Electrochemical and Solid-State Letters, 14 (5) H225-H228 (2011)

C 1099-0062/2011/14(5)/H225/4/$28.00 V The Electrochemical Society

H225

Ferroelectric Polarization Effect on Al-Nb Codoped Pb(Zr0.52Ti0.48)O3/Pr0.7Ca0.3MnO3 Heterostructure Resistive Memory

El Mostafa Bourim,a,z Sangsoo Park,b Xinjun Liu,b Kuyyadi P. Biju,a Hyunsang Hwang,a,b and Alex Ignatieva,c
a

Department of Nanobio Materials and Electronics and bDepartment of Materials Science and Engineering, Gwangju Institute of Science and Technology, 261 Cheomdan-gwagiro (Oryong-dong), Buk-gu, Gwangju 500-712, Republic of South Korea c Center for Advanced Materials, University of Houston, Houston, Texas 77204-5004, USA This work presents the investigation of resistive switching memory in a perovskite heterostructure composed of an active Al-Nb codoped Pb(Zr0.52Ti0.48)O3 ferroelectric thin lm and a semiconducting Pr0.7Ca0.3MnO3 manganite-based oxide lm, both sandwiched between Pt electrodes in a parallel capacitor-like structure. Bipolar resistive switching nature was conrmed from the measured characteristics of the DC I-V hysteresis loop and resistance switching in the pulse mode. The active ferroelectric layer has been demonstrated to play a crucial role in controlling the switching memory performance (resistance state stability and high switching endurance). Ferroelectric polarization and corresponding piezoelectric effect-induced lattice strains are found to be responsible for the resistive switching characteristics in this ferroelectric/manganite heterojunction. C V 2011 The Electrochemical Society. [DOI: 10.1149/1.3556977] All rights reserved. Manuscript submitted August 6, 2010; revised manuscript received January 26, 2011. Published March 8, 2011.

Several works have been reported on strain-induced electrical resistance modulation using an all perovsikite heterostructure composed of a perovskite-type R1xAxMnO3 (R and A are trivalent rareearth and divalent alkaline-earth ions, respectively) manganite thin lm channel and a ferroelectric gate lm patterned in coplanar shaped transistor-like structure.16 In this bilayered structure, the semiconducting manganite-based oxides are used because they are known for their strong sensitivity to lattice deformations resulting from the pronounced coupling of lattice and electronic degrees of freedom. The dependence of physical properties of manganites on the lattice strain effect has been interpreted qualitatively within the strength change of the doubleexchange interaction and Jahn-Teller electron lattice coupling via modifying Mn-O bound length and/or Mn-O-Mn bound angle.710 For instance, the investigation of strain effect-induced resistance modulation in La0.7Sr0.3MnO3, La0.7Ca0.3MnO3 and Pr0.5Ca0.5MO3 has demonstrated that compressive strain usually reduces resistivity while tensile strain gives rise to an opposite effect.46 Therefore, a perovskite ferroelectric material could be used to modulate the manganite layer channel resistance either by the ferroelectric-eld effect11 or by the ferroelectric polarization and corresponding piezoelectric eld-induced lattice strain effect, or by their combination.16 In this letter is reported the electrical characterization of an allperovskite heterostructure composed of an active Al-Nb codoped Pb(Zr0.58Ti0.42)O3 ferroelectric thin lm (referred to as PZT) and a semiconducting Pr0.7Ca0.3MnO3 (PCMO) layer, both sandwiched between parallel Pt electrodes in a capacitor-like structure. The DC IV hysteresis characteristics and the electrical pulse triggering resistance switching behavior have exhibited a bipolar switching nature for the resistance modulation in this ferroelectric/manganite heterojunction. A mechanism based on strain transfer at the PZT/PCMO interface by the ferroelectric polarization and corresponding piezoelectric effect is suggested for describing the resistive switching properties. Good resistance switching performance could be expected when minimizing the external constraint effects on the device structure. Thin lms of chemical compositions 0.05(Al0.5Nb0.5)O3 0.95 Pb(Zr0.52Ti0.48)O3 and Pr0.7Ca0.3MnO3 were grown by pulsed laser deposition technique (KrF laser excimer k 248 nm). Al and Nb were used as doping elements of PZT because they can permit easy domain wall mobility and good stability of the polarization.12 The fabrication process of the Pt/PZT/PCMO/Pt device consisted in depositing rst the PCMO lm and then the PZT lm on a platinized titanium/silicon oxide/silicon substrate at temperatures and oxygen ambient pressures of 650 C/50 mTorr and 6008C/250 mTorr,
z

