Search Results (32)

An Al₂O₃/AlN stack deposited via Atomic Layer Deposition (ALD) methods as a gate insulator for silicon carbide (4H-SiC) has been investigated, focusing on the effects of different Al₂O₃ deposition processes on the nitride layer. In particular, dielectric stacks, consisting of a 10 nm AlN interface (001)-oriented layer directly grown on a 4H–SiC substrate and in 20 nm of additional amorphous Al₂O₃ layers were synthesized in sequential deposition runs by thermal ALD (T-ALD) or plasma-enhanced ALD (PEALD) methods. The evolution of the phenomena occurring at the Al₂O₃/AlN interfaces has been established by in situ ellipsometry measurements. Strong effects of the oxygen plasma because of the O-Al-N bond formation have been clearly observed and corroborated by ex situ structural and electrical characterizations, especially in the case of the plasma-enhanced Al₂O₃ process. In particular, the Al₂O₃/AlN bilayer grown by the Al₂O₃ T-ALD method exhibited good insulating behavior and an 8.7-high dielectric constant was measured. By contrast, the Al₂O₃/AlN bilayer grown by the Al₂O₃ PEALD method demonstrated poor insulating properties. Full article

Membrane separation is an efficient approach for volatile organic compound (VOC) recovery from industrial off-gases due to its low energy consumption, compact design, and operational simplicity. Membrane-based VOC recovery critically depends on the membrane material, which must exhibit high VOC permeability and selectivity under mixed-gas conditions. In this study, novel highly selective membranes for VOC removal based on polydecylmethylsiloxane (PAMS-10) were synthesized using both polydimethylsiloxane and various α,ω-dienes as cross-linkers: 1,7-octadiene (OD), 1,9-decadiene (DD), and 1,11-dodecadiene (DdD). The influence of cross-linker concentration and length on mechanical, structural, sorption, and transport properties was examined extensively. The combination of three independent experimental methods (time-lag, vapor permeation, and in situ spectroscopic ellipsometry) revealed that increasing α,ω-diene concentration and decreasing its length led to a reduction in the diffusivity and permeability of permanent gases, gaseous hydrocarbons, and VOC vapors. For VOC/N₂ separation, the slightly cross-linked OD-1 membrane and the DdD-5 membrane, cross-linked with long 1,11-dodecadiene, demonstrated outstanding mixed-gas selectivities of 950/921/314/840 and 940/1084/233/1106 for toluene/n-octane/i-octane/n-butyl acetate, respectively. Notably, the DD-5 membrane, cross-linked with 1,9-decadiene, matching the length of the PAMS-10 side chain substituent, exhibited the best mechanical properties and mixed-gas selectivity comparable to the ideal selectivity, a unique behavior attributed to optimal supramolecular organization. Full article

The optical properties, electronic structure and morphology of thin films of the polymer donor PTB7-Th blended with either the fullerene acceptor PC70BM or the non-fullerene acceptor ZY-4Cl were systematically investigated to evaluate their annealing-induced evolution. Thin films were characterized using UV–Vis–NIR absorption spectroscopy, spectroscopic ellipsometry, ATR-FTIR spectroscopy, atomic force microscopy (AFM), and nano-IR analysis. In situ stepwise thermal annealing revealed distinct changes in absorption edge parameters, indicating thermally induced modifications in the electronic structure of the blend films. Ellipsometric analysis showed that elevated temperatures significantly affect the refractive index and extinction coefficient spectra. AFM measurements demonstrated markedly different surface morphology evolution for the two blend systems, with pronounced needle-shaped crystallites formation observed in PTB7-Th:ZY-4Cl films after annealing at 100 °C. Nano-IR characterization identified these crystallites as predominantly PTB7-Th, indicating phase separation driven by thermal treatment. The combined optical and structural results reveal distinct annealing-induced changes in the blend. Finally, BHJ solar cells, based on PTB7-Th:PC70BM and PTB7-Th:ZY-4Cl active layers, were fabricated, and their photovoltaic response was demonstrated. Full article

The thermal behavior of a three-layer structure—glass/ITO/TAPC/CBP/BPhen—in an OLED system was investigated using in situ spectroscopic ellipsometry during controlled heating from room temperature to 120 °C over 60 min, simulating the ageing process and analyzing degradation kinetics. Variations in Ψ and Δ spectra were observed across the entire 0.7–5.9 eV spectral range, with five distinct anomalies, particularly in the UV region. An anomaly at approximately 66 °C was attributed to the glass transition temperature T_g of BPhen, while another two at around 82 °C and at around 112 °C corresponded to the first-order phase transition of TAPC and T_g of CBP, respectively. The origins of the remaining anomalies at 91 °C and 112 °C were explored in this study, with a focus on interphase layer formation and morphological changes that emerge during heating. These findings provide insights into the stability of OLEDs under thermal stress. Full article

