DataVXApplied Physics APaper
journal article·2026-08Open access

Investigation on the effect of oxygen-rich annealing on electrical and material properties of sol-gel derived zirconium oxide gate dielectric thin films

Tahsinul Huq, Joon Huang Chuah, Mohd Faizul Mohd Sabri, Chia Ching Kee, Chee Zing Tok, Jia Ren Tan, Shuye Zhang, Peisan E Sharel, Prastika Krisma Jiwanti, Yew Hoong Wong

Applied Physics A· Volume 132· Issue 8
Publisher pageOpen full text
Source abstract

Abstract

Abstract Solution-processed zirconium oxide (ZrO 2 ) thin films are attractive as low-cost high-k dielectrics for thin-film transistors and flexible electronics. In this work, ~ 35 nm sol–gel ZrO 2 films were synthesized from zirconium n-propoxide via multi-layer spin coating on Si and annealed at 400–600 °C in either 100% O 2 or 25% O 2 / 75% N 2 atmospheres. Comprehensive electrical characterization revealed that pure O 2 annealing suppressed oxygen vacancies more effectively than 25% O 2 , resulting in significantly reduced leakage current densities (~ 10 − 6 A/cm 2 at + 2.0 V for 600 °C annealing temperature). All samples maintained high dielectric constants above 22, matching dense ZrO 2 produced by vacuum-based methods. XPS confirmed an increase in Zr–O lattice bonding with temperature, while electrical analysis showed Schottky emission as the dominant leakage mechanism. These findings demonstrate that oxygen-rich annealing provides a simple yet effective route to enhance the reliability of sol-gel derived ZrO 2 gate dielectrics, offering insights on defects for optimizing high-k materials in next-generation electronic devices.
Source: crossref · Quality: baseline

Research context

Electronic materialsMaterials processing

OpenAlex topics: Semiconductor materials and devices · Copper Interconnects and Reliability · Ferroelectric and Negative Capacitance Devices

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (62)

