J. Semicond. > 2017, Volume 38 > Issue 8 > 084004
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SEMICONDUCTOR DEVICES

Investigation on interfacial and electrical properties of Ge MOS capacitor with different NH3-plasma treatment procedure

Xiaoyu Liu, Jingping Xu, Lu Liu, Zhixiang Cheng, Yong Huang and Jingkang Gong

+ Author Affiliations

 Corresponding author: Jingping Xu, Email:jpxu@hust.edu.cn

DOI: 10.1088/1674-4926/38/8/084004

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Abstract: The effects of different NH3-plasma treatment procedures on interfacial and electrical properties of Ge MOS capacitors with stacked gate dielectric of HfTiON/TaON were investigated. The NH3-plasma treatment was performed at different steps during fabrication of the stacked gate dielectric, i.e. before or after interlayer (TaON) deposition, or after deposition of high-k dielectric (HfTiON). It was found that the excellent interface quality with an interface-state density of 4.79×1011 eV-1cm-2 and low gate leakage current (3.43×10-5A/cm2 at Vg=1 V) could be achieved for the sample with NH3-plasma treatment directly on the Ge surface before TaON deposition. The involved mechanisms are attributed to the fact that the NH3-plasma can directly react with the Ge surface to form more Ge-N bonds, i.e. more GeOxNy, which effectively blocks the inter-diffusion of elements and suppresses the formation of unstable GeOx interfacial layer, and also passivates oxygen vacancies and dangling bonds near/at the interface due to more N incorporation and decomposed H atoms from the NH3-plasma.

Key words: Ge MOS, NH3-plasma treatment, TaON interlayer, stacked gate dielectric



