Oxide Atomic Layer Deposition Research Articles

Characterization of the Local Atomic Structure of ALD Coated Interfaces

To accelerate technological innovations using atomic layer deposition (ALD) coatings, we need to establish better understanding of structure-property relationships for ALD films. Historically, the ALD community has had difficulty connecting the atomic structure of ALD films with their performance, largely because of the significant challenge in determining the atomic-scale structure of ultrathin ALD films that are often amorphous, polycrystalline, or defective. In this work, we describe a series of recent efforts that collectively aim to improve understanding of the atomic structure of ALD coatings and inform structure-property understanding. These efforts employ experimental measurements including (a) inert-transfer XPS, (b) in-situ synchrotron high energy X-ray diffraction, and (c) cryogenic electron diffraction. Of particular focus in this talk is the use of X-ray and electron diffraction measurements in combination with pair distribution function (PDF) analysis and reverse Monte Carlo (RMC) structural modeling. We describe a newly developed approach employing alternating RMC and molecular statics steps (RMC-MS) that improves the physical accuracy of model structures derived from experimental diffraction data with minimal additional computational cost over conventional RMC modeling. We also describe efforts using localized cryogenic electron diffraction and PDF analysis (cryo-ePDF) with a ≤ 5 nm spot size to measure atomic structure at ALD interfaces. Together, these advances allow us to quantify differences in the atomic structure as a function of position through the depth of ALD films. A simple two-phase model comprised of bulk and interfacial layers with distinct atomic structure features is consistent with our measurements for both aluminum oxide and zinc oxide ALD coatings. The approaches we report yield atomic structure models that can be used to inform computational studies of the properties if ALD films and will aid in the selection and modification of ALD coating chemistries to address technological needs.

Atomic layer deposition of oxide coatings on porous metal and polymer structures fabricated by additive manufacturing methods (laser-based powder bed fusion, material extrusion, material jetting)

Complex porous 316 L stainless steel, Ti-6Al-4V, Ti-6Al-7Nb, ULTEM™ 1010 and MED610™ polymer structures were produced with additive manufacturing methods. The structures were surface functionalized by atomic layer deposition of titanium, zinc and zirconium oxide coatings with a thickness between 14 and 43 nm. Deep and narrow structures with aspect ratios >10 could be coated. Titanium oxide films are mostly amorphous when plasma-assisted deposition is used and contain nanocrystalline anatase when deposited by thermal atomic layer deposition. The deposited titanium oxide grains ranged in size from ∼20 to 60 nm. In interior parts of the fractured porous polymer model structures with pore sizes of 1–2 mm, both thermal and plasma-assisted titanium oxide thin films and partly delamination were detected. X-ray photoelectron spectroscopy analysis revealed almost stoichiometric composition and dominance of the Ti (IV) oxidation state at a 250 °C deposition temperature. Zinc oxide coatings in porous polymer model structures partly delaminate as well, while adhesion and homogeneity is higher for printed Ti-6Al-7Nb lattice structures with a 0.5-mm mesh size. Zirconium oxide coatings on Ti-6Al-4V lattice structures with a 0.8-mm mesh size are comparable to zinc oxide coatings but are mostly crystalline. This is attributed to the relatively high, 300 °C deposition temperature. The findings demonstrate potential but also limitations of combined additive manufacturing and atomic layer deposition for medicine and energy production applications. In addition, the results confirm previous studies that metallic and polymeric substrate materials and process conditions strongly influence the coating structure and composition, and individual development of each intended application is required.

Atomic Layer Deposition of Metal Oxides and Chalcogenides for High Performance Transistors.

