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Plasma-induced bond evolution enables low-temperature fabrication of dense SiNx barriers for high-reliability phase-change memory

Wanchun Ren1, §, , Chun Li1, §, Dan Chen1, Qian Gao1, Peng Bi2, , Jingdan Deng1, Tianyu Ma1, Tingting Liu1, Yang Gao1 and Huihui Guo1

+ Author Affiliations

 Corresponding author: Wanchun Ren, rwch_qw@163.com; Peng Bi, bipeng010@swust.edu.cn

DOI: 10.1088/1674-4926/26020056CSTR: 32376.14.1674-4926.26020056

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Abstract: The thermal sensitivity of phase-change memory (PCM) poses a stringent thermal budget for back-end encapsulation, demanding high-performance diffusion barriers processable at low temperatures. Conventional low-temperature silicon nitride (SiNx) films, however, are typically porous and prone to oxidation due to abundant metastable Si–H/N–H bonds. Herein, we propose an in-situ plasma cycling strategy that reconstructs the bonding network of plasma-enhanced chemical vapor deposition (PECVD) SiNx at a record-low temperature of 200 °C. Through controlled Ar/N2 plasma exposure, we cleave metastable bonds and reorganize into a continuous Si–N network, achieving a near-theoretical density of 3.4 g/cm3 (a 61.9% increase) and a 143.8% enhancement in Si–N bonding proportion. The resulting 40-nm barrier effectively suppresses Te/O interdiffusion, reduces wet-etch rate by ~67%, and maintains thermal confinement within 1.6% deviation. Integrated into PCM devices, this barrier yields a 98.7% SET/RESET operation yield and a 1.4-fold wider resistance window. This work not only provides a reliable encapsulation solution for PCM but also establishes a generalizable plasma-mediated interfacial engineering approach for advanced electronic devices under thermal constraints.

Key words: plasma-induced bond evolution, silicon nitride (SiNx), interfacial densification, low-temperature deposition, diffusion barrier, phase-change memory (PCM)



