Chemical Vapor Deposition

Cover image for Vol. 19 Issue 4‐6

Special Issue: Functional Materials by Atomic Layer Deposition

June 2013

Volume 19, Issue 4-6

Pages 75–220

Issue edited by: Mato Knez, Qin Yong

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Contents
    5. Editorial
    6. Review
    7. Full Papers
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  2. Masthead

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Contents
    5. Editorial
    6. Review
    7. Full Papers
    1. Masthead: (Chem. Vap. Deposition 4–5–6/2013)

      Version of Record online: 17 JUN 2013 | DOI: 10.1002/cvde.201390005

  3. Contents

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Contents
    5. Editorial
    6. Review
    7. Full Papers
    1. You have free access to this content
  4. Editorial

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Contents
    5. Editorial
    6. Review
    7. Full Papers
    1. Special Issue: Functional Materials by Atomic Layer Deposition (pages 80–81)

      Mato Knez and Yong Qin

      Version of Record online: 17 JUN 2013 | DOI: 10.1002/cvde.201302001

  5. Review

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    3. Masthead
    4. Contents
    5. Editorial
    6. Review
    7. Full Papers
    1. Recent Developments of Atomic Layer Deposition Processes for Metallization (pages 82–103)

      Dr. Wei-Min Li

      Version of Record online: 21 MAY 2013 | DOI: 10.1002/cvde.201300052

      Recent developments of ALD processes for metallization are reviewed from the chemistry point of view. Most of the ALD-produced conducting materials are formed in a typical AB sequence from two reactants, including elemental metals, binary, ternary, and more complex systems such as doping and nanolamination, In addition, an ABC sequence with a surface controlled ALD reaction is also possible. A double replacement reaction mechanism is proposed with examples of novel ALD processes such as TaCxNy, WCx, and WNxCy.

  6. Full Papers

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Contents
    5. Editorial
    6. Review
    7. Full Papers
    1. A Micro-pulse Process of Atomic Layer Deposition of Iron Oxide Using Ferrocene and Ozone Precursors and Ti-Doping (pages 104–110)

      Xianglin Li, Ng Chin Fan and Hong Jin Fan

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/cvde.201207030

      A micro-pulse ALD process is developed for fast deposition of Fe2O3 on both planar and high aspect ratio substrates (nanowires and AAO channels). By introducing TiO2 co-deposition, a linear growth rate can be maintained up to 600 cycles, corresponding to a thickness of 33 nm. A controllable Ti-doping into Fe2O3 films is achievable by adjusting the ALD cycle ratios of TiO2 and Fe2O3.

    2. Atomic Layer Deposition of LiF Thin Films from Lithd and TiF4 Precursors (pages 111–116)

      Miia Mäntymäki, Jani Hämäläinen, Esa Puukilainen, Frans Munnik, Mikko Ritala and Markku Leskelä

      Version of Record online: 14 MAY 2013 | DOI: 10.1002/cvde.201207026

      A deposition method for lithium fluoride thin films by ALD onto Si substrates is described. The deposited films are analyzed by UV-Vis spectrometry, FESEM, XRD, AFM, and ERDA. This deposition process produces crystalline LiF films with high purity and a refractive index close to that of bulk LiF. The roughness of the films increases with increasing deposition temperature.

    3. Modeling of Precursors for Atomic Layer Deposition of Magnesium and Calcium Oxide (pages 117–124)

      Ivan Kazadojev, David J. Otway and Simon D. Elliott

      Version of Record online: 14 MAY 2013 | DOI: 10.1002/cvde.201207025

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      A study of magnesium and calcium precursor molecules with various ligands is presented in order to predict which ligands would be the most successful in atomic layer deposition (ALD) of the metal oxides. The work investigates one aspect of this, surface reactivity between ligands and hydroxyl groups, via a gas-phase model with energetics computed at the level of density functional theory (DFT).

    4. Room-Temperature ALD of Metal Oxide Thin Films by Energy-Enhanced ALD (pages 125–133)

      Stephen E. Potts, Harald B. Profijt, Robin Roelofs and Wilhelmus M. M. Kessels

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/cvde.201207033

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      Room-temperature (25°C) atomic layer deposition (RT-ALD) processes enabled by energy-enhanced ALD are investigated, using Al2O3, TiO2, and SiO2 as examples. It is suggested that, for viable RT-ALD processes, it is essential that both the metal-organic precursor and the co-reactant be sufficiently reactive with the surface groups left after the preceding respective RT-ALD half-cycle. Other criteria, such as volatile metal-organic precursors and short purge times are desirable.