Atomic layer deposition (ALD) is a deposition technique well‐suited to produce high‐quality thin film materials at the nanoscale for applications in transistors. This review comprehensively describes the latest developments in ALD of metal oxides (MOs) and chalcogenides with tunable bandgaps, compositions, and nanostructures for the fabrication of high‐performance field‐effect transistors. By ALD various n‐type and p‐type MOs, including binary and multinary semiconductors, can be deposited and applied as channel materials, transparent electrodes, or electrode interlayers for improving charge‐transport and switching properties of transistors. On the other hand, MO insulators by ALD are applied as dielectrics or protecting/encapsulating layers for enhancing device performance and stability. Metal chalcogenide semiconductors and their heterostructures made by ALD have shown great promise as novel building blocks to fabricate single channel or heterojunction materials in transistors. By correlating the device performance to the structural and chemical properties of the ALD materials, clear structure–property relations can be proposed, which can help to design better‐performing transistors. Finally, a brief concluding remark on these ALD materials and devices is presented, with insights into upcoming opportunities and challenges for future electronics and integrated applications.

A Tandem Interfaced (Ni3 S2 -MoS2 )@TiO2 Composite Fabricated by Atomic Layer Deposition as Efficient HER Electrocatalyst.

Reported herein is a highly active and durable hydrogen evolution reaction (HER) electrocatalyst, which is constructed following a tandem interface strategy and functional in alkaline and even neutral medium (pH ≈ 7). The ternary composite material, consisting of conductive nickel foam (NF) substrate, Ni3 S2 -MoS2 heterostructure, and TiO2 coating, is synthesized by the hydrothermal method and atomic layer deposition (ALD) technique. Representative results include: (1) versatile characterizations confirm the proposed composite structure and strong electronic interactions among comprised sulfide and oxide species; (2) the material outperforms commercial Pt/C by recording an overpotential of 115mV and a Tafel slope of 67mV dec-1 under neutral conditions. A long-term stability in alkaline electrolytes up to 200 h and impressive overall water splitting behavior (1.56V @ 10mA cm-2 ) are documented; (3) implementation of ALD oxide tandem layer is crucial to realize the design concept with superior HER performance by modulating a variety of heterointerface and intermediates electronic structure.

Characterization of Interface and Bulk Traps in Ultrathin Atomic Layer-Deposited Oxide Semiconductor MOS Capacitors With HfO2/In2O3 Gate Stack by C-V and Conductance Method

Oxide semiconductors have attracted revived interest for complementary metal–oxide–semiconductor (CMOS) back-end-of-line (BEOL) compatible devices for monolithic 3-dimensional (3D) integration. To obtain a high-quality oxide/semiconductor interface and bulk semiconductor, it is critical to enhance the performance of oxide semiconductor transistors. Atomic layer-deposited (ALD) indium oxide (In2O3) has been reported with superior performance such as high drive current, high mobility, steep subthreshold slope, and ultrathin channel. In this work, the interface and bulk traps in the MOS gate stack of ALD In2O3 transistors are systematically studied by using the C–V and conductance method. A low EOT of 0.93 nm is achieved directly from the accumulation capacitance in C–V measurement, indicating a high-quality gate oxide and oxide/semiconductor interface. Defects in bulk In2O3 with energy levels in the subgap are confirmed to be responsible for the conductance peak in GP/ω versus ω curves by TCAD simulation of C–V and G–V characteristics. A high n-type doping of 1×1020/cm3 is extracted from C–V measurement. A high subgap density of states (DOS) of 3.3×1020 cm−3 eV−1 is achieved using the conductance method, which contributes to the high n-type doping and high electron density. The high n-type doping further confirms the capability of channel thickness scaling because the charge neutrality level aligns deeply inside the conduction band.