Show source-provided references
1. Y.H. Wong, K.Y. Cheong, ZrO 2 thin films on Si substrate. J. Mater. Sci. Mater. Electron. 21(10), 980–993 (2010). https://doi.org/10.1007/s10854-010-0144-510.1007/s10854-010-0144-5 ↗
2. J. Xie et al., Research progress of high dielectric constant zirconia-based materials for gate dielectric application. Coatings. 10(7) (2020). https://doi.org/10.3390/coatings1007069810.3390/coatings10070698 ↗
3. M.T. Soo et al., Elaboration and characterization of sol-gel derived ZrO 2 thin films treated with hot water. Appl. Surf. Sci. 258, 5250–5258 (2012). https://doi.org/10.1016/j.apsusc.2012.02.00810.1016/j.apsusc.2012.02.008 ↗
4. S.J. Park, B.S. Yu, J.Y. Jeon, B.C. Kang, T.J. Ha, Sol-gel based zirconium dioxide dielectrics by oxygen-annealing at low temperature for highly stable and robust flexible resistive random access memory. J. Alloys Compd. 825 (2020). https://doi.org/10.1016/j.jallcom.2020.15408610.1016/j.jallcom.2020.154086 ↗
5. S.J. Park, T.J. Ha, Sol-gel-based metal-oxide thin-film transistors for high-performance flexible NMOS inverters. J. Alloys Compd. 912 (2022). https://doi.org/10.1016/j.jallcom.2022.16522810.1016/j.jallcom.2022.165228 ↗
6. Y. Gong et al., Room Temperature Fabrication of High Quality ZrO2 Dielectric Films for High Performance Flexible Organic Transistor Applications. IEEE Electron. Device Lett. 39(2), 280–283 (2018). https://doi.org/10.1109/LED.2017.278394510.1109/LED.2017.2783945 ↗
7. A. Liu et al., Room-temperature fabrication of ultra-thin ZrOx dielectric for high-performance InTiZnO thin-film transistors, Curr. Appl. Phys. 14(SUPPL. 1) (2014). https://doi.org/10.1016/j.cap.2013.11.04510.1016/j.cap.2013.11.045 ↗
8. X. Dong et al., Room-temperature UV-ozone assisted solution process for zirconium oxide films with high dielectric properties. Ceram. Int. 43(17), 15205–15213 (2017). https://doi.org/10.1016/j.ceramint.2017.08.05510.1016/j.ceramint.2017.08.055 ↗
9. A.T. Oluwabi et al., Influence of post-UV/Ozone treatment of ultrasonic-sprayed zirconium oxide dielectric films for a low-temperature oxide thin film transistor. Mater. (Basel). 13(1), 1–14 (2020). https://doi.org/10.3390/ma1301000610.3390/ma13010006 ↗
10. D. Wang, J. Lu, Y. Jeon, S. Ouyang, Y. Xie, H.H. Fong, Low temperature solution processed high-κ zirconium oxide gate insulator by Broadband-UV annealing. Org. Electron. 57, 341–344 (2018). https://doi.org/10.1016/j.orgel.2018.03.00210.1016/j.orgel.2018.03.002 ↗
11. S. Wang, G. Xia, A facile low-cost preparation of high-k ZrO2 dielectric films for superior thin-film transistors. Ceram. Int. 45, 23666–23672 (2019). https://doi.org/10.1016/j.ceramint.2019.08.08010.1016/j.ceramint.2019.08.080 ↗
12. G. Xia, S. Wang, Rapid and facile low-temperature solution production of ZrO2 films as high-k dielectrics for flexible low-voltage thin-film transistors. Ceram. Int. 45(13), 16482–16488 (2019). https://doi.org/10.1016/j.ceramint.2019.05.18110.1016/j.ceramint.2019.05.181 ↗
13. Z. Liang et al., Zirconium-aluminum-oxide dielectric layer with high dielectric and relatively low leakage prepared by spin-coating and the application in thin-film transistor. Coatings. 10(3) (2020). https://doi.org/10.3390/coatings1003028210.3390/coatings10030282 ↗
14. K.N. Woods et al., High-κ Lanthanum Zirconium Oxide Thin Film Dielectrics from Aqueous Solution Precursors. ACS Appl. Mater. Interfaces. 9(12), 10897–10903 (2017). https://doi.org/10.1021/acsami.7b0091510.1021/acsami.7b00915 ↗
15. W. Yang, K. Song, Y. Jung, S. Jeong, J. Moon, Solution-deposited Zr-doped AlOx gate dielectrics enabling high-performance flexible transparent thin film transistors. J. Mater. Chem. C 1(27), 4275–4282 (2013). https://doi.org/10.1039/c3tc30550c10.1039/c3tc30550c ↗
