Journal of Electronic Materials

A change of switching direction in chromium oxide thin films

--Manuscript Draft-Manuscript Number: Full Title: Article Type: Keywords: Corresponding Author: JEMS-D-13-00943R1 A change of switching direction in chromium oxide thin films Original Research Chromium oxide, Resistance switching, grain boundaries, electrochemical redox reactions, Oxygen ion migrations Bach Thang Phan, PhD University of Science, Vietnam National University HoChiMinh, VIET NAM

Corresponding Author Secondary Information: Corresponding Author's Institution: Corresponding Author's Secondary Institution: First Author: First Author Secondary Information: Order of Authors: Kim Ngoc Pham Trung Do Nguyen Bang Tam Thi Dao Kieu Hanh Thi Ta Cao Vinh Tran Van Hieu Nguyen Sang Sub Kim Shinya Maenosono, Professor Bach Thang Phan, PhD Order of Authors Secondary Information: Abstract: We investigated the switching behavior of the as-deposited CrOX and post-annealed CrOy films with various electrodes (Top electrode: Ag, Ti and Bottom electrode: Pt, FTO). The resistance switching strongly depends on electrode materials and postannealed treatment. In the Pt devcies, only the Ag/CrOx/Pt device exhibited a clockwise I-V hysteresis, while no resistance switching was observed in the Ag/CrOy/Pt, Ti/CrOx/Pt and Ti/CrOy/Pt devices. In the FTO devices, the Ag/CrOx/FTO device exhibited a clockwise I-V hysteresis. In contrast, the Ag/CrOy/FTO device and both the Ti/CrOx/FTO, Ti/CrOy/FTO devices presented an anticlockwise I-V hysteresis. The switching direction depends not only on electrode materials but also on the postannealed treatment, in which the density of grain boundaries is varied. Consequently, the density of grain boundaries controls the kinds of charge carrier involved in the switching process. The as-deposited CrOx films with high density of grain boundaries exhibited the Ag filament paths mediated by electrochemical redox reaction in spite of the bottom electrode materials (Pt and FTO). The post-annealed CrOy films with low density of grain boundaries suppressed the electrochemical redox reaction in the Ag/CrOy/Pt but promoted a short-range movement of O2- ions through the bottom interface controlled resistance switching in the Ag/CrOy/FTO. The electrochemical redox reactions controlled resistance switching only occur in oxides with a high density of grain boundaries or dislocations. Kim Ngoc Pham University of Science, Vietnam National University

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Response to Reviewer Comments

Dear Editor and Reviewers We would like to thank for all your comments. Based on the comments, we did additional experiments and renewed the previously submitted text. Please revaluate the revised text.

The below is our reply for the Reviewers comments:

Reviewer #1: The authors report bipolar switching behaviour of CrOx with Ag top electrode and three different bottom electrodes. CrOx is well known as a switching material so that there are many publications on its switching properties. This reviewer can find neither new experimental findings nor better understanding in this manuscript. Apart from the lack of novelty, there are several flaws that should be revised. For instance, it does not make sense the way that the authors drew the conclusion that the observed switching is not attributed to Ag ion migration. This reviewer cannot see any logical support. In addition, fitting current-voltage curves using some conduction equations does not seem to tell the conduction mechanism. As far as this reviewer knows, I-V curves, especially those during set or on-switching, show huge cycle-tocycle variations, and thus, such an analysis is not a proper way to figure out the mechanism. The bias polarity shown in Fig. 8 is not consistent with the explanation written in the manuscript. Figure 8 is case of positive voltage application induced set or on-switching. However, the I-V curves in the manuscript exhibit the polarity the other way around.

From our searching, there are only two published papers on resistance switching of Chromium oxides thins films reported by Chens group [S. C. Chen ,T. C. Chang, S. Y. Chen, C. W. Chen, S. C. Chen, S. M. Sze, M. J. Tsai, M. J. Kao, F. S. Y. Huang, Solid-State Electronics. 62, 40 (2011); S. C. Chen, T. C. Chang, S. Y. Chen. H. W. Li, C. W. Chen, S. M. Sze, F. S. Y. Huang, and Y. H. Tai, Electrochemical and Solid-State Letters. 14, H103 (2011). We are very happy to be informed about other publications.

Most of publications do the analysis of electrical conductions from the I-V characteristics and then make the associated resistance switching mechanisms. In our study, the I-V hysteresis

curves is very stable over hundreds of switching cycles, such as the I-V characteristics of the asdeposited Ag/CrOX/FTO device as shown in Figure 1 below.

Figure 1: I-V hysteresis curves of the as-deposited Ag/CrOx/FTO device for over hundreds of switching cycles.

Recently, two famous scientists on ReRAM research have published two review papers on ReRAM [R. Waser etal., Adv. Mater. 21, 2632 (2009) and C. S. Hwang etal., Rep. Prog. Phys. 75, 076502 (2012)], in which they mentioned about the combination of an inert electrode and a reactive electrode is the prerequisite condition for the electrochemical redox reactions. Based on the reviewers comments, we did an additional experiments with electrode and thermal treatment dependence to exam the role of Ag ion migration. With the new our results presented in the revised text, we argured that the as-deposited CrOx films with high density of grain

boundaries in the Ag/CrOx/FTO and Ag/CrOx/Pt devices, exhibited the Ag filament paths mediated by electrochemical redox reaction in spite of the bottom electrode materials (Pt and FTO). However, the post-annealed CrOy films with low density of grain boundaries suppressed the electrochemical redox reaction in the Ag/CrOy/Pt but promoted a short-range movement of O2- ions through the bottom interface controlled resistance switching in the Ag/CrOy/FTO. We suggested the electrochemical redox reactions controlled resistance switching only occur in oxides with a high density of grain boundaries or dislocations. The detail contents are presented in the revised text. The reviewer is correct about our flaws on Fig. 8.