    5. Influence of Subsurface Hybrid Material Growth on the Mechanical Properties of Atomic Layer Deposited Thin Films on Polymers (pages 134–141)

      Yujie Sun, Richard P. Padbury, Halil I. Akyildiz, Matthew P. Goertz, Jeremy A. Palmer and Jesse S. Jur

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/cvde.201207042

      The mechanical properties of Al2O3 ALD coatings on polyamide 6 are examined by nano-indentation and flexure testing to determine the influence of a sub-surface hybrid layer formed during the ALD process. The results show the importance of the consideration of this hybrid layer on the use of these materials in future flexible electronic and encapsulation applications.

    6. Organic-Inorganic Hybrid Nano-laminates Fabricated by Ozone-assisted Molecular-atomic Layer Deposition (pages 142–148)

      Jie Huang, Mingun Lee, Antonio Lucero and Jiyoung Kim

      Version of Record online: 14 MAY 2013 | DOI: 10.1002/cvde.201207041

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      Organic thin films are deposited using a novel layer-by-layer deposition approach named molecular-atomic-layer-deposition (MALD). Organic molecules are introduced into the reaction chamber in the vapor phase to construct the backbone of polymeric thin films on the substrate with the help of an ALD linker and ozone gas. MALD of organic-inorganic nano-laminates can also be achieved by alternating inorganic ALD and organic MLD layers, as illustrated in the cross-sectional TEM.

    7. Photocatalytic Properties of WO3/TiO2 Core/Shell Nanofibers prepared by Electrospinning and Atomic Layer Deposition (pages 149–155)

      Imre Miklós Szilágyi, Eero Santala, Mikko Heikkilä, Viljami Pore, Marianna Kemell, Timur Nikitin, Georg Teucher, Tamás Firkala, Leonid Khriachtchev, Markku Räsänen, Mikko Ritala and Markku Leskelä

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/cvde.201207037

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      TiO2 thin films (1.5–20 nm) are grown by ALD on electrospun WO3 nanofibers. The WO3/1.5 nm TiO2 composite nanofiber has the highest photocatalytic activity, and it is a better photocatalyst under visible light when compared to bare WO3 and Degussa TiO2.

    8. A Water-free Low Temperature Process for Atomic Layer Deposition of Al2O3 Films (pages 156–160)

      Jiao-Jiao Guo, Ming-Da Li, Qing-Qing Sun, Wen Yang, Peng Zhou, Shi-Jin Ding and David Wei Zhang

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/cvde.201207032

      O2 and H2O are generally not suitable oxidants for low temperature atomic layer deposition on the organic materials because they can degrade most organic materials. An alternative oxidant, acetic acid (CH3COOH) instead of H2O, is investigated for low temperature atomic layer deposition of Al2O3. The growth behaviors and film properties of the Al2O3 film are studied in detail and the growth mechanism of this new process is investigated on the atomic scale.

    9. Low-Temperature Atomic Layer Deposition of Tungsten using Tungsten Hexafluoride and Highly-diluted Silane in Argon (pages 161–166)

      Berç Kalanyan, Mark D. Losego, Christopher J. Oldham and Gregory N. Parsons

      Version of Record online: 31 MAY 2013 | DOI: 10.1002/cvde.201307053

      Tungsten films are deposited by ALD using dilute SiH4 as the silicon source. Growth rates of 6.0 ± 0.5 Å per cycle are observed between 200 and 300°C. Analysis by AES and depth-profile SIMS show a silicon content of <5 at.-% in the W films. Higher deposition temperatures favor lower Si incorporation. A dilute silane co-reactant offers an alternative to pure silane with better process safety and 4.5 Å per cycle growth at low temperature (150°C).

    10. Atmospheric Pressure Plasma ALD of Titanium Oxide (pages 167–173)

      Detlef Theirich, Roman Müller, Kirill Zilberberg, Sara Trost, Andreas Behrendt and Thomas Riedl

      Version of Record online: 14 MAY 2013 | DOI: 10.1002/cvde.201207039

      Atmospheric-pressure plasma atomic layer deposition (APP-ALD) of TiOx at room temperature is reported for the first time. The application of the resulting TiOx layers as electron-extraction interlayers in inverted organic solar cells (OSCs) is demonstrated. The characteristics of OSCs based on APP-ALD-grown TiOx are similar to those of OSCs based on TiOx prepared by low-pressure thermal ALD or sol-gel processing.

