar type (diameter and accuracy), each of which was subjected to a different treatment. It was necessary to obtain the reference values of the metrological parameters with high accuracy, which involved measuring the spheres with a coordinate measuring machine (CMM) by contact probing. Likewise, spheres were scanned by a laser triangulation sensor mounted on the same CMM. The results derived from both the contact and laser measurements and before and after treating the surfaces were used to compare four parameters: point density, sphere diameter, sphere form deviation, and standard deviation of the best-fit sphere to the corresponding point cloud. This research has revealed that acid etching produces better optical qualities on the surfaces than the mirror-like original ones, thus enhancing the laser sensor capturing ability. However, such chemical etching has affected the metrological characteristics of the spheres to a greater extent than that produced by sandblasting. This difference is due to the variability of the chemical etching, caused by the high aggressiveness of the acid, which makes the process very sensitive to the time of exposure to the acid and the orientations of the spheres in the bath.     

Unusual Dependence of the Diamond Growth Rate on the Methane Concentration in the Hot Filament Chemical Vapor Deposition Process

Although the growth rate of diamond increased with increasing methane concentration at the filament temperature of 2100 °C during a hot filament chemical vapor deposition (HFCVD), it decreased with increasing methane concentration from 1% CH₄ –99% H₂ to 3% CH₄ –97% H₂ at 1900 °C. We investigated this unusual dependence of the growth rate on the methane concentration, which might give insight into the growth mechanism of a diamond. One possibility would be that the high methane concentration increases the non-diamond phase, which is then etched faster by atomic hydrogen, resulting in a decrease in the growth rate with increasing methane concentration. At 3% CH₄ –97% H₂, the graphite was coated on the hot filament both at 1900 °C and 2100 °C. The graphite coating on the filament decreased the number of electrons emitted from the hot filament. The electron emission at 3% CH₄ –97% H₂ was 13 times less than that at 1% CH₄ –99% H₂ at the filament temperature of 1900 °C. The lower number of electrons at 3% CH₄ –97% H₂ was attributed to the formation of the non-diamond phase, which etched faster than diamond, resulting in a lower growth rate.     

Application of Electrophoretic Deposition as an Advanced Technique of Inhibited Polymer Films Formation on Metals from Environmentally Safe Aqueous Solutions of Inhibited Formulations

The presented paper analyzes polymer films formed from aqueous solutions of organosilanes, corrosion inhibitors and their compositions. Methods of depositing inhibited films on metal samples, such as dipping and exposure of the sample in a modifying solution, as well as an alternative method, electrophoretic deposition (EPD), are discussed. Information is provided on the history of the EPD method, its essence, production process, areas of application of this technology, advantages over existing analogues, as well as its varieties. The article considers the promise of using the EPD method to form protective inhibited polymer films on metal surfaces from aqueous solutions of inhibitor formulations consisting of molecules of organosilanes and corrosion inhibitors.     

Catalyst-Less and Transfer-Less Synthesis of Graphene on Si(100) Using Direct Microwave Plasma Enhanced Chemical Vapor Deposition and Protective Enclosures

In this study, graphene was synthesized on the Si(100) substrates via the use of direct microwave plasma-enhanced chemical vapor deposition (PECVD). Protective enclosures were applied to prevent excessive plasma etching of the growing graphene. The properties of synthesized graphene were investigated using Raman scattering spectroscopy and atomic force microscopy. Synthesis time, methane and hydrogen gas flow ratio, temperature, and plasma power effects were considered. The synthesized graphene exhibited n-type self-doping due to the charge transfer from Si(100). The presence of compressive stress was revealed in the synthesized graphene. It was presumed that induction of thermal stress took place during the synthesis process due to the large lattice mismatch between the growing graphene and the substrate. Importantly, it was demonstrated that continuous horizontal graphene layers can be directly grown on the Si(100) substrates if appropriate configuration of the protective enclosure is used in the microwave PECVD process.     