Reviewer #2: A resistance switching resistive random access memory (ReRAM) is important for the next-generation information storage. This topic is of interest for the electronic material or device physics community. In this manuscript, the authors reported the electrical conduction and bipolar resistance switching of a Chromium oxide (CrxOy) thin film. The experimental results demonstrated that the CrxOy thin films exhibited a high potential for applications in ReRAM. Currently, there is a competitive argument on the role of the oxygen vacancy migration and electro-chemical conducting filament in controlling resistance switching of oxide thin films. Here, through the analyses of the current-voltage (I-V) characteristics of metal/CrxOy/metal devices and the influence of negative bias (-Vmax) with respect to the bottom electrode materials (Pt, FTO, and Ti), the electrical conduction and resistance switching mechanisms were discussed in detail. Base on that, I have realized that the significant contribution of this manuscript is to explain the field-induced resistance switching of the CrxOy-based ReRAM is due to the migration of oxygen vacancies. In addition, the analytical methods presented in this manuscript are helpful in clearly understanding resistance switching mechanism and also in guiding the design of materials for ReRAM. The manuscript is publishable with answering the following questions:

1. I found that Chang's group has published two papers on resistance switching of structures of Pt/Cr2O3/TiN or Pt/Cr2O3/Pt [Solid-State Electronics 62, 40 (2011) and Electrochemical and Solid-State Letters, 14, H103 (2011)]. In those works, they discussed the resistance switching is because the TiN reacts with oxygen easily but the Pt does not. It well known that the resistance switching mechanism strongly depends on electrode materials. In current manuscript, the authors investigated the resistance switching behavior of Chromium oxide with three kinds of bottom electrode: an inert Pt electrode, an active Ti electrode and a uorine tin oxide FTO electrode. The experimental results provided by this manuscript may give the wider picture of resistance switching of chromium oxide films. In order to provide a complete picture, the authors should include the mentioned papers and state their progress into the manuscript. We referred two publications from Chens group in the revised text.

2. In experimental section, the voltage profile for I-V measurement, the film thicknesses of the top and bottom electrodes, and device area should be presented. The voltage profile for the IV measurement was 0 V + (-)Vmax 0 V - (+)Vmax 0 V. The bottom electrode was biased and the top electrode was grounded. The thickness of the top electrode (Ag and Ti) is about 100 nm. The bottom electrodes ( FTO and Pt/Ti/SiO2/Si) are commercial products. 3. The authors presented the XRD of thin film deposited on glass and stated that the thin films exist in an amorphous phase (Fig. 1). It is true that the available literature always reports amorphous oxides when sputter deposited at room temperature which is understandable based on ground of insufficient energy provided by the process for crystallization to occur. In addition, this can happen even if the underlying electrode would be oriented. Did the authors investigate the XRD measurement of thin film deposited on an oriented bottom electrode (FTO, PT or Ti)? We also run the XRD measurements of chromium oxide thin films on an oriented FTO bottom electrode and we can not observed the crystalline peaks of chromium oxides.

4. It would be helpful if the authors can provide the reference after the states of "Among these various materials, TMOs have great advantages in the simple fabrication and in their compatibility to CMOS processes (page 2, line 28), and "However, chromium oxide thin films are rarely reported as a potential material for ReRAM applications, although the role of the Cr dopant in the resistance switching of SrTiO and SrZrO has been reported (page 2, line 38) and "Since the filamentary rupture controlled by Joule heating displays no polarity dependence, the thermal effects are not expected to play a dominant role in the reset process" (page 5, line 12) We added the reference for these statements , Ref. 1, 3, 5-8.

5. Figure 8 describes the schematic representation of potential barrier modulation with oxygen vacancies under negative biases. In this manuscript, the authors investigated several kinds of bottom electrode material, therefore, the "FTO" should be replaced by "Bottom electrode". Also, please check again the notation of ground connection in Fig. 8. In the revised text, we remove Figure 8 and its discussions.

6. In addition, I have a comment regarding Fig. 8, It would be helpful if the authors can briefly explain the meanings of Figs. 8(a),(b),(c) perhaps in Figure Caption In the revised text, we remove Figure 8 and its discussions.

Marked Manuscript

A change of switching direction in chromium oxide thin films

Ngoc Kim Pham1, Do Trung Nguyen1, Bang Tam Thi Dao1, Kieu Hanh Thi Ta1, Vinh Cao Tran2, Van Hieu Nguyen3, Sang Sub Kim4, Shinya Maenosono5 and Thang Bach Phan1,2,* Faculty of Materials Science, University of Science, Vietnam National University, Ho Chi Minh City, Vietnam 2 Laboratory of Advanced Materials, University of Science, Vietnam National University, Ho Chi Minh City, Vietnam 3 Faculty of Physics and Physics Engineering, University of Science, Vietnam National University, Ho Chi Minh City, Vietnam 4 Department of Materials Science and Engineering, Inha University, Republic of Korea 5 Japan Advanced Institute of Science and Technology, Nomi, Ishikawa, Japan
1

