Effect of ion bombardment on the structural and optical properties of TiO2 thin films deposited from oxygen/titanium tetraisopropoxide inductively coupled plasma

Li, Dayu; Carette, Michèle; Granier, A.; Landesman, Jean-Pierre; Goullet, Antoine

doi:10.1016/j.tsf.2015.07.015

Cited by 21 publications

(21 citation statements)

References 44 publications

(52 reference statements)

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“…and material properties. Furthermore, the trends in material property variation reported for substrate biasing during conventional flux-controlled deposition processes (PECVD or PVD) are similar to those observed in the surface-controlled PEALD processes of this work for all films 44 , 57 − 60 except SiN x . Enhancing ion energies during PEALD of SiN x with relatively small ⟨ V bias ⟩ (<−100 V) lowered mass density, refractive index, and compressive stress while simultaneously increasing WER which are opposite to the trends reported for SiN x PECVD or PVD processes with substrate biasing.…”

Section: Discussionsupporting

confidence: 78%

Tuning Material Properties of Oxides and Nitrides by Substrate Biasing during Plasma-Enhanced Atomic Layer Deposition on Planar and 3D Substrate Topographies

Faraz

Knoops

Verheijen

et al. 2018

ACS Appl. Mater. Interfaces

130

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Oxide and nitride thin-films of Ti, Hf, and Si serve numerous applications owing to the diverse range of their material properties. It is therefore imperative to have proper control over these properties during materials processing. Ion-surface interactions during plasma processing techniques can influence the properties of a growing film. In this work, we investigated the effects of controlling ion characteristics (energy, dose) on the properties of the aforementioned materials during plasma-enhanced atomic layer deposition (PEALD) on planar and 3D substrate topographies. We used a 200 mm remote PEALD system equipped with substrate biasing to control the energy and dose of ions by varying the magnitude and duration of the applied bias, respectively, during plasma exposure. Implementing substrate biasing in these forms enhanced PEALD process capability by providing two additional parameters for tuning a wide range of material properties. Below the regimes of ion-induced degradation, enhancing ion energies with substrate biasing during PEALD increased the refractive index and mass density of TiOx and HfOx and enabled control over their crystalline properties. PEALD of these oxides with substrate biasing at 150 °C led to the formation of crystalline material at the low temperature, which would otherwise yield amorphous films for deposition without biasing. Enhanced ion energies drastically reduced the resistivity of conductive TiNx and HfNx films. Furthermore, biasing during PEALD enabled the residual stress of these materials to be altered from tensile to compressive. The properties of SiOx were slightly improved whereas those of SiNx were degraded as a function of substrate biasing. PEALD on 3D trench nanostructures with biasing induced differing film properties at different regions of the 3D substrate. On the basis of the results presented herein, prospects afforded by the implementation of this technique during PEALD, such as enabling new routes for topographically selective deposition on 3D substrates, are discussed.

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Section: Discussionsupporting

confidence: 78%

Tuning Material Properties of Oxides and Nitrides by Substrate Biasing during Plasma-Enhanced Atomic Layer Deposition on Planar and 3D Substrate Topographies

Faraz

Knoops

Verheijen

et al. 2018

ACS Appl. Mater. Interfaces

130

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“…Also by comparing the n values with the anatase and rutile films which have been investigated in our previous study, [17] it is found that the optical index of the film has been increased greatly under the condition of higher ion energy, close to the one of anatase film deposited by PECVD. This is mainly due to the change in composition and also probably to the presence of rutile phase in the case of Ti rich film.…”

Section: Optical Propertiesmentioning

confidence: 82%

“…The low pressure radiofrequency inductively coupled plasma such as the one used in this study, indeed offers the possibility to control independently the ion density (fixed by the power coupled to the plasma source) and the ion energy (by biasing the substrate). It has been mentioned in the previous papers [17,18] that the ion energy (E i ) can be estimated to be 15 eV at V f and was increased to 75 eV at The deposition of an inorganic film and the formation of CO, CO 2 , and OH in the gas should be mainly due to the oxygen atoms which are involved in oxidation reactions, both at the film surface and in the plasma phase. [19] The optical emission spectra recorded during the film growth show a strong emission from excited CO, H, and OH.…”

