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Design of Nanostructured Materials by Atomic Layer Deposition and Its Applications

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

Deadline for manuscript submissions: closed (31 October 2018) | Viewed by 49498

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Dr. Mikhael Bechelany

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European Institute of Membranes (IEM), University of Montpellier, 34090 Montpellier, France
Interests: atomic layer deposition; photocatalysis; electrospinning; nanomaterials; sensors; thin films
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Prof. Dr. Seppo Honkanen

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

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Institute of Photonics, University of Eastern Finland, Joensuu, Finland
Interests: nanofabrication; thin films; nanolaminates and multilayers; nanostructures; electromagnetic surface waves and plasmonics; X-ray; UV; THz; IR; light field control; environmental sensing; sources and detectors; materials
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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

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Nanomaterials is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2900 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

thin film
nanomaterial
interface
surface modification
nanostructured material
energy
health
environment

Published Papers (9 papers)

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Research

11 pages, 3022 KiB

Open AccessArticle

Preparation and Characterization of Microsphere ZnO ALD Coating Dedicated for the Fiber-Optic Refractive Index Sensor

by Paulina Listewnik, Marzena Hirsch, Przemysław Struk, Matthieu Weber, Mikhael Bechelany and Małgorzata Jędrzejewska-Szczerska

Nanomaterials 2019, 9(2), 306; https://doi.org/10.3390/nano9020306 - 23 Feb 2019

Cited by 24 | Viewed by 5180

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 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

(This article belongs to the Special Issue Design of Nanostructured Materials by Atomic Layer Deposition and Its Applications)

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21 pages, 7901 KiB

Open AccessArticle

Titania Nanotubes/Hydroxyapatite Nanocomposites Produced with the Use of the Atomic Layer Deposition Technique: Estimation of Bioactivity and Nanomechanical Properties

by Aleksandra Radtke, Michalina Ehlert, Tomasz Jędrzejewski, Beata Sadowska, Marzena Więckowska-Szakiel, Jani Holopainen, Mikko Ritala, Markku Leskelä, Michał Bartmański, Marek Szkodo and Piotr Piszczek

Nanomaterials 2019, 9(1), 123; https://doi.org/10.3390/nano9010123 - 19 Jan 2019

Cited by 20 | Viewed by 4801

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 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

(This article belongs to the Special Issue Design of Nanostructured Materials by Atomic Layer Deposition and Its Applications)

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17 pages, 3251 KiB

Open AccessArticle

Fracture Mechanics and Oxygen Gas Barrier Properties of Al₂O₃/ZnO Nanolaminates on PET Deposited by Atomic Layer Deposition

by Vipin Chawla, Mikko Ruoho, Matthieu Weber, Adib Abou Chaaya, Aidan A. Taylor, Christophe Charmette, Philippe Miele, Mikhael Bechelany, Johann Michler and Ivo Utke

Nanomaterials 2019, 9(1), 88; https://doi.org/10.3390/nano9010088 - 11 Jan 2019

Cited by 40 | Viewed by 4943

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 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

(This article belongs to the Special Issue Design of Nanostructured Materials by Atomic Layer Deposition and Its Applications)

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13 pages, 5923 KiB

Open AccessArticle

Systematic Study of the SiO_x Film with Different Stoichiometry by Plasma-Enhanced Atomic Layer Deposition and Its Application in SiO_x/SiO₂ Super-Lattice

by Hong-Ping Ma, Jia-He Yang, Jian-Guo Yang, Li-Yuan Zhu, Wei Huang, Guang-Jie Yuan, Ji-Jun Feng, Tien-Chien Jen and Hong-Liang Lu