Covalent Immobilization of Organic Photosensitizers on the Glass Surface: Toward the Formation of the Light-Activated Antimicrobial Nanocoating

Two highly efficient commercial organic photosensitizers—azure A (AA) and 5-(4-aminophenyl)-10,15,20-(triphenyl)porphyrin (APTPP)—were covalently attached to the glass surface to form a photoactive monolayer. The proposed straightforward strategy consists of three steps, i.e., the initial chemical grafting of 3-aminopropyltriethoxysilane (APTES) followed by two chemical postmodification steps. The chemical structure of the resulting mixed monolayer (MIX_TC_APTES@glass) was widely characterized by X-ray photoelectron (XPS) and Raman spectroscopies, while its photoactive properties were investigated in situ by UV–Vis spectroscopy with α-terpinene as a chemical trap. It was shown that both photosensitizers retain their activity toward light-activated generation of reactive oxygen species (ROS) after immobilization on the glassy surface and that the resulting nanolayer shows high stability. Thanks to the complementarity of the spectral properties of AA and APTPP, the effectiveness of the ROS photogeneration under broadband illumination can be optimized. The reported light-activated nanocoating demonstrated promising antimicrobial activity toward Escherichia coli (E. coli), by reducing the number of adhered bacteria compared to the unmodified glass surface.     

Enhanced Cyclability of Cr8O21 Cathode for PEO-Based All-Solid-State Lithium-Ion Batteries by Atomic Layer Deposition of Al2O3

Cr₈O₂₁ can be used as the cathode material in all-solid-state batteries with high energy density due to its high reversible specific capacity and high potential plateau. However, the strong oxidation of Cr₈O₂₁ leads to poor compatibility with polymer-based solid electrolytes. Herein, to improve the cycle performance of the battery, Al₂O₃ atomic layer deposition (ALD) coating is applied on Cr₈O₂₁ cathodes to modify the interface between the electrode and the electrolyte. X-ray photoelectron spectroscopy, scanning electron microscope, transmission electron microscope, and Fourier transform infrared spectroscopy, etc., are used to estimate the morphology of the ALD coating and the interface reaction mechanism. The electrochemical properties of the Cr₈O₂₁ cathodes are investigated. The results show that the uniform and dense Al₂O₃ layer not only prevents the polyethylene oxide from oxidization but also enhances the lithium-ion transport. The 12-ALD-cycle-coated electrode with approximately 4 nm Al₂O₃ layer displays the optimal cycling performance, which delivers a high capacity of 260 mAh g⁻¹ for the 125th cycle at 0.1C with a discharge-specific energy of 630 Wh kg⁻¹.     

Influence of Conditioning Temperature on Defects in the Double Al2O3/ZnO Layer Deposited by the ALD Method

In this work, we present the results of defects analysis concerning ZnO and Al₂O₃ layers deposited by atomic layer deposition (ALD) technique. The analysis was performed by the X-band electron paramagnetic resonance (EPR) spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) methods. The layers were either tested as-deposited or after 30 min heating at 300 °C and 450 °C in Ar atmosphere. TEM and XPS investigations revealed amorphous nature and non-stoichiometry of aluminum oxide even after additional high-temperature treatment. EPR confirmed high number of defect states in Al₂O₃. For ZnO, we found the as-deposited layer shows ultrafine grains that start to grow when high temperature is applied and that their crystallinity is also improved, resulting in good agreement with XPS results which indicated lower number of defects on the layer surface.     

The Role of Ambient Gas and Pressure on the Structuring of Hard Diamond-Like Carbon Films Synthesized by Pulsed Laser Deposition

Hard carbon thin films were synthesized on Si (100) and quartz substrates by the Pulsed Laser Deposition (PLD) technique in vacuum or methane ambient to study their suitability for applications requiring high mechanical resistance. The deposited films’ surface morphology was investigated by scanning electron microscopy, crystalline status by X-ray diffraction, packing and density by X-ray reflectivity, chemical bonding by Raman and X-ray photoelectron spectroscopy, adherence by “pull-out” measurements and mechanical properties by nanoindentation tests. Films synthesized in vacuum were a-C DLC type, while films synthesized in methane were categorized as a-C:H. The majority of PLD films consisted of two layers: one low density layer towards the surface and a higher density layer in contact with the substrate. The deposition gas pressure played a crucial role on films thickness, component layers thickness ratio, structure and mechanical properties. The films were smooth, amorphous and composed of a mixture of sp³-sp² carbon, with sp³ content ranging between 50% and 90%. The thickness and density of the two constituent layers of a film directly determined its mechanical properties.