Reaction Mechanism Studies on Titanium Isopropoxide–Water Atomic Layer Deposition Process

Rahtu, Antti; Ritala, Mikko

doi:10.1002/1521-3862(20020116)8:1<21::aid-cvde21>3.0.co;2-0

Cited by 131 publications

(157 citation statements)

References 29 publications

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“…The transition from amorphous to anatase TiO 2 has been reported 180 C in the thermal ALD. 31 The mechanisms of the reaction between TTIP and water were studied by Rahtu and Ritala 37 and Aarik et al 31 using deuterated water to identify them. It was found that between 150 and 250 C half of the isopropoxide ligands are released during the TTIP pulse in reaction with hydroxyl groups and the other half are released during the water pulse.…”

Section: Water Processsupporting

confidence: 64%

“…Xie et al 36 measured a growth rate of 0.03-0.15 Å /cycle between 50 and 150 C. They also reported an increase in the growth rate in the temperature range of 50-150 C, which does not agree with the results of this study. Both Rahtu and Ritala 37 and Ritala and Leskelii 38 reported a growth rate of 0.15 Å /cycle at substrate reported of 1.5 Å /cycle at the same substrate temperature. Sinha et al 40 also measured the growth rate at 160 C, which was 0.68 Å /cycle.…”

Section: Water Processmentioning

confidence: 99%

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Low temperature temporal and spatial atomic layer deposition of TiO2 films

Aghaee

Maydannik

Johansson

et al. 2015

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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Document VersionPublisher's PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication:• A submitted manuscript is the author's version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Titanium dioxide films were grown by atomic layer deposition (ALD) using titanium tetraisopropoxide as a titanium precursor and water, ozone, or oxygen plasma as coreactants. Low temperatures (80-120 C) were used to grow moisture barrier TiO 2 films on polyethylene naphthalate. The maximum growth per cycle for water, ozone, and oxygen plasma processes were 0.33, 0.12, and 0.56 Å /cycle, respectively. X-ray photoelectron spectrometry was used to evaluate the chemical composition of the layers and the origin of the carbon contamination was studied by deconvoluting carbon C1s peaks. In plasma-assisted ALD, the film properties were dependent on the energy dose supplied by the plasma. TiO 2 films were also successfully deposited by using a spatial ALD (SALD) system based on the results from the temporal ALD. Similar properties were measured compared to the temporal ALD deposited TiO 2 , but the deposition time could be reduced using SALD. The TiO 2 films deposited by plasma-assisted ALD showed better moisture barrier properties than the layers deposited by thermal processes. Water vapor transmission rate values lower than 5 Â 10 À4 g day À1 m À2 (38 C and 90% RH) was measured for 20 nm of TiO 2 film deposited by plasma-assisted ALD.

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Section: Water Processsupporting

confidence: 64%

Section: Water Processmentioning

confidence: 99%

Low temperature temporal and spatial atomic layer deposition of TiO2 films

Aghaee

Maydannik

Johansson

et al. 2015

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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“…A first category directly monitors physical changes. Examples are quartz crystal microbalance [5][6][7][8] measuring mass change, four-point probe 9 measuring electronic resistivity, and thermopile 10 measuring the reaction enthalpies. A second category of techniques probes the gas species that are being consumed and formed during the various chemical reactions involved in the ALD process.…”

Section: Introductionmentioning

confidence: 93%

“…A second category of techniques probes the gas species that are being consumed and formed during the various chemical reactions involved in the ALD process. Examples are quadrupole mass spectrometry, 7,8,11 optical emission spectroscopy, 12,13 and Fourier transformed infrared (FTIR) absorption spectroscopy. 14 A last category uses light from either the infrared or visual range to monitor the optical properties of the surface and/or the deposited layer.…”

Section: Introductionmentioning

confidence: 99%

In situ synchrotron based x-ray techniques as monitoring tools for atomic layer deposition

Devloo-Casier

Ludwig

Detavernier

et al. 2013

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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Atomic layer deposition (ALD) is a thin film deposition technique that has been studied with a variety of in situ techniques. By exploiting the high photon flux and energy tunability of synchrotron based x-rays, a variety of new in situ techniques become available. X-ray reflectivity, grazing incidence small angle x-ray scattering, x-ray diffraction, x-ray fluorescence, x-ray absorption spectroscopy, and x-ray photoelectron spectroscopy are reviewed as possible in situ techniques during ALD. All these techniques are especially sensitive to changes on the (sub-)nanometer scale, allowing a unique insight into different aspects of the ALD growth mechanisms.

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“…3 Its variability is generally explained by the dependence of the permittivity on the crystalline phase, deposition method and process parameters of the TiO 2 . Various techniques such as thermal 4 or anodic oxidation, 5 electron beam evaporation, 6 chemical vapor deposition (CVD), 7 plasma-enhanced chemical vapor deposition, 8 sol-gel methods, 9 reactive sputtering methods, 10,11 and atomic layer deposition (ALD) [12][13][14] have been reported for TiO 2 thin film fabrication. Among them, ALD seems highly suitable for obtaining conformal films with uniform thickness even at low temperatures, 15,16 allowing the manufacturing of insulator films with desired and reproducible properties.…”

Section: Introductionmentioning

confidence: 99%

Anomalous C-V response correlated to relaxation processes in TiO2 thin film based-metal-insulator-metal capacitor: Effect of titanium and oxygen defects

Marichy

Sylvestre

Pinna

2015

Journal of Applied Physics

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Capacitance-voltage (C V) and capacitance-frequency (C f) measurements are performed on atomic layer deposited TiO 2 thin films with top and bottom Au and Pt electrodes, respectively, over a large temperature and frequency range. A sharp capacitance peak/discontinuity (C V anomalous) is observed in the C V characteristics at various temperatures and voltages. It is demonstrated that this phenomenon is directly associated with oxygen vacancies. The C V peak irreversibility and dissymmetry at the reversal dc voltage are attributed to difference between the Schottky contacts at the metal/TiO 2 interfaces. Dielectric analyses reveal two relaxation processes with degeneration of the activation energy. The low trap level of 0.60 0.65 eV is associated with the first ionized oxygen vacancy at low temperature, while the deep trap level of 1.05 eV is associated to the second ionized oxygen vacancy at high temperature. The DC conductivity of the films exhibits a transition temperature at 200 C, suggesting a transition from a conduction regime governed by ionized oxygen vacancies to one governed by interstitial Ti 3þ ions. Both the C V anomalous and relaxation processes in TiO 2 arise from oxygen vacancies, while the conduction mechanism at high temperature is governed by interstitial titanium ions. V C 2015 AIP Publishing LLC.

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Reaction Mechanism Studies on Titanium Isopropoxide–Water Atomic Layer Deposition Process

Cited by 131 publications

References 29 publications

Low temperature temporal and spatial atomic layer deposition of TiO2 films

Low temperature temporal and spatial atomic layer deposition of TiO2 films

In situ synchrotron based x-ray techniques as monitoring tools for atomic layer deposition

Anomalous C-V response correlated to relaxation processes in TiO2 thin film based-metal-insulator-metal capacitor: Effect of titanium and oxygen defects

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