Fabrication of epitaxial W-doped VO2 nanostructured films for terahertz modulation using the solvothermal process

Alexey V Ivanov; Artem Yu. Tatarenko; Andrei Gorodetsky; Olga N. Makarevich; Miguel Navarro-Cia; Artem M. Makarevich; Andrey R. Kaula; Andrei A. Eliseev; Olga V. Boytsova

doi:10.1021/acsanm.1c02081

Fabrication of epitaxial W-doped VO₂ nanostructured films for terahertz modulation using the solvothermal process

Alexey V Ivanov
, Artem Yu. Tatarenko
, Andrei Gorodetsky
, Olga N. Makarevich
, Miguel Navarro-Cia
, Artem M. Makarevich
, Andrey R. Kaula
, Andrei A. Eliseev
, Olga V. Boytsova

Research output: Contribution to journal › Article › peer-review

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Abstract

We report a feasible and high-throughput method for high-quality W-doped VO₂ nanostructured epitaxial films on r-sapphire substrate fabrication. Single-phase, smooth vanadium dioxide thin films with uniform distribution of tungsten (up to 2.3%) are formed using the solvothermal process from ethylene glycol/water V⁴⁺ and W⁶⁺ solutions. Compositional analysis by X-ray photoelectron and energy-dispersive X-ray spectroscopy (XPS and EDX, respectively); structural analysis (X-ray diffraction, Raman spectroscopy, selected area electron diffraction (SAED)); and detailed analysis of the surface morphology and substrate–film interface using scanning electron microscopy, atomic force microscopy, and high-resolution transmission electron microscopy (SEM, AFM, HRTEM, respectively) confirm the formation of nanoscale (50–60 nm) epitaxial W:VO₂ (M₁) on r-sapphire with epitaxial relationships (100)VO₂∥(101̅2)Al₂O₃ and [010]VO₂∥[011̅0]Al₂O₃. The nanostructured films demonstrate excellent terahertz (THz) transmission properties: a phase transition temperature of 31 °C, a huge THz modulation depth of over 60%, and broad bandwidth (≥2 THz) operation. Hence, they can be efficiently used as active material for tunable THz manipulation devices.

Original language	English
Pages (from-to)	10592-10600
Number of pages	9
Journal	ACS Applied Nano Materials
Volume	4
Issue number	10
Early online date	8 Oct 2021
DOIs	https://doi.org/10.1021/acsanm.1c02081
Publication status	Published - 22 Oct 2021

Bibliographical note

Funding Information:
A.V.I. thanks The Foundation for Assistance to Small Innovative Enterprises in Science and Technology (Grant No. 15291GU/2020). THz characterization was supported by EPSRC (Grant No. EP/S018395/1). A.A.G. thanks MagicPlot LLC for providing a copy of MagicPlot Pro plotting and fitting software. M.N.-C. acknowledges support from the Royal Society (Grant Nos. IEC/NSFC/191104 and IES/R3/183131) and the University of Birmingham (Birmingham Fellowship). The authors are thankful to the JRC PMR IGIC RAS, the Shared Use Centre “Centre of Physical and Physicochemical Methods of Analysis and Study of the Properties and Surface Characteristics of Nanostructures, Materials, and Products” UdmFRC UB RAS, and M. V. Lomonosov Moscow State University Program of Development for partial support of instrumental studies.

Publisher Copyright:
© 2021 American Chemical Society.

Keywords

Terahertz
VO2
metal−insulator transition
nanostructured film
W-doping
solvothermal synthesis
THz modulator

Access to Document

10.1021/acsanm.1c02081Licence: None: All rights reserved

IvanovAV2021Fabrication
This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Nano Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acsanm.1c02081
Accepted author manuscript, 1.59 MBLicence: None: All rights reserved
IvanovAV2021Fabrication_Supplementary_information
This document is the Accepted Manuscript version - supplementary information - of a Published Work that appeared in final form in ACS Applied Nano Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acsanm.1c02081
Accepted author manuscript, 812 KBLicence: None: All rights reserved

