NANO LETTER LETTERS Piezotronic Nanowire-Based Resistive Switches As programmable Electromechanical memories Wenzhuo Wu and Zhong Lin Wang School of Material Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0245, United States (Supporting Information ABSTRACT: We present the first piezoelectrically modulated resistive switching device based on piezotronic ZnO nanowire (NW), through which the write/ read access of the memory cell is programmed via electrome & wges created at the semicon ductor/metal interface under externally applied deformation by E=1.17% he piezoelectric effect, the resistive switching characteristics of le cell can be modulated in a controlled manner, and the logic levels of the strain stored in the cell can be recorded and read out,which has the potential for integrating with NEMS technology to achieve micro/nanosystems capable for intelli- gent and self-sufficient multidimensional operations KEYWORDS: ZnO nanowire, Piezotronic effect, resistive switching, memory, flexible electron he concept of complementing field effect transistors(FETs) a Zno piezotronic Nw that is in contact with Au electrodes with two-terminal hysteretic resistive switches has recently fabricated by lithography(Methods)on a flexible PET substrate attracted a great interest in implementing and scaling novel( from DuPont, thickness 1.25 mm). The two electrodes are nonvolatile resistive memories for ultrahigh density mem- labeled as the drain(D)and source(S)electrodes of the PRM ory storage, and logic applications",with characteristics such cell. The single-crystalline ZnO NWs used in PRM devices were as high-density, low cost, fast write/re accessit speed and synthesized via a physical vapor deposition process with long endurance/retention time. Notably, previous existing diameters of 500 nm and lengths of 50 um( Figure lal inset nonvolatile resistive memories are all based on electrically The PRM cells were then treated in oxygen plasma for 30 min switchable resistance change by means of formation of con-(Methods )before further characterization. Once the substrate is ductive filaments, charge-transfer-induced conformational deformed, a pure tensile/compressive strain is created in the Nw hange, electrochemical or field-assisted drift since the mechanical behavior of the entire cell structure is diffusion of charged ions 4,6, 4 in various oxides and ionic determined by the substrate( Figure 1b).All of the I-V curves onductors. These devices are electrically programmed presented was measured at a sweeping frequency of 0.1 Hz at and they are not suitable for direct interfacing with actuation/ room temperature unless otherwise noted. Several key features triggering other than electrical inputs. For applications such as can be observed from the representative hysteretic I-V curve human-computer interfacing, sensing/actuating in nanorobo. obtained(Methods)for a single ZnO PRM cell(treated with tics,and smart MEMS/NEMS, . y a direct interfacing of 30 min oxygen plasma) without applying an external strain electronics with mechanical actions is required. Here we pre-(Figure la1). First, as the bias voltage increased from 0 sent the first piezoelectrically modulated resistive switching 10 V, the output current of the PRM cell increased abruptly device based on piezotronic ZnO nanowire(NW), through at 5.73 V, which is defined as the threshold point Vth,s.An which the write/read access of the memory cell is programmed abrupt transition and switching from high-resistance state(HRS) via electromechanical modulation. Adjusted by the strain to low-resistance state(LRS)occurred at Vth.s. Second, as the induced polarization charges created at the semiconductor/ voltage was subsequently decreased toward negative values, metal interface under externally applied deformation by the the PRM cell switched back to the high-resistance OFF state. piezoelectric effect, the resistive switching characteristics of the Third, when the bias voltage exceeded certain negative values cell can be modulated in a controlled manner, and the logic (Vth, D=-5Vin Figure la1), the PRM cell was turned to the ON levels of the strain stored in the cell can be recorded and read state again and subsequent decrease in magnitude of the negative out, which has the potential for integrating with NEMS bias voltage switched the PRM cell back to the OFF state. This technology to achieve micro/nanosystems capable for intelli gent and self-sufficient multidimensional operations. Received: March 30, 2011 The basic structure of the piezoelectrically modulated resi Revised: June 1, 2011 memory(PRM)is shown in Figure lal(inset), which consists of Published: June 22,2011 ACS Publications o 2011 American Chemical society 2779 d. dolora/0101/h201074a| Nano Lett.2011.112779-2785