Section: Plasma Characterization and Film Deposition Ratementioning

confidence: 99%

“…In addition, even for the same composition the n values obtained in this study are higher than the ones reported in the literature. [8,9,12,17] For example, the n values (at 550 nm) of TiO 2 /SiO 2 films deposited by ion beam induced and plasma-enhanced chemical vapor deposition [9] were reported to be equal to~1.52,~1.67, 1.75-1.90 for x = 0,15, 0.4, and 0.8, respectively.…”

Section: Optical Propertiesmentioning

confidence: 99%

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Ion impingement effect on the structure and optical properties of Ti_xSi_1−xO₂ films deposited by ICP‐PECVD

Dai

Goullet

et al. 2019

Plasma Processes & Polymers

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TixSi1−xO2 films are grown by plasma‐enhanced chemical vapor deposition from oxygen‐rich O2/titanium tetraisopropoxide/hexamethyldisiloxane radiofrequency inductively coupled plasmas at low pressure. By applying a substrate bias of −50 V, the ion energy is increased from 15 to 75 eV, which has almost no effect on the by‐products, whereas the deposition rate is decreased and the Ti/Si atomic ratio in the film is increased. For the lowest hexamethyldisiloxane fraction in precursor, applying a −50 V bias leads to the formation of TiO2 in rutile phase in the film. The film optical properties (optical index and band gap) are shown to be mainly governed by the film chemical composition.

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“…In our previous studies, PECVD processes were used to yield some nanocolumnar structures with different phases including amorphous, anatase and rutile [35][36]. Actually these processes exhibit favorable features such as low deposition temperature, good film adhesion, high purity, good step coverage and easy control of reaction parameters [28,37].…”

Section: Introductionmentioning

confidence: 99%

Nanostructure and photocatalytic properties of TiO2 films deposited at low temperature by pulsed PECVD

Bulou

Gautier

et al. 2019

Applied Surface Science

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The nanostructure and photocatalytic properties of TiO 2 thin films deposited by PECVD on silicon substrates were investigated. The films were grown at low temperature (< 120 °C) in an rf inductively coupled oxygen/titanium tetraisopropoxide plasma, in continuous and pulsed modes with different plasma-on time (via variation of the duty cycle, DC). All the films exhibit nano-columnar structures, but the reduction of plasma-on time by decreasing the duty cycle for pulsed mode leads to a more homogenous morphology with a diminished column size, and a decrease in the surface roughness. TiO 2 layers containing a high amount of anatase were grown at substrate temperatures less than 100 °C corresponding to DC ≥ 40%, then the crystallization was hindered with the decrease of DC, even inducing amorphous films for DC ≤ 10%. Moreover, the films deposited below 100 °C with deposition conditions where 50% ≤ DC ≤ 75% were shown to present a high photocatalytic activity, likely due to the presence of anatase crystalline nanocolumns at the surface.

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Effect of ion bombardment on the structural and optical properties of TiO2 thin films deposited from oxygen/titanium tetraisopropoxide inductively coupled plasma

Cited by 21 publications

References 44 publications

Tuning Material Properties of Oxides and Nitrides by Substrate Biasing during Plasma-Enhanced Atomic Layer Deposition on Planar and 3D Substrate Topographies

Tuning Material Properties of Oxides and Nitrides by Substrate Biasing during Plasma-Enhanced Atomic Layer Deposition on Planar and 3D Substrate Topographies

Ion impingement effect on the structure and optical properties of Ti_xSi_1−xO₂ films deposited by ICP‐PECVD

Nanostructure and photocatalytic properties of TiO2 films deposited at low temperature by pulsed PECVD

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Effect of ion bombardment on the structural and optical properties of TiO2 thin films deposited from oxygen/titanium tetraisopropoxide inductively coupled plasma

Cited by 21 publications

References 44 publications

Tuning Material Properties of Oxides and Nitrides by Substrate Biasing during Plasma-Enhanced Atomic Layer Deposition on Planar and 3D Substrate Topographies

Tuning Material Properties of Oxides and Nitrides by Substrate Biasing during Plasma-Enhanced Atomic Layer Deposition on Planar and 3D Substrate Topographies

Ion impingement effect on the structure and optical properties of TixSi1−xO2 films deposited by ICP‐PECVD

Nanostructure and photocatalytic properties of TiO2 films deposited at low temperature by pulsed PECVD

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Ion impingement effect on the structure and optical properties of Ti_xSi_1−xO₂ films deposited by ICP‐PECVD