Experimental demonstration of transmissive-type terahertz digital metamaterial based on microfluidic system
Navarro-Cia, M. (Principal Investigator)
The Royal Society
31/03/20 → 30/03/24
Project: Research Councils
THEIA: fast super-resolution TeraHErtz mIcroscopy for nAtural Sciences
Navarro-Cia, M. (Principal Investigator)
Engineering & Physical Science Research Council
1/08/19 → 31/03/21
Project: Research
THz propagation models for complex medical environments
Navarro-Cia, M. (Principal Investigator)
The Royal Society
21/02/19 → 20/02/23
Project: Research

Cite this

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title = "Fabrication of epitaxial W-doped VO2 nanostructured films for terahertz modulation using the solvothermal process",

abstract = "We report a feasible and high-throughput method for high-quality W-doped VO2 nanostructured epitaxial films on r-sapphire substrate fabrication. Single-phase, smooth vanadium dioxide thin films with uniform distribution of tungsten (up to 2.3\%) are formed using the solvothermal process from ethylene glycol/water V4+ and W6+ solutions. Compositional analysis by X-ray photoelectron and energy-dispersive X-ray spectroscopy (XPS and EDX, respectively); structural analysis (X-ray diffraction, Raman spectroscopy, selected area electron diffraction (SAED)); and detailed analysis of the surface morphology and substrate–film interface using scanning electron microscopy, atomic force microscopy, and high-resolution transmission electron microscopy (SEM, AFM, HRTEM, respectively) confirm the formation of nanoscale (50–60 nm) epitaxial W:VO2 (M1) on r-sapphire with epitaxial relationships (100)VO2∥(101̅2)Al2O3 and [010]VO2∥[011̅0]Al2O3. The nanostructured films demonstrate excellent terahertz (THz) transmission properties: a phase transition temperature of 31 °C, a huge THz modulation depth of over 60\%, and broad bandwidth (≥2 THz) operation. Hence, they can be efficiently used as active material for tunable THz manipulation devices.",

keywords = "Terahertz, VO2, metal−insulator transition, nanostructured film, W-doping, solvothermal synthesis, THz modulator",

author = "Ivanov, \{Alexey V\} and Tatarenko, \{Artem Yu.\} and Andrei Gorodetsky and Makarevich, \{Olga N.\} and Miguel Navarro-Cia and Makarevich, \{Artem M.\} and Kaula, \{Andrey R.\} and Eliseev, \{Andrei A.\} and Boytsova, \{Olga V.\}",

note = "Funding Information: A.V.I. thanks The Foundation for Assistance to Small Innovative Enterprises in Science and Technology (Grant No. 15291GU/2020). THz characterization was supported by EPSRC (Grant No. EP/S018395/1). A.A.G. thanks MagicPlot LLC for providing a copy of MagicPlot Pro plotting and fitting software. M.N.-C. acknowledges support from the Royal Society (Grant Nos. IEC/NSFC/191104 and IES/R3/183131) and the University of Birmingham (Birmingham Fellowship). The authors are thankful to the JRC PMR IGIC RAS, the Shared Use Centre “Centre of Physical and Physicochemical Methods of Analysis and Study of the Properties and Surface Characteristics of Nanostructures, Materials, and Products” UdmFRC UB RAS, and M. V. Lomonosov Moscow State University Program of Development for partial support of instrumental studies. Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

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doi = "10.1021/acsanm.1c02081",

language = "English",

volume = "4",

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journal = "ACS Applied Nano Materials",

issn = "2574-0970",

publisher = "American Chemical Society",

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AU - Ivanov, Alexey V

AU - Tatarenko, Artem Yu.

AU - Gorodetsky, Andrei

AU - Makarevich, Olga N.

AU - Navarro-Cia, Miguel

AU - Makarevich, Artem M.

AU - Kaula, Andrey R.

AU - Eliseev, Andrei A.

AU - Boytsova, Olga V.