[1]
Liu Q C, Wei T, Zheng Y H, et al. Picosecond operation of optoelectronic hybrid phase change memory based on Si-doped Sb films. Adv Funct Mater, 2025, 35(11): 2417128 doi: 10.1002/adfm.202417128
[2]
Wu B, Wei T, Hu J, et al. Thermal stability and high speed for optoelectronic hybrid phase-change memory based on Cr doped Ge2Sb2Te5 thin film. Ceram Int, 2023, 49(23): 37837 doi: 10.1016/j.ceramint.2023.09.112
[3]
Wei T, Wang Q, Song S N, et al. Reversible phase-change characteristics and structural origin in Cr doped Ge2Sb2Te5 thin films. Thin Solid Films, 2020, 716: 138434 doi: 10.1016/j.tsf.2020.138434
[4]
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[5]
Shangguan D D, Wang B L, Wang C, et al. Fabrication and properties of a dense SiC NWs-toughened α-Si3N4 composite coating on porous Si3N4 ceramics. Int J Appl Ceram Technol, 2020, 17(2): 501 doi: 10.1111/ijac.13419
[6]
Kamataki K, Sasaki Y, Nagao I, et al. Low-temperature fabrication of silicon nitride thin films from a SiH4+N2 gas mixture by controlling SiNx nanoparticle growth in multi-hollow remote plasma chemical vapor deposition. Mater Sci Semicond Process, 2023, 164: 107613 doi: 10.1016/j.mssp.2023.107613
[7]
Minh N Q, Van Nong N, Oda O, et al. Low-temperature growth at 225 °C and characterization of carbon nanowalls synthesized by radical injection plasma-enhanced chemical vapor deposition. Vacuum, 2024, 224: 113180 doi: 10.1016/j.vacuum.2024.113180
[8]
Surana V K, Ganguly S, Saha D. Performance improvement in AlGaN/GaN high-electron-mobility transistors by low-temperature inductively coupled plasma–chemical vapor deposited SiNx as gate dielectric and surface passivation. Phys Status Solidi A, 2022, 219(24): 2200509 doi: 10.1002/pssa.202200509
[9]
Zhang C, Wu M, Wang P C, et al. Stability of SiNx prepared by plasma-enhanced chemical vapor deposition at low temperature. Nanomaterials, 2021, 11(12): 3363 doi: 10.3390/nano11123363
[10]
Rogov A B, Shayapov V R. The role of cathodic current in PEO of aluminum: Influence of cationic electrolyte composition on the transient current-voltage curves and the discharges optical emission spectra. Appl Surf Sci, 2017, 394: 323 doi: 10.1016/j.apsusc.2016.10.115
[11]
Kasalica B, Radić-Perić J, Perić M, et al. The mechanism of evolution of microdischarges at the beginning of the PEO process on aluminum. Surf Coat Technol, 2016, 298: 24 doi: 10.1016/j.surfcoat.2016.04.044
[12]
Troughton S C, Nominé A, Dean J, et al. Effect of individual discharge cascades on the microstructure of plasma electrolytic oxidation coatings. Appl Surf Sci, 2016, 389: 260 doi: 10.1016/j.apsusc.2016.07.106
[13]
Oleksak R P, Devaraj A, Herman G S. Atomic-scale structural evolution of Ta–Ni–Si amorphous metal thin films. Mater Lett, 2016, 164: 9 doi: 10.1016/j.matlet.2015.10.112
[14]
Naghdali S, Schiester M, Waldl H, et al. Improving the elemental and imaging accuracy in atom probe tomography of (Ti, Si)N single and multilayer coatings using isotopic substitution of N. Ultramicroscopy, 2025, 276: 114200 doi: 10.1016/j.ultramic.2025.114200
[15]
Nekipelov S V, Sekushin N A, Krzhizhanovskaya M G, et al. Electrical and optical properties and XPS spectra of pyrochlore Bi1.65Mn0.5Cr0.5Nb2O9 -. Ceram Int, 2025, 51(19): 28587 doi: 10.1016/j.ceramint.2025.04.068
