Current Applied Physics 10 (2010) e68e70

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Current Applied Physics

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Analysis of interface switching for Nb doped SrTiO3 single crystal device using complex impedance spectroscopy
Joonmyoung Lee a,*, El Mostafa Bourim a, Dongku Shin b, Jong-Sook Lee b, Dong-jun Seong a, Jubong Park a, Wootae Lee a, Man Chang a, Seungjae Jung a, Jungho Shin a, Hyunsang Hwang a,c
Department of Materials Science and Engineering, Gwangju Institute of Science and Technology, 261 Cheomdan-gwagiro (Oryong-dong), Buk-gu, Gwangju 500-712, Republic of Korea School of Materials Science and Engineering, Chonnam National University, 77 Yongbongro, Buk-gu, Gwangju 500-757, Republic of Korea c Department of Nanobio Materials and Electronics, Gwangju Institute of Science and Technology, 261 Cheomdan-gwagiro (Oryong-dong), Buk-gu, Gwangju 500-712, Republic of Korea
b a

a r t i c l e

i n f o

a b s t r a c t
To analyze the switching mechanism of Nb doped SrTiO3 (Nb:STO) single crystal in a high resistive state (HRS) and low resistive state (LRS), we performed a complex impedance spectroscopy in the frequency domain. We demonstrated the domination of the oxygen vacancies to the resistive switching. Based on the impedance spectroscopy in the HRS and LRS, we concluded that the origin of resistive switching is due to the combination of Schottky junction and a generation of conduction electron from oxygen vacancies. The calculation of activation energies in each resistance state has been performed comparatively, which proposed that a rst ionization of oxygen vacancies is responsible for the switching. 2009 Elsevier B.V. All rights reserved.

Article history: Received 17 August 2009 Received in revised form 24 September 2009 Accepted 28 September 2009 Available online 6 December 2009 Keywords: ReRAM Impedance Mechanism

1. Introduction To overcome the scaling limit of the current memory such as ash memory and dynamic random access memory (DRAM), many researchers have evaluated feasibility of the resistive RAM (ReRAM) as the potential candidate. The resistive switching behavior was observed in various materials such as binary oxide [1,2], Programmable Metallization Cell (PMC) [3] and perovskite material [48]. Perovskite material is one of the most promising materials due to the fast switching speed and feasibility of multi-bit process. However, the switching mechanism of perovskite material is not yet fully understood. Several models have been suggested to explain the origins of switching in these materials, such as the formation and rupture of laments [4], insulatorconductor transition at the lm oxide/electrode interface [5] and switching related to the modulation of potential barrier between the oxide and metal electrode by applying voltages [6,7]. Recently, the switching mechanism of Nb doped SrTiO3 (Nb:STO) single crystal is suggested that the modulation of Schottky barrier in interface traps is the origin of resistive switching [9]. However, it is needs to elucidate the switching mechanism in detail for further investigation.

Impedance spectroscopy (IS) is a highly practical tool to investigate the electrical properties of dielectric lms and to model their electrical behavior based on equivalent electric circuits composed of different basic electric components [10,11]. IS technique under frequency domain can lead to separate the interface based conduction from total electrical conduction responses in sandwiched metalinsulator/semiconductor/metal structures. This means that IS technique can be the clue to classify the mechanism of interface switching. In this study, we performed complex impedance measurements for low resistance state (LRS) and high resistance state (HRS) of Pt/ Nb:STO/Pt memory stacks using IS technique under frequency domain. Moreover, the activation energy of the conductivity in each resistance state was calculated to evidence the possible origin of resistive switching. 2. Experiments We used a single crystalline Nb:STO (1 0 0) substrate with 1.5 1.5 cm size with 0.5 mm thickness to avoid the effect of grain boundary and defect on the thin lm. The surface of the sample was cleaned in trichloroethylene, acetone, and methanol solutions for 10 min, respectively. After the conventional lithography, we deposited 100 nm-thick Pt top electrodes with an area of 50 lm 50 lm using magnetron sputtering system. The dc

* Corresponding author. Tel.: +82 2 970 2378; fax: +82 2 970 2304. E-mail address: destiny@gist.ac.kr (J. Lee). 1567-1739/$ - see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.cap.2009.12.016

