Special Issue "Design of Nanostructured Materials by Atomic Layer Deposition and Its Applications"

A special issue of Nanomaterials (ISSN 2079-4991).

Deadline for manuscript submissions: closed (31 October 2018)

Special Issue Editors

Guest Editor
Dr. Mikhael Bechelany

Chargé de recherches CNRS, Institut Européen des Membranes (IEMM, ENSCM UM CNRS UMR5635), Place Eugène Bataillon, 34095 MONTPELLIER Cedex 5, France
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Interests: thin films; 2D materials; Atomic Layer Deposition; nanostructure; nanocomposites; nanowires, electrospinning; sensor; biosensor
Guest Editor
Prof. Dr. Seppo Honkanen

Institute of Photonics, University of Eastern Finland, Yliopistonranta 1, 70210 Kuopio, Finland
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Interests: guided-wave optics; telecommunications application; sensors
Guest Editor
Prof. Dr. Matthieu Roussey

Institute of Photonics, University of Eastern Finland, Yliopistonranta 1, 70210 Kuopio, Finland
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Interests: lab-on-chip; lab-on-fiber; integrated telecommunication components; novel waveguide platforms; atomic layer deposition for photonics; SERS; bio-applications

Special Issue Information

Dear Colleagues,

Atomic layer deposition (ALD) is a thin film deposition technique allowing for sub-nanometer thickness control, as well as excellent uniformity and conformality on demanding substrates. Although ALD is typically used for the synthesis of oxides nanomaterials, it has been shown that nitrides and metals can also be prepared using this technique.

This Special Issue will aim at gathering resources in the area of the design of nanostructured materials using ALD for different applications such as health, environment and renewable energy. Contributions related to advanced materials design, novel materials properties and original characterization techniques will be as well considered.

This Special Issue will deal with: (i) the design of nanostructured materials with controlled morphology, geometry and crystallinity, (ii) the tuning of interfaces for the obtained materials, (iii) the study of the dependence of the physical-chemical properties on the geometric parameter, and (iv) the investigation of new applications.

Dr. Mikhael Bechelany
Prof. Dr. Seppo Honkanen
Prof. Dr. Matthieu Roussey
Guest Editors

Manuscript Submission Information

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Keywords

  • thin film
  • nanomaterial
  • interface
  • surface modification
  • nanostructured material
  • energy
  • health
  • environment

Published Papers (9 papers)