Nanomaterials 2019, 9(1), 55; https://doi.org/10.3390/nano9010055 - 03 Jan 2019

Cited by 54 | Viewed by 5682

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 SiO_x 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 (SiO_1.8 and SiO_1.6) 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 SiO_x 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 SiO_1.8 and SiO_1.6 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 SiO_x film. After we obtained the Si-rich silicon oxide film deposition, the SiO_1.6/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 SiO_x film to a larger extent through further optimizing plasma-enhanced atomic layer deposition processes, and hence improve the photoluminescence properties of SiO_x/SiO₂ super-lattices. Full article

(This article belongs to the Special Issue Design of Nanostructured Materials by Atomic Layer Deposition and Its Applications)

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14 pages, 4439 KiB

Open AccessArticle

Measurements of Microstructural, Chemical, Optical, and Electrical Properties of Silicon-Oxygen-Nitrogen Films Prepared by Plasma-Enhanced Atomic Layer Deposition

by Hong-Ping Ma, Hong-Liang Lu, Jia-He Yang, Xiao-Xi Li, Tao Wang, Wei Huang, Guang-Jie Yuan, Fadei F. Komarov and David Wei Zhang

Nanomaterials 2018, 8(12), 1008; https://doi.org/10.3390/nano8121008 - 05 Dec 2018

Cited by 20 | Viewed by 5771

Abstract

In this study, silicon nitride (SiN_x) 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 SiN_x film. Full article

(This article belongs to the Special Issue Design of Nanostructured Materials by Atomic Layer Deposition and Its Applications)

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14 pages, 4125 KiB

Open AccessArticle

Boron Nitride as a Novel Support for Highly Stable Palladium Nanocatalysts by Atomic Layer Deposition

by Matthieu Weber, Cassandre Lamboux, Bruno Navarra, Philippe Miele, Sandrine Zanna, Maxime E. Dufond, Lionel Santinacci and Mikhael Bechelany

Nanomaterials 2018, 8(10), 849; https://doi.org/10.3390/nano8100849 - 18 Oct 2018

Cited by 22 | Viewed by 4531

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 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 BN_xO_y, 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

(This article belongs to the Special Issue Design of Nanostructured Materials by Atomic Layer Deposition and Its Applications)

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14 pages, 3697 KiB

Open AccessArticle

Investigating the Trimethylaluminium/Water ALD Process on Mesoporous Silica by In Situ Gravimetric Monitoring

by Verena E. Strempel, Kristian Knemeyer, Raoul Naumann d’Alnoncourt, Matthias Driess and Frank Rosowski

Nanomaterials 2018, 8(6), 365; https://doi.org/10.3390/nano8060365 - 24 May 2018

Cited by 17 | Viewed by 4702

Abstract

A low amount of AlO_x 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

(This article belongs to the Special Issue Design of Nanostructured Materials by Atomic Layer Deposition and Its Applications)

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19 pages, 2593 KiB

Open AccessArticle

Suppressing the Photocatalytic Activity of TiO₂ Nanoparticles by Extremely Thin Al₂O₃ Films Grown by Gas-Phase Deposition at Ambient Conditions

by Jing Guo, Hao Van Bui, David Valdesueiro, Shaojun Yuan, Bin Liang and J. Ruud Van Ommen

Nanomaterials 2018, 8(2), 61; https://doi.org/10.3390/nano8020061 - 24 Jan 2018

Cited by 31 | Viewed by 7308

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 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

(This article belongs to the Special Issue Design of Nanostructured Materials by Atomic Layer Deposition and Its Applications)

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6469 KiB

Open AccessArticle

Transparent and Flexible Capacitors with an Ultrathin Structure by Using Graphene as Bottom Electrodes

by Tao Guo, Guozhen Zhang, Xi Su, Heng Zhang, Jiaxian Wan, Xue Chen, Hao Wu and Chang Liu

Nanomaterials 2017, 7(12), 418; https://doi.org/10.3390/nano7120418 - 28 Nov 2017

Cited by 11 | Viewed by 5084

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 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

(This article belongs to the Special Issue Design of Nanostructured Materials by Atomic Layer Deposition and Its Applications)

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