High-barrier, flexible, hydrophobic, and biodegradable cellulose-based films prepared by ascorbic acid regeneration and low temperature plasma technologies.

Regenerated cellulose (RC) films are considered a sustainable packaging material that can replace non-degradable petroleum-based plastics. However, their susceptibility to water vapor and oxygen can limit their effectiveness in protecting products. This study introduces a novel approach for enhancing RC films to create durable, flexible, hydrophobic, high-barrier, and biodegradable packaging materials. By exploring the impact of ascorbic acid coagulation bath treatment and plasma-enhanced chemical vapor deposition (PECVD) on the properties of RC films, we found that the coagulation bath treatment facilitated the organized reconfiguration of cellulose chains, while PECVD applied a dense SiOx coating on the film surface. The results demonstrated a significant enhancement in water vapor and oxygen barrier properties of the composite film, almost reaching the level of commercial barrier films. Moreover, the composite film displayed exceptional biodegradability, fully degrading in soil within 35 days. Additionally, it showcased impressive mechanical strength, hydrophobic characteristics, and freshness preservation, positioning it as a valuable option for bio-based high-barrier packaging applications.

Covalent Functionalization of Silicon with Plasma-Grown "Fuzzy" Graphene: Robust Aqueous Photoelectrodes for CO2 Reduction by Molecular Catalysts.

Carbon electrodes are ideal for electrochemistry with molecular catalysts, exhibiting facile charge transfer and good stability. Yet for solar-driven catalysis with semiconductor light absorbers, stable semiconductor/carbon interfaces can be difficult to achieve, and carbon's high optical extinction means it can only be used in ultrathin layers. Here, we demonstrate a plasma-enhanced chemical vapor deposition process that achieves well-controlled deposition of out-of-plane "fuzzy" graphene (FG) on thermally oxidized Si substrates. The resulting Si|FG interfaces possess a silicon oxycarbide (SiOC) interfacial layer, implying covalent bonding between Si and the FG film that is consistent with the mechanical robustness observed from the films. The FG layer is uniform and tunable in thickness and optical transparency by deposition time. Using p-type Si|FG substrates, noncovalent immobilization of cobalt phthalocyanine (CoPc) molecular catalysts was employed for the photoelectrochemical reduction of CO2 in aqueous solution. The Si|FG|CoPc photocathodes exhibited good catalytic activity, yielding a current density of ∼1 mA/cm2, Faradaic efficiency for CO of ∼70% (balance H2), and stable photocurrent for at least 30 h at -1.5 V vs Ag/AgCl under 1-sun illumination. The results suggest that plasma-deposited FG is a robust carbon electrode for molecular catalysts and suitable for further development of aqueous-stable Si photocathodes for CO2 reduction.

Investigation of Field Emission Properties of Carbon Nanotube Arrays of Different Morphologies.

This article presents, for the first time, a comparative analysis of the emission characteristics of large-area field-effect cathodes (LAFE) based on carbon nanotubes (CNTs) of various morphologies according to key parameters using a unique computerized technique. The work presents a description of a technology for creating various CNT arrays and their comprehensive structure characterization. All CNT arrays synthesized by the catalytic PECVD method on a silicon substrate showed a high degree of chemical purity under the presented technological conditions. In some cases, nanoisland films of Fe were used as a catalyst; in others, thin films of NiO were used, which were deposited on a silicon wafer by chemical vapor deposition (CVD) and atomic layer deposition (ALD), respectively. As a result of these studies, it turned out that an array with a thick CNT coating has good resistance to the action of strong electric fields, fairly good uniformity of distribution of emission centers, a fairly high selection current (2.88 mA/cm2 at 4.53 V/µm), and compliance with the normal current mode according to the "orthodox" test, which makes the morphology of such structures the most promising for further technological optimization of CNT-based cathodes for various practical applications.

Gas-Phase Fabrication and Photocatalytic Activity of TiO2 and TiO2-CuO Nanoparticulate Thin Films.