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Research

Open AccessArticle Preparation and Characterization of Microsphere ZnO ALD Coating Dedicated for the Fiber-Optic Refractive Index Sensor
Nanomaterials 2019, 9(2), 306; https://doi.org/10.3390/nano9020306
Received: 5 January 2019 / Revised: 11 February 2019 / Accepted: 19 February 2019 / Published: 23 February 2019
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Abstract
We report the fabrication of a novel fiber-optic sensor device, based on the use of a microsphere conformally coated with a thin layer of zinc oxide (ZnO) by atomic layer deposition (ALD), and its use as a refractive index sensor. The microsphere was [...] Read more.
We report the fabrication of a novel fiber-optic sensor device, based on the use of a microsphere conformally coated with a thin layer of zinc oxide (ZnO) by atomic layer deposition (ALD), and its use as a refractive index sensor. The microsphere was prepared on the tip of a single-mode optical fiber, on which a conformal ZnO thin film of 200 nm was deposited using an ALD process based on diethyl zinc (DEZ) and water at 100 °C. The modified fiber-optic microsphere was examined using scanning electron microscopy and Raman spectroscopy. Theoretical modeling has been carried out to assess the structure performance, and the performed experimental measurements carried out confirmed the enhanced sensing abilities when the microsphere was coated with a ZnO layer. The fabricated refractive index sensor was operating in a reflective mode of a Fabry–Pérot configuration, using a low coherent measurement system. The application of the ALD ZnO coating enabled for a better measurement of the refractive index of samples in the range of the refractive index allowed by the optical fiber. The proof-of-concept results presented in this work open prospects for the sensing community and will promote the use of fiber-optic sensing technologies. Full article
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Open AccessArticle Titania Nanotubes/Hydroxyapatite Nanocomposites Produced with the Use of the Atomic Layer Deposition Technique: Estimation of Bioactivity and Nanomechanical Properties
Nanomaterials 2019, 9(1), 123; https://doi.org/10.3390/nano9010123
Received: 21 December 2018 / Revised: 14 January 2019 / Accepted: 15 January 2019 / Published: 19 January 2019
Cited by 1 | PDF Full-text (7901 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Titanium dioxide nanotubes/hydroxyapatite nanocomposites were produced on a titanium alloy (Ti6Al4V/TNT/HA) and studied as a biocompatible coating for an implant surface modification. As a novel approach for this type of nanocomposite fabrication, the atomic layer deposition (ALD) method with an extremely low number [...] Read more.
Titanium dioxide nanotubes/hydroxyapatite nanocomposites were produced on a titanium alloy (Ti6Al4V/TNT/HA) and studied as a biocompatible coating for an implant surface modification. As a novel approach for this type of nanocomposite fabrication, the atomic layer deposition (ALD) method with an extremely low number of cycles was used to enrich titania nanotubes (TNT) with a very thin hydroxyapatite coating. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used for determination of the structure and the surface morphology of the fabricated nanocoatings. The biointegration activity of the layers was estimated based on fibroblasts’ proliferation on the TNT/HA surface. The antibacterial activity was determined by analyzing the ability of the layers to inhibit bacterial colonization and biofilm formation. Mechanical properties of the Ti6Al4V/TNT/HA samples were estimated by measuring the hardness, Young’s module, and susceptibility to scratching. The results revealed that the nanoporous titanium alloy coatings enriched with a very thin hydroxyapatite layer may be a promising way to achieve the desired balance between biofunctional and biomechanical properties of modern implants. Full article
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Open AccessArticle Fracture Mechanics and Oxygen Gas Barrier Properties of Al2O3/ZnO Nanolaminates on PET Deposited by Atomic Layer Deposition
Nanomaterials 2019, 9(1), 88; https://doi.org/10.3390/nano9010088
Received: 7 November 2018 / Revised: 10 December 2018 / Accepted: 21 December 2018 / Published: 11 January 2019
Cited by 1 | PDF Full-text (3251 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Rapid progress in the performance of organic devices has increased the demand for advances in the technology of thin-film permeation barriers and understanding the failure mechanisms of these material systems. Herein, we report the extensive study of mechanical and gas barrier properties of [...] Read more.