Impact of interlayer insulator formation methods on HfOx ferroelectricity in the metal–ferroelectric–insulator–semiconductor stack

It has been reported that the HfOx-based metal–ferroelectric–insulator–semiconductor (MFIS) stack is one of the most feasible structures for memory applications in ferroelectric devices. In addition, in MFIS stacks, the formation of a high-quality thin insulator is considered to be a crucial process, because it determines the device performance and reliability. In this study, the effects of different SiO2 thin interfacial layers (ILs) formed by chemical oxidation and atomic layer deposition (ALD) on the ferroelectricity of HfOx were investigated in MFIS stacks. Notably, the IL formation method affected the crystallization temperature of HfOx ferroelectricity. In particular, the chemical oxide IL sample was sufficiently crystallized only at an RTA temperature greater than 800 °C, whereas the ALD oxide IL sample began to undergo a complete ferroelectric phase transition from a low temperature (600 °C). The x-ray analysis verified that the IL formation method affected the initial film state of the HfOx layer by modulating the Hf-O bonding states, resulting in a different temperature dependence for ferroelectricity formation during the subsequent crystallization annealing stage. Consequently, it was confirmed that stable polarization (2Pr > 30 μC/cm2) could be obtained over a wide temperature range (600–800 °C) through IL material engineering; this could facilitate the integration of HfOx-based ferroelectric devices in terms of the heat budget and the application of ferroelectric devices as commercial devices.

Surface Engineering Suppresses the Failure of Biphasic Sodium Layered Cathode for High Performance Sodium‐Ion Batteries

AbstractIn the process of upgrading energy storage structures, sodium‐ion batteries (SIBs) are regarded as the most promising candidates for large‐scale grid storage systems. However, the difficulty in further improving their specific capacity and lifespan has become a major obstacle to promoting extensive application. Herein, by optimizing synthesis conditions, a biphasic‐Na2/3Ni1/3Mn2/3O2 cathode that exhibits an ultrahigh capacity of ≈200 mAh g‐1 without the involvement of anion redox reactions is successfully synthesized. Nevertheless, there is significant electrochemical performance degradation because of failure at the cathode‐electrolyte interface as revealed by comprehensive analyses. Further in‐depth research proves that the surface side reactions that occur at high operating voltages and the transition metal dissolution that occurs in low voltage are the root causes of electrode surface failure. Therefore, the metal oxide atomic layer deposition (ALD) protective layer is deliberately chosen to suppress such failures. The coating effectively blocks corrosion of the cathode material by the electrolyte and successfully anchors the transition metal ions on the particle surface. As a result, the cycle stability and rate performance of the electrode are improved considerably. This surface engineering strategy could provide concepts with broad applicability for suppressing the failure of sodium layered cathodes.

Selective-Area, Water-Free Atomic Layer Deposition of Metal Oxides on Graphene Defects.

Passivating defective regions on monolayer graphene with metal oxides remains an active area of research for graphene device integration. To effectively passivate these regions, a water-free atomic layer deposition (ALD) recipe was developed and yielded selective-area ALD (sa-ALD) of mixed-metal oxides onto line defects in monolayer graphene. The anisotropically deposited film targeted high-energy defect sites that were formed during synthesis or transfer of the graphene layer. The passivating layer exceeded 10 nm thickness with minimal deposition onto the basal plane of graphene. The mixed-metal oxide film was of comparable quality to films deposited using nonselective water-based ALD methods, as shown by X-ray photoelectron spectroscopy. The development of sa-ALD techniques to target defect regions on the graphene sheet, while keeping the basal plane intact, will provide a new mechanism to passivate graphene defects and modify the electronic and physical properties of graphene.

Extended Barrier Lifetime of Partially Cracked Organic/Inorganic Multilayers for Compliant Implantable Electronics

Flexible and soft bioelectronics display conflicting demands on miniaturization, compliance, and reliability. Here, the authors investigate the design and performance of thin encapsulation multilayers against hermeticity and mechanical integrity. Partially cracked organic/inorganic multilayer coatings are demonstrated to display surprisingly year-long hermetic lifetime under demanding mechanical and environmental loading. The thin hermetic encapsulation is grown in a single process chamber as a continuous multilayer with dyads of atomic layer deposited (ALD) Al2 O3 -TiO2 and chemical vapor deposited Parylene C films with strong interlayer adhesion. Upon tensile loading, tortuous diffusion pathways defined along channel cracks in the ALD oxide films and through tough Parylene films efficiently postpone the hermeticity failure of the partially cracked coating. The authors assessed the coating performance against prolonged exposure to biomimetic physiological conditions using coated magnesium films, platinum interdigitated electrodes, and optoelectronic devices prepared on stretchable substrates. Designed extension of the lifetime preventing direct failures reduces from over 5 years yet tolerates the lifetime of 3 years even with the presence of critical damage, while others will directly fail less than two months at 37 °C. This strategy should accelerate progress on thin hermetic packaging for miniaturized and compliant implantable electronics.