[1]
Goley P S, Hudait M K. Germanium based field-effect transistors:challenges and opportunities. Materials, 2014, 7(3):2301 doi: 10.3390/ma7032301
[2]
Ohno T, Nakayama D, Samukawa S. Al and Ge simultaneous oxidation using neutral beam post-oxidation for formation of gate stack structures. Appl Phys Lett, 2015, 107(13):133107 doi: 10.1063/1.4932385
[3]
Ji F, Xu J P, Lai P T, et al. Improved interfacial properties of Ge MOS capacitor with high-k dielectric by using TaON/GeON dual interlayer. IEEE Electron Device Lett, 2011, 32(2):122 doi: 10.1109/LED.2010.2092749
[4]
Xu J P, Zhang X F, Li C X, et al. Improved electrical properties of Ge p-MOSFET with gate dielectric by using interlayer. IEEE Electron Device Lett, 2008, 29(10):1155 doi: 10.1109/LED.2008.2004282
[5]
Li H, Guo Y, Robertson J. AlN-GeO2 based gate stack for improved reliability of Ge MOSFETs. Microelectron Eng, 2015, 147:168 doi: 10.1016/j.mee.2015.04.081
[6]
Gao F, Lee S J, Pan J S, et al. Surface passivation using ultrathin AlNx film for Ge-metal-oxide-semiconductor devices with hafnium oxide gate dielectric. Appl Phys Lett, 2005, 86(11):3501 doi: 10.1007/s11432-014-5180-y
[7]
Lee C H, Tabata T, Nishimura T, et al. Ge/GeO2 interface control with high pressure oxidation for improving electrical characteristics. Appl Phys Express, 2009, 2(7):071404 doi: 10.1143/APEX.2.071404/meta
[8]
Xie R, He W, Yu M, et al. Effects of fluorine incorporation and forming gas annealing on high-k gated germanium metal-oxide-semiconductor with GeO2 surface passivation. Appl Phys Lett, 2008, 93(7):3504 doi: 10.1063/1.2966367?journalCode=apl
[9]
Li X F, Liu X J, Cao Y Q, et al. Improved interfacial and electrical properties of atomic layer deposition HfO2 films on Ge with La2O3 passivation. Appl Surf Sci, 2013, 264:783 doi: 10.1016/j.apsusc.2012.10.127
[10]
Bethge O, Henkel C, Abermann S, et al. Stability of La2O3 and GeO2 passivated Ge surfaces during ALD of ZrO2 high-k dielectric. Appl Surf Sci, 2012, 258(8):3444 doi: 10.1016/j.apsusc.2011.11.094
[11]
Bethge O, Zimmermann C, Lutzer B, et al. Effective reduction of trap density at the Y2O3/Ge interface by rigorous high-temperature oxygen annealing. J Appl Phys, 2014, 116(21):214111 doi: 10.1063/1.4903533
[12]
Zimmermann C, Bethge O, Winkler K, et al. Improving the ALD-grown Y2O3/Ge interface quality by surface and annealing treatments. Appl Surf Sci, 2016, 369:377 doi: 10.1016/j.apsusc.2016.02.066
[13]
Chi X, Lan X, Lu C, et al. An improvement of HfO2/Ge interface by in situ remote N2 plasma pretreatment for Ge MOS devices. Mater Res Express, 2016, 3(3):035012 doi: 10.1088/2053-1591/3/3/035012
[14]
Lin M, Li M, An X, et al. Surface passivation of the Ge substrate by novel nitrogen plasma immersion treatment. Semicond Sci Tech, 2013, 28(8):085010 doi: 10.1088/0268-1242/28/8/085010
[15]
Sardashti K, Hu K T, Tang K, et al. Nitride passivation of the interface between high-k dielectrics and SiGe. Appl Phys Lett, 2016, 108(1):011604 doi: 10.1063/1.4939460
[16]
Xie Q, Musschoot J, Schaekers M, et al. Ultrathin GeOxNy interlayer formed by in situ NH3 plasma pretreatment for passivation of germanium metal-oxide-semiconductor devices. Appl Phys Lett, 2010, 97(22):2902 http://adsabs.harvard.edu/abs/2010ApPhL..97v2902X
[17]
Cao Y Q, Chen J, Liu X J, et al. HfO2/GeOxNy/Ge gate stacks with sub-nanometer capacitance equivalent thickness and low interface trap density by in situ NH3 plasma pretreatment. Appl Surf Sci, 2015, 325:13 doi: 10.1016/j.apsusc.2014.11.073
[18]
Cheng C C, Chien C H, Luo G L, et al. Study of thermal stability of HfOxNy/Ge capacitors using postdeposition annealing and NH3 plasma pretreatment. J Electrochem Soc, 2007, 154(7):G155 doi: 10.1149/1.2734875
[19]