respectively. The typical thickness of the deposited PZT lm was $15 nm while that for PCMO lms was varied from 20 to 240 nm. X-ray diffraction analyses conrmed both deposited lms were polycrystalline. The PZT thin lm was crystallized with the tetragonal perovskite phase preferentially in (110) plane. Top Pt electrodes (TP) of square area 100 100 lm2 and 100 nm thick were deposited through a stencil shadow mask by using magnetron-sputtering. The electrical characterizations of the device were done using standard systems: an Agilent 4155C Semiconductor Parameter Analyzer for current-voltage (I-V) measurements, an Agilent B1500A Semiconductor Device Analyzer for capacitance/conductance-voltage (C/GV) measurements, and pulse voltage stresses were applied by an Agilent 41501 B SMU and a Pulse Generator Expander for pulse programming measurements. All the bias was applied with respect to the TE while the bottom electrode (BE) was grounded (see schematic conguration of the device structure in the inset (a) of Fig. 1). Figure 1 shows the typical DC I-V characteristics of the fabricated Pt/PZT/PCMO($60 nm)/Pt capacitor-like stack for several repeated V-sweep cycles at room temperature. After the rst V-sweep (0 ! 2V ! 0 ! 2V ! 0) referred to as electroforming in which the current underwent an abrupt decrease in the positive

E-mail: e.bourim@gmail.com

Figure 1. (Color online) DC I-V hysteresis characteristics of Pt/PZT/ PCMO($60 nm)/Pt layered structure. V-sweep range of 0 ! 2V ! 0 ! 2V ! 0 (dashed line) corresponds to electroforming. Inset (a) is a schematic conguration of device and measurement setup, inset (b) shows probing of resistance states in the positive voltage region.

Downloaded 15 Mar 2011 to 203.237.47.37. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp

H226

Electrochemical and Solid-State Letters, 14 (5) H225-H228 (2011)

voltage region (dashed curve in Fig. 1) that is probably related to a strong switching polarization current (charging-discharging at the capacitor electrodes) resulting from the rst reorientation and reversal of ferroelectric domains in PZT lm, an increase of the voltage sweeping bias amplitude to Vmax 64 V with adoption of current compliance to protect the sample from a hard breakdown results in wide open and reversible I-V hysteresis loops with counter clockwise evolution in both positive and negative voltage regions as shown by arrows in the I-V plots of Fig. 1. The recorded I-V curves representing up to 20 successive voltage sweep cycles exhibit a near-perfect stability and reproducibility as well as highly symmetrical hysteresis curves that pass through the origin of I-V axes. Checking the electrical transport properties after the application of a V-sweep cycle of positive or negative polarity demonstrated that a large positive V-sweep cycle (>2.5 V) induces a low resistance state (LRS) in the positive voltage region as is probed by the repeated read-out at 2 V (inset (b) of Fig.1), and a subsequent application of a large negative V-sweep cycle (<2.5 V) induces a high resistance state (HRS) as is probed as well in the positive voltage region by the repeated read-out at 2 V (inset (b) of Fig. 1). Note that the resistance switching states can also be established in the negative voltage region and probed by a negative read bias. Thereby, applying a large negative V-sweep induces the LRS and a large positive V-sweep induces the HRS. Consequently, the hetero-structured PZT/PCMO device exhibited a bistable resistance switching memory controlled by bipolar switching mode, and since the resistance state changes immediately while the voltage reverses the polarity; the HRS/LRS should be probed with a read voltage of same polarity. Switching characteristics in bias pulse mode were also examined, demonstrating the ability of the Pt/PZT/PCMO/Pt structure device for data storage. Figure 2 shows resistance change under a pulse train of 200 alternating serial pulses of positive and negative polarity with bias pulse amplitude of 63 V and pulse width and period of 100 and 200 ms, respectively. Positive and negative pulses reversibly switched the resistance between LRS and HRS yielding an electric pulse induced resistance change ratio HR/LR of about 283 under a read voltage of 1 V. The HRS resistance was observed to reach a stable value immediately after reversing the pulse polarity (from 3 to 3 V), while the LRS resistance needed additional pulses to reach a saturated value. Resistance switching can also be generated under successive alternate 6Vpulse, however a poor stability of the LRS with tendency to increase rapidly as the pulse cycle number increases was observed (inset of Fig. 2). In identifying the mechanism dealing with resistance switching in the Pt/PZT/PCMO/Pt device, the PCMO thickness effect on electric transports was investigated. The I-V characteristics measured