Abstract We investigated the switching behavior of the as-deposited CrOX and post-annealed CrOy films with various electrodes (Top electrode: Ag, Ti and Bottom electrode: Pt, FTO). The resistance switching strongly depends on electrode materials and post-annealed treatment. In the Pt devcies, only the Ag/CrOx/Pt device exhibited a clockwise I-V hysteresis, while no resistance switching was observed in the Ag/CrOy/Pt, Ti/CrOx/Pt and Ti/CrOy/Pt devices. In the FTO devices, the Ag/CrOx/FTO device exhibited a clockwise I-V hysteresis. In contrast, the Ag/CrOy/FTO device and both the Ti/CrOx/FTO, Ti/CrOy/FTO devices presented an anticlockwise I-V hysteresis. The switching direction depends not only on electrode materials but also on the post-annealed treatment, in which the density of grain boundaries is varied. Consequently, the density of grain boundaries controls the kinds of charge carrier involved in the switching process. The as-deposited CrOx films with high density of grain boundaries exhibited the Ag filament paths mediated by electrochemical redox reaction in spite of the bottom electrode materials (Pt and FTO). The post-annealed CrOy films with low density of grain boundaries suppressed the electrochemical redox reaction in the Ag/CrOy/Pt but promoted a

short-range movement of O2- ions through the bottom interface controlled resistance switching in the Ag/CrOy/FTO. The electrochemical redox reactions controlled resistance switching only occur in oxides with a high density of grain boundaries or dislocations.

Key words: Chromium oxide, Resistance switching, grain boundaries, electrochemical redox reactions, Oxygen ion migrations
1,2,*

Corresponding author: Phone: +84 121 790 7700 Fax: +84 8 3835 0831 E-mail: pbthang@hcmus.edu.vn

1. INTRODUCTION Recent research has demonstrated that non-volatile resistance switching resistive random access memory (ReRAM) is a promising alternative to floating gate technology beyond the 32 nm technology node. Oxide-based ReRAM structures exploit the functionality of capacitor structures where the oxide materials, such as perovskite (Cr-doped SrTiO3, Cr-doped SrZrO3, Pr0.7Ca0.3MnO3, etc.) [1-8], chalcogenide materials (GeSbTe) [9], transition metal oxides (TMOs), or binary oxides (NiO, TiO2, CuOx, HfO2, ZrOx, ZnO, Nb2O5, Al2O3, WOx) [10-15] are sandwiched between two metal electrodes. Choosing a material that is compatible to CMOS processes is one of key challenges in current research concerning ReRAM. Among these various materials, TMOs have great advantages in the simple fabrication and in their compatibility to CMOS processes [16]. It has been established that chromium oxide thin films are known to be widely applicable in catalysis, solar thermal energy collectors, and as black matrix films in liquid crystal displays [17,18]. Although the role of the Cr dopant in the resistance switching of SrTiO3 and SrZrO3 has been reported [1,3, 5-8], there are few published papers on switching behaviors of chromium oxide thin films. Chen et al., studied the Pt/Cr2O3/Pt and Pt/Cr2O3/TiN structures and reported that the switching behaviors is observed only in the Pt/Cr2O3/TiN structure and switching mechanism is controlled by oxygen migration through the Cr2O3 and TiN interface [19, 20]. Currently, roles of the top and bottom electrodes on switching behavior of many oxide systems have been overviewed [21,22]. There are two competitive switching models related to the nature of electrode materials, such as oxygen migration in structure with at least one oxide electrode and electrochemical redox reactions in structure with inert and reactive electrodes (Ag, Cu and Pt). It seems that in the above switching models, the kind of electrode materials plays a dominant factor in switching mechanism. However, we think that the density of extended

defects, such as grain boundaries or dislocations, will be more important as the dimensions of switching cell continue to shrink and approach the size of individual grains in oxide films. The post-annealed treatment can control grain sizes and density of grain boundaries in oxides, which significantly affect a movement of charge carriers through oxides. Therefore, in this study, we reported the effect of the electrode materials and the post-annealed treatment on the switching behavior of the Chromium oxide thin films. 2. EXPERIMENTAL PROCEDURES The 100-nm-thick of Ag, Ti and chromium oxide films were fabricated using the DC sputtering technique at room temperature, from metallic Ag, Ti and Cr targets on Fluorine Tin Oxide FTO, Pt substrates. The deposition process of 100-nm-thick chromium oxides was executed under the total pressure PAr+O2 of 7 10-3 Torr, and the mixture ratio of oxygen to argon gas, PO2/PAr+O2, was fixed at 6%. Before the top electrode deposition, the as-deposited CrOx films were annealed at 5000 C in air for 3 hours. The post-annealed films are denoted as CrOy films. During the deposition of the top electrode (Ag, Ti) in an argon environment at 7 10-3 Torr, a mask was used for top electrode patterning. The crystalline phases of the thin films were characterized in -2 mode by D8 Advance (Bruker) X-ray diffractometer (XRD) with Cu K radiation ( = 0.154 nm). The surface morphologies of the films were obtained using scanning electron microscopy (SEM) (JSM-7401F, JEOL). Current-voltage (IV) measurements were carried out using a semiconductor characterization system (Keithley 4200 SCS) and probe station. The voltage profile for the IV measurement was 0 V - (+) Vmax 0 V + (-) Vmax 0 V. The bottom electrode was biased and the top electrode was grounded.

