ACS Applied Materials & Interfaces, volume 13, issue 27, pages 32531-32541

Structural, Optical, and Electronic Properties of Cu-Doped TiNxOy Grown by Ammonothermal Atomic Layer Deposition

Baron F A 1
, 
Mikhlin Yurii L 2
, 
Molokeev Maxim S. 1, 3
, 
Rautskiy Mikhail V 1
, 
Tarasov Ivan 1
, 
Volochaev Mikhail N. 1, 4
, 
Shanidze Lev V 1
, 
Lukyanenko Anna V 1, 3
, 
Smolyarova Tatiana E 1, 3
, 
Konovalov Stepan O 4
, 
Zelenov Fyodor V 4
, 
Tarasov A S 1, 3
, 
Volkov Nikita V 1
1
 
2
 
3
 
4
 
Publication type: Journal Article
Publication date: 2021-06-28
Quartile SCImago
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ISSN: 
General Materials Science
Abstract
Copper-doped titanium oxynitride (TiNxOy) thin films were grown by atomic layer deposition (ALD) using the TiCl4 precursor, NH3, and O2 at 420 °C. Forming gas was used to reduce the background oxygen concentration and to transfer the copper atoms in an ALD chamber prior to the growth initiation of Cu-doped TiNxOy. Such forming gas-mediated Cu-doping of TiNxOy films had a pronounced effect on their resistivity, which dropped from 484 ± 8 to 202 ± 4 μΩ cm, and also on the resistance temperature coefficient (TCR), which decreased from 1000 to 150 ppm °C-1. We explored physical mechanisms causing this reduction by performing comparative analysis of atomic force microscopy, X-ray photoemission spectroscopy, X-ray diffraction, optical spectra, low-temperature transport, and Hall measurement data for the samples grown with and without forming gas doping. The difference in the oxygen concentration between the films did not exceed 6%. Copper segregated to the TiNxOy surface where its concentration reached 0.72%, but its penetration depth was less than 10 nm. Pronounced effects of the copper doping by forming gas included the TiNxOy film crystallite average size decrease from 57-59 to 32-34 nm, considerably finer surface granularity, electron concentration increase from 2.2(3) × 1022 to 3.5(1) × 1022 cm-3, and the electron mobility improvement from 0.56(4) to 0.92(2) cm2 V-1 s-1. The DC resistivity versus temperature R(T) measurements from 4.2 to 300 K showed a Cu-induced phase transition from a disordered to semimetallic state. The resistivity of Cu-doped TiNxOy films decreased with the temperature increase at low temperatures and reached the minimum near T = 50 K revealing signatures of the quantum interference effects similar to 2D Cu thin films, and then, semimetallic behavior was observed at higher temperatures. In TiNxOy films grown without forming gas, the resistivity decreased with the temperature increase as R(T) = - 1.88T0.6 + 604 μΩ cm with no semimetallic behavior observed. The medium range resistivity and low TCR of Cu-doped TiNxOy make this material an attractive choice for improved matching resistors in RF analog circuits and Si complementary metal-oxide-semiconductor integrated circuits.
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Baron F. A. et al. Structural, Optical, and Electronic Properties of Cu-Doped TiNxOy Grown by Ammonothermal Atomic Layer Deposition // ACS Applied Materials & Interfaces. 2021. Vol. 13. No. 27. pp. 32531-32541.
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Baron F. A., Mikhlin Y. L., Molokeev M. S., Rautskiy M. V., Tarasov I., Volochaev M. N., Shanidze L. V., Lukyanenko A. V., Smolyarova T. E., Konovalov S. O., Zelenov F. V., Tarasov A. S., Volkov N. V. Structural, Optical, and Electronic Properties of Cu-Doped TiNxOy Grown by Ammonothermal Atomic Layer Deposition // ACS Applied Materials & Interfaces. 2021. Vol. 13. No. 27. pp. 32531-32541.
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TY - JOUR
DO - 10.1021/ACSAMI.1C08036
UR - https://doi.org/10.1021%2FACSAMI.1C08036
TI - Structural, Optical, and Electronic Properties of Cu-Doped TiNxOy Grown by Ammonothermal Atomic Layer Deposition
T2 - ACS Applied Materials & Interfaces
AU - Mikhlin, Yurii L
AU - Rautskiy, Mikhail V
AU - Volochaev, Mikhail N.
AU - Lukyanenko, Anna V
AU - Konovalov, Stepan O
AU - Zelenov, Fyodor V
AU - Volkov, Nikita V
AU - Shanidze, Lev V
AU - Baron, F A
AU - Molokeev, Maxim S.
AU - Tarasov, Ivan
AU - Smolyarova, Tatiana E
AU - Tarasov, A S
PY - 2021
DA - 2021/06/28 00:00:00
PB - American Chemical Society (ACS)
SP - 32531-32541
IS - 27
VL - 13
PMID - 34181393
SN - 1944-8244
SN - 1944-8252
ER -
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@article{2021_Baron,
author = {Yurii L Mikhlin and Mikhail V Rautskiy and Mikhail N. Volochaev and Anna V Lukyanenko and Stepan O Konovalov and Fyodor V Zelenov and Nikita V Volkov and Lev V Shanidze and F A Baron and Maxim S. Molokeev and Ivan Tarasov and Tatiana E Smolyarova and A S Tarasov},
title = {Structural, Optical, and Electronic Properties of Cu-Doped TiNxOy Grown by Ammonothermal Atomic Layer Deposition},
journal = {ACS Applied Materials & Interfaces},
year = {2021},
volume = {13},
publisher = {American Chemical Society (ACS)},
month = {jun},
url = {https://doi.org/10.1021%2FACSAMI.1C08036},
number = {27},
pages = {32531--32541},
doi = {10.1021/ACSAMI.1C08036}
}
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Baron, F. A., et al. “Structural, Optical, and Electronic Properties of Cu-Doped TiNxOy Grown by Ammonothermal Atomic Layer Deposition.” ACS Applied Materials & Interfaces, vol. 13, no. 27, Jun. 2021, pp. 32531-32541. https://doi.org/10.1021%2FACSAMI.1C08036.
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