Figure 3. (Color online) DC I-V characteristics of Pt/PZT/PCMO/Pt structure with different thickness of PCMO layer; plot (a) for $120 nm, plot (b) for $180 nm and plot (c) for $240 nm.

with PCMO layer thickness greater than 120 nm did not manifest any hysteresis loop as shown in Fig. 3. Such behavior indicates that the electric transport properties in this device are controlled by the PZT/PCMO heterojunction interface, and that the observed thickness dependence of the switching property may be related to the insufcient inuence on PCMO volume beneath PZT by the ferroelectric effect or to a higher mechanical stress induced in the PZT lm (by thermal expansion coefcient difference between PZT and PCMO) that hinders the switching of ferroelectric dipoles as the PCMO thickness increases.13 Other works correlating the resistance change with the ferroelectric switching have postulated Metal/ PZT Schottky barrier modulation by the ferroelectric polarization effect,14,15 or resistive switching associated with ferroelectric tunneling junctions,16 or modulation of charge carriers of PCMO at the interface by ferroelectric eld effect.11 These models predict that the HRS and the LRS are set up with biases of opposite polarities, and that the resistance switching takes place just at the coercive voltage VC corresponding to the polarization reversal. Such behaviors are markedly different from our investigated system for which the LRS can be induced by both bias polarities, and that the resistive switching happens not immediately at VC ($0.25 V) but at a higher voltage (>$2.5 V) as illustrated in Fig. 4 by the simultaneous

Figure 2. (Color online) Switching characteristics in V-pulse mode for Pt/ PZT/PCMO($60 nm)/Pt layered structure. Main plot shows switching under pulse train of alternated 200 serial pluses of opposite bias polarity. Inset shows switching under successive alternate pulses of opposite polarity.

Figure 4. (Color online) C/G-V characteristics of Pt/PZT/PCMO($60 nm)/ Pt structure measured at ac 250 mV and 100 kHz for a V-sweep cycle of 3 V ! 3 V ! 3 V. Arrows (dotted and dashed lines) indicate the sweeping directions and C/G evolutions. Inset shows C/G-V evolution in a short V-sweep range of 1.5 V ! 1.5 V ! 1.5 V, the C-V hysteresis indicates clearly the ferroelectric nature of PZT lm.

Downloaded 15 Mar 2011 to 203.237.47.37. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp

Electrochemical and Solid-State Letters, 14 (5) H225-H228 (2011) measurements of capacitance (C) and conductance (G). Our investigations are further differentiated by the sensitivity of observed switching to the thickness of the PCMO layer with a specic thickness requirement of between 20 and $100 nm. By analogy to the resistance modulation based on strain exchange in ferroelectric/ferromagnetic heterostructured systems in coplanar transistor like structure,1,2,46 the resistive switching in the Pt/PZT/ PCMO/Pt parallel capacitor-like structure can be well explained by invoking the PZT ferroelectricity/piezoelectricity-induced lattice strain. Further, since the deposited PZT lm was textured in the (110) orientation, it is favorable for a ferroelectric domain structure established at 90 , with which the polarization reversal passes through the built-up of 90 domain walls favorable for realizing a high remnant PZT deformation. Therefore, according to I-V hysteresis evolution in the Pt/PZT/PCMO/Pt device, the electric-eld induced resistance modulation can be explained as follows. Upon the application of a positive bias sweep up to 4 V, the resulted polarization orientation in the PZT induces a remnant expansion of PZT lattice along the applied electric eld accompanied with its contraction in the in-plane direction due to the Poisson effect. This PZT lattice distortion results in transferring of in-plane compressive strains to the PCMO layer thus decreasing its resistance; and the device evolves to LRS (in this step the leakage current ow is mostly limited by the PZT resistance). The subsequent increase of the negative bias sweep will generate, by converse piezoelectric effect, a contraction of PZT lattice parallel to the applied eld direction simultaneously accompanied with its expansion in the in-plane direction. Such PZT lattice distortion results in a transfer of in-plane tensile strains to the PCMO lm that, with the starting of the polarization reversal nucleation, will release the previously induced compressive strain in PCMO (induced during positive bias sweep), thus, causing the PCMO resistance to increase and device switching to the HRS. Consequently, a signicant part of the applied voltage drops across the PCMO layer preventing the polarization reversal in PZT to be fully reached. As the negative voltage sweep continues increasing, then when a signicant voltage drop across the PZT layer, that exceeds VC, is reached, the full ferroelectric polarization reversal along the applied electric eld takes place. The resultant change in polarization orientation induces a remnant expansion of PZT lattice normal to the plane accompanied with its contraction in the in-plane direction, and again imposes an in-plane compressive strain on the PCMO lm causing the PCMO resistance to decrease and device switching to the LRS (in this step again the leakage current ow is mostly limited by the PZT resistance). Once the bias sweep is reversed to positive polarity, the converse piezoelectric effect which contracts the PZT lattice normal to the plane and the beginning of ferroelectric dipoles reversal results in releasing the previous induced in-plane remnant compressive strains (induced during the negative bias sweep) on the PCMO layer, and thus, the PCMO resistance increases with device recovering its HRS. Yet again, as the positive bias sweep continues increasing and when the potential drop across PZT layer is enough for a high polarization reversal, the resulted permanent PZT expansion and the associated PCMO contraction cause the device resistance to evolve to LRS. Note that the peaks observed in C-V hysteresis (Fig. 4) do not correspond to a full ferroelectric domain reversal. Regarding the instability of LRS, this can be related to the relaxation of the remnant mechanical strain induced by the ferroelectric polarization.17 Given that our fabricated heterostructure is made of continuous lms (Fig. 5a), the polarized electroded PZT zone will undergo an in-plane tensile stresses (r) due to unswitched 90 ferroelectric domains in the lm region surrounding the top electrode; as is depicted in Fig. 5b. Consequently, the relaxation of the constrained electroded PZT volume will impose a continual release of the compressive strains in the PCMO lm and thus be the main cause for disturbing LRS stability and affecting the resistive switching performance. To examine the effect of the external surrounding boundaries on the PZT/PCMP coupling, a simple vertical mesastructure free of lateral constraints, as is simply drawn in Fig. 5c, was fabricated through standard photolithography, lift-off, and ion etching and then