Published: June 22, 2011 r2011 American Chemical Society 2779 dx.doi.org/10.1021/nl201074a | Nano Lett. 2011, 11, 2779–2785 LETTER pubs.acs.org/NanoLett Piezotronic Nanowire-Based Resistive Switches As Programmable Electromechanical Memories Wenzhuo Wu and Zhong Lin Wang* School of Material Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0245, United States bS Supporting Information The concept of complementing field effect transistors (FETs) with two-terminal hysteretic resistive switches has recently attracted a great interest in implementing and scaling novel nonvolatile resistive memories15 for ultrahigh density memory storage6,7 and logic applications8,9 with characteristics such as high-density, low cost, fast write/read accessing speed and long endurance/retention time.10 Notably, previous existing nonvolatile resistive memories are all based on electrically switchable resistance change10 by means of formation of conductive filaments,5,11 charge-transfer-induced conformational change,12 electrochemical processes,13 or field-assisted drift/ diffusion of charged ions3,4,6,14 in various oxides and ionic conductors.1517 These devices are electrically programmed and they are not suitable for direct interfacing with actuation/ triggering other than electrical inputs. For applications such as human-computer interfacing, sensing/actuating in nanorobotics, and smart MEMS/NEMS,18,19 a direct interfacing of electronics with mechanical actions is required. Here we present the first piezoelectrically modulated resistive switching device based on piezotronic ZnO nanowire (NW), through which the write/read access of the memory cell is programmed via electromechanical modulation. Adjusted by the straininduced polarization charges created at the semiconductor/ metal interface under externally applied deformation by the piezoelectric effect, the resistive switching characteristics of the cell can be modulated in a controlled manner, and the logic levels of the strain stored in the cell can be recorded and read out, which has the potential for integrating with NEMS technology to achieve micro/nanosystems capable for intelligent and self-sufficient multidimensional operations.18,20 The basic structure of the piezoelectrically modulated resistive memory (PRM) is shown in Figure 1a1 (inset), which consists of a ZnO piezotronic NW that is in contact with Au electrodes fabricated by lithography (Methods) on a flexible PET substrate (from DuPont, thickness ∼1.25 mm). The two electrodes are labeled as the drain (D) and source (S) electrodes of the PRM cell. The single-crystalline ZnO NWs used in PRM devices were synthesized via a physical vapor deposition process21 with diameters of 500 nm and lengths of 50 μm (Figure 1a1 inset). The PRM cells were then treated in oxygen plasma for 30 min (Methods) before further characterization. Once the substrate is deformed, a pure tensile/compressive strain is created in the NW since the mechanical behavior of the entire cell structure is determined by the substrate (Figure 1b). All of the IV curves presented was measured at a sweeping frequency of 0.1 Hz at room temperature unless otherwise noted. Several key features can be observed from the representative hysteretic IV curve obtained (Methods) for a single ZnO PRM cell (treated with 30 min oxygen plasma) without applying an external strain (Figure 1a1). First, as the bias voltage increased from 0 to 10 V, the output current of the PRM cell increased abruptly at 5.73 V, which is defined as the threshold point Vth,S. An abrupt transition and switching from high-resistance state (HRS) to low-resistance state (LRS) occurred at Vth,S. Second, as the voltage was subsequently decreased toward negative values, the PRM cell switched back to the high-resistance OFF state. Third, when the bias voltage exceeded certain negative values (Vth,D = 5 V in Figure 1a1), the PRM cell was turned to the ON state again and subsequent decrease in magnitude of the negative bias voltage