CuO-loaded TiO2 nanomaterials have applications in pollutant degradation via photocatalysis. However, the existing methods of fabricating these nanomaterials involve liquid-phase processes, which require several steps and typically generate liquid waste. In this study, TiO2 and TiO2-CuO nanoparticulate thin films were successfully fabricated through a one-step gas-phase approach involving a combination of plasma-enhanced chemical vapor deposition and physical vapor deposition. The resulting films consisted of small, spherical TiO2 nanoparticles with observable CuO on the TiO2 surface. Upon annealing in air, the TiO2 nanoparticles were crystallized, and CuO was completely oxidized. The photocatalytic activity of TiO2-CuO/H2O2, when introduced into the rhodamine 6G degradation system, was substantially enhanced under both ultraviolet and visible light irradiation. Moreover, this study highlights the influence of pH on the photocatalytic activity; TiO2-CuO/H2O2 exhibited the highest photocatalytic activity at pH 13, with a reaction rate constant of 0.99 h-1 cm-2 after 180 min of visible light irradiation. These findings could facilitate the development of nanoparticulate thin films for enhanced pollutant degradation in wastewater treatment.

SiONx Coating Regulates Mesenchymal Stem Cell Antioxidant Capacity via Nuclear Erythroid Factor 2 Activity under Toxic Oxidative Stress Conditions.

Healing in compromised and complicated bone defects is often prolonged and delayed due to the lack of bioactivity of the fixation device, secondary infections, and associated oxidative stress. Here, we propose amorphous silicon oxynitride (SiONx) as a coating for the fixation devices to improve both bioactivity and bacteriostatic activity and reduce oxidative stress. We aimed to study the effect of increasing the N/O ratio in the SiONx to fine-tune the cellular activity and the antioxidant effect via the NRF2 pathway under oxidative stress conditions. The in vitro studies involved using human mesenchymal stem cells (MSCs) to examine the effect of SiONx coatings on osteogenesis with and without toxic oxidative stress. Additionally, bacterial growth on SiONx surfaces was studied using methicillin-resistant Staphylococcus aureus (MRSA) colonies. NRF2 siRNA transfection was performed on the hMSCs (NRF2-KD) to study the antioxidant response to silicon ions. The SiONx implant surfaces showed a >4-fold decrease in bacterial growth vs. bare titanium as a control. Increasing the N/O ratio in the SiONx implants increased the alkaline phosphatase activity >1.5 times, and the other osteogenic markers (osteocalcin, RUNX2, and Osterix) were increased >2-fold under normal conditions. Increasing the N/O ratio in SiONx enhanced the protective effects and improved cell viability against toxic oxidative stress conditions. There was a significant increase in osteocalcin activity compared to the uncoated group, along with increased antioxidant activity under oxidative stress conditions. In NRF2-KD cells, there was a stunted effect on the upregulation of antioxidant markers by silicon ions, indicating a role for NRF2. In conclusion, the SiONx coatings studied here displayed bacteriostatic properties. These materials promoted osteogenic markers under toxic oxidative stress conditions while also enhancing antioxidant NRF2 activity. These results indicate the potential of SiONx coatings to induce in vivo bone regeneration in a challenging oxidative stress environment.

Graphene nanowalls grown on copper mesh.

Graphene nanowalls (GNWs) can be described as extended nanosheets of graphitic carbon where the basal planes are perpendicular to a substrate. Generally, existing techniques to grow films of GNWsare based on plasma-enhanced chemical vapor deposition (PECVD) and the use of diverse substrate materials (Cu, Ni, C, etc) shaped as foils or filaments. Usually, patterned films rely on substrates priorly modified by costly cleanroom procedures. Hence, we report here the characterization, transfer and application of wafer-scale patterned GNWsfilms that were grown on Cu meshes using low-power direct-current PECVD. Reaching wall heights of ∼300 nm, mats of vertically-aligned carbon nanosheets covered square centimeter wire meshes substrates, replicating well the thread dimensions and the tens of micrometer-wide openings of the meshes. Contrastingly, the same growth conditions applied to Cu foils resulted in limited carbon deposition, mostly confined to the substrate edges. Based on the wet transfer procedure turbostratic and graphitic carbon domains co-exist in the GNWsmicrostructure. Interestingly, these nanoscaled patterned films were quite hydrophobic, being able to reverse the wetting behavior of SiO2surfaces. Finally, we show that the GNWscan also be used as the active material for C-on-Cu anodes of Li-ion battery systems.

UV-Induced Synthesis of Hybrid HMDSO/SiO2 Thin Films with Compositional Gradients for High-Performance Atomic Oxygen Resistance.