Huang Y, Xu J P, Liu L, et al. N2-plasma-treated Ga2O3 (Gd2O3 as interface passivation layer for Ge MOS capacitor with HfTiON gate dielectric. IEEE Trans Electron Devices, 2016, 63(7):2838 doi: 10.1109/TED.2016.2565691
[20]
Xie R, Yu M, Lai M Y, et al. High-k gate stack on germanium substrate with fluorine incorporation. Appl Phys Lett, 2008, 92(16):3505 https://www.researchgate.net/publication/224406145_High-k_gate_stack_on_germanium_substrate_with_fluorine_incorporation
[21]
Kim G S, Kim S H, Kim J K, et al. Surface passivation of germanium using SF6 plasma to reduce source/drain contact resistance in germanium n-FET. IEEE Electron Device Lett, 2015, 36(8):745 doi: 10.1109/LED.2015.2440434
[22]
Oshima Y, Shandalov M, Sun Y, et al. Hafnium oxide/germanium oxynitride gate stacks on germanium:capacitance scaling and interface state density. Appl Phys Lett, 2009, 94(18):3102 doi: 10.1063/1.3116624
[23]
Oshima Y, Sun Y, Kuzum D, et al. Chemical bonding, interfaces, and defects in hafnium oxide/germanium oxynitride gate stacks on Ge (100). J Electrochem Soc, 2008, 155(12):G304 doi: 10.1149/1.2995832
[24]
Li C C, Chang-Liao K S, Fu C H, et al. Improved electrical characteristics high-k gated MOS devices with in-situ remote plasma treatment in atomic layer deposition. Microelectron Eng, 2013, 109:64 doi: 10.1016/j.mee.2013.03.060
[25]
Xu J P, Lai P T, Li C X, et al. Improved electrical properties of germanium MOS capacitors with gate dielectric grown in wet-NO ambient. IEEE Electron Device Lett, 2006, 27(6):439 doi: 10.1109/LED.2006.874124
[26]
Terman L M. An investigation of surface states at a silicon/silicon oxide interface employing metal-oxide-silicon diodes. Solid-State Electron, 1962, 5(5):285 doi: 10.1016/0038-1101(62)90111-9
[27]
Wang L S, Xu J P, Liu L, et al. Plasma-nitrided Ga2O3 (Gd2O3) as interfacial passivation layer for InGaAs metal-oxide-semiconductor capacitor with HfTiON gate dielectric. IEEE Trans Electron Devices, 2015, 62(4):1235 doi: 10.1109/TED.2015.2396972
[28]
Yuan W Y, Xu J P, Liu L, et al. Improved interfacial and electrical properties of Ge MOS devices with ZrON/GeON dual passivation layer. J Semicond, 2016, 37(5):054004 doi: 10.1088/1674-4926/37/5/054004
[29]
Taylor J A, Lancaster G M, Rabalais J W. Chemical reactions of N2+ ion beams with group Ⅳ elements and their oxides. J Electron Spectrosc Relat Phenom, 1978, 13(3):435 doi: 10.1016/0368-2048(78)85047-6
[30]
Chuang J C, Chen M C. Properties of thin Ta-N films reactively sputtered on Cu/SiO2/Si substrates. Thin Solid Films, 1998, 322(1):213 http://www.sciencedirect.com/science/article/pii/S0040609097009140
[31]
Larkins F P, Lubenfeld A. The Auger spectrum of solid ammonia. J Electron Spectrosc Relat Phenom, 1979, 15(1):137 doi: 10.1016/0368-2048(79)87024-3
[32]
Pashutski A, Folman M. Low temperature XPS studies of NO and N2O adsorption on Al (100). Surf Sci, 1989, 216(3):395 doi: 10.1016/0039-6028(89)90383-X
[33]
Wu N, Zhang Q C, Zhu C X, et al. Effect of surface NH3 anneal on the physical and electrical properties of HfO2 films on Ge substrate. Appl Phys Lett, 2004, 84(19):3741 doi: 10.1063/1.1737057
[34]
Ji F, Xu J P, Huang Y, et al. Improved interfacial and electrical properties of Ge-based metal-oxide-semiconductor capacitor with LaTaON passivation layer. IEEE Trans Electron Devices, 2014, 61(11):3608 doi: 10.1109/TED.2014.2356597
[35]
Suzuki A, Nonaka H. Plasma diagnostics for NH3 plasmas using a quartz sensor at various pressures. Jpn J Appl Phys, 2011, 50(1S1):01AA03 doi: 10.7567/JJAP.50.01AA03
[36]
Yasui K, Arayama T, Okutani S, et al. Generation of ammonia plasma using a helical antenna and nitridation of GaAs surface. Appl Surf Sci, 2003, 212:619 http://www.sciencedirect.com/science/article/pii/S0169433203001351
Fig. 1.  Schematic diagram of NH$_{\rm{3}}$-plasma treatment at different stages of gate stack deposition.