3. RESULTS AND DISCUSSION Figure 1 shows the I-V characteristics of the as-deposited TE/CrOx/Pt devices and the post-annealed TE/CrOy/Pt devices, TE is Ag and Ti electrodes. Only the as-deposited Ag/CrOx/Pt device shows a clockwise I-V hysteresis (Fig. 1a), while the three other devices have no I-V hysteresis behavior (Fig. 1b-1d). With the clockwise I-V switching hysteresis (CWS), the initial high-resistance state (HRS) was changed to a low-resistance state (LRS) as a negative bias (0 -Vmax) applied to the Pt bottom electrode. The device remained in the LRS for subsequently descending, and the LRS was progressively changed to the HRS only by a voltage sweep in the positive voltage region (0 +Vmax). In order to exam the role of bottom electrode in the resistance switching characteristics, we replaced the Pt metallic electrode by the FTO oxide metallic electrode. Figure 2 displays the IV characteristics of the as-deposited TE/CrOx/FTO devices and the post-annealed TE/CrOy/FTO devices, TE is also the Ag and Ti electrodes. All four devices show the bipolar resistance switching characteristics. However, the switching direction changed with top electrode materials and post-annealed treatment. Among the four devices, only the Ag/CrOx/FTO device (Fig. 2a) shows the same clockwise I-V hysteresis as the as-deposited Ag/CrOx/Pt device (Fig. 1a), while the other three devices, Ag/CrOy/FTO, Ti/CrOx/FTO and Ti/CrOy/FTO, follow an anticlockwise I-V hysteresis. For the anticlockwise switching (ACWS) as shown in Fig. 2b-2d, the initial high-resistance state (HRS) was changed to a low-resistance state (LRS) through the application of a positive bias (0 +Vmax) to the FTO bottom electrode. The device remained in the LRS for subsequently descending, and the LRS was progressively changed to the HRS only by a voltage sweep in the negative voltage region (0 -Vmax).

It is highly noted that in the as-deposited CrOx devices with the FTO bottom electrode, replacing the Ag top electrode by the Ti electrode caused the change of switching direction, CWS to ACWS. In addition, the change of switching direction in the Ag devices also was induced by the post-annealed treatment, from the CWS to the ACWS for the as-deposited Ag/CrOx/FTO device to the post-annealed Ag/CrOy/FTO device, respectively. In contrast, the switching direction remains in the Ti devices, both the as-deposited Ti/CrOx/FTO device and the post-annealed Ti/CrOy/FTO device have the same anticlockwise switching hysteresis. For the five switching devices mentioned above, an endurance test has been carried out, as shown in Fig. 3. All devices present a clear reversible switching for over 100 cycles. Based on the nature of electrode, a reactive Ag electrode and an inert Pt electrode along with the clockwise switching (CWS), it seems that the switching mechanism in the as-deposited Ag/CrOx/Pt device is controlled by the electrochemical redox reactions [21,22]. Since both the as-deposited Ag/CrOx/Pt device (Fig. 1a) and the as-deposited Ag/CrOx/FTO device (Fig. 2a) follow the same clockwise switching behavior. Therefore, it can say that the switching mechanism in the as-deposited Ag/CrOx/FTO structure is also controlled by the electrochemical redox reactions. Recently, Waser et al., overviewed the resistance switching phenomena in metal oxides based on electrochemical metallization, in which a combination of an inert electrode and a reactive electrode is the prerequisite condition for the electrochemical redox reactions [21]. However, no resistance switching presents in the post-deposited Ag/CrOy/Pt device although both the Ag top and the Pt bottom electrodes are the reactive and the inert electrodes, respectively. This abnormal behavior will be argued in the following parts. In comparison between the as-deposited Ag/CrOx/Pt device (Fig. 1a) and the as-deposited Ti/CrOx/Pt device (Fig. 1c), since Ag+ and Vo2+ are the positive charges and the resistance switching does not occur

in the as-deposited Ti/CrOx/Pt device, it can be concluded that oxygen vacancies do not contribute into the switching mechanisms. Among the four post-annealed devices (Fig. 1b and 1d, Fig. 2b and 2d), only two devices with the FTO bottom electrode, Ag/CrOy/FTO and Ti/CrOy/FTO, present the ACWS behavior, which is also occurs in the as-deposited Ti/CrOx/FTO device (Fig. 2c). Therefore, the resistance switching mechanism in the as-deposited Ti/CrOx/FTO device and the two post-annealed Ag/CrOy/FTO and Ti/CrOy/FTO devices is probably controlled by the O2- oxygen ions. In order to explain why the post-annealed Ag/CrOy/FTO structure followed the ACWS behavior, while the as-deposited Ag/CrOx/FTO structure followed the CWS behavior, we took the FESEM images of the as-deposited CrOx and post-annealed CrOy films. Figure 4 presents the FESEM images of the as-deposited CrOx surface (Fig. 4a) and the post-annealed CrOy surface (Fig. 4b). Looking at the three positions named as 1, 2 and 3 in the both images, it is clear that the surface morphology seen in the Fig. 4a indicates a high density of irregularly small shaped particles with clear grain boundaries, while the Fig. 4b depicts larger particles with unclear grain boundaries. Based on the switching direction, CWS and ACWS behavior, and FESEM images of the as-deposited film and the post-annealed film, the resistance switching mechanism in these five switching devices can be explained as follows. The resistance switching mechanism of the CWS devices, the as-deposited Ag/CrOx/FTO device and the as-deposited Ag/CrOx/Pt device, is modeled in Figure 5. The Ag+ ions easily drift through the high density of grain boundaries in the as-deposited CrOx films to connect the bottom electrode. As the Ag metallic path forms, the resistance switching is controlled by the electrochemical redox reactions. As mentioned above, the electrochemical redox reactions

