Journal of Materials Science

, Volume 55, Issue 7, pp 2881–2890 | Cite as

The electronics transport mechanism of grain and grain boundary in semiconductive hafnium oxynitride thin film

  • Zude Lin
  • Xiuyan Li
  • Yujin Zeng
  • Minmin You
  • Fangfang Wang
  • Jingquan LiuEmail author
Electronic materials


HfOxNy thin film was deposited on oxidized silicon substrate; its physical structure and chemical composition were studied in detail by X-ray diffractometer, scanning electron microscopy, field emission transmission electron microscope and X-ray photoelectron spectrometer. Microtemperature sensors with high sensitivity based on the film were fabricated. To clarify the conduction process of grain, grain boundary (GB) and the whole film, temperature-dependent AC impedances of a sensor were measured and analyzed in 40–300 K. The results show that at all of the measured temperatures, the resistance of grain is much larger than that of GB, and its rising rates with the temperature reduction are also much larger than that of GB, indicating that the resistive property of HfOxNy thin film is determined by grain. In addition, it has been confirmed that the conduction process of both the HfOxNy film and GB is dominated by thermal activation and Mott variable-range hopping (VRH) in relatively high and low temperature range, respectively. The conduction process of the grain obeys Mott VRH in the whole considered temperature range, while the Mott characteristic temperature is changed. These results provide new insights into the performance enhancement of the transition metal oxynitride-based temperature sensors.



This work was partially funded by the National Key R&D Program of China under grant 2017YFB1002501, the National Natural Science Foundation of China (No. 61728402), the Research Program of Shanghai Science and Technology Committee (17JC1402800), the Program of Shanghai Academic/Technology Research Leader (18XD1401900). The authors are also grateful to the Center for Advanced Electronic Materials and Devices (AEMD) of Shanghai Jiao Tong University.