N1 - Funding Information: A.V.I. thanks The Foundation for Assistance to Small Innovative Enterprises in Science and Technology (Grant No. 15291GU/2020). THz characterization was supported by EPSRC (Grant No. EP/S018395/1). A.A.G. thanks MagicPlot LLC for providing a copy of MagicPlot Pro plotting and fitting software. M.N.-C. acknowledges support from the Royal Society (Grant Nos. IEC/NSFC/191104 and IES/R3/183131) and the University of Birmingham (Birmingham Fellowship). The authors are thankful to the JRC PMR IGIC RAS, the Shared Use Centre “Centre of Physical and Physicochemical Methods of Analysis and Study of the Properties and Surface Characteristics of Nanostructures, Materials, and Products” UdmFRC UB RAS, and M. V. Lomonosov Moscow State University Program of Development for partial support of instrumental studies. Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/10/22

Y1 - 2021/10/22

N2 - We report a feasible and high-throughput method for high-quality W-doped VO2 nanostructured epitaxial films on r-sapphire substrate fabrication. Single-phase, smooth vanadium dioxide thin films with uniform distribution of tungsten (up to 2.3%) are formed using the solvothermal process from ethylene glycol/water V4+ and W6+ solutions. Compositional analysis by X-ray photoelectron and energy-dispersive X-ray spectroscopy (XPS and EDX, respectively); structural analysis (X-ray diffraction, Raman spectroscopy, selected area electron diffraction (SAED)); and detailed analysis of the surface morphology and substrate–film interface using scanning electron microscopy, atomic force microscopy, and high-resolution transmission electron microscopy (SEM, AFM, HRTEM, respectively) confirm the formation of nanoscale (50–60 nm) epitaxial W:VO2 (M1) on r-sapphire with epitaxial relationships (100)VO2∥(101̅2)Al2O3 and [010]VO2∥[011̅0]Al2O3. The nanostructured films demonstrate excellent terahertz (THz) transmission properties: a phase transition temperature of 31 °C, a huge THz modulation depth of over 60%, and broad bandwidth (≥2 THz) operation. Hence, they can be efficiently used as active material for tunable THz manipulation devices.

AB - We report a feasible and high-throughput method for high-quality W-doped VO2 nanostructured epitaxial films on r-sapphire substrate fabrication. Single-phase, smooth vanadium dioxide thin films with uniform distribution of tungsten (up to 2.3%) are formed using the solvothermal process from ethylene glycol/water V4+ and W6+ solutions. Compositional analysis by X-ray photoelectron and energy-dispersive X-ray spectroscopy (XPS and EDX, respectively); structural analysis (X-ray diffraction, Raman spectroscopy, selected area electron diffraction (SAED)); and detailed analysis of the surface morphology and substrate–film interface using scanning electron microscopy, atomic force microscopy, and high-resolution transmission electron microscopy (SEM, AFM, HRTEM, respectively) confirm the formation of nanoscale (50–60 nm) epitaxial W:VO2 (M1) on r-sapphire with epitaxial relationships (100)VO2∥(101̅2)Al2O3 and [010]VO2∥[011̅0]Al2O3. The nanostructured films demonstrate excellent terahertz (THz) transmission properties: a phase transition temperature of 31 °C, a huge THz modulation depth of over 60%, and broad bandwidth (≥2 THz) operation. Hence, they can be efficiently used as active material for tunable THz manipulation devices.

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KW - VO2

KW - metal−insulator transition

KW - nanostructured film

KW - W-doping

KW - solvothermal synthesis

KW - THz modulator

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U2 - 10.1021/acsanm.1c02081

DO - 10.1021/acsanm.1c02081

M3 - Article

SN - 2574-0970

VL - 4

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EP - 10600

JO - ACS Applied Nano Materials

JF - ACS Applied Nano Materials

IS - 10

ER -

Fabrication of epitaxial W-doped VO2 nanostructured films for terahertz modulation using the solvothermal process

Abstract

Bibliographical note

Keywords

Access to Document

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Projects

Experimental demonstration of transmissive-type terahertz digital metamaterial based on microfluidic system

THEIA: fast super-resolution TeraHErtz mIcroscopy for nAtural Sciences

THz propagation models for complex medical environments

Cite this

Fabrication of epitaxial W-doped VO₂ nanostructured films for terahertz modulation using the solvothermal process