Tungsten oxide (WO₃) electrochromic devices are obtaining increasing interest due to their color change and thermal regulation. However, most previous work focuses on the absorption or transmission spectra of materials, rather than the optical parameters evolution in full spectrum in the electrochromic processes. Herein, we developed a systematic protocol of ex situ methods to clarify the evolutions of subtle structure changes, Raman vibration modes, and optical parameters of WO₃ thin films in electrochromic processes as stimulated by dosage-dependent Li⁺ insertion. We obtained the below information by ex situ spectroscopic ellipsometry. (1) Layer-by-layer Li⁺ embedding mechanism demonstrated by individual film thickness analysis. (2) The details of its optical leap in the Brillouin zone in the full spectral. (3) The optical constants varied with the Li⁺ insertion in the ultraviolet, visible, and near-infrared bands, demonstrating the potential for applications in chip fabrication, deep-sea exploration, and optical measurements. (4) Simulated angular modulation laws of WO₃ films for full spectra in different Li⁺ insertion states. This ex situ method to study the optical properties of electrochromic devices are important for monitoring phase transition kinetics, the analysis of optical leaps, and the study of ion diffusion mechanisms and the stoichiometry-dependent changes in optical constants over the full spectral. This work shows that electrochromic films in Li⁺ surface permeation can be applied in the field of zoom lenses, optical phase modulators, and other precision optical components. Our work provides a new solution for the development of zoom lenses and a new application scenario for the application of electrochromic devices. Full article

Hybrid strategies that combine conventional top-down lithography with bottom-up molecular assembly are of interest for a range of applications including nanolithography and sensors. Interest in these strategies stems from the ability to create complex architectures over large areas with molecular-scale control and precision. The molecular-ruler process typifies this approach where the sequential layer-by-layer assembly of mercaptoalkanoic acid molecules and metal ions are combined with conventional top-down lithography to create precise, registered nanogaps. However, the quality of the metal-ligated mercaptoalkanoic acid multilayer is a critical characteristic in generating reproducible and robust nanoscale structures via the molecular-ruler process. Therefore, we explore the assembly of alkanethiolate monolayers, mercaptohexadecanoic acid (MHDA) monolayers, and Cu-ligated MHDA multilayers on Au{111} substrates using atomic force microscopy and in situ dynamic spectroscopic ellipsometry. The chemical film thicknesses in situ dynamic spectroscopic ellipsometry agree with previous ex situ surface analytical methods. Moreover, in situ dynamic spectroscopic ellipsometry provides insight into the assembly process without interrupting the assembly process and potentially altering the characteristics of the resulting chemical film. By following the real-time dynamics of each deposition step, the assembly of the Cu-ligated MHDA multilayers can be optimized to minimize deposition time while having minimal impact to the quality of the chemical film. Full article

In this article, this research demonstrates the influence of in-situ introduction of H₂ into the working gas on the physical properties of post-annealed In₂O₃ thin films and the performance of associated devices. A gradual increase in the H₂ ratio leads to improved film quality, as indicated by spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscope analyses showing a reduction in defect states such as band-tail states and V_O in the film, and a smoother surface morphology with the root mean square roughness approximately 0.446 nm. Furthermore, this hydrogen doping effect results in a distinct shift in the device’s threshold voltage toward the positive direction, and an improvement in the field-effect mobility and subthreshold swing. Consequently, a high-performance In₂O₃:H TFT is developed, exhibiting a field-effect mobility of 47.8 cm²/Vs, threshold voltage of −4.1 V and subthreshold swing of 0.25 V/dec. These findings highlight the potential of in-situ H doping as a promising approach to regulate In₂O₃-based TFTs. Full article

This work presents a new ultra-high vacuum cluster tool to perform systematic studies of the early growth stages of atomic layer deposited (ALD) ultrathin films following a surface science approach. By combining operando (spectroscopic ellipsometry and quadrupole mass spectrometry) and in situ (X-ray photoelectron spectroscopy) characterization techniques, the cluster allows us to follow the evolution of substrate, film, and reaction intermediates as a function of the total number of ALD cycles, as well as perform a constant diagnosis and evaluation of the ALD process, detecting possible malfunctions that could affect the growth, reproducibility, and conclusions derived from data analysis. The homemade ALD reactor allows the use of multiple precursors and oxidants and its operation under pump and flow-type modes. To illustrate our experimental approach, we revisit the well-known thermal ALD growth of Al₂O₃ using trimethylaluminum and water. We deeply discuss the role of the metallic Ti thin film substrate at room temperature and 200 °C, highlighting the differences between the heterodeposition (<10 cycles) and the homodeposition (>10 cycles) growth regimes at both conditions. This surface science approach will benefit our understanding of the ALD process, paving the way toward more efficient and controllable manufacturing processes. Full article