  1. 1.
    Gu ZQ, Hu CQ, Fan XF, Xu L, Wen M, Meng QN, Zhao L, Zheng XL, Zheng WT (2014) On the nature of point defect and its effect on electronic structure of rocksalt hafnium nitride films. Acta Mater 81:315–325CrossRefGoogle Scholar
  2. 2.
    Huang HH, Fan XF, Hu CQ, Singh DJ, Jiang Q, Zheng WT (2015) Transformation of electronic properties and structural phase transition from HfN to Hf3N4. J Phys Condens Matter 27:225501CrossRefGoogle Scholar
  3. 3.
    Lin ZD, Zhan GH, You MM, Yang B, Chen X, Wang XL, Zhang WP, Liu JQ (2018) NTC thin film temperature sensors for cryogenics region with high sensitivity and thermal stability. Appl Phys Lett 113:133504CrossRefGoogle Scholar
  4. 4.
    Garbrecht M, Schroeder JL, Hultman L, Birch J, Saha B, Sands TD (2016) Microstructural evolution and thermal stability of HfN/ScN, ZrN/ScN, and Hf0.5Zr0.5N/ScN metal/semiconductor superlattices. J Mater Sci 51:8250–8258. CrossRefGoogle Scholar
  5. 5.
    Grosser M, Seidel H, Schmid U (2017) Microstructure and mechanical properties of sputter deposited tantalum nitride thin films after high temperature loading. Thin Solid Films 629:69–78CrossRefGoogle Scholar
  6. 6.
    Jia LW, Lu HP, Ran YJ, Zhao SJ, Liu HN, Li YL, Jiang ZT, Wang Z (2019) Structural and dielectric properties of ion beam deposited titanium oxynitride thin films. J Mater Sci 54:1452–1461. CrossRefGoogle Scholar
  7. 7.
    Lee YB, Oh IK, Cho EN, Moon P, Kim H, Yun I (2015) Characterization of HfOxNy thin film formation by in situ plasma enhanced atomic layer deposition using NH3 and N2 plasmas. Appl Surf Sci 349:757–762CrossRefGoogle Scholar
  8. 8.
    Pant G, Gnade A, Kim MJ, Wallace RM, Gnade BE, Quevedo-Lopez MA, Kirsch PD, Krishnan S (2006) Comparison of electrical and chemical characteristics of ultrathin HfON versus HfSiON dielectrics. Appl Phys Lett 89:032904CrossRefGoogle Scholar
  9. 9.
    Jiang R, Xie E, Chen Z, Zhang ZX (2006) Electrical property of HfOxNy–HfO2–HfOxNy sandwich-stack films. Appl Surf Sci 253:2421–2424CrossRefGoogle Scholar
  10. 10.
    Dalapati GK, Sridhara A, Wong ASW, Chia CK, Chi DZ (2009) HfOxNy gate dielectric on p-GaAs. Appl Phys Lett 94:073502CrossRefGoogle Scholar
  11. 11.
    Choi J, Puthenkovilakam R, Chang JP (2006) Effect of nitrogen on the electronic properties of hafnium oxynitrides. J Appl Phys 99:053705CrossRefGoogle Scholar
  12. 12.
    Suarez-Segovia C, Leroux C, Caubet P, Domengie F, Reimbold G, Romano G, Gourhant O, Joseph V, Ghibaudo G (2015) Effective work function modulation by sacrificial gate aluminum diffusion on HfON-based 14 nm NMOS devices. Microelectron Eng 147:113–116CrossRefGoogle Scholar
  13. 13.
    Gu ZQ, Huang HH, Zhang S, Wang XY, Gao J, Zhao L, Zheng WT, Hu CQ (2016) Optical reflectivity and hardness improvement of hafnium nitride films via tantalum alloying. Appl Phys Lett 109:232102CrossRefGoogle Scholar
  14. 14.
    Seo HS, Lee TY, Petrov I, Greene JE (2005) Epitaxial and polycrystalline HfNx (0.8 ≤ x ≤ 1.5) layers on MgO (001): film growth and physical properties. J Appl Phys 97:083521CrossRefGoogle Scholar
  15. 15.
    Liu M, Fang Q, He G, Zhu LQ, Pan SS, Zhang LD (2006) Chemical compositions and optical properties of HfOxNy thin films at different substrate temperatures. Mat Sci Semicond Process 9:876–879CrossRefGoogle Scholar
  16. 16.
    Farrell IL, Reeves RJ, Preston ARH, Ludbrook BM, Downes JE, Ruck BJ, Durbin SM (2010) Tunable electrical and optical properties of hafnium nitride thin films. Appl Phys Lett 96:071914CrossRefGoogle Scholar
  17. 17.
    Tang WM, Leung CH, Lai PT (2011) Enhanced sensing performance of MISiC schottky-diode hydrogen sensor by using HfON as gate insulator. IEEE Sens J 11:2940–2946CrossRefGoogle Scholar
  18. 18.
    Mott NF (1990) Metal-insulator transitions, 2nd edn. Taylor & Francis Ltd, LondonCrossRefGoogle Scholar
  19. 19.
    Bhatti IN, Rawat R, Banerjee A, Pramanik AK (2014) Temperature evolution of magnetic and transport behavior in 5d Mott insulator Sr2IrO4: significance of magneto-structural coupling. J Phys Condens Matter 27:016005CrossRefGoogle Scholar
  20. 20.
    Parisini A, Gorni M, Nath A, Belsito L, Rao Mulpuri V, Nipoti R (2015) Remarks on the room temperature impurity band conduction in heavily Al+ implanted 4H-SiC. J Appl Phys 118:035101CrossRefGoogle Scholar
  21. 21.
    Li ZG, Peng LP, Zhang JC, Li J, Zeng Y, Luo YC, Zhan ZQ, Meng LB, Zhou MJ, Wu WD (2017) Transition between Efros–Shklovskii and Mott variable-range hopping conduction in polycrystalline germanium thin films. Semicond Sci Technol 32:035010CrossRefGoogle Scholar