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Fig. 2.  (Color online) HF (1 MHz) $C$-$V$ curves of all the samples, swept in two directions (from inversion to accumulation and back).

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Fig. 3.  (Color online) Frequency dispersion of $C$-$V$ curves for all the samples, measured at 1 MHz and 100 kHz.

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Fig. 4.  (Color online) Gate leakage current density ($J_{\rm g})$ versus gate voltage ($V_{\rm g})$ for all the samples.

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Fig. 5.  (Color online) XPS spectra of (a) N 1s and (b) O 1s for the three NH$_{\rm{3}}$-plasma treated samples.

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Fig. 6.  (Color online) Ge 2p XPS spectra of the three samples. (a) Ge-NH$_{\rm{3}}$ sample. (b) TaON-NH$_{\rm{3}}$. (c) HfTiON-NH$_{\rm{3}}$ sample.

DownLoad: Full-Size Img PowerPoint

Table 1.   Electrical and physical parameters extracted from HF $C$-$V$ curves for all the samples.

Table 2.   Energy position and atomic percentage of the species in Fig. 6.
[1]
Goley P S, Hudait M K. Germanium based field-effect transistors:challenges and opportunities. Materials, 2014, 7(3):2301 doi: 10.3390/ma7032301
[2]
Ohno T, Nakayama D, Samukawa S. Al and Ge simultaneous oxidation using neutral beam post-oxidation for formation of gate stack structures. Appl Phys Lett, 2015, 107(13):133107 doi: 10.1063/1.4932385
[3]
Ji F, Xu J P, Lai P T, et al. Improved interfacial properties of Ge MOS capacitor with high-k dielectric by using TaON/GeON dual interlayer. IEEE Electron Device Lett, 2011, 32(2):122 doi: 10.1109/LED.2010.2092749
[4]
Xu J P, Zhang X F, Li C X, et al. Improved electrical properties of Ge p-MOSFET with gate dielectric by using interlayer. IEEE Electron Device Lett, 2008, 29(10):1155 doi: 10.1109/LED.2008.2004282
[5]
Li H, Guo Y, Robertson J. AlN-GeO2 based gate stack for improved reliability of Ge MOSFETs. Microelectron Eng, 2015, 147:168 doi: 10.1016/j.mee.2015.04.081
[6]
Gao F, Lee S J, Pan J S, et al. Surface passivation using ultrathin AlNx film for Ge-metal-oxide-semiconductor devices with hafnium oxide gate dielectric. Appl Phys Lett, 2005, 86(11):3501 doi: 10.1007/s11432-014-5180-y
[7]
Lee C H, Tabata T, Nishimura T, et al. Ge/GeO2 interface control with high pressure oxidation for improving electrical characteristics. Appl Phys Express, 2009, 2(7):071404 doi: 10.1143/APEX.2.071404/meta
[8]
Xie R, He W, Yu M, et al. Effects of fluorine incorporation and forming gas annealing on high-k gated germanium metal-oxide-semiconductor with GeO2 surface passivation. Appl Phys Lett, 2008, 93(7):3504 doi: 10.1063/1.2966367?journalCode=apl
[9]
Li X F, Liu X J, Cao Y Q, et al. Improved interfacial and electrical properties of atomic layer deposition HfO2 films on Ge with La2O3 passivation. Appl Surf Sci, 2013, 264:783 doi: 10.1016/j.apsusc.2012.10.127
[10]
Bethge O, Henkel C, Abermann S, et al. Stability of La2O3 and GeO2 passivated Ge surfaces during ALD of ZrO2 high-k dielectric. Appl Surf Sci, 2012, 258(8):3444 doi: 10.1016/j.apsusc.2011.11.094
[11]
Bethge O, Zimmermann C, Lutzer B, et al. Effective reduction of trap density at the Y2O3/Ge interface by rigorous high-temperature oxygen annealing. J Appl Phys, 2014, 116(21):214111 doi: 10.1063/1.4903533
[12]
Zimmermann C, Bethge O, Winkler K, et al. Improving the ALD-grown Y2O3/Ge interface quality by surface and annealing treatments. Appl Surf Sci, 2016, 369:377 doi: 10.1016/j.apsusc.2016.02.066
[13]
Chi X, Lan X, Lu C, et al. An improvement of HfO2/Ge interface by in situ remote N2 plasma pretreatment for Ge MOS devices. Mater Res Express, 2016, 3(3):035012 doi: 10.1088/2053-1591/3/3/035012
[14]
Lin M, Li M, An X, et al. Surface passivation of the Ge substrate by novel nitrogen plasma immersion treatment. Semicond Sci Tech, 2013, 28(8):085010 doi: 10.1088/0268-1242/28/8/085010
[15]
Sardashti K, Hu K T, Tang K, et al. Nitride passivation of the interface between high-k dielectrics and SiGe. Appl Phys Lett, 2016, 108(1):011604 doi: 10.1063/1.4939460
[16]
Xie Q, Musschoot J, Schaekers M, et al. Ultrathin GeOxNy interlayer formed by in situ NH3 plasma pretreatment for passivation of germanium metal-oxide-semiconductor devices. Appl Phys Lett, 2010, 97(22):2902 http://adsabs.harvard.edu/abs/2010ApPhL..97v2902X