[16]
Olaniyan I, Blázquez Martínez A, Hevelke V V, et al. Optically induced irreversible ferroelastic and ferroelectric switching in epitaxial BaTiO3 films on silicon. ACS Nano, 2025, 19(43): 37534 doi: 10.1021/acsnano.5c05309
[17]
Park Y, Shin Y E, Park J, et al. Ferroelectric multilayer nanocomposites with polarization and stress concentration structures for enhanced triboelectric performances. ACS Nano, 2020, 14(6): 7101 doi: 10.1021/acsnano.0c01865
[18]
Wen J L, Ma T B, Zhang W W, et al. Atomistic insights into Cu chemical mechanical polishing mechanism in aqueous hydrogen peroxide and glycine: ReaxFF reactive molecular dynamics simulations. J Phys Chem C, 2019, 123(43): 26467 doi: 10.1021/acs.jpcc.9b08466
[19]
Gao F, Weber W J. Atomic-scale simulations of cascade overlap and damage evolution in silicon carbide. J Mater Res, 2003, 18(8): 1877 doi: 10.1557/JMR.2003.0262
[20]
Elmas S, Rafighi M, Mohammadigharehbagh R, et al. Preparation of semi-transparent V2AlC thin films using the thermionic vacuum arc technique: Crystal and substrate effects on the electrochemical performance. Eur Phys J Plus, 2026, 141(3): 339 doi: 10.1140/epjp/s13360-026-07506-x
[21]
Chen J W, Zhao Y K, Guo Y J, et al. Unveiling the substrate effect: A combined experimental and simulation study of field emission from carbon nanotubes on stainless steel and silicon. Electron Mater Lett, 2026: 1
[22]
Kang X X, Zhong X L, Chen Z F, et al. Development and characterization of high temperature plasma nitridation process for advanced CMOS technology application. 2021 IEEE 14th International Conference on ASIC (ASICON), 2021: 1
[23]
Shi S J, Cui H P, Tian H C, et al. Exploring a new method for high-performance TPSiV preparation through innovative Si–H/Pt curing system in VSR/TPU blends. E Polym, 2024, 24: 20240081 doi: 10.1515/epoly-2024-0081
[24]
Sinha A K, Levinstein H J, Smith T E, et al. Reactive plasma deposited Si-N films for MOS-LSI passivation. J Electrochem Soc, 1978, 125(4): 601 doi: 10.1149/1.2131509
[25]
Miklaszewska P, Aszyk M, Sowiński P, et al. Chromogenic azomacrocycles with imidazole residue–Part II: Effect of spacer type and N–H orientation on chromogenic and spectroscopic properties. Dyes Pigm, 2026, 251: 113696 doi: 10.1016/j.dyepig.2026.113696
[26]
Li L, Song S N, Zhang Z H, et al. Superlattice-like film for high data retention and high speed phase change random access memory. Solid State Electron, 2016, 120: 52 doi: 10.1016/j.sse.2016.03.005
[27]
Miao L, Chen L. Interfacial reliability of Al/Sb2Te3 and W/Sb2Te3 for phase change memory application. Mater Sci Semicond Process, 2025, 199: 109876 doi: 10.1016/j.mssp.2025.109876
Fig. 1.  (Color online) Progressive structural densification of SiNx films via in-situ plasma cycling. Cross-sectional TEM images of SiNx films: (a) as-deposited, (b) after 11 cycles at 300 W, (c) 11 cycles at 500 W, and (d) 35 cycles at 300 W. (e) Film density quantified by RBS, demonstrating a significant increase from 2.1 g/cm3 to a near-theoretical value of 3.4 g/cm3 after the optimal treatment (300 W, 35 cycles).

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Fig. 2.  (Color online) Chemical bonding evolution and elemental distribution in SiNx films under plasma treatment. (a) Si–N and (b) Si–O bonding proportions measured by XPS after different plasma cycles. (c) Schematic of bond evolution: metastable intermediates convert to a stable Si-N network under plasma cycling. Elemental RBS depth profiles of (d) as-deposited, (e) 11 cycles, and (f) 35 cycles, showing improved nitrogen incorporation and oxidation resistance.

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Fig. 3.  (Color online) Atomic-scale bond evolution pathway revealed by ReaxFF MD simulations. (a) Initial molecular model composed of NH3 and SiH4. (b) Bond reorganization after deposition, showing formation of Si–N clusters and release of small molecules. (c) Further cross-linking and densification after incorporating nitrogen atoms, illustrating the transition to a continuous Si–N network.

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Fig. 4.  (Color online) Barrier performance of plasma-densified SiNx films. (a) TOF-SIMS depth profiles showing suppressed Te and O interdiffusion. (b) Wet etch rate reduction demonstrating enhanced chemical stability after plasma ycling.

DownLoad: Full-Size Img PowerPoint
Fig. 5.  (Color online) Thermal simulation of PCM cells (a) without and (b) with the 40-nm SiNx barrier layer, showing minimal peak temperature perturbation.

DownLoad: Full-Size Img PowerPoint
Fig. 6.  (Color online) Cross-sectional TEM images of PCM devices with different SiNx barrier thicknesses. (a) No barrier: severe sidewall oxidation and BEC voids. (b) 15-nm barrier: partial oxidation and residual voids. (c) 40 nm barrier: sharp, continuous GST/SiNx interface without oxidation or voids.(d) Full device stack with 40-nm barrier.

DownLoad: Full-Size Img PowerPoint
Fig. 7.  (Color online) Device switching characteristics (a) without barrier and (b) with 40 nm SiNx barrier, demonstrating significantly improved SET/RESET yield and resistance window.

DownLoad: Full-Size Img PowerPoint
[1]
Liu Q C, Wei T, Zheng Y H, et al. Picosecond operation of optoelectronic hybrid phase change memory based on Si-doped Sb films. Adv Funct Mater, 2025, 35(11): 2417128 doi: 10.1002/adfm.202417128
[2]
Wu B, Wei T, Hu J, et al. Thermal stability and high speed for optoelectronic hybrid phase-change memory based on Cr doped Ge2Sb2Te5 thin film. Ceram Int, 2023, 49(23): 37837 doi: 10.1016/j.ceramint.2023.09.112
[3]
Wei T, Wang Q, Song S N, et al. Reversible phase-change characteristics and structural origin in Cr doped Ge2Sb2Te5 thin films. Thin Solid Films, 2020, 716: 138434 doi: 10.1016/j.tsf.2020.138434
[4]
Wang H, Lu Z L, Qi Z, et al. Preparation and oxidation resistance study of silicon nitride coatings on graphite surfaces by chemical vapor deposition. Carbon Technol., 2023, 42(01): 34
[5]
Shangguan D D, Wang B L, Wang C, et al. Fabrication and properties of a dense SiC NWs-toughened α-Si3N4 composite coating on porous Si3N4 ceramics. Int J Appl Ceram Technol, 2020, 17(2): 501 doi: 10.1111/ijac.13419
[6]
Kamataki K, Sasaki Y, Nagao I, et al. Low-temperature fabrication of silicon nitride thin films from a SiH4+N2 gas mixture by controlling SiNx nanoparticle growth in multi-hollow remote plasma chemical vapor deposition. Mater Sci Semicond Process, 2023, 164: 107613 doi: 10.1016/j.mssp.2023.107613
[7]
Minh N Q, Van Nong N, Oda O, et al. Low-temperature growth at 225 °C and characterization of carbon nanowalls synthesized by radical injection plasma-enhanced chemical vapor deposition. Vacuum, 2024, 224: 113180 doi: 10.1016/j.vacuum.2024.113180
[8]
Surana V K, Ganguly S, Saha D. Performance improvement in AlGaN/GaN high-electron-mobility transistors by low-temperature inductively coupled plasma–chemical vapor deposited SiNx as gate dielectric and surface passivation. Phys Status Solidi A, 2022, 219(24): 2200509 doi: 10.1002/pssa.202200509
[9]
Zhang C, Wu M, Wang P C, et al. Stability of SiNx prepared by plasma-enhanced chemical vapor deposition at low temperature. Nanomaterials, 2021, 11(12): 3363 doi: 10.3390/nano11123363
[10]
Rogov A B, Shayapov V R. The role of cathodic current in PEO of aluminum: Influence of cationic electrolyte composition on the transient current-voltage curves and the discharges optical emission spectra. Appl Surf Sci, 2017, 394: 323 doi: 10.1016/j.apsusc.2016.10.115
[11]
Kasalica B, Radić-Perić J, Perić M, et al. The mechanism of evolution of microdischarges at the beginning of the PEO process on aluminum. Surf Coat Technol, 2016, 298: 24 doi: 10.1016/j.surfcoat.2016.04.044
[12]
Troughton S C, Nominé A, Dean J, et al. Effect of individual discharge cascades on the microstructure of plasma electrolytic oxidation coatings. Appl Surf Sci, 2016, 389: 260 doi: 10.1016/j.apsusc.2016.07.106
[13]
Oleksak R P, Devaraj A, Herman G S. Atomic-scale structural evolution of Ta–Ni–Si amorphous metal thin films. Mater Lett, 2016, 164: 9 doi: 10.1016/j.matlet.2015.10.112
[14]
Naghdali S, Schiester M, Waldl H, et al. Improving the elemental and imaging accuracy in atom probe tomography of (Ti, Si)N single and multilayer coatings using isotopic substitution of N. Ultramicroscopy, 2025, 276: 114200 doi: 10.1016/j.ultramic.2025.114200
[15]
Nekipelov S V, Sekushin N A, Krzhizhanovskaya M G, et al. Electrical and optical properties and XPS spectra of pyrochlore Bi1.65Mn0.5Cr0.5Nb2O9 -. Ceram Int, 2025, 51(19): 28587 doi: 10.1016/j.ceramint.2025.04.068
[16]
Olaniyan I, Blázquez Martínez A, Hevelke V V, et al. Optically induced irreversible ferroelastic and ferroelectric switching in epitaxial BaTiO3 films on silicon. ACS Nano, 2025, 19(43): 37534 doi: 10.1021/acsnano.5c05309
[17]
Park Y, Shin Y E, Park J, et al. Ferroelectric multilayer nanocomposites with polarization and stress concentration structures for enhanced triboelectric performances. ACS Nano, 2020, 14(6): 7101 doi: 10.1021/acsnano.0c01865
[18]
Wen J L, Ma T B, Zhang W W, et al. Atomistic insights into Cu chemical mechanical polishing mechanism in aqueous hydrogen peroxide and glycine: ReaxFF reactive molecular dynamics simulations. J Phys Chem C, 2019, 123(43): 26467 doi: 10.1021/acs.jpcc.9b08466
[19]
Gao F, Weber W J. Atomic-scale simulations of cascade overlap and damage evolution in silicon carbide. J Mater Res, 2003, 18(8): 1877 doi: 10.1557/JMR.2003.0262
[20]
Elmas S, Rafighi M, Mohammadigharehbagh R, et al. Preparation of semi-transparent V2AlC thin films using the thermionic vacuum arc technique: Crystal and substrate effects on the electrochemical performance. Eur Phys J Plus, 2026, 141(3): 339 doi: 10.1140/epjp/s13360-026-07506-x
[21]
Chen J W, Zhao Y K, Guo Y J, et al. Unveiling the substrate effect: A combined experimental and simulation study of field emission from carbon nanotubes on stainless steel and silicon. Electron Mater Lett, 2026: 1
[22]
Kang X X, Zhong X L, Chen Z F, et al. Development and characterization of high temperature plasma nitridation process for advanced CMOS technology application. 2021 IEEE 14th International Conference on ASIC (ASICON), 2021: 1
[23]
Shi S J, Cui H P, Tian H C, et al. Exploring a new method for high-performance TPSiV preparation through innovative Si–H/Pt curing system in VSR/TPU blends. E Polym, 2024, 24: 20240081 doi: 10.1515/epoly-2024-0081
[24]
Sinha A K, Levinstein H J, Smith T E, et al. Reactive plasma deposited Si-N films for MOS-LSI passivation. J Electrochem Soc, 1978, 125(4): 601 doi: 10.1149/1.2131509
[25]
Miklaszewska P, Aszyk M, Sowiński P, et al. Chromogenic azomacrocycles with imidazole residue–Part II: Effect of spacer type and N–H orientation on chromogenic and spectroscopic properties. Dyes Pigm, 2026, 251: 113696 doi: 10.1016/j.dyepig.2026.113696
[26]
Li L, Song S N, Zhang Z H, et al. Superlattice-like film for high data retention and high speed phase change random access memory. Solid State Electron, 2016, 120: 52 doi: 10.1016/j.sse.2016.03.005
[27]
Miao L, Chen L. Interfacial reliability of Al/Sb2Te3 and W/Sb2Te3 for phase change memory application. Mater Sci Semicond Process, 2025, 199: 109876 doi: 10.1016/j.mssp.2025.109876