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switching characteristics of the fabricated memory stacks were measured at room temperature by using a HP4155C semiconductor parameter analyzer (SPA). For evaluating a feasibility of fast switching, ac endurance also was measured with HP4155C SPA expanded system. Ac impedance spectra were measured by using solartron analyzer at different controlled temperatures from 164 C to 151 C. To reduce errors from the thermal expansion under high temperature, samples were connected with the impedance analyzer using aluminum metal wiring technique. The ac signal amplitude was xed at 100 mV and the frequency was swept from 1 Hz to 1 MHz. All measured impedance data was simulated by Z-view program. 3. Result and discussion Fig. 1(a) shows the IV characteristics of Pt/Nb:STO/Pt stack. As illustrated in the inset of Fig 1(a), the bias voltage was applied to the top electrode while the bottom electrode was kept grounded. Dc bias was sweep from 2.5 V to + 1.5 V using double sweep method. Thereby applying a positive bias near 1.5 V, the resistance decreases to LRS, and negative bias near 2.5 V leads to increase the resistance to HRS. It shows 3 order of resistance ratio (HRS/ LRS) at 0.1 V. As shown in Fig. 1(b), Pt/Nb:STO/Pt memory stack shows good ac endurance characteristics. The set/reset voltages were + 3.0 V and 3.0 V, respectively. The programming time was

100 ls for switching to both resistance states. No degradation of resistance ratio was observed over 105 cycles. To analyze the switching mechanism in detail, we monitored the two electronic resistance states (HRS and LRS) using impedance spectroscopy as shown in Fig. 2. Complex impedances of the analyzed resistance states measured at room temperature and their corresponding equivalent circuits are shown in Fig. 2. Just one single semicircle, in the impedance complex plane, was observed in HRS and LRS. This result indicates that both states have the same origin. Furthermore, these results predict that only one component corresponding to a highly resistive material in the sandwiched structure which could affect the switching. Accordingly, the HRS can be modeled by a simple equivalent circuit as shown in the inset of Fig. 2. The LRS also can be similarly simulated using the same equivalent circuit model under 3% error values, but lowered both in real and imaginary impedance values. According to previous work for lament based switching [10,12], these results indicate that highly conduction path does not exist in off and on state. If there is the conduction path, all current ows through the path and the entirely different impedance spectra are observed [10]. Therefore, based on these results, lament model can be excluded as switching mechanism in Pt/Nb:STO/Pt structure. It is well known that for small grain sizes (<100 nm) the bulk impedance should only be slightly inuenced by varying the applied dc bias, whereas the depletion layer impedance should clearly dependent on the applied dc bias variation [13]. This was indeed found for both investigated resistance states (data not presented here) which means that the overall resistance in the sandwiched memory structure is dominated by the depletion layer resulting from the Schottky contact at the Pt/Nb:STO interface. Fig. 3(a) shows the complex plots of Pt/Nb:STO/Pt stack at HRS in the temperature range from 164 C to 151 C. The value of impedance was found closely related to the frequency and temperature. As temperature increased, the entire impedance value was decreased. In the investigated temperature range, except the one resistive component which is taking part in the impedance complex plane, no other component was manifested. Hence, this indicates that the dominant switching factors were still maintained in the different exploited temperatures. The LRS case also showed the same trend. To nd out the dominant switching factors, the values of activation energy controlling the conductivity in LRS and HRS were calculated in Fig 3(b), supposing the following relationship:

Fig. 1. (a) Typical IV curve of Pt/Nb:STO/Pt stack. On/off ratio are about 3 orders at 0.1 V. The inset shows a simple diagram of that stack. We applied dc bias on the Pt top electrode, while the bottom electrode was grounded. (b) Ac endurance properties, the set/reset voltage were +3 V and 3 V, respectively.

Fig. 2. The complex impedance spectra of Pt/Nb:STO/Pt stack under LRS and HRS. The inset shows the short equivalent circuit for simulation. All data are simulated successfully under 3% error values.

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Fig. 3. (a) The complex plot of Pt/Nb:STO/Pt stack at HRS in the temperature range from 164 C to 151 C. The LRS case also showed the same trend. (b) The values of activation energy under LRS, HRS. The values are near 0.11 eV.

r r0 exp

Ea kT

where, r is the conductivity, Ea is the activation energy, k is Boltzmans constant and T is the absolute temperature. Besides, it is well known that the creation of the oxygen vacancies will produce the conducting electrons two times in the titanate-based perovskite oxides [14,15].