H227

Figure 5. (Color online) Sketched scenario of unswitched ferroelectric domain effect on the polarized region under top electrode. (a) Before bias application. (b) Induced remnant deformation after bias application. (c) A simply drawn mesastructure free of external constraint effect. Note that the depicted arrangement of unit cells, in the not poled region, is just a simplied representation and does not represent the real unit cells orientation in the investigated PZT lm.

electrically characterized. Figure 6 presents the obtained I-V hysteresis characteristic for such mesastructured device with a thinner PCMO layer thickness of $20 nm that may generate less stress in PZT lm. No electroforming was observed in the rst V-sweep, but two apparent humps of different sizes appeared in both voltage regions, just when the bias changed the polarity. They disappeared when the V-sweep was limited in a small voltage bias range (inset (a) of Fig. 6). Probably, these humps are related to the switching polarization current due to the easy ferroelectric dipoles switching within less constrained PZT in the mesastructure, and they can take

Figure 6. (Color online) DC I-V hysteresis characteristics of the mesastructured Pt/PZT/PCMO($20 nm)/Pt device for 10 consecutive V-sweeps cycles of 0 ! 4 V ! 0 ! 4 V! 0 V. Arrows (dashed lines) indicate the sweeping directions and the current evolution. Inset (a) shows the I-V evolution for 10 consecutive V-sweeps in a short V-sweep range of 0 ! 1.5 V ! 0 ! 1.5 V!0. Insets (b) and (c) show switching characteristics in V-pulse mode (Pulse amplitude: 63 V, pulse width: 100 ms, pulse period: 200 ms and read voltage at 1 V).

Downloaded 15 Mar 2011 to 203.237.47.37. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp

H228

Electrochemical and Solid-State Letters, 14 (5) H225-H228 (2011) National Research Laboratory (NRL) Programs of the Korea Science and Engineering Foundation (KOSEF), the World Class University (WCU) program at GIST through a grant provided in 2009 by the Ministry of Education, Science and Technology (MEST) of Korea (Project No. R31-20008-000-10026-0), and the Robert A. Welch Foundation through grant E-632.
Gwangju Institute of Science and Technology assisted in meeting the publication costs of this article.