16. C. Guo, K. Tuokedaerhan, Z. Huang, Z. Cai, M. Ibraimov, S. Sailanbek, Interfacial optimization and enhancement of electrical properties of Ti-doped ZrO2 gate dielectric films prepared by the sol-gel method. Solid State Commun. 398, 115860 (2025). https://doi.org/10.1016/j.ssc.2025.11586010.1016/j.ssc.2025.115860 ↗
17. H. Cai, K. Tuokedaerhan, Z. Lu, R. Zhang, H. Du, Interface tuning and electrical property optimization of La-doped ZrO2 gate dielectric based on solution driving. Vacuum. 217, 112542 (2023). https://doi.org/10.1016/j.vacuum.2023.11254210.1016/j.vacuum.2023.112542 ↗
18. C. Guo, K. Tuokedaerhan, X. Shen, Y. Sagidolda, Z. Azamat, Interfacial modulation and optimization of the electrical properties of ZrGdOx composite films prepared using a UVO-assisted sol–gel method. RSC Adv. 15(3), 2231–2241 (2025). https://doi.org/10.1039/d4ra07704k10.1039/d4ra07704k ↗
19. M. Bizarro, J.C. Alonso, A. Ortiz, ZrAlO ternary oxide as a candidate for high-k dielectrics. Mater. Sci. Semicond. Process. 9(6), 1090–1096 (2006). https://doi.org/10.1016/j.mssp.2006.10.02810.1016/j.mssp.2006.10.028 ↗
20. M. Bizarro, J.C. Alonso, A. Ortiz, The Effect of the Process Conditions on the Synthesis of Zirconium-Aluminum Oxide Thin Films Prepared by Ultrasonic Spray Pyrolysis. J. Electrochem. Soc. 152(11), F179 (2005). https://doi.org/10.1149/1.203960710.1149/1.2039607 ↗
21. J.W. Jo et al., Highly stable and imperceptible electronics utilizing photoactivated heterogeneous sol-gel metal-oxide dielectrics and semiconductors. Adv. Mater. 27(7), 1182–1188 (2015). https://doi.org/10.1002/adma.20140429610.1002/adma.201404296 ↗
22. P. Pujar et al., High-Intensity Ultrasound-Assisted Low-Temperature Formulation of Lanthanum Zirconium Oxide Nanodispersion for Thin-Film Transistors. ACS Appl. Mater. Interfaces. 12(40), 44926–44933 (2020). https://doi.org/10.1021/acsami.0c1119310.1021/acsami.0c11193 ↗
23. W.J. Scheideler, A. Zeumault, V. Subramanian, Engineering high-k LaxZr1-xOy dielectrics for high-performance fully-solution-processed transparent transistors, in Device Research Conference - Conference Digest, DRC (2015), vol. 2015, pp. 205–206. https://doi.org/10.1109/DRC.2015.717563510.1109/DRC.2015.7175635 ↗
24. P. Vitanov, A. Harizanova, T. Ivanova, C. Trapalis, N. Todorova, Sol-gel ZrO2 and ZrO2-Al2O3 nanocrystalline thin films on Si as high-k dielectrics. Mater. Sci. Eng. B 165(3), 178–181 (2009). https://doi.org/10.1016/j.mseb.2009.09.00210.1016/j.mseb.2009.09.002 ↗
25. K.N. Woods et al., Tunable high-: κ ZrxAl1-xOy thin film dielectrics from all-inorganic aqueous precursor solutions. RSC Adv. 7(62), 39147–39152 (2017). https://doi.org/10.1039/c7ra08362a10.1039/c7ra08362a ↗
26. D.Q. Xiao et al., Interfacial modulation and electrical properties improvement of solution-processed ZrO2gate dielectrics upon Gd incorporation. J. Alloys Compd. 699, 415–420 (2017). https://doi.org/10.1016/j.jallcom.2016.12.37610.1016/j.jallcom.2016.12.376 ↗
27. J. Peng et al., Properties-adjustable alumina-zirconia nanolaminate dielectric fabricated by spin-coating. Nanomaterials. 7(12) (2017). https://doi.org/10.3390/nano712041910.3390/nano7120419 ↗
28. Y. Gong et al., Solution processable high quality ZrO2 dielectric films for low operation voltage and flexible organic thin film transistor applications. J. Phys. D Appl. Phys. 51(11) (2018). https://doi.org/10.1088/1361-6463/aaac1b10.1088/1361-6463/aaac1b ↗
29. W. He et al., Surface Modification on Solution Processable ZrO2 High-k Dielectrics for Low Voltage Operations of Organic Thin Film Transistors. J. Phys. Chem. C 120(18), 9949–9957 (2016). https://doi.org/10.1021/acs.jpcc.6b0363810.1021/acs.jpcc.6b03638 ↗
30. T. Huq, Y.H. Wong, J.H. Chuah, P.K. Jiwanti, W. Azeem, C.-K. Tan, Solution processed zirconium oxide dielectric thin films for electronic applications. J. Mater. Sci. Mater. Electron. 35(20), 1388 (2024). https://doi.org/10.1007/s10854-024-13136-910.1007/s10854-024-13136-9 ↗