Titanium dioxide (TiO₂) in the form of thin films has attracted enormous attention for photocatalysis. It combines the fundamental properties of TiO₂ as a large bandgap semiconductor with the advantage of thin films, making it competitive with TiO₂ powders for recycling and maintenance in photocatalytic applications. There are many aspects affecting the photocatalytic performance of thin film structures, such as the nanocrystalline size, surface morphology, and phase composition. However, the quantification of each influencing aspect needs to be better studied and correlated. Here, we prepared a series of TiO₂ thin films using a sol-gel process and spin-coated on p-type, (100)-oriented silicon substrates with a native oxide layer. The as-deposited TiO₂ thin films were then annealed at different temperatures from 400 °C to 800 °C for 3 h in an ambient atmosphere. This sample synthesis provided systemic parameter variation regarding the aspects mentioned above. To characterize thin films, several techniques were used. Spectroscopic ellipsometry (SE) was employed for the investigation of the film thickness and the optical properties. The results revealed that an increasing annealing temperature reduced the film thickness with an increase in the refractive index. Atomic force microscopy (AFM) was utilized to examine the surface morphology, revealing an increased surface roughness and grain sizes. X-ray diffractometry (XRD) and UV-Raman spectroscopy were used to study the phase composition and crystallite size. The annealing process initially led to the formation of pure anatase, followed by a transformation from anatase to rutile as the annealing temperature increased. An overall enhancement in crystallinity was also observed. The photocatalytic properties of the thin films were tested using the photocatalytic decomposition of acetone gas in a home-built solid (photocatalyst)–gas (reactant) reactor. The composition of the gas mixture in the reaction chamber was monitored using in situ Fourier transform infrared spectroscopy. Finally, all of the structural and spectroscopic characteristics of the TiO₂ thin films were quantified and correlated with their photocatalytic properties using a correlation matrix. This provided a good overview of which film properties affect the photocatalytic efficiency the most. Full article

The dissolution of zinc oxide is investigated using spectroscopic ellipsometry to investigate its suitability as a platform for biosensing applications. The results indicate that once the ZnO surface has been functionalised, it is suitably protected, and no significant dissolving of the ZnO occurs. The binding kinetics of the SARS-CoV-2 spike protein on aptamer-functionalised zinc oxide surfaces are subsequently investigated. Values are extracted for the refractive index and associated optical constants for both the aptamer layer used and the protein itself. It is shown that upon an initial exposure to the protein, a rapid fluctuation in the surface density is observed. After around 20 min, this effect stabilises, and a fixed increase in the surface density is observed, which itself increases as the concentration of the protein is increased. This technique and setup are demonstrated to have a limit-of-detection down to 1 nanomole (nM) and display a linear response to concentrations up to 100 nM. Full article

Delayed atomic layer deposition (ALD) of ZnO, i.e., area selective (AS)-ALD, was successfully achieved on silicon wafers (Si\SiO₂) terminated with tris(dimethylamino)methylsilane (TDMAMS). This resist molecule was deposited in a home-built, near-atmospheric pressure, flow-through, gas-phase reactor. TDMAMS had previously been shown to react with Si\SiO₂ in a single cycle/reaction and to drastically reduce the number of silanols that remain at the surface. ZnO was deposited in a commercial ALD system using dimethylzinc (DMZ) as the zinc precursor and H₂O as the coreactant. Deposition of TDMAMS was confirmed by spectroscopic ellipsometry (SE), X-ray photoelectron spectroscopy (XPS), and wetting. ALD of ZnO, including its selectivity on TDMAMS-terminated Si\SiO₂ (Si\SiO₂\TDMAMS), was confirmed by in situ multi-wavelength ellipsometry, ex situ SE, XPS, and/or high-sensitivity/low-energy ion scattering (HS-LEIS). The thermal stability of the TDMAMS resist layer, which is an important parameter for AS-ALD, was investigated by heating Si\SiO₂\TDMAMS in air and nitrogen at 330 °C. ALD of ZnO takes place more readily on Si\SiO₂\TDMAMS heated in the air than in N₂, suggesting greater damage to the surface heated in the air. To better understand the in situ ALD of ZnO on Si\SiO₂\TDMAMS and modified (thermally stressed) forms of it, the ellipsometry results were plotted as the normalized growth per cycle. Even one short pulse of TDMAMS effectively passivates Si\SiO₂. TDMAMS can be a useful, small-molecule inhibitor of ALD of ZnO on Si\SiO₂ surfaces. Full article