A flexible, dense, defect-free, highly adhesive, and highly dissociation energy-rich protective coating is essential to enhance the atomic oxygen (AO) resistance of polymeric materials in a low Earth orbit (LEO). In this work, a dense, defect-free hybrid HMDSO/SiO2 thin film coating with compositional gradients on the surface of polyimide was synthesized using vacuum-ultraviolet (VUV) irradiation. The effects of VUV irradiation on the morphology, optical transmittance, and chemical components of plasma-polymerized HMDSO (pp-HMDSO) thin-film coatings deposited on the polyimide surface were investigated in depth. There were no defects such as cracks and holes in the surface morphology of pp-HMDSO films after VUV irradiation, but the surface roughness increased slightly, and the corresponding optical transmittance decreased slightly. The chemical components of pp-HMDSO films were changed in the depth direction starting from the top of the surface, forming hybrid HMDSO/SiO2 thin films with compositional gradients. The component gradient HMDSO/SiO2 composite coating further enhanced the atomic oxygen resistance of the polyimide due to the surface layer of the UV-modified coating enriched with high dissociation energy SiOx material. Therefore, this work provides a facile UV-induced synthesis method to prepare dense, defect-free, and highly dissociation energy-rich protective gradient coatings, which are promising not only for excellent AO protection in LEO but also for potential application in water-oxygen barrier films.

Advancements in Plasma-Enhanced Chemical Vapor Deposition for Producing Vertical Graphene Nanowalls.

In recent years, vertical graphene nanowalls (VGNWs) have gained significant attention due to their exceptional properties, including their high specific surface area, excellent electrical conductivity, scalability, and compatibility with transition metal compounds. These attributes position VGNWs as a compelling choice for various applications, such as energy storage, catalysis, and sensing, driving interest in their integration into next-generation commercial graphene-based devices. Among the diverse graphene synthesis methods, plasma-enhanced chemical vapor deposition (PECVD) stands out for its ability to create large-scale graphene films and VGNWs on diverse substrates. However, despite progress in optimizing the growth conditions to achieve micrometer-sized graphene nanowalls, a comprehensive understanding of the underlying physicochemical mechanisms that govern nanostructure formation remains elusive. Specifically, a deeper exploration of nanometric-level phenomena like nucleation, carbon precursor adsorption, and adatom surface diffusion is crucial for gaining precise control over the growth process. Hydrogen's dual role as a co-catalyst and etchant in VGNW growth requires further investigation. This review aims to fill the knowledge gaps by investigating VGNW nucleation and growth using PECVD, with a focus on the impact of the temperature on the growth ratio and nucleation density across a broad temperature range. By providing insights into the PECVD process, this review aims to optimize the growth conditions for tailoring VGNW properties, facilitating applications in the fields of energy storage, catalysis, and sensing.

Controllable Anchoring of Graphitic Carbon Nitride on MnO2 Nanoarchitectures for Oxygen Evolution Electrocatalysis.

The design and fabrication of eco-friendly and cost-effective (photo)electrocatalysts for the oxygen evolution reaction (OER) is a key research goal for a proper management of water splitting to address the global energy crisis. In this work, we focus on the preparation of supported MnO2/graphitic carbon nitride (g-CN) OER (photo)electrocatalysts by means of a novel preparation strategy. The proposed route consists of the plasma enhanced-chemical vapor deposition (PE-CVD) of MnO2 nanoarchitectures on porous Ni scaffolds, the anchoring of controllable g-CN amounts by an amenable electrophoretic deposition (EPD) process, and the ultimate thermal treatment in air. The inherent method versatility and flexibility afforded defective MnO2/g-CN nanoarchitectures, featuring a g-CN content and nano-organization tunable as a function of EPD duration and the used carbon nitride precursor. Such a modulation had a direct influence on OER functional performances, which, for the best composite system, corresponded to an overpotential of 430 mV at 10 mA/cm2, a Tafel slope of ≈70 mV/dec, and a turnover frequency of 6.52 × 10-3 s-1, accompanied by a very good time stability. The present outcomes, comparing favorably with previous results on analogous systems, were rationalized on the basis of the formation of type-II MnO2/g-CN heterojunctions, and yield valuable insights into this class of green (photo)electrocatalysts for end uses in solar-to-fuel conversion and water treatment.

Change in Electrical/Mechanical Properties of Plasma Polymerized Low Dielectric Constant Films after Etching in CF4/O2 Plasma for Semiconductor Multilevel Interconnects.