switched the PRM cell back to the OFF state. This Received: March 30, 2011 Revised: June 1, 2011 ABSTRACT: We present the first piezoelectrically modulated resistive switching device based on piezotronic ZnO nanowire (NW), through which the write/read access of the memory cell is programmed via electromechanical modulation. Adjusted by the strain-induced polarization charges created at the semiconductor/metal interface under externally applied deformation by the piezoelectric effect, the resistive switching characteristics of the cell can be modulated in a controlled manner, and the logic levels of the strain stored in the cell can be recorded and read out, which has the potential for integrating with NEMS technology to achieve micro/nanosystems capable for intelligent and self-sufficient multidimensional operations. KEYWORDS: ZnO nanowire, Piezotronic effect, resistive switching, memory, flexible electronics
Nano Letters LETTER a2 30-min Oxygen plasm 0.4 20-min Oxygen plas 0.015 10-min Oxygen plasma 55-2.50 Vos (v) Vos (v) vos (v Figure 1. Effects of oxygen plasma treatment on electrical properties of ZnO PRM cells. (a)(al-a3)I-Vcharacteristics of ZnO PRM cells after 30, 20, and 10 min oxygen plasma treatment, respectively. The sweeping frequency is 0. 1 Hz (al inset)Atomic force microscopy image of one ZnO PRM cell. (b)Optical image of the large-scale as-fabricated PRM cells after printing transfer of ZnO NWs and lithography patterning of metal electrodes. (c) Statistical distributions of the Vahs and Vth, p peaks for PRM cells with different periods of oxygen plasma treatment. Red, blue, and black lines are for PRM cells with 30, 20, and 10 min oxygen plasma treatment, respectively. hysteretic sweeping sequence is indicated by arrowheads in and current range of the I-V curves for these samples. with Figure lal. The overall resistive switching observed for a single increasing the period of time of treatment with oxygen plasma, PRM cell is unipolar since the switching sequence is independent the threshold voltage of the PRM cell increased accordingly and of the polarity of the bias voltage(Figure lal), which can be increased hysteresis was also observed in the I-V curve understood by the symmetry in structures of the PRM cells.(Figure lal-a3). If the PRM cell was treated with argon Current rectification, which can minimize cross talk between plasma, the threshold voltage decreased and the conductance individual memory cells and solve the sneak path problem in increased with respect to the pristine one, and finally the observed, suggesting that the PRM cell can be modeled as two mation Figure S2). The observed variations in the I-V curves back-to-back Schottky barriers connected in series with the Nw of the PRM cells, which were fabricated using the ZnO NWs in the metal-semiconductor-metal(M-S-M) configuration synthesized under the same experimental condition, are be and the LRS state of the cell is dictated by Schottky-like transport cause oxygen vacancies are capable of influencing the Schottky at one of the Au/ZnO interfaces, which will be discussed contacts between ZnO and metal electrodes. The synthesis Noticeably,the I-V characteristic of the PRM cell is NWs used in the reported piezotronic devices 19,26/no details later condition(argon atmosphere at high temperature )for pristine PRM cells tended to create a large amount of oxyger ZnO NW based piezotronic devices, I9(orange line in St vacancies in the ZnO NWs, which possibly induced the porting Information Figure S1), which is proposed to result observed lower threshold voltages of 0.5-0.7 v due to the from the oxygen-plasma treatment prior to the measurement, as high density of oxygen vacancies near the metal-ZnO interface elaborated in the following. In order to investigate the effect of and pinning of the ZnO Fermi level close to the Vo. defect retreatment on the performance of the PRM cell, six groups of level. If, however, the pristine ZnO NWs were treated with PRM cells were electrically characterized after different plasma additional oxygen plasma for a prolonged period of time, the pretreatments(Methods ). The first three groups were treate xygen vacancies cou ith oxygen plasma for 30, 20, and 10 min, respectively and the which contributed to the observed increase in threshold vol- typical I-V curves are shown in Figure lal-a3. The rest of the tages as well as