Since the discovery of ionic liquids (ILs) as a new class of liquid that can survive in a vacuum at room temperature, they have been aimed at being characterized with vacuum analysis techniques and used in vacuum processes for the last two decades. In this review, our state-of-the-art of the vacuum engineering of ILs will be introduced. Beginning with nanoscale vacuum deposition of IL films and their thickness-dependent ionic conductivity, there are presented some new applications of the ellipsometry to in situ monitoring of the thickness of IL films and their glass transitions, and of the surface thermal fluctuation spectroscopy to investigation of the rheological properties of IL films. Furthermore, IL-VLS (vapor-liquid-solid) growth, a vacuum deposition via IL, has been found successful, enhancing the crystallinity of vacuum-deposited crystals and films, and sometimes controlling their surface morphology and polymorphs. Among recent applications of ILs are the use of metal ions-containing IL and thin film nano IL gel. The former is proposed as a low temperature evaporation source of metals, such as Ta, in vacuum deposition, while the latter is demonstrated to work as a gate electrolyte in an electric double layer organic transistor. Full article

Thin film thermo-responsive hydrogels have become a huge interest in applications such as smart drug-delivery systems or sensor/actuator technology. So far, mostly, the response of such hydrogels has been measured only by varying the temperature in a liquid environment, but studies of the response towards humidity and temperature are rare because of experimental limitations. Often the swelling measurements are performed on samples placed on a stage that can be heated/cooled, while vapors enter the permeation chamber at their own temperature. This thermal difference leads to some uncertainties on the exact relative humidity to which the sample is exposed to. In this study, we explored the possibility of performing swelling measurements under thermal equilibrium by placing the sample and an interferometer, as a detector, in an environmental chamber and therefore exposing the smart hydrogel to adjustable temperatures and relative humidity conditions while measuring the hydrogel’s thin film thickness changes. As a case study, we used thin films of the thermo-responsive hydrogel, poly N-vinylcaprolactam deposited by initiated chemical vapor deposition (iCVD). Similar thin films were previously characterized by in situ ellipsometry while the sample was heated on a stage and exposed to humid air produced at room temperature. The comparison between the two measurement methods showed that while measurements in the presence of thermal gradients are limited mostly to low humidity, measurements in thermal equilibrium are restricted only by the operation limits of the used environmental chamber. Full article

As low-temperature plasma plays an important role in semiconductor manufacturing, plasma diagnostics have been widely employed to understand changes in plasma according to external control parameters, which has led to the achievement of appropriate plasma conditions normally termed the process window. During plasma etching, shifts in the plasma conditions both within and outside the process window can be observed; in this work, we utilized various plasma diagnostic tools to investigate the causes of these shifts. Cutoff and emissive probes were used to measure the electron density and plasma potential as indicators of the ion density and energy, respectively, that represent the ion energy flux. Quadrupole mass spectrometry was also used to show real-time changes in plasma chemistry during the etching process, which were in good agreement with the etching trend monitored via in situ ellipsometry. The results show that an increase in the ion energy flux and a decrease in the fluorocarbon radical flux alongside an increase in the input power result in the breaking of the process window, findings that are supported by the reported SiO₂ etch model. By extending the SiO₂ etch model with rigorous diagnostic measurements (or numerous diagnostic methods), more intricate plasma processing conditions can be characterized, which will be beneficial in applications and industries where different input powers and gas flows can make notable differences to the results. Full article

Polymers represent materials that are applied in almost all areas of modern life, therefore, the characterization of polymer layers using different methods is of great importance. In this review, the main attention is dedicated to the non-invasive and label-free optical and acoustic methods, namely spectroscopic ellipsometry (SE) and quartz crystal microbalance with dissipation (QCM-D). The specific advantages of these techniques applied for in situ monitoring of polymer layer formation and characterization, biomolecule immobilization, and registration of specific interactions were summarized and discussed. In addition, the exceptional benefits and future perspectives of combined spectroscopic ellipsometry and QCM-D (SE/QCM-D) in one measurement are overviewed. Recent advances in the discussed area allow us to conclude that especially significant breakthroughs are foreseen in the complementary application of both QCM-D and SE techniques for the investigation of polymer structure and assessment of the interaction between biomolecules such as antigens and antibodies, receptors and ligands, and complementary DNA strands. Full article