controlled resistance switching just occurs in oxides with an inert electrode and a reactive electrode [21,22]. Therefore, if it is true, further detail study on the role FTO electrode in the electrochemical redox reactions is needed. With the three ACWS devices, the as-deposited Ti/CrOx/FTO device, the two postannealed Ag/CrOy/FTO and Ti/CrOy/FTO devices, the resistance switching mechanism is modeled in Figure 6. The resistance switching involves back and forth drift of O2- through the bottom interface. Since the polycrystalline phase of the FTO electrode is suggested to act as the reservoir of defects such as Vo2+ sites and simultaneously O2- ions. The FTO electrode contains enough vacancy sites near the interface, which can easily provide resting sites for the migrating O2- ions. This implies that the FTO electrode can be treated as an O2- ion source. The O2- ions move in short-range from the bulk oxide films through the bottom interface into the FTO bottom electrode during the positive polarity process. This movements of O2- ions is associated with the formation of an oxygen vacancies Vo2+ in the bulk oxide films near the bottom interface, consequently, the set process occurs (HRS to LRS). During the negative polarity process, the O 2ions move back from the FTO bottom electrode to the bulk oxide films and annihilate oxygen vacancies Vo2+ at the interface, resulting in the reset process (LRS to HRS). Based on the electrochemical redox reactions controlled the resistance switching, the metal ions Ag+ start from the top interface and drift through grain boundaries in the bulk oxide layer to connect the Pt bottom electrode. In the post-annealed Ag/CrOy/Pt device, the low density of grain boundaries in the CrOy films suppresses the long-range migration of Ag+ ions to the bottom Pt interface, the Ag metallic path cannot form. In case of the as-deposited Ti/CrOx/Pt device and the post-annealed Ti/CrOy/Pt device, Ti cannot be oxidized to be Ti ions. In addition,

the bottom Pt interface is not the reservoir of defects such as Vo2+ sites and simultaneously O2ions as the FTO electrode. Therefore, the resistance switching does not exist in these devices. Many ReRAM publications mentioned about the role of grain boundaries but it is hard to see the argument on the density of grain boundaries [21,22]. The reduction of grain boundaries in oxide due to the post-annealed treatment can limit the migration of ions. It is suggested that the electrochemical redox reactions controlled resistance switching only occur in oxides with a high density of grain boundaries or dislocations. 4. CONCLUSIONS The resistance switching in chromium oxide thin films strongly depends on the electrode materials (Ag and Ti as top electrode, FTO and Pt as bottom electrode) and the post-annealed treatment. The as-deposited CrOx films in the Ag/CrOx/FTO and Ag/CrOx/Pt devices exhibit the clockwise I-V hysteresis, in which the Ag filament paths mediated by electrochemical redox reactions controls the resistance switching mechanism. The as-deposited Ti/CrOx/FTO, the two post-annealed Ag/CrOy/FTO and Ti/CrOy/FTO devices show the anticlockwise I-V hysteresis. Switching mechanism of the anticlockwise I-V hysteresis is the back and forth drift of O2through the bottom interface under the polarity biases. The as-deposited Ti/CrOx/Pt, the postannealed Ag/CrOy/Pt and Ti/CrOy/Pt devices have no resistance switching characteristics. The change of switching direction is controlled not only by the electrode material but also by the density of grain boundaries in chromium oxide films, which is affected by the post-annealed treatment. The density of grain boundaries controls the movement of charge carriers involved in the resistance switching mechanism, a long-range migration of Ag+ ions in the clockwise switching devices and a short-range movement of O2- ions in the anticlockwise switching

devices. In this study, the key finding is that the electrochemical redox reaction is induced not only by the electrode materials (inert and reactive materials) but also by the density of grain boundaries in host oxide materials. In addition, further detail study on the role FTO electrode in the electrochemical redox reaction is also needed.

ACKNOWLEDGMENTS This work was funded by National Foundation of Science and Technology Development of Vietnam (NAFOSTED 103.02-2012.50).

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Figure captions

Fig. 1.

I-V characteristics of the as-deposited TE/CrOx/Pt devices and the post-annealed TE/CrOy/Pt devices, TE is Ag and Ti electrodes.

Fig. 2.

I-V characteristics of the as-deposited TE/CrOx/FTO devices and the postannealed TE/CrOy/FTO devices, TE is Ag and Ti electrodes.

Fig. 3.

Endurance performance of the switching devices, (a) Ag/CrOx/FTO, (b) Ag/CrOy/FTO, (c) Ti/CrOx/FTO, (d) Ti/CrOy/FTO, and (e) Ag/CrOx/Pt.

Fig. 4.

SEM images of (a) the as-deposited CrOx films and (b) the post-annealed CrOy films.

Fig. 5.

Switching model of the clockwise I-V hysteresis devices: the Ag filament paths mediated by electrochemical redox reaction.

Fig. 6.

Switching model of the anticlockwise I-V hysteresis devices: Negative O2oxygen ions migration under polarity biases.

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Manuscript Click here to download Manuscript: Revised manuscript.doc Click here to view linked References 1 2 3 4 A change of switching direction in chromium oxide thin films 5 6 7 Ngoc Kim Pham1, Do Trung Nguyen1, Bang Tam Thi Dao1, Kieu Hanh Thi Ta1, Vinh Cao 8 9 Tran2, Van Hieu Nguyen3, Sang Sub Kim4, Shinya Maenosono5 and Thang Bach Phan1,2,* 10 11 1 12 Faculty of Materials Science, University of Science, Vietnam National University, Ho Chi 13 Minh City, Vietnam 14 2 Laboratory of Advanced Materials, University of Science, Vietnam National University, Ho 15 Chi Minh City, Vietnam 16 3 17 Faculty of Physics and Physics Engineering, University of Science, Vietnam National 18 University, Ho Chi Minh City, Vietnam 19 4 Department of Materials Science and Engineering, Inha University, Republic of Korea 20 5 Japan Advanced Institute of Science and Technology, Nomi, Ishikawa, Japan 21 22 23 24 Abstract 25 26 We investigated the switching behavior of the as-deposited CrOX and post-annealed CrOy 27 28 29 films with various electrodes (Top electrode: Ag, Ti and Bottom electrode: Pt, FTO). The 30 31 resistance switching strongly depends on electrode materials and post-annealed treatment. In the 32 33 34 Pt devcies, only the Ag/CrOx/Pt device exhibited a clockwise I-V hysteresis, while no resistance 35 36 switching was observed in the Ag/CrOy/Pt, Ti/CrOx/Pt and Ti/CrOy/Pt devices. In the FTO 37 38 39 devices, the Ag/CrOx/FTO device exhibited a clockwise I-V hysteresis. In contrast, the 40 41 Ag/CrOy/FTO device and both the Ti/CrOx/FTO, Ti/CrOy/FTO devices presented an 42 43 anticlockwise I-V hysteresis. The switching direction depends not only on electrode materials 44 45 46 but also on the post-annealed treatment, in which the density of grain boundaries is varied. 47 48 Consequently, the density of grain boundaries controls the kinds of charge carrier involved in the 49 50 51 switching process. The as-deposited CrOx films with high density of grain boundaries exhibited 52 53 the Ag filament paths mediated by electrochemical redox reaction in spite of the bottom 54 55 56 electrode materials (Pt and FTO). The post-annealed CrOy films with low density of grain 57 58 boundaries suppressed the electrochemical redox reaction in the Ag/CrOy/Pt but promoted a 59 60 61 62 63 64 65

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short-range movement of O2- ions through the bottom interface controlled resistance switching in the Ag/CrOy/FTO. The electrochemical redox reactions controlled resistance switching only occur in oxides with a high density of grain boundaries or dislocations.

Key words: Chromium oxide, Resistance switching, grain boundaries, electrochemical redox reactions, Oxygen ion migrations
1,2,*

Corresponding author: Phone: +84 121 790 7700 Fax: +84 8 3835 0831 E-mail: pbthang@hcmus.edu.vn

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1. INTRODUCTION Recent research has demonstrated that non-volatile resistance switching resistive random access memory (ReRAM) is a promising alternative to floating gate technology beyond the 32 nm technology node. Oxide-based ReRAM structures exploit the functionality of capacitor structures where the oxide materials, such as perovskite (Cr-doped SrTiO3, Cr-doped SrZrO3, Pr0.7Ca0.3MnO3, etc.) [1-8], chalcogenide materials (GeSbTe) [9], transition metal oxides (TMOs), or binary oxides (NiO, TiO2, CuOx, HfO2, ZrOx, ZnO, Nb2O5, Al2O3, WOx) [10-15] are sandwiched between two metal electrodes. Choosing a material that is compatible to CMOS processes is one of key challenges in current research concerning ReRAM. Among these various materials, TMOs have great advantages in the simple fabrication and in their compatibility to CMOS processes [16]. It has been established that chromium oxide thin films are known to be widely applicable in catalysis, solar thermal energy collectors, and as black matrix films in liquid crystal displays [17,18]. Although the role of the Cr dopant in the resistance switching of SrTiO3 and SrZrO3 has been reported [1,3, 5-8], there are few published papers on switching behaviors of chromium oxide thin films. Chen et al., studied the Pt/Cr2O3/Pt and Pt/Cr2O3/TiN structures and reported that the switching behaviors is observed only in the Pt/Cr2O3/TiN structure and switching mechanism is controlled by oxygen migration through the Cr2O3 and TiN interface [19, 20]. Currently, roles of the top and bottom electrodes on switching behavior of many oxide systems have been overviewed [21,22]. There are two competitive switching models related to the nature of electrode materials, such as oxygen migration in structure with at least one oxide electrode and electrochemical redox reactions in structure with inert and reactive electrodes (Ag, Cu and Pt). It seems that in the above switching models, the kind of electrode materials plays a dominant factor in switching mechanism. However, we think that the density of extended

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defects, such as grain boundaries or dislocations, will be more important as the dimensions of switching cell continue to shrink and approach the size of individual grains in oxide films. The post-annealed treatment can control grain sizes and density of grain boundaries in oxides, which significantly affect a movement of charge carriers through oxides. Therefore, in this study, we reported the effect of the electrode materials and the post-annealed treatment on the switching behavior of the Chromium oxide thin films. 2. EXPERIMENTAL PROCEDURES The 100-nm-thick of Ag, Ti and chromium oxide films were fabricated using the DC sputtering technique at room temperature, from metallic Ag, Ti and Cr targets on Fluorine Tin Oxide FTO, Pt substrates. The deposition process of 100-nm-thick chromium oxides was executed under the total pressure PAr+O2 of 7 10-3 Torr, and the mixture ratio of oxygen to argon gas, PO2/PAr+O2, was fixed at 6%. Before the top electrode deposition, the as-deposited CrOx films were annealed at 5000 C in air for 3 hours. The post-annealed films are denoted as CrOy films. During the deposition of the top electrode (Ag, Ti) in an argon environment at 7 10-3 Torr, a mask was used for top electrode patterning. The crystalline phases of the thin films were characterized in -2 mode by D8 Advance (Bruker) X-ray diffractometer (XRD) with Cu K radiation ( = 0.154 nm). The surface morphologies of the films were obtained using scanning electron microscopy (SEM) (JSM-7401F, JEOL). Current-voltage (IV) measurements were carried out using a semiconductor characterization system (Keithley 4200 SCS) and probe station. The voltage profile for the IV measurement was 0 V - (+) Vmax 0 V + (-) Vmax 0 V. The bottom electrode was biased and the top electrode was grounded.

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3. RESULTS AND DISCUSSION Figure 1 shows the I-V characteristics of the as-deposited TE/CrOx/Pt devices and the post-annealed TE/CrOy/Pt devices, TE is Ag and Ti electrodes. Only the as-deposited Ag/CrOx/Pt device shows a clockwise I-V hysteresis (Fig. 1a), while the three other devices have no I-V hysteresis behavior (Fig. 1b-1d). With the clockwise I-V switching hysteresis (CWS), the initial high-resistance state (HRS) was changed to a low-resistance state (LRS) as a negative bias (0 -Vmax) applied to the Pt bottom electrode. The device remained in the LRS for subsequently descending, and the LRS was progressively changed to the HRS only by a voltage sweep in the positive voltage region (0 +Vmax). In order to exam the role of bottom electrode in the resistance switching characteristics, we replaced the Pt metallic electrode by the FTO oxide metallic electrode. Figure 2 displays the IV characteristics of the as-deposited TE/CrOx/FTO devices and the post-annealed TE/CrOy/FTO devices, TE is also the Ag and Ti electrodes. All four devices show the bipolar resistance switching characteristics. However, the switching direction changed with top electrode materials and post-annealed treatment. Among the four devices, only the Ag/CrOx/FTO device (Fig. 2a) shows the same clockwise I-V hysteresis as the as-deposited Ag/CrOx/Pt device (Fig. 1a), while the other three devices, Ag/CrOy/FTO, Ti/CrOx/FTO and Ti/CrOy/FTO, follow an anticlockwise I-V hysteresis. For the anticlockwise switching (ACWS) as shown in Fig. 2b-2d, the initial high-resistance state (HRS) was changed to a low-resistance state (LRS) through the application of a positive bias (0 +Vmax) to the FTO bottom electrode. The device remained in the LRS for subsequently descending, and the LRS was progressively changed to the HRS only by a voltage sweep in the negative voltage region (0 -Vmax).

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It is highly noted that in the as-deposited CrOx devices with the FTO bottom electrode, replacing the Ag top electrode by the Ti electrode caused the change of switching direction, CWS to ACWS. In addition, the change of switching direction in the Ag devices also was induced by the post-annealed treatment, from the CWS to the ACWS for the as-deposited Ag/CrOx/FTO device to the post-annealed Ag/CrOy/FTO device, respectively. In contrast, the switching direction remains in the Ti devices, both the as-deposited Ti/CrOx/FTO device and the post-annealed Ti/CrOy/FTO device have the same anticlockwise switching hysteresis. For the five switching devices mentioned above, an endurance test has been carried out, as shown in Fig. 3. All devices present a clear reversible switching for over 100 cycles. Based on the nature of electrode, a reactive Ag electrode and an inert Pt electrode along with the clockwise switching (CWS), it seems that the switching mechanism in the as-deposited Ag/CrOx/Pt device is controlled by the electrochemical redox reactions [21,22]. Since both the as-deposited Ag/CrOx/Pt device (Fig. 1a) and the as-deposited Ag/CrOx/FTO device (Fig. 2a) follow the same clockwise switching behavior. Therefore, it can say that the switching mechanism in the as-deposited Ag/CrOx/FTO structure is also controlled by the electrochemical redox reactions. Recently, Waser et al., overviewed the resistance switching phenomena in metal oxides based on electrochemical metallization, in which a combination of an inert electrode and a reactive electrode is the prerequisite condition for the electrochemical redox reactions [21]. However, no resistance switching presents in the post-deposited Ag/CrOy/Pt device although both the Ag top and the Pt bottom electrodes are the reactive and the inert electrodes, respectively. This abnormal behavior will be argued in the following parts. In comparison between the as-deposited Ag/CrOx/Pt device (Fig. 1a) and the as-deposited Ti/CrOx/Pt device (Fig. 1c), since Ag+ and Vo2+ are the positive charges and the resistance switching does not occur

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in the as-deposited Ti/CrOx/Pt device, it can be concluded that oxygen vacancies do not contribute into the switching mechanisms. Among the four post-annealed devices (Fig. 1b and 1d, Fig. 2b and 2d), only two devices with the FTO bottom electrode, Ag/CrOy/FTO and Ti/CrOy/FTO, present the ACWS behavior, which is also occurs in the as-deposited Ti/CrOx/FTO device (Fig. 2c). Therefore, the resistance switching mechanism in the as-deposited Ti/CrOx/FTO device and the two post-annealed Ag/CrOy/FTO and Ti/CrOy/FTO devices is probably controlled by the O2- oxygen ions. In order to explain why the post-annealed Ag/CrOy/FTO structure followed the ACWS behavior, while the as-deposited Ag/CrOx/FTO structure followed the CWS behavior, we took the FESEM images of the as-deposited CrOx and post-annealed CrOy films. Figure 4 presents the FESEM images of the as-deposited CrOx surface (Fig. 4a) and the post-annealed CrOy surface (Fig. 4b). Looking at the three positions named as 1, 2 and 3 in the both images, it is clear that the surface morphology seen in the Fig. 4a indicates a high density of irregularly small shaped particles with clear grain boundaries, while the Fig. 4b depicts larger particles with unclear grain boundaries. Based on the switching direction, CWS and ACWS behavior, and FESEM images of the as-deposited film and the post-annealed film, the resistance switching mechanism in these five switching devices can be explained as follows. The resistance switching mechanism of the CWS devices, the as-deposited Ag/CrOx/FTO device and the as-deposited Ag/CrOx/Pt device, is modeled in Figure 5. The Ag+ ions easily drift through the high density of grain boundaries in the as-deposited CrOx films to connect the bottom electrode. As the Ag metallic path forms, the resistance switching is controlled by the electrochemical redox reactions. As mentioned above, the electrochemical redox reactions

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controlled resistance switching just occurs in oxides with an inert electrode and a reactive electrode [21,22]. Therefore, if it is true, further detail study on the role FTO electrode in the electrochemical redox reactions is needed. With the three ACWS devices, the as-deposited Ti/CrOx/FTO device, the two postannealed Ag/CrOy/FTO and Ti/CrOy/FTO devices, the resistance switching mechanism is modeled in Figure 6. The resistance switching involves back and forth drift of O2- through the bottom interface. Since the polycrystalline phase of the FTO electrode is suggested to act as the reservoir of defects such as Vo2+ sites and simultaneously O2- ions. The FTO electrode contains enough vacancy sites near the interface, which can easily provide resting sites for the migrating O2- ions. This implies that the FTO electrode can be treated as an O2- ion source. The O2- ions move in short-range from the bulk oxide films through the bottom interface into the FTO bottom electrode during the positive polarity process. This movements of O2- ions is associated with the formation of an oxygen vacancies Vo2+ in the bulk oxide films near the bottom interface, consequently, the set process occurs (HRS to LRS). During the negative polarity process, the O2ions move back from the FTO bottom electrode to the bulk oxide films and annihilate oxygen vacancies Vo2+ at the interface, resulting in the reset process (LRS to HRS). Based on the electrochemical redox reactions controlled the resistance switching, the metal ions Ag+ start from the top interface and drift through grain boundaries in the bulk oxide layer to connect the Pt bottom electrode. In the post-annealed Ag/CrOy/Pt device, the low density of grain boundaries in the CrOy films suppresses the long-range migration of Ag+ ions to the bottom Pt interface, the Ag metallic path cannot form. In case of the as-deposited Ti/CrOx/Pt device and the post-annealed Ti/CrOy/Pt device, Ti cannot be oxidized to be Ti ions. In addition,

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the bottom Pt interface is not the reservoir of defects such as Vo2+ sites and simultaneously O2ions as the FTO electrode. Therefore, the resistance switching does not exist in these devices. Many ReRAM publications mentioned about the role of grain boundaries but it is hard to see the argument on the density of grain boundaries [21,22]. The reduction of grain boundaries in oxide due to the post-annealed treatment can limit the migration of ions. It is suggested that the electrochemical redox reactions controlled resistance switching only occur in oxides with a high density of grain boundaries or dislocations. 4. CONCLUSIONS The resistance switching in chromium oxide thin films strongly depends on the electrode materials (Ag and Ti as top electrode, FTO and Pt as bottom electrode) and the post-annealed treatment. The as-deposited CrOx films in the Ag/CrOx/FTO and Ag/CrOx/Pt devices exhibit the clockwise I-V hysteresis, in which the Ag filament paths mediated by electrochemical redox reactions controls the resistance switching mechanism. The as-deposited Ti/CrOx/FTO, the two post-annealed Ag/CrOy/FTO and Ti/CrOy/FTO devices show the anticlockwise I-V hysteresis. Switching mechanism of the anticlockwise I-V hysteresis is the back and forth drift of O2through the bottom interface under the polarity biases. The as-deposited Ti/CrOx/Pt, the postannealed Ag/CrOy/Pt and Ti/CrOy/Pt devices have no resistance switching characteristics. The change of switching direction is controlled not only by the electrode material but also by the density of grain boundaries in chromium oxide films, which is affected by the post-annealed treatment. The density of grain boundaries controls the movement of charge carriers involved in the resistance switching mechanism, a long-range migration of Ag+ ions in the clockwise switching devices and a short-range movement of O2- ions in the anticlockwise switching

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devices. In this study, the key finding is that the electrochemical redox reaction is induced not only by the electrode materials (inert and reactive materials) but also by the density of grain boundaries in host oxide materials. In addition, further detail study on the role FTO electrode in the electrochemical redox reaction is also needed.

ACKNOWLEDGMENTS This work was funded by National Foundation of Science and Technology Development of Vietnam (NAFOSTED 103.02-2012.50).

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Figure captions

Fig. 1.

I-V characteristics of the as-deposited TE/CrOx/Pt devices and the post-annealed TE/CrOy/Pt devices, TE is Ag and Ti electrodes.

Fig. 2.

I-V characteristics of the as-deposited TE/CrOx/FTO devices and the postannealed TE/CrOy/FTO devices, TE is Ag and Ti electrodes.

Fig. 3.

Endurance performance of the switching devices, (a) Ag/CrOx/FTO, (b) Ag/CrOy/FTO, (c) Ti/CrOx/FTO, (d) Ti/CrOy/FTO, and (e) Ag/CrOx/Pt.

Fig. 4.

SEM images of (a) the as-deposited CrOx films and (b) the post-annealed CrOy films.

Fig. 5.

Switching model of the clockwise I-V hysteresis devices: the Ag filament paths mediated by electrochemical redox reaction.

Fig. 6.

Switching model of the anticlockwise I-V hysteresis devices: Negative O2oxygen ions migration under polarity biases.

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