[17]
Cao Y Q, Chen J, Liu X J, et al. HfO2/GeOxNy/Ge gate stacks with sub-nanometer capacitance equivalent thickness and low interface trap density by in situ NH3 plasma pretreatment. Appl Surf Sci, 2015, 325:13 doi: 10.1016/j.apsusc.2014.11.073
[18]
Cheng C C, Chien C H, Luo G L, et al. Study of thermal stability of HfOxNy/Ge capacitors using postdeposition annealing and NH3 plasma pretreatment. J Electrochem Soc, 2007, 154(7):G155 doi: 10.1149/1.2734875
[19]
Huang Y, Xu J P, Liu L, et al. N2-plasma-treated Ga2O3 (Gd2O3 as interface passivation layer for Ge MOS capacitor with HfTiON gate dielectric. IEEE Trans Electron Devices, 2016, 63(7):2838 doi: 10.1109/TED.2016.2565691
[20]
Xie R, Yu M, Lai M Y, et al. High-k gate stack on germanium substrate with fluorine incorporation. Appl Phys Lett, 2008, 92(16):3505 https://www.researchgate.net/publication/224406145_High-k_gate_stack_on_germanium_substrate_with_fluorine_incorporation
[21]
Kim G S, Kim S H, Kim J K, et al. Surface passivation of germanium using SF6 plasma to reduce source/drain contact resistance in germanium n-FET. IEEE Electron Device Lett, 2015, 36(8):745 doi: 10.1109/LED.2015.2440434
[22]
Oshima Y, Shandalov M, Sun Y, et al. Hafnium oxide/germanium oxynitride gate stacks on germanium:capacitance scaling and interface state density. Appl Phys Lett, 2009, 94(18):3102 doi: 10.1063/1.3116624
[23]
Oshima Y, Sun Y, Kuzum D, et al. Chemical bonding, interfaces, and defects in hafnium oxide/germanium oxynitride gate stacks on Ge (100). J Electrochem Soc, 2008, 155(12):G304 doi: 10.1149/1.2995832
[24]
Li C C, Chang-Liao K S, Fu C H, et al. Improved electrical characteristics high-k gated MOS devices with in-situ remote plasma treatment in atomic layer deposition. Microelectron Eng, 2013, 109:64 doi: 10.1016/j.mee.2013.03.060
[25]
Xu J P, Lai P T, Li C X, et al. Improved electrical properties of germanium MOS capacitors with gate dielectric grown in wet-NO ambient. IEEE Electron Device Lett, 2006, 27(6):439 doi: 10.1109/LED.2006.874124
[26]
Terman L M. An investigation of surface states at a silicon/silicon oxide interface employing metal-oxide-silicon diodes. Solid-State Electron, 1962, 5(5):285 doi: 10.1016/0038-1101(62)90111-9
[27]
Wang L S, Xu J P, Liu L, et al. Plasma-nitrided Ga2O3 (Gd2O3) as interfacial passivation layer for InGaAs metal-oxide-semiconductor capacitor with HfTiON gate dielectric. IEEE Trans Electron Devices, 2015, 62(4):1235 doi: 10.1109/TED.2015.2396972
[28]
Yuan W Y, Xu J P, Liu L, et al. Improved interfacial and electrical properties of Ge MOS devices with ZrON/GeON dual passivation layer. J Semicond, 2016, 37(5):054004 doi: 10.1088/1674-4926/37/5/054004
[29]
Taylor J A, Lancaster G M, Rabalais J W. Chemical reactions of N2+ ion beams with group Ⅳ elements and their oxides. J Electron Spectrosc Relat Phenom, 1978, 13(3):435 doi: 10.1016/0368-2048(78)85047-6
[30]
Chuang J C, Chen M C. Properties of thin Ta-N films reactively sputtered on Cu/SiO2/Si substrates. Thin Solid Films, 1998, 322(1):213 http://www.sciencedirect.com/science/article/pii/S0040609097009140
[31]
Larkins F P, Lubenfeld A. The Auger spectrum of solid ammonia. J Electron Spectrosc Relat Phenom, 1979, 15(1):137 doi: 10.1016/0368-2048(79)87024-3
[32]
Pashutski A, Folman M. Low temperature XPS studies of NO and N2O adsorption on Al (100). Surf Sci, 1989, 216(3):395 doi: 10.1016/0039-6028(89)90383-X
[33]
Wu N, Zhang Q C, Zhu C X, et al. Effect of surface NH3 anneal on the physical and electrical properties of HfO2 films on Ge substrate. Appl Phys Lett, 2004, 84(19):3741 doi: 10.1063/1.1737057
[34]
Ji F, Xu J P, Huang Y, et al. Improved interfacial and electrical properties of Ge-based metal-oxide-semiconductor capacitor with LaTaON passivation layer. IEEE Trans Electron Devices, 2014, 61(11):3608 doi: 10.1109/TED.2014.2356597
[35]
Suzuki A, Nonaka H. Plasma diagnostics for NH3 plasmas using a quartz sensor at various pressures. Jpn J Appl Phys, 2011, 50(1S1):01AA03 doi: 10.7567/JJAP.50.01AA03
[36]
Yasui K, Arayama T, Okutani S, et al. Generation of ammonia plasma using a helical antenna and nitridation of GaAs surface. Appl Surf Sci, 2003, 212:619 http://www.sciencedirect.com/science/article/pii/S0169433203001351