The roles of atomic layer deposition (ALD) coatings on the stability of FeF3 Na-ion cathodes

Atomic layer deposition (ALD) has been used to stabilize Na-ion battery (SIB) electrodes but the role of ALD coatings and the mechanism of the improvements remain unclear, particularly in conversion-type cathodes. Here, we study for the first time the influence of alumina and titania (Al2O3 and TiO2) ALD coatings on conversion FeF3 cathodes in SIBs. Post-mortem analysis revealed that active material in both samples developed a small fraction of iron oxyfluoride (FeOF) during cycling. Similarly, the in-situ fluorination of both ALD oxide coatings led to the formation of aluminum and titanium oxyfluorides. The aluminum oxyfluoride formed a conformal passivating layer that was well adhered to the cathode electrolyte interphase (CEI). As a result, the Al2O3 coating reduced direct contact between the active material and the liquid electrolyte, minimized active material dissolution and significantly improved the overall electrochemical performance of FeF3 cathodes in SIBs. In contrast, the in-situ fluorination of the TiO2 ALD layer failed to produce a defect-free passivating layer and was inefficient in preventing side reactions, leading to the inferior performance.

Atomic Layer Nucleation Engineering: Inhibitor-Free Area-Selective Atomic Layer Deposition of Oxide and Nitride

Area-selective atomic layer deposition (AS-ALD) has attracted attention due to the process demand for semiconductor device scaling. Here, we propose the “atomic layer nucleation engineering (ALNE)” technique, an inhibitor-free AS-ALD of an oxide (Al2O3) and a nitride (AlN) with nearly 100% selectivity between the dielectric (SiO2) and the metal (Pt). The key is to add a radio-frequency substrate bias after precursor exposure and purge in each ALD cycle, where the energy from the ignited plasma selectively removes the precursors on the metal owing to the relatively lower binding energy compared to those on the dielectric, thereby inhibiting the film growth on the metal. This critical step enables the AS-ALD without selectivity loss up to 100 ALD cycles, leading to significant thickness differences of ∼14.9 and ∼8.7 nm for Al2O3 and AlN between the dielectric and metal surfaces. The realization of AS-ALD of Al2O3 and AlN by ALNE is also confirmed on the Pt/SiO2 patterned substrate. The ALNE offers a novel concept and approach to achieve high-selectivity AS-ALD, which is critical to further extension of Moore’s law.

Nano-Laminated Metal Oxides/Polyamide Stretchable Moisture- and Gas-Barrier Films by Integrated Atomic/Molecular Layer Deposition.

Stretchable barrier films capable of maintaining high levels of moisture- and gas-barrier performance under significant mechanical strains are a critical component for wearable/flexible electronics and other devices, but realization of stretchable moisture-barrier films has not been possible due to the inevitable issues of strain-induced rupturing compounded with moisture-induced swelling of a stretched barrier film. This study demonstrates nanolaminated polymer/metal oxide stretchable moisture-barrier films fabricated by a novel molecular layer deposition (MLD) process of polyamide-2,3 (PA-2,3) integrated with atomic layer deposition (ALD) metal oxide processes and an in situ surface-functionalization technique. The PA-2,3 surface upon in situ functionalization with H2O2 vapor offers adequate surface chemisorption sites for rapid nucleation of ALD oxides, minimizing defects at the PA-2,3/oxide interfaces in the nanolaminates. The integrated ALD/MLD process enables facile deposition and precise structural control of many-layered oxide/PA-2,3 nanolaminates, where the large number of PA-2,3 nanolayers provide high tolerance against mechanical stretching and flexing thanks to their defect-decoupling and stress-buffering functions, while the large number of oxide nanolayers shield against swelling by moisture. Specifically, a nanolaminate with 72 pairs of alternating 2 nm (5 cycles) PA-2,3 and 0.5 nm HfO2 (five cycles) maintains its water vapor transmission rate (WVTR) at the 10-6 g/m2 day level upon 10% tensile stretching and 2 mm-radius bending, a significant breakthrough for the wearable/flexible electronics technologies.