the hysteresis loop of the I-V curves, as shown three groups of PRM cells were treated with argon plasma for in Figure la1-a3 30, 20, and 10 min and their individual typical I-V curves are The capability in designing the switching characteristics of the shown in Supporting Information Figure Sl, respectively. The PRM cell in a controllable manner is further confirmed by the I-V curve of the PRM cell directly assembled without pre- sharp and distinct statistical distributions of the Vth.s and ve treatment(pristine PRM cell)is also plotted in Supporting peaks for PRM cells with different periods of oxygen plasma Information Figure SI for comparison. It can be seen clearly treatment with Vh. s=6.15+0.39Vand Vth D=-512+0.03V, that significant changes occur in the shape, threshold voltage Vth,s=3.18+ 0. 20 V and Vth, D=-267+ 0.22 V as well as 2780 dx. dolora/0.102/n201074a| Nano Lert.2011l27792785
2780 dx.doi.org/10.1021/nl201074a |Nano Lett. 2011, 11, 2779–2785 Nano Letters LETTER hysteretic sweeping sequence is indicated by arrowheads in Figure 1a1. The overall resistive switching observed for a single PRM cell is unipolar since the switching sequence is independent of the polarity of the bias voltage10 (Figure 1a1), which can be understood by the symmetry in structures of the PRM cells. Current rectification, which can minimize cross talk between individual memory cells and solve the sneak path problem in potential large-scale ultrahigh density applications,22,23 was also observed, suggesting that the PRM cell can be modeled as two back-to-back Schottky barriers connected in series with the NW in the metalsemiconductormetal (MSM) configuration and the LRS state of the cell is dictated by Schottky-like transport at one of the Au/ZnO interfaces, which will be discussed in details later. Noticeably, the IV characteristic of the PRM cell is significantly different from those observed in previous single ZnO NW based piezotronic devices18,19 (orange line in Supporting Information Figure S1), which is proposed to result from the oxygen-plasma treatment prior to the measurement, as elaborated in the following. In order to investigate the effect of pretreatment on the performance of the PRM cell, six groups of PRM cells were electrically characterized after different plasma pretreatments (Methods). The first three groups were treated with oxygen plasma for 30, 20, and 10 min, respectively and the typical IV curves are shown in Figure 1a1a3. The rest of the three groups of PRM cells were treated with argon plasma for 30, 20, and 10 min and their individual typical IV curves are shown in Supporting Information Figure S1, respectively. The IV curve of the PRM cell directly assembled without pretreatment (pristine PRM cell) is also plotted in Supporting Information Figure S1 for comparison. It can be seen clearly that significant changes occur in the shape, threshold voltage and current range of the IV curves for these samples. With increasing the period of time of treatment with oxygen plasma, the threshold voltage of the PRM cell increased accordingly and increased hysteresis was also observed in the IV curve (Figure 1a1a3). If the PRM cell was treated with argon plasma, the threshold voltage decreased and the conductance increased with respect to the pristine one, and finally the rectification disappeared in the IV curve (Supporting Information Figure S2). The observed variations in the IV curves of the PRM cells, which were fabricated using the ZnO NWs synthesized under the same experimental condition, are because oxygen vacancies are capable of influencing the Schottky contacts between ZnO and metal electrodes.24 The synthesis condition (argon atmosphere at high temperature21) for ZnO NWs used in the reported piezotronic devices19,26,32 and pristine PRM cells tended to create a large amount of oxygen vacancies in the ZnO NWs, which possibly induced the observed lower threshold voltages of 0.50.7 V due to the high density of oxygen vacancies near the metalZnO interface and pinning of the ZnO Fermi level close to the Vo3 3 defect level.24 If, however, the pristine ZnO NWs were treated with additional oxygen plasma for a prolonged period of time, the concentration of oxygen vacancies could be largely reduced, which contributed to the observed increase in threshold voltages as well as the hysteresis loop of the IV curves, as shown in Figure 1a1a3. The capability in designing the switching characteristics of the PRM cell in a controllable manner is further confirmed by the sharp and distinct statistical distributions of the Vth,S and Vth,D peaks for PRM cells with different periods of oxygen plasma treatment with Vth,S = 6.15 ( 0.39 V and Vth,D = 5.12 ( 0.03 V, Vth,S = 3.18 ( 0.20 V and Vth,D = 2.67 ( 0.22 V as well as Figure 1. Effects of oxygen plasma treatment on electrical properties of ZnO PRM cells. (a) (a1a3)IV characteristics of ZnO PRM cells after 30, 20, and 10 min oxygen plasma treatment, respectively. The sweeping frequency is 0.1 Hz. (a1 inset) Atomic force microscopy image of one ZnO PRM cell. (b) Optical image of the large-scale as-fabricated PRM cells after printing transfer of ZnO NWs and lithography patterning of metal electrodes. (c) Statistical distributions of the Vth,S and Vth,D peaks for PRM cells with different periods of oxygen plasma treatment. Red, blue, and black lines are for PRM cells with 30, 20, and 10 min oxygen plasma treatment, respectively
Nano Letters LETTER 200K 90K Figure 2. Temperature-dependent I-V measurements of PRM cells at ondition.(a)I-Vcharacteristics of ZnO PRM cells at 300,200, and 90K, respectively. The sweeping frequency is 0.1 Hz ( Inset)Schematic bias condition of the PRM cell when Schottky barrier at source side reversely biased. (b) Dependence of threshold voltages on temperat (in black )and Vehp (in red)increased in magnitudes almost linearly with the decreasing temperature. The hysteresis loop increased with the g temperature. Vhs=0.74+0.51 Vand Vuh. D=-068+0. 20 V for PRM cells of the current for PRM cell at very large bias(V=+10 V)were with treatment for 30, 20, and 10 min, respectively, by oxygen almost constant and independent of temperature( Figure 2a plasma( Figure 1c). The predictable electrical properties of these and Supporting Information Figure $3) nO NWs with controlled treatment process enable the repro- Although the nature of resistive switching and related charge ducible assembly of NW structures at large quantity for further transport process at microscale in M-S-M structures is still applications. The slight difference and asymmetry observed under debate, the movement of charged species that mod- between Vths and Vth. D within each group of PRM cells is ulates the current flow seems to be a dominant mechanism. 3 possibly induced by the nonuniform geometry of the Zno Drift/diffusion of defects such as positively charged oxyge NW, as indicated by the AFM image inset in Figure lal. It is vacancies under applied electrical field has been suggested to well-known that the Schottky barrier height(SBH) induced at change the electronic barrier at the metal/semiconductor inter- metal/semiconductor interface can be affected by factors such as face, which possibly results in the observed resistive switching the geometry and effective areas of the contact. Moreover, the Oxygen vacancies are known to be one of the predominant ionic interface/ surface states can also shift the SBH. In addition, the defects in ZnO and can influence the Schottky contacts morphology of the ZnO NWs has been monitored before and between ZnO and metal electrodes. On the basis of the after the plasma treatment and bvious variations are observed experimental results, (Supporting Information Figure S3). Notably, as can be seen from transport of charged dopants and electrons under applied electric the semilogarithmic plots of the data presented in Figure lal-a3 field is adopted and modified to explain the hysteretic switchi Supporting Information Figure S9), the PRM cells gradually lose behavior of the PRM cell without external deformation applied their nonvolatility as the period of oxygen plasma treatment increases. The drift /diffusion of the oxygen vacancies toward the interface The nonvolatility of PRM cells with 10 min oxygen plasma treatment effectively reduces the local SBH, while the drift/diffusion of can be observed by sweeping only at positive voltages(0-1 V) and vacancies away from the interface increases the SBH. the high-conductance state is not lost at small bias in subsequent The hysteretic switching sequences obtained at different sweeps(for 20 cycles), which indicates this kind of cells do have temperatures can be characterized by four typical regions: (1) the memory effect(Supporting Information Figure S10). The PRM O-A(2)A-B-O(3)O-C and(4)C-D-0, as labeled in cells with 30 min oxygen plasma, however, did not show the same Figure 2a as an example For easy discussion, the bias is set to be nonvolatility in current experiment. applied on the drain(d)electrode with respect to the source Temperature-dependent I-V measurements(Methods (S)side(Inset sketch in Figure 2a). The overall macroscopic were performed to obtain further insight into the switching resistance of the PRM cell is RPRM=Rs RNw +Rp, where Rs mechanism of the PRM cell without applying external deforma- and Rp are the electrical resistances contributed by Schottky tions.Representative result acquired from an Au/ZnO-NW/Au barriers at source and drain sides that may vary during the PRM cell clearly demonstrates the variations with temperature experiment and RNw is the intrinsic resistance of the ZnO Nw. in the hysteretic I-V switching characteristics(Figure 2a). The It has been previously demonstrated that for semiconductor hreshold turn-on voltage for the reversely biased Schottky NWbased M-S-Mstructure, the I-V transport characteristic barrier of the PRM cell increased almost linearly with decreas is normally dictated by the reversely biased Schottky barrier are(Fi b), and the hysteresis loop inc As the bias volt with the decreasing temperature( Figure 2a). The magnitudes drain side forward-biased, the voltage drops mainly at the 2781
2781 dx.doi.org/10.1021/nl201074a |Nano Lett. 2011, 11, 2779–2785 Nano Letters LETTER Vth,S = 0.74 ( 0.51 V and Vth,D = 0.68 ( 0.20 V for PRM cells with treatment for 30, 20, and 10 min, respectively, by oxygen plasma (Figure 1c). The predictable electrical properties of these ZnO NWs with controlled treatment process enable the reproducible assembly of NW structures at large quantity for further applications. The slight difference and asymmetry observed between Vth,S and Vth,D within each group of PRM cells is possibly induced by the nonuniform geometry of the ZnO NW, as indicated by the AFM image inset in Figure 1a1. It is well-known that the Schottky barrier height (SBH) induced at metal/semiconductor interface can be affected by factors such as the geometry and effective areas of the contact.25 Moreover, the interface/surface states can also shift the SBH.25 In addition, the morphology of the ZnO NWs has been monitored before and after the plasma treatment and no obvious variations are observed (Supporting Information Figure S3). Notably, as can be seen from the semilogarithmic plots of the data presented in Figure 1a1a3 (Supporting Information Figure S9), the PRM cells gradually lose their nonvolatility asthe period of oxygen plasmatreatment increases. The nonvolatility of PRM cells with 10 min oxygen plasma treatment can be observed by sweeping only at positive voltages (01 V) and the high-conductance state is not lost at small bias in subsequent sweeps (for 20 cycles), which indicates this kind of cells do have the memory effect (Supporting Information Figure S10). The PRM cells with 30 min oxygen plasma, however, did not show the same nonvolatility in current experiment. Temperature-dependent IV measurements (Methods) were performed to obtain further insight into the switching mechanism of the PRM cell without applying external deformations. Representative resultacquired from an Au/ZnO-NW/Au PRM cell clearly demonstrates the variations with temperature in the hysteretic IV switching characteristics (Figure 2a). The threshold turn-on voltage for the reversely biased Schottky barrier of the PRM cell increased almost linearly with decreasing temperature (Figure 2b), and the hysteresis loop increased with the decreasing temperature (Figure 2a). The magnitudes of the current for PRM cell at very large bias (V = (10 V) were almost constant and independent of temperature (Figure 2a and Supporting Information Figure S3). Although the nature of resistive switching and related charge transport process at microscale in MSM structures is still under debate,15 the movement of charged species that modulates the current flow seems to be a dominant mechanism.3 Drift/diffusion of defects such as positively charged oxygen vacancies under applied electrical field has been suggested to change the electronic barrier at the metal/semiconductor interface, which possibly results in the observed resistive switching.4 Oxygen vacancies are known to be one