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    Received: 14 February 2026 Revised: 22 April 2026 Online: Accepted Manuscript: 27 May 2026

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      Article Navigation >  Journal of Semiconductors  > 2026  > Accepted Manuscript
      Wanchun Ren, Chun Li, Dan Chen, Qian Gao, Peng Bi, Jingdan Deng, Tianyu Ma, Tingting Liu, Yang Gao, Huihui Guo. Plasma-induced bond evolution enables low-temperature fabrication of dense SiNx barriers for high-reliability phase-change memory[J]. Journal of Semiconductors, 2026, In Press. doi: 10.1088/1674-4926/26020056 ****W C Ren, C Li, D Chen, Q Gao, P Bi, J D Deng, T Y Ma, T T Liu, Y Gao, and H H Guo, Plasma-induced bond evolution enables low-temperature fabrication of dense SiNx barriers for high-reliability phase-change memory[J]. J. Semicond., 2026, accepted doi: 10.1088/1674-4926/26020056
      Citation:
      Wanchun Ren, Chun Li, Dan Chen, Qian Gao, Peng Bi, Jingdan Deng, Tianyu Ma, Tingting Liu, Yang Gao, Huihui Guo. Plasma-induced bond evolution enables low-temperature fabrication of dense SiNx barriers for high-reliability phase-change memory[J]. Journal of Semiconductors, 2026, In Press. doi: 10.1088/1674-4926/26020056 ****
      W C Ren, C Li, D Chen, Q Gao, P Bi, J D Deng, T Y Ma, T T Liu, Y Gao, and H H Guo, Plasma-induced bond evolution enables low-temperature fabrication of dense SiNx barriers for high-reliability phase-change memory[J]. J. Semicond., 2026, accepted doi: 10.1088/1674-4926/26020056
      shu

      Plasma-induced bond evolution enables low-temperature fabrication of dense SiNx barriers for high-reliability phase-change memory

      DOI: 10.1088/1674-4926/26020056
      CSTR: 32376.14.1674-4926.26020056
      • 1.

        Microsystem Center, School of Information and Control Engineering, Southwest University of Science and Technology, Mianyang, 621010, China

      • 2.

        School of Mathematics and Physics, Southwest University of Science and Technology, Mianyang, 621010, China

      More Information
      • Wanchun Ren received his Ph.D. from University of Chinese Academy of Sciences in 2013. He is currently a teacher at Southwest University of Science and Technology. His research interests include MEMS device and reliability
      • Chun Li is currently a master student at Southwest University of Science and Technology, under the supervision of Dr. Wanchun Ren. Her research focuses on magnetoelectric heterostructures
      • Dan Chen is a master student at Southwest University of Science and Technology, under the supervision of Dr. Wanchun Ren. Her main research direction is microelectronic packaging
      • Qian Gao is a master student at Southwest University of Science and Technology under the supervision of Dr. Wanchun Ren. Her research focuses on thin-film bulk acoustic wave materials and devices
      • Peng Bi received his Ph.D. from Sichuan University in 2013. He is currently a teacher at Southwest University of Science and Technology. His research interests include computational physics and computational materials science
      • Jingdan Deng is a master student at Southwest University of Science and Technology under the supervision of Dr. Wanchun Ren. Her research focuses on readout circuit for bulk acoustic wave magnetic field sensors
      • Tianyu Ma is an undergraduate student at Southwest University of Science and Technology, under the supervision of Dr. Wanchun Ren. Her research interests primarily focus on lithography and battery management systems
      • Tingting Liu received her Ph.D. from USTC in 2015. She is currently an associate professor at Southwest University of Science and Technology. Her research interests include microfluidics and MEMS devices
      • Yang Gao received his Ph.D. from Beijing Institute of Technology in 2000. He is a professor at Southwest University of Science and Technology. His research interests include advanced MEMS devices and their applications
      • Huihui Guo received his Ph.D. from Southwest Jiaotong University in 2013. He is a professor at Southwest University of Science and Technology. His research primarily focuses on gas sensor technology and MEMS/NEMS devices
      • Corresponding author: rwch_qw@163.com; bipeng010@swust.edu.cn
      • Received Date: 2026-02-14
      • Revised Date: 2026-04-22
        • Available Online: 2026-05-27

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