Fe Doping in LiMn1.5Ni0.5O4 by Atomic Layer Deposition Followed by Annealing: Depths and Occupation Sites

The development of high-voltage cathodes is very important to meet the pursuit of high energy and power density for next-generation lithium-ion batteries. LiMn1.5Ni0.5O4 (LMNO), as one of the most promising high-voltage cathodes, is still challenged by unstable surface chemistry, metal dissolution, and structure transition during charge/discharge cycling. In this work, a porous structure combined with Fe doping in LMNO was achieved by iron oxide (FeOx) atomic layer deposition (ALD) and postannealing. The formation of the porous structure was closely related to FeOx ALD, and the sites of Fe doping in LMNO spinel were also controlled by annealing temperature. After this modification, Li+ transport and cycling stability were both significantly improved.

Optimal design of novel precursor materials for the atomic layer deposition using computer-aided molecular design

Nanomaterials and nanostructures with multi-functional properties found widespread applications such as electronics, optics, and coatings that can be fabricated using Atomic Layer Deposition (ALD). ALD is a vapor phase deposition technique to generate thin films of metals and metal oxides on a substrate. In this process, a precursor, which often comprises of organic functional groups that surround the depositing metal, chemisorbs on the substrate or reacts with the surface sites and with each other. Precursor chemisorption on the substrate leads ALD to be a self-limiting process. Thus, the precursor(s) should be chosen in a way to enhance deposition based on the ALD conditions. For a given application, it is practically impossible to carry out a large number of experiments using numerous precursors with varied deposition conditions to find the one that maximizes the growth rate in ALD. In addition, only existing precursors can be tested experimentally. The overall objective of this work is to develop a computational tool for the in-silico design of precursor materials using adsorbate solid solution theory (ASST). In the first part of this paper, we apply the ASST to derive properties of the functional groups present in the precursor using a new Group Contribution Method (GCM). The GCM is successfully derived and compared with the experimental data from ALD. The method shows good agreement and is useful for the design of novel materials. In the second part of this paper, using the thermodynamic properties as obtained from GCM, we develop a computer-aided molecular design (CAMD) framework for the optimal design of novel precursor materials with enhanced deposition properties for the ALD of metal oxides and metals. The metaheuristic efficient ant colony optimization algorithm (EACO) developed in-house is used for both parts. CAMD is a combinatorial optimization methodology, where molecules with optimal desired properties are generated from functional groups. The precursor selection optimization problem is posed as a mixed integer nonlinear programming problem, which is solved using EACO. The ALD growth kinetics is used as an objective of optimization and a solution is validated with thermodynamic constraints. Along with the number of groups, the temperature is also included in the optimization framework as decision variables. Forty-one novel titanium precursor molecular structures for ALD are generated with growth rates ranging from 1.23 Å/cycle to as high as 1.65 Å/cycle. Thus, these precursors have shown growth rates higher than the known titanium precursors. ALD growth rate is found to be a function of the combination of the precursor functional groups as well as temperature with a complex correlation among them.

Atomic layer deposition of thin-film sodium manganese oxide cathode materials for sodium ion batteries.

To improve the performance of sodium ion batteries (NIBs), we need to better understand the materials chemistry occurring at the surface of NIB cathode materials. In this work, we aim to form thin films of sodium manganese oxide (NMO) cathode materials for NIBs using atomic layer deposition (ALD) with the vision to isolate and study these interfacial processes in the absence of bulk NMO. We combine established chemistries for ALD of manganese oxide (MnOx) using Mn(thd)3/O3 and sodium hydroxide (NaOH) using NaOtBu/H2O and adjust the sequence and ratios of these two chemistries to form NaxMnyO alloy films. We identify that increasing the O3 exposure during Mn(thd)3/O3 ALD beyond previously reported values increases the growth rate of MnOx from 0.23 to 0.62 Å per cycle and provides improved uniformity, yielding predominantly Mn5O8. Furthermore, alloying Mn(thd)3/O3 with NaOtBu/H2O mutually enhances the growth rate of both ALD chemistries, yielding a growth rate of ∼9 Å per supercycle for a 1 : 1 cycle ratio. This enhancement in growth arises from sub-surface reactions, including the reaction of NaOtBu to a depth of ∼1.3 nm into bulk MnOx to form Na2MnOx. By tuning cycle ratios and growth conditions, we demonstrate control over the NaxMnyO composition and measure different electrochemical properties depending on the composition. The formation of NMO thin films with controlled thickness and composition established in this work provides a means to systematically study interfacial processes occurring in NMO cathode materials for NIBs.

Atomic Layer Deposition of Hafnium Oxide on InAs: Insight from Time-Resolved in Situ Studies

III-V semiconductors, such as InAs, with an ultrathin high-κ oxide layer have attracted a lot of interests in recent years as potential next-generation metal-oxide-semiconductor field-effect transistors, with increased speed and reduced power consumption. The deposition of the high-κ oxides is nowadays based on atomic layer deposition (ALD), which guarantees atomic precision and control over the dimensions. However, the chemistry and the reaction mechanism involved are still partially unknown. This study reports a detailed time-resolved analysis of the ALD of high-κ hafnium oxide (HfOx) on InAs(100). We use ambient pressure X-ray photoemission spectroscopy and monitor the surface chemistry during the first ALD half-cycle, i.e., during the deposition of the metalorganic precursor. The removal of In and As native oxides, the adsorption of the Hf-containing precursor molecule, and the formation of HfOx are investigated simultaneously and quantitatively. In particular, we find that the generally used ligand exchange model has to be extended to a two-step model to properly describe the first half-cycle in ALD, which is crucial for the whole process. The observed reactions lead to a complete removal of the native oxide and the formation of a full monolayer of HfOx already during the first ALD half-cycle, with an interface consisting of In-O bonds. We demonstrate that a sufficiently long duration of the first half-cycle is essential for obtaining a high-quality InAs/HfO2 interface. (Less)

Commonalities of Atomic Layer Deposition of Oxide Coatings on Activated Carbons for 3.5 V Electric Double Layer Supercapacitors

High voltage electric double layer capacitors with reliable cycling performance are in high demand for energy storage applications. In this research, studies of the process-structure-property relations of commercial activated carbon (AC) electrode modified with atomic layer deposition (ALD) have been performed in terms of coating of various oxide compounds. These investigations have yielded similar enhancements of cycling performance at high voltages (3.5V) enabled by the ALD coating of oxides on AC surfaces. The commonalities are the phenomenal increase in capacitance retention of coin cell supercapacitors after 1000 charge/discharge cycles regardless of the electric nature of ALD deposited oxides. Minor differences in coating morphologies and uniformities were observed between the aluminum oxide, titanium oxide, and manganese-cobalt oxide. ALD coating of these oxides of about 20-growth cycle (1-2 nm in thickness) was found to effectively result in reliable cycling performance, lower impedance, and significantly low leakage current. The authors proposed a modified Gouy-Chapman-Stern model to explain the remarkable increase in operating voltage and cycling performance by the increased Stern layer thickness due to the ALD oxide coating. These results demonstrate that the ALD oxide coating has excellent potential for activated carbons for high operating voltage and energy density supercapacitor.

