Ion-bombardment-induced reduction in vacancies and its enhanced effect on conductivity and reflectivity in hafnium nitride films

Gu, Zhiqing; Wang, Jiafu; Hu, Chaoquan; Zhang, Xiaobo; Dang, Jianchen; Zhang, Sam; Gao, Jing; Wang, Xiaoyi; Chen, Hong; Zheng, Weitao

doi:10.1007/s00339-016-0308-0

Cited by 3 publications

(4 citation statements)

References 34 publications

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Section: Discussionsupporting

confidence: 78%

“…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 ,− 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. , Even for substrate biasing during PEALD, the mass density of TiO x as a function of ⟨ V bias ⟩ increased for films in this work but decreased for films deposited in previous work reported by Profijt et al, who used different Ti precursors. , The unique trends in property variation with substrate biasing signify how the effects of controlling ion-surface interactions can be highly material and/or process specific.…”

Section: Discussionsupporting

confidence: 77%

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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%

Section: Discussionsupporting

confidence: 77%

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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“…In near-stoichiometric films, a significant increase in the electron mean free path leads to higher reflectivity. Negative substrate bias also improves optical reflectivity due to reduced nitrogen and hafnium vacancies in the film. , Similarly, the optical properties of ZrN are also improved by tuning the growth parameters. − However, simultaneous tuning of all of the growth parameters to achieve the highest optical reflectivity achievable in HfN and ZrN films remains unexplored. In this work, we demonstrate record-high solar and infrared reflectance of epitaxial stoichiometric HfN and ZrN thin films by optimizing all of the growth parameters.…”

Section: Introductionmentioning

confidence: 99%

“…Negative substrate bias also improves optical reflectivity due to reduced nitrogen and hafnium vacancies in the film. 32,33 Similarly, the optical properties of ZrN are also improved by tuning the growth parameters. 34−36 However, simultaneous tuning of all of the growth parameters to achieve the highest optical reflectivity achievable in HfN and ZrN films remains unexplored.…”

Section: ■ Introductionmentioning

confidence: 99%

Refractory Plasmonic Hafnium Nitride and Zirconium Nitride Thin Films as Alternatives to Silver for Solar Mirror Applications

Das

Biswas

Maurya

et al. 2022

ACS Appl. Mater. Interfaces

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Harnessing solar energy by employing concentrated solar power (CSP) systems requires materials with high electrical conductivity and optical reflectivity. Silver, with its excellent optical reflectance, is traditionally used as a reflective layer in solar mirrors for CSP technologies. However, silver is soft and expensive, quickly tarnishes, and requires a protective layer of glass for practical applications. Moreover, supply-side constraints and high-temperature instability of silver have led to the search for alternative materials that exhibit high solar and infrared reflectance. Transition metal nitrides, such as titanium nitride, have emerged as alternative plasmonic materials to gold starting from a spectral range of ∼500 nm. However, to achieve high solar reflection (∼320–2500 nm), materials with epsilon-near-zero starting from the near-ultraviolet (UV) spectral region are required. Here, we show the development of refractory epitaxial hafnium nitride (HfN) and zirconium nitride (ZrN) thin films as excellent mirrors with a solar reflectivity of ∼90.3% and an infrared reflectivity of ∼95%. Low-loss and high-quality epsilon-near-zero resonance at near-UV (∼340–380 nm) spectral regions are achieved in HfN and ZrN by carefully controlling the stoichiometry, leading to a sharp increase in the reflection edge that is on par with silver. Temperature-dependent reflectivity and dielectric constants are further measured to demonstrate their high-temperature suitability. The development of refractory epitaxial HfN and ZrN thin films with high solar and infrared reflectance makes them excellent alternative plasmonic materials to silver and would pave their applications in CSP, daytime radiative cooling, and others.

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Optical coatings of durability based on transition metal nitrides

Guo

et al. 2019

Thin Solid Films

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Ion-bombardment-induced reduction in vacancies and its enhanced effect on conductivity and reflectivity in hafnium nitride films

Cited by 3 publications

References 34 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

Refractory Plasmonic Hafnium Nitride and Zirconium Nitride Thin Films as Alternatives to Silver for Solar Mirror Applications

Optical coatings of durability based on transition metal nitrides

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