    11. Molecular Hybrid Structures by Atomic Layer Deposition – Deposition of Alq3, Znq2 and Tiq4 (q = 8-hydroxyquinoline) (pages 174–179)

      Ola Nilsen, Kristoffer Robin Haug, Terje Finstad and Helmer Fjellvåg

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/cvde.201207043

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      Thin films of metal quinolines based on 8-hydroxyquinoline (q) and aluminum (Alq3), zinc (Znq2), and titanium (possibly Tiq4) are deposited using ALD in the temperature range 85–200 °C. This demonstrates the ALD growth of structures based on weak van der Waals forces. The Alq3 material proves stable towards exposure to water during deposition. Films of both Alq3 and Znq2 are significantly photoluminescent active.

    12. Atomic Layer Deposition of Al-doped ZnO Films Using Aluminum Isopropoxide as the Al Precursor (pages 180–185)

      Xu Qian, Yanqiang Cao, Binglei Guo, Haifa Zhai and Aidong Li

      Version of Record online: 16 MAY 2013 | DOI: 10.1002/cvde.201207051

      Al-doped ZnO (AZO) films are deposited by atomic layer deposition (ALD) on borosilicate glass and Si using diethylzinc and aluminum isopropoxide as Zn and Al precursors, respectively. The effects of Zn/Al ALD cycle ratio and the Al source temperature on the Al dopant concentration and resistivity of AZO films are investigated. The AZO films deposited at an Al source temperature of 120°C show the lowest resistivity.

    13. Atomic Layer Deposition of W:Al2O3 Nanocomposite Films with Tunable Resistivity (pages 186–193)

      Anil U. Mane and Jeffrey W. Elam

      Version of Record online: 14 MAY 2013 | DOI: 10.1002/cvde.201307054

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      Nanocomposite W:Al2O3 films are prepared by atomic layer deposition (ALD) using tungsten hexafluoride (WF6) and disilane (Si2H6) for the W ALD and trimethyl aluminum (TMA) and H2O for the Al2O3 ALD. Cross-sectional TEM reveals the film structure to be metallic nanoparticles (∼1 nm) embedded in an amorphous matrix. The resistivity of these films can be tuned over 1012–108 Ω cm by adjusting the W cycle percentage between 10 and 30% W.

    14. AlxTayOz Mixture Coatings Prepared Using Atomic Layer Deposition for Corrosion Protection of Steel (pages 194–203)

      Emma Härkönen, Dr. Belén Díaz, Dr. Jolanta Światowska, Dr. Vincent Maurice, Dr. Antoine Seyeux, Dr. Martin Fenker, Dr. Lajos Tóth, Dr. György Radnóczi, Philippe Marcus and Mikko Ritala

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/cvde.201207028

      Corrosion protection of steel with 50 nm AlxTayOz mixture coatings of varying composition, produced using atomic layer deposition (ALD), is studied. Analysis of the morphology, composition, and protective properties of the coatings shows that the coatings are conformal, uniform, and very low in defect density. The corrosion durability of steel is significantly improved with all mixture coatings. Furthermore, the mixtures are found to be superior to ALD-produced Al2O3, Ta2O5, and Al2O3/Ta2O5 nano-laminate coatings

    15. Molecular Layer Deposition of Zircone and ZrO2/Zircone Alloy Films: Growth and Properties (pages 204–212)

      Byoung H. Lee, Virginia R. Anderson and Steven M. George

      Version of Record online: 22 MAY 2013 | DOI: 10.1002/cvde.201207045

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      Hybrid organic/inorganic films based on zirconium are grown using molecular layer deposition (MLD). Zirconium alkoxide films, known as “zircones”, are grown using sequential exposures of zirconium tert-butoxide and ethylene glycol. ZrO2/zircone alloys are fabricated by combining ZrO2 atomic layer deposition (ALD) and zircone MLD. The composition and properties of the ZrO2/zircone alloys are varied by changing the relative number of ZrO2 ALD and zircone MLD cycles in the reaction sequence.

    16. Thin Films of High-k Oxides and ZnO for Transparent Electronic Devices (pages 213–220)

      Sylwia Gieraltowska, Lukasz Wachnicki, Bartlomiej S. Witkowski, Elzbieta Guziewicz and Marek Godlewski

      Version of Record online: 29 MAY 2013 | DOI: 10.1002/cvde.201207029

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      Oxide-based thin film devices and sensor structures deposited on transparent substrates are investigated. All oxide elements in these structures are deposited using ALD. The composite dielectrics consisting of pairs of Al2O3, HfO2, ZrO2, or TiO2 are used as insulators in capacitors and transistor structures, with ZnO layers deposited as channel and gate layers. The structures are obtained at low temperature, which enables their deposition on elastic, transparent substrates.

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