Rapid progress in the performance of organic devices has increased the demand for advances in the technology of thin-film permeation barriers and understanding the failure mechanisms of these material systems. Herein, we report the extensive study of mechanical and gas barrier properties of Al2O3/ZnO nanolaminate films prepared on organic substrates by atomic layer deposition (ALD). Nanolaminates of Al2O3/ZnO and single compound films of around 250 nm thickness were deposited on polyethylene terephthalate (PET) foils by ALD at 90 °C using trimethylaluminium (TMA) and diethylzinc (DEZ) as precursors and H2O as the co-reactant. STEM analysis of the nanolaminate structure revealed that steady-state film growth on PET is achieved after about 60 ALD cycles. Uniaxial tensile strain experiments revealed superior fracture and adhesive properties of single ZnO films versus the single Al2O3 film, as well as versus their nanolaminates. The superior mechanical performance of ZnO was linked to the absence of a roughly 500 to 900 nm thick sub-surface growth observed for single Al2O3 films as well as for the nanolaminates starting with an Al2O3 initial layer on PET. In contrast, the gas permeability of the nanolaminate coatings on PET was measured to be 9.4 × 10−3 O2 cm3 m−2 day−1. This is an order of magnitude less than their constituting single oxides, which opens prospects for their applications as gas barrier layers for organic electronics and food and drug packaging industries. Direct interdependency between the gas barrier and the mechanical properties was not established enabling independent tailoring of these properties for mechanically rigid and impermeable thin film coatings. Full article
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Open AccessArticle Systematic Study of the SiOx Film with Different Stoichiometry by Plasma-Enhanced Atomic Layer Deposition and Its Application in SiOx/SiO2 Super-Lattice
Nanomaterials 2019, 9(1), 55; https://doi.org/10.3390/nano9010055
Received: 13 December 2018 / Revised: 26 December 2018 / Accepted: 27 December 2018 / Published: 3 January 2019
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Abstract
Atomic scale control of the thickness of thin film makes atomic layer deposition highly advantageous in the preparation of high quality super-lattices. However, precisely controlling the film chemical stoichiometry is very challenging. In this study, we deposited SiOx film with different stoichiometry [...] Read more.
Atomic scale control of the thickness of thin film makes atomic layer deposition highly advantageous in the preparation of high quality super-lattices. However, precisely controlling the film chemical stoichiometry is very challenging. In this study, we deposited SiOx film with different stoichiometry by plasma enhanced atomic layer deposition. After reviewing various deposition parameters like temperature, precursor pulse time, and gas flow, the silicon dioxides of stoichiometric (SiO2) and non-stoichiometric (SiO1.8 and SiO1.6) were successfully fabricated. X-ray photo-electron spectroscopy was first employed to analyze the element content and chemical bonding energy of these films. Then the morphology, structure, composition, and optical characteristics of SiOx film were systematically studied through atomic force microscope, transmission electron microscopy, X-ray reflection, and spectroscopic ellipsometry. The experimental results indicate that both the mass density and refractive index of SiO1.8 and SiO1.6 are less than SiO2 film. The energy band-gap is approved by spectroscopic ellipsometry data and X-ray photo-electron spectroscopy O 1s analysis. The results demonstrate that the energy band-gap decreases as the oxygen concentration decreases in SiOx film. After we obtained the Si-rich silicon oxide film deposition, the SiO1.6/SiO2 super-lattices was fabricated and its photoluminescence (PL) property was characterized by PL spectra. The weak PL intensity gives us greater awareness that more research is needed in order to decrease the x of SiOx film to a larger extent through further optimizing plasma-enhanced atomic layer deposition processes, and hence improve the photoluminescence properties of SiOx/SiO2 super-lattices. Full article
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Open AccessArticle Measurements of Microstructural, Chemical, Optical, and Electrical Properties of Silicon-Oxygen-Nitrogen Films Prepared by Plasma-Enhanced Atomic Layer Deposition
Nanomaterials 2018, 8(12), 1008; https://doi.org/10.3390/nano8121008
Received: 17 November 2018 / Revised: 1 December 2018 / Accepted: 3 December 2018 / Published: 5 December 2018
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Abstract
In this study, silicon nitride (SiNx) thin films with different oxygen concentration (i.e., SiON film) were precisely deposited by plasma enhanced atomic layer deposition on Si (100) substrates. Thus, the effect of oxygen concentration on film properties is able to be [...] Read more.
In this study, silicon nitride (SiNx) thin films with different oxygen concentration (i.e., SiON film) were precisely deposited by plasma enhanced atomic layer deposition on Si (100) substrates. Thus, the effect of oxygen concentration on film properties is able to be comparatively studied and various valuable results are obtained. In detail, x-ray reflectivity, x-ray photoelectron spectroscopy, atomic force microscopy, and spectroscopic ellipsometry are used to systematically characterize the microstructural, optical, and electrical properties of SiON film. The experimental results indicate that the surface roughness increases from 0.13 to 0.2 nm as the oxygen concentration decreases. The refractive index of the SiON film reveals an increase from 1.55 to 1.86 with decreasing oxygen concentration. Accordingly, the band-gap energy of these films determined by oxygen 1s-peak analysis decreases from 6.2 to 4.8 eV. Moreover, the I-V tests demonstrate that the film exhibits lower leakage current and better insulation for higher oxygen concentration in film. These results indicate that oxygen affects microstructural, optical, and electrical properties of the prepared SiNx film. Full article
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Open AccessArticle Boron Nitride as a Novel Support for Highly Stable Palladium Nanocatalysts by Atomic Layer Deposition
Nanomaterials 2018, 8(10), 849; https://doi.org/10.3390/nano8100849
Received: 24 September 2018 / Revised: 8 October 2018 / Accepted: 16 October 2018 / Published: 18 October 2018
Cited by 1 | PDF Full-text (4125 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The ability to prepare controllable nanocatalysts is of great interest for many chemical industries. Atomic layer deposition (ALD) is a vapor phase technique enabling the synthesis of conformal thin films and nanoparticles (NPs) on high surface area supports and has become an attractive [...] Read more.
The ability to prepare controllable nanocatalysts is of great interest for many chemical industries. Atomic layer deposition (ALD) is a vapor phase technique enabling the synthesis of conformal thin films and nanoparticles (NPs) on high surface area supports and has become an attractive new route to tailor supported metallic NPs. Virtually all the studies reported, focused on Pd NPs deposited on carbon and oxide surfaces. It is, however, important to focus on emerging catalyst supports such as boron nitride materials, which apart from possessing high thermal and chemical stability, also hold great promises for nanocatalysis applications. Herein, the synthesis of Pd NPs on boron nitride (BN) film substrates is demonstrated entirely by ALD for the first time. X-ray photoelectron spectroscopy indicated that stoichiometric BN formed as the main phase, with a small amount of BNxOy, and that the Pd particles synthesized were metallic. Using extensive transmission electron microscopy analysis, we study the evolution of the highly dispersed NPs as a function of the number of ALD cycles, and the thermal stability of the ALD-prepared Pd/BN catalysts up to 750 °C. The growth and coalescence mechanisms observed are discussed and compared with Pd NPs grown on other surfaces. The results show that the nanostructures of the BN/Pd NPs were relatively stable up to 500 °C. Consequent merging has been observed when annealing the samples at 750 °C, as the NPs’ average diameter increased from 8.3 ± 1.2 nm to 31 ± 4 nm. The results presented open up exciting new opportunities in the field of catalysis. Full article
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Open AccessArticle Investigating the Trimethylaluminium/Water ALD Process on Mesoporous Silica by In Situ Gravimetric Monitoring
Nanomaterials 2018, 8(6), 365; https://doi.org/10.3390/nano8060365
Received: 24 April 2018 / Revised: 19 May 2018 / Accepted: 21 May 2018 / Published: 24 May 2018
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Abstract
A low amount of AlOx was successfully deposited on an unordered, mesoporous SiO2 powder using 1–3 ALD (Atomic Layer Deposition) cycles of trimethylaluminium and water. The process was realized in a self-built ALD setup featuring a microbalanceand a fixed particle bed. [...] Read more.