place only when the ferroelectric dipoles are fully reversed under a larger V-sweep (> j 62.5 V j ). Note that no specic difference was observed in the C/G-V hysteresis characteristics of the mesastructured device (data not presented here) relatively to the device with continuous PZT/PCMO lm stacked structure. Furthermore, for such conned structure, switching characteristics in bias pulse mode with alternating serial pulses of positive and negative polarity (inset (b) of Fig. 6) demonstrated that both the HRS and LRS reached a stable value immediately after reversing the pulse polarity. Also, good bipolar switching endurance with stable LRS was measured under alternating pulses of opposite polarity, as shown in inset (c) of Fig. 6. However, the HRS/LRS ratio was found to decrease to less than one order when the pulse width was 1 ls. Generally, the response time of piezoelectric stack is limited by the speed of sound in the material. Since the natural frequency of PZT stacked on a silicon substrate has been reported to be in the range of kHz to MHz,18,19 therefore, a high switching speed on the order of nanosecond should be expected by optimizing the PZT/PCMO bi-layers stiffnesses and dimensions, parameters, that practically inuence the electromechanical response vibration of piezoelectric actuators. In summary, resistance modulation in a Pt/PZT/PCMO/Pt structure stacked in a parallel capacitor-like conguration has demonstrated a bistable resistance state switching memory behavior controlled by bipolar switching mode. The model of ferroelectric polarization and corresponding converse piezoelectric effects-induced lattice strain was found to describe qualitatively the resistive switching mechanism due to the thin nature of the PCMO lm. By assuring the stability of the ferroelectric domain states in the PZT thin lms from any lateral constraints imposed from the device surrounding, PZT/PCMO heterojunction demonstrated good resistive switching stability, which makes it a potential candidate for RRAM applications. However, more investigations are needed to better understand the effective mechanism(s) behind the complex electrical transport properties in ferroelectric/manganite coupling in capacitor-like structures. Acknowledgments This work was supported by National Research Program of the 0.1 Tera-bit Non-volatile Memory Development Project, the

References
1. C. Thiele, K. Dorr, L. Schultz, E. Beyreuther, and W. M. Lin, Appl. Phys. Lett., 87, 162512 (2005) 2. C. Thiele, K. Dorr, S. Fahler, L. Schultz, D. C. Meyer, A. A. Levin, and P. Pauer, Appl. Phys. Lett., 87, 262502 (2005). 3. K. Dorr and C. Thiele, Phys. Status Solidi B, 243, 21 (2006). 4. R. K. Zheng, Y. Wang, J. Wang, K. S. Wong, H. L. W. Chan. C. L. Choy, and H. S. Luo, Phys. Rev. B, 74, 094427 (2006). 5. R. K. Zheng, Y. Wang, H. L. W. Chan, C. L. Choy, and H. S. Luo, Phys. Rev. B, 75, 212102 (2007). 6. R. K. Zheng, C. Chao, H. L. W. Chan, C. L. Choy, and H. S. Luo, Phys. Rev. B, 75, 024110 (2007). 7. A. J. Millis, T. Darling, and A. Migliori, J. Appl. Phys., 83, 1588 (1998). 8. Y. Lu, J. Klein, F. Herbstritt, J. B. Philipp, A. Marx, and R. Gross, Phys. Rev. B, 73, 184406 (2006). 9. X. J. Chen, S. Soltan, H. Zhang, and H. U. Habermeier, Phys. Rev. B, 65, 174402 (2002). 10. X. J. Chen, H.-U. Habermeier, H. Zhang, G. Gu, M. Varela, J. Santamaria, and C. C. Almasan, Phys. Rev. B, 72, 104403 (2005). 11. S. Mathews, R. Ramesh, T. Venkatesan, and J. Benedetto, Science, 276, 238 (1997). 12. S. Aggarwal and R. Ramesh, Annu. Rev. Mater. Sci., 28, 463 (1998). 13. K. Fujito, N. Wakiya, N. Mizutani, and K. Shinozaki, Jpn. J. Appl. Phys., 44, 6900 (2005). 14. P. W. M. Blom, R. M. Wolf, J. F. M. Cillessen, and M. P. C. M. Krijn, Phys. Rev. Lett., 73, 2107 (1994). 15. Z. W. Xing, N. J. Wu, and A. Ignatiev, Appl. Phys. Lett., 91, 052106 (2007). 16. H. Kohlstedt, N. A. Pertsev, J. R. Contreras, and R. Waser, Phys. Rev. B, 72, 125341 (2005). 17. S. H. Baek, H. W. Jang, C. M. Folkman, Y. L. Li, B. Winchester, J. X. Zhang, Q. He, Y. H. Chu, C. T. Nelson, M. S. Rzchowski, Nature Mater., 9, 309 (2010). 18. A. L. Kholkin, Ch. Wutchrich, D. V. Taylor, and N. Setter, Rev. Sci. Instrum., 67, 1935 (1996). 19. Q. Zhou, J. M. Cannata, R. J. Meyer, Jr., D. J. Van Tol, S. Tadigadapa, W. J. Hughes, K. K. Shung, and S. Trolier-McKinstry, IEEE Trans. Ultrason., Ferroelectr., Freq. Control, 52, 350 (2005).

Downloaded 15 Mar 2011 to 203.237.47.37. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp