Nitrogen: A promising doping strategy for high-performance ovonic threshold switching selectors

Gu, Rongchuan; Yuan, Shaojie; Wang, Huan; Xu, Qundao; Tang, Siqi; Xu, Meng; Qiao, Chong; Wang, Cai-Zhuang; Wang, Songyou; Xu, Ming; Miao, Xiangshui

doi:10.1016/j.jallcom.2024.176011

Nitrogen: A promising doping strategy for high-performance ovonic threshold switching selectors

Journal Article · Tue Aug 13 00:00:00 EDT 2024 · Journal of Alloys and Compounds

DOI:https://doi.org/10.1016/j.jallcom.2024.176011· OSTI ID:2481302

Gu, Rongchuan ^[1]; Yuan, Shaojie ^[1]; Wang, Huan ^[1]; Xu, Qundao ^[1]; Tang, Siqi ^[1]; Xu, Meng ^[2]; Qiao, Chong ^[3]; Wang, Cai-Zhuang ^[4]; Wang, Songyou ^[5]; Xu, Ming ^[1]; Miao, Xiangshui ^[1]

Huazhong University of Science and Technology, Wuhan (China); Hubei Yangtze Memory Laboratories, Wuhan (China)
University of Hong Kong (China)
Nanyang Institute of Technology (China)
Ames Laboratory, and Iowa State University, Ames, IA (United States)
Fudan University, Shanghai (China)

The Ovonic Threshold Switching (OTS) selector serves as an essential component in the development of three-dimensional high-density memory integration technology. Nevertheless, the state-of-the-art high-performance OTS materials usually contain toxic elements such as arsenic (As), posing significant risks to both environmental and human health. Nitrogen (N), which belongs to the same group as arsenic (As), has emerged as a highly promising alternative for As doping. However, the underlying mechanisms that govern N-based OTS materials have not yet been extensively investigated. In this study, we delve into the effects of N doping on the structural, bonding, and electronic properties of amorphous GeSe (a-GeNSe) by ab initio molecular dynamics simulations to bridge the knowledge gap. Our findings indicate that upon N doping in a-GeSe, the formation of robust Ge-N bonds, along with N-centered tetrahedral and triangular structures, resulting in the sluggish atomic movement that enhances the thermal stability and endurance of a-GeNSe. The OTS characteristics are significantly influenced by the material’s electronic band structure, and thus the relatively slow performance drift can be attributed to the stabilization of mid-gap states, a result of N doping which effectively slows down the aging process of chalcogenide glass. Moreover, the increased mobility gap in a-GeNSe raises the threshold voltage (V_th), making it more compatible with commercially available phase-change memory materials. Furthermore, our findings reveal the extensive impact of the N element on a typical OTS material and offer valuable perspectives for alternative doping strategies that could potentially supplant As practices.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: National Science and Technology Major Project of China; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 2481302

Report Number(s):: AL-J--150

Journal Information:: Journal of Alloys and Compounds, Journal Name: Journal of Alloys and Compounds Vol. 1005; ISSN 0925-8388

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (64)