  22. 22.
    Zanatta AR, Chambouleyron I (1992) Transport properties of nitrogen-doped hydrogenated amorphous germanium films. Phys Rev B 46:2119–2125CrossRefGoogle Scholar
  23. 23.
    Lu CL, Quindeau A, Deniz H, Preziosi D, Hesse D, Alexe M (2014) Crossover of conduction mechanism in Sr2IrO4 epitaxial thin films. Appl Phys Lett 105:082407CrossRefGoogle Scholar
  24. 24.
    Leonarska A, Kadziołka-Gaweł M, Szeremeta AZ, Bujakiewicz-Koronska R, Kalvane A, Molak A (2017) Electric relaxation and Mn3+/Mn4+ charge transfer in Fe-doped Bi12MnO20–BiMn2O5 structural self-composite. J Mater Sci 52:2222–2231. CrossRefGoogle Scholar
  25. 25.
    Irvine JTS, Sinclair DC, West AR (1990) Electroceramics: characterization by impedance spectroscopy. Adv Mater 2(3):132–138CrossRefGoogle Scholar
  26. 26.
    Schmidt R, Brinkman AW (2007) Studies of the temperature and frequency dependent impedance of an electroceramic functional oxide NTC thermistor. Adv Funct Mater 17:3170–3174CrossRefGoogle Scholar
  27. 27.
    Kumar VP, Dayal V, Hadimani RL, Bhowmik RN, Jiles DC (2015) Magnetic and electrical properties of Ti-substituted lanthanum bismuth manganites. J Mater Sci 50:3562–3575. CrossRefGoogle Scholar
  28. 28.
    Ricote S, Bonanos N, Manerbino A, Sullivan NP, Coors WG (2014) Effects of the fabrication process on the grain boundary resistance in BaZr0.9Y0.1O3-δ. J Mater Chem A 2:6107CrossRefGoogle Scholar
  29. 29.
    He L, Lin ZY (2011) Studies of temperature dependent ac impedance of a negative temperature coefficient Mn–Co–Ni–O thin film thermistor. Appl Phys Lett 98:242112CrossRefGoogle Scholar
  30. 30.
    Liu JS, Lu HL, Xu SS, Wang PF, Ding SJ, Zhang DW (2016) Influence of NH3 annealing on the chemical states of HfO2/Al2O3 stacks studied by X-ray photoelectron spectroscopy. Vacuum 124:60–64CrossRefGoogle Scholar
  31. 31.
    Zhou QG, Zhai JW (2013) Resistive switching characteristics of Pt/TaOx/HfNx structure and its performance improvement. AIP Adv 3:032102CrossRefGoogle Scholar
  32. 32.
    Wang XJ, Liu M, Zhang LD (2012) Temperature dependence of chemical states and band alignments in ultrathin HfOxNy/Si gate stacks. J Phys D Appl Phys 45:335103CrossRefGoogle Scholar
  33. 33.
    Yun SN, Zhou HW, Wang L, Zhang H, Ma TL (2013) Economical hafnium oxygen nitride binary/ternary nanocomposite counter electrode catalysts for high-efficiency dye-sensitized solar cells. J Mater Chem A 1:1341CrossRefGoogle Scholar
  34. 34.
    Brandt BL, Rubin LG (1982) Low-temperature thermometry in high magnetic fields. V. Carbon-glass resistors. Rev Sci Instrum 53(8):1129–1136CrossRefGoogle Scholar
  35. 35.
    Yotsuya T, Kakehi Y, Ishida T (2011) Thin film temperature sensor for cryogenic region with small magnetoresistance. Cryogenics 51:546–549CrossRefGoogle Scholar
  36. 36.
    Yotsuya T, Yoshitake M, Kodamat T (1997) Low-temperature thermometer using sputtered ZrNx thin film. Cryogenics 37:817–822CrossRefGoogle Scholar
  37. 37.
    Monea BF, Ionete EI, Spiridon SI, Leca A, Stanciu A, Petre E, Vaseashta A (2017) Single wall carbon nanotubes based cryogenic temperature sensor platforms. Sensors 17:2071CrossRefGoogle Scholar
  38. 38.
    Courts SS, Swinehart PR (2003) Review of Cernox™ (Zirconium Oxy-Nitride) thin film resistance temperature sensors. AIP Conf Proc 684:393CrossRefGoogle Scholar
  39. 39.
    Bivas S, Jagaran A, Timothy DS, Umesh VW (2010) Electronic structure, phonons, and thermal properties of ScN, ZrN, and HfN: a first-principles study. J Appl Phys 107:033715CrossRefGoogle Scholar
  40. 40.
    Eric KKA, Michael KED, Samuel NAD, Osei A, Francis KA, Bright KA, Robert KN (2017) Indirect phase transition of refractory nitrides compounds of: TiN, ZrN and HfN crystal structures. Comput Mater Sci 137:75–84CrossRefGoogle Scholar
  41. 41.
    Bazhanov DI, Knizhnik AA, Safonov AA, Bagatur’yants AA (2005) Structure and electronic properties of zirconium and hafnium nitrides and oxynitrides. J Appl Phys 97:044108CrossRefGoogle Scholar
  42. 42.
    Liu ZTY, Burton BP, Khare SV, Gall D (2017) First-principles phase diagram calculations for the rocksalt-structure quasibinary systems TiN–ZrN, TiN–HfN and ZrN–HfN. J Phys Condens Matter 29:035401CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.National Key Laboratory of Science and Technology on Micro/Nano Fabrication, Key Laboratory for Thin Film and Micro Fabrication of Ministry of Education, Department of Micro/Nano-ElectronicsShanghai Jiao Tong UniversityShanghaiChina

Personalised recommendations