As semiconductor chips have been integrated to enhance their performance, a low-dielectric-constant material, SiCOH, with a relative dielectric constant k ≤ 3.5 has been widely used as an intermetal dielectric (IMD) material in multilevel interconnects to reduce the resistance-capacitance delay. Plasma-polymerized tetrakis(trimethylsilyoxy)silane (ppTTMSS) films were created using capacitively coupled plasma-enhanced chemical vapor deposition with deposition plasma powers ranging from 20 to 60 W and then etched in CF4/O2 plasma using reactive ion etching. No significant changes were observed in the Fourier-transform infrared spectroscopy (FTIR) spectra of the ppTTMSS films after etching. The refractive index and dielectric constant were also maintained. As the deposition plasma power increased, the hardness and elastic modulus increased with increasing ppTTMSS film density. The X-ray photoelectron spectroscopy (XPS) spectra analysis showed that the oxygen concentration increased but the carbon concentration decreased after etching owing to the reaction between the plasma and film surface. With an increase in the deposition plasma power, the hardness and elastic modulus increased from 1.06 to 8.56 GPa and from 6.16 to 52.45 GPa. This result satisfies the hardness and elastic modulus exceeding 0.7 and 5.0 GPa, which are required for the chemical-mechanical polishing process in semiconductor multilevel interconnects. Furthermore, all leakage-current densities of the as-deposited and etched ppTTMSS films were measured below 10-6 A/cm2 at 1 MV/cm, which is generally acceptable for IMD materials.

Plasma-Induced Surface Modification of Sapphire and Its Influence on Graphene Grown by Plasma-Enhanced Chemical Vapour Deposition.

In this work, we study the influence of the different surface terminations of c-plane sapphire substrates on the synthesis of graphene via plasma-enhanced chemical vapor deposition. The different terminations of the sapphire surface are controlled by a plasma process. A design of experiments procedure was carried out to evaluate the major effects governing the plasma process of four different parameters: i.e., discharge power, time, pressure and gas employed. In the characterization of the substrate, two sapphire surface terminations were identified and characterized by means of contact angle measurements, being a hydrophilic (hydrophobic) surface and the fingerprint of an Al- (OH-) terminated surface, respectively. The defects within the synthesized graphene were analyzed by Raman spectroscopy. Notably, we found that the ID/IG ratio decreases for graphene grown on OH-terminated surfaces. Furthermore, two different regimes related to the nature of graphene defects were identified and, depending on the sapphire terminated surface, are bound either to vacancy or boundary-like defects. Finally, studying the density of defects and the crystallite area, as well as their relationship with the sapphire surface termination, paves the way for increasing the crystallinity of the synthesized graphene.

Back-End-of-Line Compatible Large-Area Molybdenum Disulfide Grown on Flexible Substrate: Enabling High-Performance Low-Power Memristor Applications.

Transition-metal dichalcogenides (TMDs) in flexible technology can offer large-area scalability and high-density integration with a low power consumption. However, incorporating large-area TMDs in a flexible platform is lacking in state-of-the-art data storage technology owing to the high process temperature of TMDs. Low-temperature growth of TMDs can bridge mass production in flexible technology and reduce the complexity of the transferring process. Here, we introduce a crossbar memory array enabled by low-temperature (250 °C) plasma-assisted chemical vapor deposited MoS2 directly grown on a flexible substrate. The low-temperature sulfurization induces nanograins of MoS2 with multiple grain boundaries, allowing the path for charge particles, which leads to the formation of conducting filaments. The back-end-of-line compatible MoS2-based crossbar memristors exhibit robust resistance switching (RS) behavior with a high on/off current ratio of approximately ∼105, excellent endurance (>350 cycles), retention (>200000 s), and low operating voltage (∼±0.5 V). Furthermore, the MoS2 synthesized at low temperature on a flexible substrate facilitates RS characteristics demonstrated under strain states and exhibits excellent RS performance. Thus, the use of direct-grown MoS2 on a polyimide (PI) substrate for high-performance cross-bar memristors can transform emerging flexible electronics.

Thickness-dependent carrier transport of PdSe2films grown by plasma-assisted metal selenization.

Atomically thin narrow-bandgap layered PdSe2has attracted much attention due to its rich and unique electrical properties. For silicon-compatible device integration, direct wafer-scale preparation of high-quality PdSe2thin film on a silicon substrate is highly desired. Here, we present the low-temperature synthesis of large-area polycrystalline PdSe2films grown on SiO2/Si substrates by plasma-assisted metal selenization and investigate their charge carrier transport behaviors. Raman analysis, depth-dependent x-ray photoelectron spectroscopy, and cross-sectional transmission electron microscopy were used to reveal the selenization process. The results indicate a structural evolution from initial Pd to intermediate PdSe2-xphase and eventually to PdSe2. The field-effect transistors fabricated from these ultrathin PdSe2films exhibit strong thickness-dependent transport behaviors. For thinner films (4.5 nm), a record high on/off ratio of 104was obtained. While for thick ones (11 nm), the maximum hole mobility is about 0.93 cm2V-1S-1, which is the record high value ever reported for polycrystalline films. These findings suggest that our low-temperature-metal-selenized PdSe2films have high quality and show great potential for applications in electrical devices.