Physics of the Switching Kinetics in Resistive Memories Menzel, Stephan; Böttger, Ulrich; Wimmer, Martin Advanced Functional Materials, Vol. 25, Issue 40 https://doi.org/10.1002/adfm.201500825	journal	June 2015
Recent Advances on Neuromorphic Devices Based on Chalcogenide Phase‐Change Materials Xu, Ming; Mai, Xianliang; Lin, Jun Advanced Functional Materials, Vol. 30, Issue 50 https://doi.org/10.1002/adfm.202003419	journal	September 2020
Tailoring Mid‐Gap States of Chalcogenide Glass by Pressure‐Induced Hypervalent Bonding Towards the Design of Electrical Switching Materials Xu, Meng; Xu, Qundao; Gu, Rongchuan Advanced Functional Materials https://doi.org/10.1002/adfm.202304926	journal	August 2023
Toward the Speed Limit of Phase‐Change Memory Shen, Jiabin; Song, Wenxiong; Ren, Kun Advanced Materials, Vol. 35, Issue 11 https://doi.org/10.1002/adma.202208065	journal	February 2023
3D Stackable and Scalable Binary Ovonic Threshold Switch Devices with Excellent Thermal Stability and Low Leakage Current for High‐Density Cross‐Point Memory Applications Yoo, Jongmyung; Kim, Seong Hun; Chekol, Solomon Amsalu Advanced Electronic Materials, Vol. 5, Issue 7 https://doi.org/10.1002/aelm.201900196	journal	May 2019
Screening Switching Materials with Low Leakage Current and High Thermal Stability for Neuromorphic Computing Wu, Renjie; Jia, Shujing; Gotoh, Tamihiro Advanced Electronic Materials, Vol. 8, Issue 9 https://doi.org/10.1002/aelm.202200150	journal	April 2022
Deep machine learning unravels the structural origin of mid‐gap states in chalcogenide glass for high‐density memory integration Xu, Meng; Xu, Ming; Miao, Xiangshui InfoMat, Vol. 4, Issue 6 https://doi.org/10.1002/inf2.12315	journal	April 2022
Ab-initio simulations of materials using VASP: Density-functional theory and beyond Hafner, Jürgen Journal of Computational Chemistry, Vol. 29, Issue 13 https://doi.org/10.1002/jcc.21057	journal	October 2008
LOBSTER : Local orbital projections, atomic charges, and chemical‐bonding analysis from projector‐augmented‐wave‐based density‐functional theory Nelson, Ryky; Ertural, Christina; George, Janine Journal of Computational Chemistry, Vol. 41, Issue 21 https://doi.org/10.1002/jcc.26353	journal	June 2020
How to Identify Lone Pairs, Van der Waals Gaps, and Metavalent Bonding Using Charge and Pair Density Methods: From Elemental Chalcogens to Lead Chalcogenides and Phase‐Change Materials Raty, Jean-Yves; Gatti, Carlo; Schön, Carl-Friedrich physica status solidi (RRL) – Rapid Research Letters, Vol. 15, Issue 11 https://doi.org/10.1002/pssr.202000534	journal	September 2021
Ring statistics analysis of topological networks: New approach and application to amorphous GeS2 and SiO2 systems Le Roux, Sébastien; Jund, Philippe Computational Materials Science, Vol. 49, Issue 1 https://doi.org/10.1016/j.commatsci.2010.04.023	journal	June 2010
Structure, bonding nature and transition dynamics of amorphous Te Qiao, Chong; Xu, Meng; Wang, Songyou Scripta Materialia, Vol. 202 https://doi.org/10.1016/j.scriptamat.2021.114011	journal	September 2021
How arsenic makes amorphous GeSe a robust chalcogenide glass for advanced memory integration Gu, Rongchuan; Xu, Meng; Qiao, Chong Scripta Materialia, Vol. 218 https://doi.org/10.1016/j.scriptamat.2022.114834	journal	September 2022
Ovonic Threshold Switch Chalcogenides: Connecting the First-Principles Electronic Structure to Selector Device Parameters Clima, Sergiu; Ravsher, Taras; Garbin, Daniele ACS Applied Electronic Materials, Vol. 5, Issue 1 https://doi.org/10.1021/acsaelm.2c01458	journal	December 2022
Phase Change Materials and Their Application to Nonvolatile Memories Raoux, Simone; Wełnic, Wojciech; Ielmini, Daniele Chemical Reviews, Vol. 110, Issue 1 https://doi.org/10.1021/cr900040x	journal	August 2009
Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations Dronskowski, Richard; Bloechl, Peter E. The Journal of Physical Chemistry, Vol. 97, Issue 33 https://doi.org/10.1021/j100135a014	journal	August 1993
Relationship between structural order and the anomalies of liquid water Errington, Jeffrey R.; Debenedetti, Pablo G. Nature, Vol. 409, Issue 6818 https://doi.org/10.1038/35053024	journal	January 2001
Nanomaterials for optical data storage Gu, Min; Zhang, Qiming; Lamon, Simone Nature Reviews Materials, Vol. 1, Issue 12 https://doi.org/10.1038/natrevmats.2016.70	journal	October 2016
Chaotic dynamics in nanoscale NbO2 Mott memristors for analogue computing Kumar, Suhas; Strachan, John Paul; Williams, R. Stanley Nature, Vol. 548, Issue 7667 https://doi.org/10.1038/nature23307	journal	August 2017
Ultrahigh drive current and large selectivity in GeS selector Jia, Shujing; Li, Huanglong; Gotoh, Tamihiro Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-18382-z	journal	September 2020
The role of arsenic in the operation of sulfur-based electrical threshold switches Wu, Renjie; Gu, Rongchuan; Gotoh, Tamihiro Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-41643-6	journal	September 2023
In silico screening for As/Se-free ovonic threshold switching materials Clima, Sergiu; Matsubayashi, Daisuke; Ravsher, Taras npj Computational Materials, Vol. 9, Issue 1 https://doi.org/10.1038/s41524-023-01043-2	journal	June 2023
Designing crystallization in phase-change materials for universal memory and neuro-inspired computing Zhang, Wei; Mazzarello, Riccardo; Wuttig, Matthias Nature Reviews Materials, Vol. 4, Issue 3 https://doi.org/10.1038/s41578-018-0076-x	journal	January 2019
Resistive switching materials for information processing Wang, Zhongrui; Wu, Huaqiang; Burr, Geoffrey W. Nature Reviews Materials, Vol. 5, Issue 3 https://doi.org/10.1038/s41578-019-0159-3	journal	January 2020
How fragility makes phase-change data storage robust: insights from ab initio simulations Zhang, Wei; Ronneberger, Ider; Zalden, Peter Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep06529	journal	October 2014
Chemical understanding of resistance drift suppression in Ge–Sn–Te phase-change memory materials Chen, Yuhan; Sun, Liang; Zhou, Yuxing Journal of Materials Chemistry C, Vol. 8, Issue 1 https://doi.org/10.1039/C9TC04810C	journal	January 2020
Unraveling the structural and bonding nature of antimony sesquichalcogenide glass for electronic and photonic applications Xu, Meng; Gu, Rongchuan; Qiao, Chong Journal of Materials Chemistry C https://doi.org/10.1039/D1TC01433A	journal	January 2021
Unravelling the atomic mechanisms of tetrahedral doping in chalcogenide glass for electrical switching materials Gu, Rongchuan; Xu, Meng; Liu, Yongpeng Journal of Materials Chemistry C, Vol. 11, Issue 44 https://doi.org/10.1039/D3TC02984K	journal	January 2023
Thermal Effects in Amorphous-Semiconductor Switching Kaplan, Theodore; Adler, David Applied Physics Letters, Vol. 19, Issue 10 https://doi.org/10.1063/1.1653754	journal	November 1971
Evidence for trap-limited transport in the subthreshold conduction regime of chalcogenide glasses Ielmini, Daniele; Zhang, Yuegang Applied Physics Letters, Vol. 90, Issue 19 https://doi.org/10.1063/1.2737137	journal	May 2007
Coexistence of tetrahedral- and octahedral-like sites in amorphous phase change materials Caravati, S.; Bernasconi, M.; Kühne, T. D. Applied Physics Letters, Vol. 91, Issue 17 https://doi.org/10.1063/1.2801626	journal	October 2007
Threshold switching in chalcogenide‐glass thin films Adler, D.; Shur, M. S.; Silver, M. Journal of Applied Physics, Vol. 51, Issue 6 https://doi.org/10.1063/1.328036	journal	June 1980
Nanosecond threshold switching of GeTe ₆ cells and their potential as selector devices Anbarasu, M.; Wimmer, Martin; Bruns, Gunnar Applied Physics Letters, Vol. 100, Issue 14 https://doi.org/10.1063/1.3700743	journal	April 2012
Effect of density of localized states on the ovonic threshold switching characteristics of the amorphous GeSe films Ahn, Hyung-Woo; Seok Jeong, Doo; Cheong, Byung-ki Applied Physics Letters, Vol. 103, Issue 4 https://doi.org/10.1063/1.4816349	journal	July 2013
Structural features of chalcogenide glass SiTe: An ovonic threshold switching material Gu, Rongchuan; Xu, Meng; Yu, Run APL Materials, Vol. 9, Issue 8 https://doi.org/10.1063/5.0059845	journal	August 2021
Unveiling the structure and electronic characteristics of amorphous GeS for high performance threshold switching Qiao, Chong; Wang, Shengzhao; Chen, Lanli Applied Physics Letters, Vol. 123, Issue 11 https://doi.org/10.1063/5.0166245	journal	September 2023
Pressure tunes electrical resistivity by four orders of magnitude in amorphous Ge2Sb2Te5 phase-change memory alloy Xu, M.; Cheng, Y. Q.; Wang, L. Proceedings of the National Academy of Sciences, Vol. 109, Issue 18 https://doi.org/10.1073/pnas.1119754109	journal	April 2012
A grid-based Bader analysis algorithm without lattice bias Tang, W.; Sanville, E.; Henkelman, G. Journal of Physics: Condensed Matter, Vol. 21, Issue 8 https://doi.org/10.1088/0953-8984/21/8/084204	journal	January 2009
Volatile threshold switching memristor: An emerging enabler in the AIoT era Zuo, Wenbin; Zhu, Qihang; Fu, Yuyang Journal of Semiconductors, Vol. 44, Issue 5 https://doi.org/10.1088/1674-4926/44/5/053102	journal	May 2023
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Nature of Atomic Bonding and Atomic Structure in the Phase-Change Ge 2 Sb 2 Te 5 Glass Xu, M.; Cheng, Y. Q.; Sheng, H. W. Physical Review Letters, Vol. 103, Issue 19 https://doi.org/10.1103/PhysRevLett.103.195502	journal	November 2009
Signature of Tetrahedral Ge in the Raman Spectrum of Amorphous Phase-Change Materials Mazzarello, Riccardo; Caravati, Sebastiano; Angioletti-Uberti, Stefano Physical Review Letters, Vol. 104, Issue 8 https://doi.org/10.1103/PhysRevLett.104.085503	journal	February 2010
Valence-Alternation Model for Localized Gap States in Lone-Pair Semiconductors Kastner, Marc; Adler, David; Fritzsche, H. Physical Review Letters, Vol. 37, Issue 22 https://doi.org/10.1103/PhysRevLett.37.1504	journal	November 1976
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Doped GeSe materials for selector applications Avasarala, Naga Sruti; Govoreanu, B.; Opsomer, K. 2017 47th European Solid-State Device Research Conference (ESSDERC) https://doi.org/10.1109/ESSDERC.2017.8066618	conference	September 2017
A stackable cross point Phase Change Memory No authors listed 2009 IEEE International Electron Devices Meeting (IEDM) https://doi.org/10.1109/IEDM.2009.5424263	conference	December 2009
Atomistic investigation of the electronic structure, thermal properties and conduction defects in Ge-rich GexSe1−x materials for selector applications Clima, S.; Govoreanu, B.; Opsomer, K. 2017 IEEE International Electron Devices Meeting (IEDM) https://doi.org/10.1109/IEDM.2017.8268323	conference	December 2017
Ultra-High Endurance and Low IOFF Selector based on AsSeGe Chalcogenides for Wide Memory Window 3D Stackable Crosspoint Memory Cheng, H. Y.; Chien, W. C.; Kuo, I. T. 2018 IEEE International Electron Devices Meeting (IEDM) https://doi.org/10.1109/IEDM.2018.8614580	conference	December 2018
Composition Optimization and Device Understanding of Si-Ge-As-Te Ovonic Threshold Switch Selector with Excellent Endurance Garbin, D.; Devulder, W.; Degraeve, R. 2019 IEEE International Electron Devices Meeting (IEDM) https://doi.org/10.1109/IEDM19573.2019.8993547	conference	December 2019
OTS Physics-based Screening for Environment-friendly Selector Materials Matsubayashi, D.; Clima, S.; Ravsher, T. 2022 International Electron Devices Meeting (IEDM) https://doi.org/10.1109/IEDM45625.2022.10019445	conference	December 2022
A 20nm 1.8V 8Gb PRAM with 40MB/s program bandwidth Choi, Youngdon; Song, Ickhyun; Park, Mu-Hui 2012 IEEE International Solid-State Circuits Conference https://doi.org/10.1109/ISSCC.2012.6176872	conference	February 2012
Performance Improvement of GeTe_x-Based Ovonic Threshold Switching Selector by C Doping Wang, Lun; Cai, Wang; He, Da IEEE Electron Device Letters, Vol. 42, Issue 5 https://doi.org/10.1109/LED.2021.3064857	journal	May 2021
Reliable Low Voltage Selector Device Technology Based on Robust SiNGeCTe Arsenic-Free Chalcogenide Ambrosi, Elia; Wu, Cheng-Hsien; Lee, Heng-Yuan IEEE Electron Device Letters, Vol. 43, Issue 10 https://doi.org/10.1109/LED.2022.3203146	journal	October 2022
Current-controlled negative resistance in thin niobium oxide films Chopra, K. L. Proceedings of the IEEE, Vol. 51, Issue 6 https://doi.org/10.1109/PROC.1963.2339	journal	January 1963
Large-scale (512kbit) integration of multilayer-ready access-devices based on mixed-ionic-electronic-conduction (MIEC) at 100% yield Burr, G. W.; Virwani, K.; Shenoy, R. S. 2012 Symposium on VLSI Technology (VLSIT) https://doi.org/10.1109/VLSIT.2012.6242451	conference	June 2012
Te-based amorphous binary OTS device with excellent selector characteristics for x-point memory applications No authors listed 2016 IEEE Symposium on VLSI Technology https://doi.org/10.1109/VLSIT.2016.7573389	conference	June 2016
Half-threshold bias Ioff reduction down to nA range of thermally and electrically stable high-performance integrated OTS selector, obtained by Se enrichment and N-doping of thin GeSe layers Avasarala, Naga Sruti; Donadio, G. L.; Witters, T. 2018 IEEE Symposium on VLSI Technology https://doi.org/10.1109/VLSIT.2018.8510680	conference	June 2018
Si Incorporation into AsSeGe Chalcogenides for High Thermal Stability, High Endurance and Extremely Low Vth Drift 3D Stackable Cross-Point Memory Cheng, H. Y.; Kuo, I. T.; Chien, W. C. 2020 IEEE Symposium on VLSI Technology https://doi.org/10.1109/VLSITechnology18217.2020.9265039	conference	June 2020
Access devices for 3D crosspoint memory Burr, Geoffrey W.; Shenoy, Rohit S.; Virwani, Kumar Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 32, Issue 4 https://doi.org/10.1116/1.4889999	journal	July 2014
Reducing the stochasticity of crystal nucleation to enable subnanosecond memory writing Rao, Feng; Ding, Keyuan; Zhou, Yuxing Science, Vol. 358, Issue 6369 https://doi.org/10.1126/science.aao3212	journal	November 2017
Elemental electrical switch enabling phase segregation–free operation Shen, Jiabin; Jia, Shujing; Shi, Nannan Science, Vol. 374, Issue 6573 https://doi.org/10.1126/science.abi6332	journal	December 2021
Keep it simple and switch to pure tellurium Calarco, Raffaella; Arciprete, Fabrizio Science, Vol. 374, Issue 6573 https://doi.org/10.1126/science.abm7316	journal	December 2021
Ovonic threshold switching selectors for three-dimensional stackable phase-change memory Zhu, Min; Ren, Kun; Song, Zhitang MRS Bulletin, Vol. 44, Issue 09 https://doi.org/10.1557/mrs.2019.206	journal	September 2019

Similar Records

How arsenic makes amorphous GeSe a robust chalcogenide glass for advanced memory integration

Journal Article · Mon May 23 20:00:00 EDT 2022 · Scripta Materialia · OSTI ID:1892310

Unveiling the nature of Ga-based chalcogenides for electrical switching selectors

Journal Article · Sat Apr 05 20:00:00 EDT 2025 · Journal of Alloys and Compounds · OSTI ID:2571450

Structure, bonding and electronic characteristics of amorphous Se

Journal Article · Mon Feb 26 19:00:00 EST 2024 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:2316187

Related Subjects

36 MATERIALS SCIENCE
Chalcogenide glass
Local structure
Mid-gap states
Molecular dynamics
N doping

Nitrogen: A promising doping strategy for high-performance ovonic threshold switching selectors

Citation Formats

References (64)

Similar Records

Related Subjects