31. I. Stambolova et al., Surface morphological and chemical features of anticorrosion zro2–tio2 coatings: Impact of zirconium precursor. Coatings. 11(6) (2021). https://doi.org/10.3390/coatings1106070310.3390/coatings11060703 ↗
32. M. Shane, M.L. Mecartney, Sol-gel synthesis of zirconia barrier coatings. J. Mater. Sci. 25(3), 1537–1544 (1990). https://doi.org/10.1007/BF0104534710.1007/BF01045347 ↗
33. S. Tsunekawa, Y. Kawazoe, T. Kojima, T. Sugimoto, Fabrication of zirconium oxide nanocrystallites and the critical size of the phase transition. Int. J. Nanosci. 5, 4–5 (2006). https://doi.org/10.1142/s0219581x0600493010.1142/s0219581x06004930 ↗
34. S. Shukla, S. Seal, Thermodynamic tetragonal phase stability in sol-gel derived nanodomains of pure zirconia. J. Phys. Chem. B 108(11), 3395–3399 (2004). https://doi.org/10.1021/jp037532x10.1021/jp037532x ↗
35. M. Popovici, J. De Graaf, M.A. Verschuuren, P.C.J. Graat, M.A. Verheijen, Zirconia thin film preparation by wet chemical methods at low temperature. Thin Solid Films. 519(2), 630–634 (2010). https://doi.org/10.1016/j.tsf.2010.08.01510.1016/j.tsf.2010.08.015 ↗
36. Y. Mansilla, M.D. Arce, C. González-Oliver, J. Basbus, H. Troiani, A. Serquis, Characterization of stabilized ZrO2 thin films obtained by sol-gel method. Appl. Surf. Sci. 569 (2021). https://doi.org/10.1016/j.apsusc.2021.15078710.1016/j.apsusc.2021.150787 ↗
37. Y. Castro, M. Aparicio, R. Moreno, A. Durán, Silica-zirconia sol-gel coatings obtained by different synthesis routes. J. Sol-Gel Sci. Technol. 35(1), 41–50 (2005). https://doi.org/10.1007/s10971-005-3213-010.1007/s10971-005-3213-0 ↗
38. R. Caruso, O. De Sanctis, A. Macías-García, E. Benavidez, S.R. Mintzer, Influence of pH value and solvent utilized in the sol-gel synthesis on properties of derived ZrO2 powders. J. Mater. Process. Technol. 152(3), 299–303 (2004). https://doi.org/10.1016/j.jmatprotec.2004.04.37110.1016/j.jmatprotec.2004.04.371 ↗
39. R. Brenier, J. Mugnier, E. Mirica, XPS study of amorphous zirconium oxide films prepared by sol-gel. Appl. Surf. Sci. 143(1), 85–91 (1999). https://doi.org/10.1016/S0169-4332(98)00901-510.1016/S0169-4332(98)00901-5 ↗
40. X. Bokhimi et al., Tetragonal nanophase stabilization in nondoped sol-gel zirconia prepared with different hydrolysis catalysts. J. Solid State Chem. 135(1), 28–35 (1998). https://doi.org/10.1006/jssc.1997.758610.1006/jssc.1997.7586 ↗
41. Y. Choi, C.K. Song, Low leakage current through zirconium oxide gate fabricated by low temperature solution process in OTFTs on plastic substrate. Org. Electron. 52, 195–199 (2018). https://doi.org/10.1016/j.orgel.2017.10.03010.1016/j.orgel.2017.10.030 ↗
42. S.M. Hwang et al., Microstructure and dielectric characteristics of high-k tetragonal ZrO 2 films with various thicknesses processed by sol-gel method. J. Nanosci. Nanatechnol. 12(4), 3350–3354 (2012). https://doi.org/10.1166/jnn.2012.563010.1166/jnn.2012.5630 ↗
43. C.G. Lee, A. Dodabalapur, Solution-processed high-k dielectric, ZrO 2, and integration in thin-film transistors. J. Electron. Mater. 41(5), 895–898 (2012). https://doi.org/10.1007/s11664-012-1905-010.1007/s11664-012-1905-0 ↗
44. J.A. Wang, M.A. Valenzuela, J. Salmones, A. Vázquez, A. García-Ruiz, X. Bokhimi, Comparative study of nanocrystalline zirconia prepared by precipitation and sol-gel methods. Catal. Today. 68, 1–3 (2001). https://doi.org/10.1016/S0920-5861(01)00319-410.1016/S0920-5861(01)00319-4 ↗
45. K. Kim et al., Sol-gel-processed amorphous-phase ZrO2 based resistive random access memory. Mater. Res. Express. 8(11) (2021). https://doi.org/10.1088/2053-1591/ac340010.1088/2053-1591/ac3400 ↗