High-Performance Graphene Nanowalls/Si Self-Powered Photodetectors with HfO2 as an Interfacial Layer.

Graphene/silicon (Si) heterojunction photodetectors are widely studied in detecting of optical signals from near-infrared to visible light. However, the performance of graphene/Si photodetectors is limited by defects created in the growth process and surface recombination at the interface. Herein, a remote plasma-enhanced chemical vapor deposition is introduced to directly grow graphene nanowalls (GNWs) at a low power of 300 W, which can effectively improve the growth rate and reduce defects. Moreover, hafnium oxide (HfO2) with thicknesses ranging from 1 to 5 nm grown by atomic layer deposition has been employed as an interfacial layer for the GNWs/Si heterojunction photodetector. It is shown that the high-k dielectric layer of HfO2 acts as an electron-blocking and hole transport layer, which minimizes the recombination and reduces the dark current. At an optimized thickness of 3 nm HfO2, a low dark current of 3.85 × 10-10, with a responsivity of 0.19 AW-1, a specific detectivity of 1.38 × 1012 as well as an external quantum efficiency of 47.1% at zero bias, can be obtained for the fabricated GNWs/HfO2/Si photodetector. This work demonstrates a universal strategy to fabricate high-performance graphene/Si photodetectors.

Fabrication of Aluminum Oxide Thin-Film Devices Based on Atomic Layer Deposition and Pulsed Discrete Feed Method.

This study demonstrates the low-temperature (<100 °C) process for growing a thin silica buffer layer and aluminum oxide by atomic layer deposition (ALD) in the same reaction chamber. Heterogeneous multilayer thin films are prepared by a dual-mode equipment based on atomic layer deposition and plasma-enhanced chemical vapor deposition (PECVD) techniques. The pulse discrete feeding method (DFM) was used to divide the precursor purging steps into smaller intervals and generate discrete feeds, which improved the saturated distribution of gas precursors, film density and deposition selectivity. The experimental results show that the process method produces a uniform microstructure and that the best film uniformity is ±2.3% and growth rate is 0.69 Å/cycle. The thickness of aluminum oxide film has a linear relationship with the cyclic growth number from 360 to 1800 cycles. Meanwhile, the structural and mechanical stress properties of aluminum oxide thin films were also verified to meet the requirements of advanced thin-film devices.

Large-Scale Plasma-Polymerized Hexamethyldisiloxane Thin Films: Role of Interelectrode Distance and Excellent Corrosion Resistance.

In comparison to the more traditional anticorrosion thin film coatings, the plasma polymerization approach offered a more efficient, dry, and straightforward procedure that made it possible to create dense films of several hundred nanometers in thickness, which has potential applications in metallic implant materials. In this paper, large-scale plasma polymerized hexamethyldisiloxane (ppHMDSO) thin film coatings were deposited on stainless steel substrates at different electrode distances to improve their corrosion resistance. The physicochemical properties and corrosion resistance of the ppHMDSO thin films as prepared at different electrode distances were characterized and gauged utilizing various characterization means. The results indicate that decreasing electrode distance accelerates monomer fragmentation and increases the oxidation process. The deposition rate and roughness of the ppHMDSO films both decreased as the electrode distance increased, while the carbonaceous group and hydrophobicity of the films enhanced. The ppHMDSO film prepared at an electrode distance of 40 mm obtained excellent elastic recovery and wear resistance and had an improved corrosion resistance, resulting in a reduction of 75% of the original corrosion behavior against the corrosion in Hank's solution. The resulting large-scale ppHMDSO thin film coatings can be further employed in implants for tissue engineering and biomaterials.

Influence of NiO ALD Coatings on the Field Emission Characteristic of CNT Arrays.

The paper presents a study of a large-area field emitter based on a composite of vertically aligned carbon nanotubes covered with a continuous and conformal layer of nickel oxide by the atomic layer deposition method. The arrays of carbon nanotubes were grown by direct current plasma-enhanced chemical vapor deposition on a pure Si substrate using a nickel oxide catalyst which was also deposited by atomic layer deposition. The emission characteristics of an array of pure vertically oriented carbon nanotubes with a structure identical in morphology, covered with a layer of thin nickel oxide, are compared using the data from a unique computerized field emission projector. The deposition of an oxide coating favorably affected the emission current fluctuations, reducing them from 40% to 15% for a pristine carbon nanotube and carbon nanotube/nickel oxide, respectively. However, the 7.5 nm nickel oxide layer coating leads to an increase in the turn-on field from 6.2 to 9.7 V/µm.

On the Mixed Gas Behavior of Organosilica Membranes Fabricated by Plasma-Enhanced Chemical Vapor Deposition (PECVD).

Selective, nanometer-thin organosilica layers created by plasma-enhanced chemical vapor deposition (PECVD) exhibit selective gas permeation behavior. Despite their promising pure gas performance, published data with regard to mixed gas behavior are still severely lacking. This study endeavors to close this gap by investigating the pure and mixed gas behavior depending on temperatures from 0 °C to 60 °C for four gases (helium, methane, carbon dioxide, and nitrogen) and water vapor. For the two permanent gases, helium and methane, the studied organosilica membrane shows a substantial increase in selectivity from αHe/CH4 = 9 at 0 °C to αHe/CH4 = 40 at 60 °C for pure as well as mixed gases with helium permeance of up to 300 GPU. In contrast, a condensable gas such as CO2 leads to a decrease in selectivity and an increase in permeance compared to its pure gas performance. When water vapor is present in the feed gas, the organosilica membrane shows even stronger deviations from pure gas behavior with a permeance loss of about 60 % accompanied by an increase in ideal selectivity αHe/CO2 from 8 to 13. All in all, the studied organosilica membrane shows very promising results for mixed gases. Especially for elevated temperatures, there is a high potential for separation by size exclusion.

Patchwork-Structured Heterointerface of 1T-WS2/a-WO3 with Sustained Hydrogen Spillover as a Highly Efficient Hydrogen Evolution Reaction Electrocatalyst.

Using tungsten disulfide (WS2) as a hydrogen evolution reaction (HER) electrocatalyst brought on several ways to surpass its intrinsic catalytic activity. This study introduces a nanodomain tungsten oxide (WO3) interface to 1T-WS2, opening a new route for facilitating the transfer of a proton to active sites, thereby enhancing the HER performance. After H2S plasma sulfurization on the W layer to realize nanocrystalline 1T-WS2, subsequent O2 plasma treatment led to the formation of amorphous WO3 (a-WO3), resulting in a patchwork-structured heterointerface of 1T-WS2/a-WO3 (WSO). Addition of a hydrophilic interface (WO3) facilitates the hydrogen spillover effect, which represents the transfer of absorbed protons from a-WO3 to 1T-WS2. Moreover, the faster response of the cathodic current peak (proton insertion) in cyclic voltammetry is confirmed by the higher degree of oxidation. The rationale behind the faster proton insertion is that the introduced a-WO3 works as a proton channel. As a result, WSO-1.2 (the ratio of 1T-WS2 to a-WO3) exhibits a remarkable HER activity in that 1T-WS2 consumes more protons provided by the channel, showing an overpotential of 212 mV at 10 mA/cm2. Density functional theory calculations also show that the WO3 phase gives higher binding energies for initial proton adsorption, while the 1T-WS2 phase shows reduced HER overpotential. This improved catalytic performance demonstrates a novel strategy for water splitting to actively elicit the related reaction via efficient proton transport.

Opto-Electrical Properties of Group IV Alloys: The Inherent Challenges of Processing Hydrogenated Germanium.

In this paper the opto-electrical nature of hydrogenated group IV alloys with optical bandgap energies ranging from 1.0 eV up to 2.3 eV are studied. The fundamental physical principles that determine the relation between the bandgap and the structural characteristics such as material density, elemental composition, void fraction and crystalline phase fraction are revealed. Next, the fundamental physical principles that determine the relation between the bandgap and electrical properties such as the dark conductivity, activation energy, and photoresponse are discussed. The unique wide range of IV valence alloys helps to understand the nature of amorphous (a-) and nanocrystalline (nc-) hydrogenated (:H) germanium films with respect to the intrinsicity, chemical stability, and photoresponse. These insights resulted in the discovery of i) a processing window that results in chemically stable Ge:H films with the lowest reported dark conductivity values down to 4.6·10-4 (Ω ·cm)-1 for chemical vapor deposited Ge:H films, and ii) O, C and Sn alloying approaches to improve the photoresponse and chemical stability of the a/nc-Ge:H alloys.