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    Received: 13 October 2016 Revised: 18 February 2017 Online: Published: 01 August 2017

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      Article Navigation >  Journal of Semiconductors  > 2017  >  38(8): 084004
      Xiaoyu Liu, Jingping Xu, Lu Liu, Zhixiang Cheng, Yong Huang, Jingkang Gong. Investigation on interfacial and electrical properties of Ge MOS capacitor with different NH3-plasma treatment procedure[J]. Journal of Semiconductors, 2017, 38(8): 084004. doi: 10.1088/1674-4926/38/8/084004 ****X Y Liu, J P Xu, L Liu, Z X Cheng, Y Huang, J K Gong. Investigation on interfacial and electrical properties of Ge MOS capacitor with different NH3-plasma treatment procedure[J]. J. Semicond., 2017, 38(8): 084004. doi: 10.1088/1674-4926/38/8/084004.
      Citation:
      Xiaoyu Liu, Jingping Xu, Lu Liu, Zhixiang Cheng, Yong Huang, Jingkang Gong. Investigation on interfacial and electrical properties of Ge MOS capacitor with different NH3-plasma treatment procedure[J]. Journal of Semiconductors, 2017, 38(8): 084004. doi: 10.1088/1674-4926/38/8/084004 ****
      X Y Liu, J P Xu, L Liu, Z X Cheng, Y Huang, J K Gong. Investigation on interfacial and electrical properties of Ge MOS capacitor with different NH3-plasma treatment procedure[J]. J. Semicond., 2017, 38(8): 084004. doi: 10.1088/1674-4926/38/8/084004.
      shu

      Investigation on interfacial and electrical properties of Ge MOS capacitor with different NH3-plasma treatment procedure

      DOI: 10.1088/1674-4926/38/8/084004

      • School of Optical and Electronic Information, Huazhong University of Science and Technology, Wuhan 430074, China

      Funds:

      the National Natural Science Foundation of China 61176100

      the National Natural Science Foundation of China 61274112

      Project supported by the National Natural Science Foundation of China (Nos. 61176100, 61274112)

      More Information
      • Corresponding author: Jingping Xu, Email:jpxu@hust.edu.cn
      • Received Date: 2016-10-13
      • Revised Date: 2017-02-18
      • Published Date: 2017-08-01

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