46. H.-C. You, F.-H. Ko, T.-F. Lei, Physical Characterization and Electrical Properties of Sol-Gel-Derived Zirconia Films. J. Electrochem. Soc. 153(6), F94 (2006). https://doi.org/10.1149/1.218618210.1149/1.2186182 ↗
47. B.G. Son et al., High-performance In-Zn-O thin-film transistors with a soluble processed ZrO2 gate insulator. Phys. Status Solidi - Rapid Res. Lett. 7(7), 485–488 (2013). https://doi.org/10.1002/pssr.20130712810.1002/pssr.201307128 ↗
48. Y.G. Ha et al., Flexible low-voltage organic thin-film transistors enabled by low-temperature, ambient solution-processable inorganic/organic hybrid gate dielectrics. J. Am. Chem. Soc. 132(49), 17426–17434 (2010). https://doi.org/10.1021/ja107079d10.1021/ja107079d ↗
49. F.C. Chiu, A review on conduction mechanisms in dielectric films. Adv. Mater. Sci. Eng. (2014). https://doi.org/10.1155/2014/57816810.1155/2014/578168 ↗
50. H. Shimizu, S. Konagai, M. Ikeda, T. Nishide, Characterization of Sol-Gel derived and crystallized ZrO2 thin films. Jpn. J. Appl. Phys. 48(10 Part 1), 1011011–1011016 (2009). https://doi.org/10.1143/JJAP.48.10110110.1143/JJAP.48.101101 ↗
51. T.J. Frankcombe, Y. Liu, Interpretation of Oxygen 1s X-ray Photoelectron Spectroscopy of ZnO. Chem. Mater. (2023). https://doi.org/10.1021/acs.chemmater.3c0080110.1021/acs.chemmater.3c00801 ↗
52. R. Yahata, H. Kozuka, Stress evolution of sol-gel-derived silica coatings during heating: The effects of the chain length of alcohols as solvents. Thin Solid Films. (2009). https://doi.org/10.1016/j.tsf.2008.08.11710.1016/j.tsf.2008.08.117 ↗
53. T.M. Parrill, Heat treatment of spun-on acid-catalyzed sol-gel silica films. J. Mater. Res. (1994). https://doi.org/10.1557/JMR.1994.072310.1557/JMR.1994.0723 ↗
54. G. Adamopoulos, S. Thomas, P.H. Wöbkenberg, D.D.C. Bradley, M.A. McLachlan, T.D. Anthopoulos, High-mobility low-voltage ZnO and Li-doped ZnO transistors based on ZrO2 high-k dielectric grown by spray pyrolysis in ambient air. Adv. Mater. 23(16), 1894–1898 (2011). https://doi.org/10.1002/adma.20100393510.1002/adma.201003935 ↗
55. M.-J. Zhao et al., Variation of Oxygen Vacancy Defects in sALD-ZnO Films Annealed in an Oxygen-Rich Ambient. ECS J. Solid State Sci. Technol. (2021). https://doi.org/10.1149/2162-8777/abd88110.1149/2162-8777/abd881 ↗
56. S.M. Hwang et al., Effect of annealing temperature on microstructural evolution and electrical properties of sol-gel processed ZrO2/Si films. Appl. Phys. Lett. 98(2) (2011). https://doi.org/10.1063/1.354178410.1063/1.3541784 ↗
57. S.M. Hwang, S.M. Lee, J.H. Choi, J.H. Lim, J. Joo, Fabrication of solution-processed InSnZnO/ZrO2 thin film transistors. J. Nanosci. Nanotechnol. 13(11), 7774–7778 (2013). https://doi.org/10.1166/jnn.2013.780710.1166/jnn.2013.7807 ↗
58. L. Xifeng, X. Enlong, Z. Jianhua, Low-temperature solution-processed zirconium oxide gate insulators for thin-film transistors. IEEE Trans. Electron. Devices. 60(10), 3413–3416 (2013). https://doi.org/10.1109/TED.2013.227820610.1109/TED.2013.2278206 ↗
59. J.B. Seon, N.K. Cho, G. Yoo, Y.S. Kim, K. Char, Solution-processed amorphous ZrO2 gate dielectric films synthesized by a non-hydrolytic sol-gel route. RSC Adv. 8(68), 39115–39119 (2018). https://doi.org/10.1039/c8ra06911e10.1039/c8ra06911e ↗
60. C.Z. Tan, Dependence of the refractive index on density, temperature, and the wavelength of the incident light. Eur. Phys. J. B (2021). https://doi.org/10.1140/epjb/s10051-021-00147-210.1140/epjb/s10051-021-00147-2 ↗
61. G. Su et al., Solution-processed, flexible, and highly transparent ZrO2:PVP hybrid dielectric layer. Org. Electron. 116 (2023). https://doi.org/10.1016/j.orgel.2023.10675910.1016/j.orgel.2023.106759 ↗
62. P. Vitanov, A. Harizanova, T. Ivanova, Characterization of ZrO2 and (ZrO2) x (Al2O3) 1- X thin films on Si substrates: effect of the Al2O3 component. J. Phys. Conf. Ser. 514(no. 1), 12011 (2014)10.1088/1742-6596/514/1/012010 ↗