A low amount of AlOx was successfully deposited on an unordered, mesoporous SiO2 powder using 1–3 ALD (Atomic Layer Deposition) cycles of trimethylaluminium and water. The process was realized in a self-built ALD setup featuring a microbalanceand a fixed particle bed. The reactor temperature was varied between 75, 120, and 200 °C. The self-limiting nature of the deposition was verified by in situ gravimetric monitoring for all temperatures. The coated material was further analyzed by nitrogen sorption, inductively coupled plasma-optical emission spectroscopy, powder X-ray diffraction, high-resolution transmission electron microscopy, attenuated total reflection Fourier transformed infrared spectroscopy, and elemental analysis. The obtained mass gains correspond to average growth between 0.81–1.10 Å/cycle depending on substrate temperature. In addition, the different mass gains during the half-cycles in combination with the analyzed aluminum content after one, two, and three cycles indicate a change in the preferred surface reaction of the trimethylaluminium molecule from a predominately two-ligand exchange with hydroxyl groups to more single-ligand exchange with increasing cycle number. Nitrogen sorption isotherms demonstrate (1) homogeneously coated mesopores, (2) a decrease in surface area, and (3) a reduction of the pore size. The experiment is successfully repeated in a scale-up using a ten times higher substrate batch size. Full article
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Open AccessArticle Suppressing the Photocatalytic Activity of TiO2 Nanoparticles by Extremely Thin Al2O3 Films Grown by Gas-Phase Deposition at Ambient Conditions
Nanomaterials 2018, 8(2), 61; https://doi.org/10.3390/nano8020061
Received: 23 November 2017 / Revised: 17 January 2018 / Accepted: 19 January 2018 / Published: 24 January 2018
Cited by 3 | PDF Full-text (2593 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
This work investigated the suppression of photocatalytic activity of titanium dioxide (TiO2) pigment powders by extremely thin aluminum oxide (Al2O3) films deposited via an atomic-layer-deposition-type process using trimethylaluminum (TMA) and H2O as precursors. The deposition [...] Read more.
This work investigated the suppression of photocatalytic activity of titanium dioxide (TiO2) pigment powders by extremely thin aluminum oxide (Al2O3) films deposited via an atomic-layer-deposition-type process using trimethylaluminum (TMA) and H2O as precursors. The deposition was performed on multiple grams of TiO2 powder at room temperature and atmospheric pressure in a fluidized bed reactor, resulting in the growth of uniform and conformal Al2O3 films with thickness control at sub-nanometer level. The as-deposited Al2O3 films exhibited excellent photocatalytic suppression ability. Accordingly, an Al2O3 layer with a thickness of 1 nm could efficiently suppress the photocatalytic activities of rutile, anatase, and P25 TiO2 nanoparticles without affecting their bulk optical properties. In addition, the influence of high-temperature annealing on the properties of the Al2O3 layers was investigated, revealing the possibility of achieving porous Al2O3 layers. Our approach demonstrated a fast, efficient, and simple route to coating Al2O3 films on TiO2 pigment powders at the multigram scale, and showed great potential for large-scale production development. Full article
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Open AccessArticle Transparent and Flexible Capacitors with an Ultrathin Structure by Using Graphene as Bottom Electrodes
Nanomaterials 2017, 7(12), 418; https://doi.org/10.3390/nano7120418
Received: 27 October 2017 / Revised: 17 November 2017 / Accepted: 24 November 2017 / Published: 28 November 2017
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Abstract
Ultrathin, transparent and flexible capacitors using graphene as the bottom electrodes were directly fabricated on polyethylene naphthalate (PEN) substrates. ZrO2 dielectric films were deposited on the treated surface of graphene by atomic layer deposition (ALD). The deposition process did not introduce any [...] Read more.
Ultrathin, transparent and flexible capacitors using graphene as the bottom electrodes were directly fabricated on polyethylene naphthalate (PEN) substrates. ZrO2 dielectric films were deposited on the treated surface of graphene by atomic layer deposition (ALD). The deposition process did not introduce any detectible defects in the graphene, as indicated by Raman measurements, guaranteeing the electrical performances of the graphene electrodes. The Aluminum-doped zinc oxide (AZO) films were prepared as the top electrodes using the ALD technique. The capacitors presented a high capacitance density (10.3 fF/μm2 at 10 kHz) and a relatively low leakage current (5.3 × 10−6 A/cm2 at 1 V). Bending tests revealed that the capacitors were able to work normally at an outward bending radius of 10 mm without any deterioration of electrical properties. The capacitors exhibited an average optical transmittance of close to 70% at visible wavelengths. Thus, it opens the door to practical applications in transparent integrated circuits. Full article
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