Oo $ V o 1=2O2
(rst ionization of the oxygen vacancies)

HRS and LRS, the combination of Schottky junction and generation of conduction electron from oxygen vacancies are the origin of the resistive switching. The calculation of activation energies in both LRS and HRS have been found to have the same values indicating that both resistance states have the same origin which excluded the lamentary model for resistive switching in Nb:STO crystal. Comparison of the activation energy to the oxygen vacancy ionization energy proposed that the rst ionization of oxygen vacancies is responsible for the switching. Acknowledgements This work was supported by the national research program of the 0.1 Terabit Non-volatile Memory Development Project and the National Research Laboratory (NRL) programs of the Korea Science and Engineering Foundation (KOSEF) and partially supported by the World Class University (WCU) program of the Ministry of Education, Science and Technology (MEST) of Korea. References
[1] M.-J. Lee, Y. Park, B.-S. Kang, S.-E. Ahn, C. Lee, K. Kim, W. Xianyu, G. Stefanovich, J.-H. Lee, S.-J. Chung, Y.-H. Kim, C.-S. Lee, J.-B. Park, I.-G. Baek, I.-K. Yoo, Tech. Digit. Int. Electron. Devices Meet. (2007) 771774. [2] Y.H. Do, J.S. Kwak, J.P. Hong, J. Korean Phys. Soc. 55 (2009) 1009. [3] D. Lee, D.-J. Seong, H. Choi, I. Jo, R. Dong, W. Xiang, S. Oh, S.-O. Seo, S. Heo, M. Jo, D.-K. Hwang, H.-K. Park, M. Chang, M. Hasan, H. Hwang, Tech. Digit. Int. Electron. Devices Meet. 30 (8) (2006) 14. [4] K. Szot, W. Speier, G. Bihlmayer, R. Waser, Nat. Mater. 5 (2006) 312. [5] Y.B. Nian, J. Strozier, N.J. Wu, X. Chen, A. Ignatiev, Phys. Rev. Lett. 98 (2007) 146303. [6] H. Sim, H. Choi, D. Lee, M. Chang, D. Choi, Y. Son, E.-H. Lee, W. Kim, Y. Park, I.-K. Yoo, H. Hwang, Tech. Digit. Int. Electron. Devices Meet. (2005) 758761. [7] A. Sawa, T. Fujii, M. Kawasaki, Y. Tokura, Appl. Phys. Lett. 85 (2004) 4073 4075. [8] S. Joo, J. Sok, J. Korean Phys. Soc. 53 (2008) 3427. [9] Dong.-j. Seong, M. Jo, D. Lee, H. Hwang, Electrochem. Solid-State Lett. 10 (2007) H168H170. [10] Y.-H. You, B.-S. Soo, J.-H. Hwang, W. Cho, S. Lee, T. Chung, C. Kim, Ki.-S. An, Appl. Phys. Lett. 89 (2006) 222105. [11] B. Behera, P. Nayak, R.N.P. Choudhary, Curr. Appl. Phys. 9 (2009) 201. [12] T. Menke, P. Meuffels, R. Dittmann, K. Szot, R. Waser, J. Appl. Phys. 105 (2009) 066104. [13] I. Denk, J. Claus, J. Maier, J. Electrochem. Soc. 144 (1997) 3526. [14] C.C. Wang, L.W. Zhang, Phys. Rev. B 62 (2000) 228. [15] Y. Xia, Z. Liu, Y. Wang, L. Shi, L. Chen, J. Yin, X. Meng, Appl. Phys. Lett. 91 (2007) 102904. [16] D. Wu, A.D. Li, N.B. Ming, Appl. Phys. Lett. 84 (2004) 4505. [17] S.H. Jeon, B.H. Park, J. Lee, B. Lee, S. Han, Appl. Phys. Lett. 89 (2006) 042904.

V o $ V o e
(second ionization of the oxygen vacancies)

V o $ V e o

here, the notation dened by Krger and Vink is adopted; VO and VO represent the oxygen vacancies carrying one and two positive charges, respectively. In Pt/Nb:STO/Pt structure, the calculated activation energies were near 0.11 eV in the entire investigated temperature range for both LRS and HRS. These values are similar to rst ionization energy (0.1 eV) [15,16]. Therefore, these results indicate that the generations of conducting electron from oxygen vacancies also lead to increase conductivity. According to previous work for rst-principle calculations [17], the change of Schottky barrier is induced by the electromigration of oxygen vacancies in response to the external bias. Besides, it can be conrmed that oxygen vacancies can make the extra contribution to the conduction by the calculation of activation energy. In the conclusion, based on the impedance data, the switching mechanism can be explained by the combination both of Schottky barrier modulation and the generation of conduction electron from oxygen vacancies. Accordingly, the LRS is induced by the accumulation of oxygen vacancies near interface, which enhances the tunneling of electrons through Schottky barrier and conducting electrons from oxygen vacancies. On the contrary, a negative biasing can switch the resistance to HRS due to the reduction of oxygen vacancies near interface. 4. Conclusion In summary, we performed ac impedance measurements by impedance spectroscopy in the frequency domain ranging from 1 Hz to 1 MHz to analyze the switching mechanism of Nb:STO single crystal. Based on the complex impedance characteristics in a