Low-Temperature Atomic Layer Deposited Oxide on Titanium Nitride Electrodes Enables Culture and Physiological Recording of Electrogenic Cells.

The performance of electrode arrays insulated by low-temperature atomic layer deposited (ALD) titanium dioxide (TiO2) or hafnium dioxide (HfO2) for culture of electrogenic cells and for recording of extracellular action potentials is investigated. If successful, such insulation may be considered to increase the stability of future neural implants. Here, insulation of titanium nitride electrodes of microelectrode arrays (MEAs) was performed using ALD of nanometer-sized TiO2 or hafnium oxide at low temperatures (100–200°C). The electrode properties, impedance, and leakage current were measured and compared. Although electrode insulation using ALD oxides increased the electrode impedance, it did not prevent stable, physiological recordings of electrical activity from electrogenic cells (cardiomyocytes and neurons). The insulation quality, estimated from leakage current measurements, was less than 100 nA/cm2 in a range of 3 V. Cardiomyocytes were successfully cultured and recorded after 5 days on the insulated MEAs with signal shapes similar to the recordings obtained using uncoated electrodes. Light-induced electrical activity of retinal ganglion cells was recorded using a complementary metal-oxide semiconductor-based MEA insulated with HfO2 without driving the recording electrode into saturation. The presented results demonstrate that low-temperature ALD-deposited TiO2 and hafnium oxide are biocompatible and biostable and enable physiological recordings. Our results indicate that nanometer-sized ALD insulation can be used to protect electrodes for long-term biological applications.

Mechanistic Investigation on Thermal Atomic Layer Deposition of Group 13 Oxides

Atomic layer deposition (ALD), based on self-limiting surface reactions, has been proven as a superior deposition method for synthesis of nanoscale thin films. In the field of oxide ALD, alumina (Al2O3) is the most widely and thoroughly studied, prominently through using trimethylaluminum (TMA) with water (H2O). However, there is less information about other group 13 element (B, Ga, and In) oxides using analogous trimethyl precursors. In this study, we investigate these precursors’ detailed adsorption and oxidation mechanisms during thermal ALD using density functional theory (DFT). The hydroxyl-terminated surface is transformed to a methyl-terminated surface after reacting with the trimethyl precursors. For such reaction, the reactivity of trimethylboron is significantly lower than other precursors. Meanwhile, using H2O, oxidation of the surface methyl is facile only for −Al–CH3, and stronger oxidants such as H2O2 or O3 are required for the oxidation reactions during ALD of B, Ga, and In oxides.

Effect of the Al2O3 Deposition Method on Parylene C: Highlights on a Nanopillar-Shaped Surface.

Parylene C (PC) has attracted tremendous attention throughout the past few years due to its extraordinary properties such as high mechanical strength and biocompatibility. When used as a flexible substrate and combined with high-κ dielectrics such as aluminum oxide (Al2O3), the Al2O3/PC stack becomes very compelling for various applications in fields such as biomedical microsystems and microelectronics. For the latter, the atomic layer deposition of oxides is particularly needed as it allows the deposition of high-quality and nanometer-scale oxide thicknesses. In this work, atomic layer deposition (ALD) and electron beam physical vapor deposition (EBPVD) of Al2O3 on a 15 μm-thick PC layer are realized and their effects on the Al2O3/PC resulting stack are investigated via X-ray photoelectron spectroscopy combined with atomic force microscopy. An ALD-based Al2O3/PC stack is found to result in a nanopillar-shaped surface, while an EBPVD-based Al2O3/PC stack yields an expected smooth surface. In both cases, the Al2O3/PC stack can be easily peeled off from the reusable SiO2 substrate, resulting in a flexible Al2O3/PC film. These fabrication processes are economic, high yielding, and suitable for mass production. Although ALD is particularly appreciated in the semiconducting industry, EBPVD is here found to be better for the realization of the Al2O3/PC flexible substrate for micro- and nanoelectronics.