of the predominant ionic defects in ZnO26 and can influence the Schottky contacts between ZnO and metal electrodes.24 On the basis of the experimental results, a general model based on the coupled transport of charged dopants and electrons under applied electric field4 is adopted and modified to explain the hysteretic switching behavior of the PRM cell without external deformation applied. The drift/diffusion of the oxygen vacancies toward the interface effectively reduces the local SBH, while the drift/diffusion of vacancies away from the interface increases the SBH. The hysteretic switching sequences obtained at different temperatures can be characterized by four typical regions: (1) OA (2) ABO (3) OC and (4) CDO, as labeled in Figure 2a as an example. For easy discussion, the bias is set to be applied on the drain (D) electrode with respect to the source (S) side (Inset sketch in Figure 2a). The overall macroscopic resistance of the PRM cell is RPRM = RS + RNW +RD, where RS and RD are the electrical resistances contributed by Schottky barriers at source and drain sides that may vary during the experiment and RNW is the intrinsic resistance of the ZnO NW. It has been previously demonstrated that for semiconductor NW based MSM structure, the IV transport characteristic is normally dictated by the reversely biased Schottky barrier side.19,27,28 As the bias voltage sweeps from O to A with the drain side forward-biased, the voltage drops mainly at the Figure 2. Temperature-dependent IV measurements of PRM cells at strain-free condition. (a)IV characteristics of ZnO PRM cells at 300, 200, and 90 K, respectively. The sweeping frequency is 0.1 Hz. (Inset) Schematic showing the bias condition of the PRM cell when Schottky barrier at source side is reversely biased. (b) Dependence of threshold voltages on temperature. Both Vth,S (in black) and Vth,D (in red) increased in magnitudes almost linearly with the decreasing temperature. The hysteresis loop increased with the decreasing temperature
Nano Letters LETTER g=1.17% E=0% E=0.76% -1.6 Strain ( %) Drain Source F thee ctively. (b)Dependence of threshold volans of PRM cell. (a)I-V characteristics of ZnO PRM cells under tensile, zero, and compressive strains Figure 3. Stain-modulated hysteret the PRM cell, while the width of the hrS window remains almost constant for different strain values. (c) Schematic of band-diagram of PRM cell under sile strain. (cl)Schottky barrier at drain side is forward biased. ( c2)Schottky barrier at drain side is reversely biased. Red solid lines represent band- diagrams after tensile strain is applied. Black dashed lines represent band-diagrams under strain free condition. The color gradient represents the distribution of piezopotential field. reversely biased source side. The total resistance of PRM cell is It can also be observed that both Vth.s and Vuh. D and hence the RPRM"Rs(with Rs RNw, RD), which is the HRS state. The width of the HRS window increased as the temperature de- lower voltage at the source side attracts oxygen vacancies creased from 350 to 90 K( Figure 2b and Supporting Information toward the interface to modify the contact barrier at the source. Figure S3). Qualitatively, this can be understood since the drift/ The switching from HRS to LRS state occurs at a larger bias diffusion of the charged ions/dopants and electrons are thermally beyond point A, in corresponding to a largely reduced SBH at activated processes Employing the rigid point ion model derived the source side. When the bias voltage sweeps from point A to by Mott and Gurney, the diffusion coefficient of oxygen point O through point B, the In(I)-V curve for region B-o vacancy is given by D=Do exp(-E/kT)and the drift velocity empty circle in Supporting Information Figure S4), shows that is v= af exp(-E/kT)sinh(qE,/2kT), where E, is the activation In(relates to Vi/4, as confirmed by the numerical fitting curve energy, k is the Boltzmann constant, a is the effective hopping (purple line in Supporting Information Figure $4). This distance for the ion to hop between potential wells, and f is the indicates that the thermionic emission-diffusion model dom- attempt-to-escape frequency. At decreased temperatures, larger ates the transport at the reverse-biased source barrier. An bias is required to attract sufficient oxygen vacancies toward the accelerated diffusion of the oxygen vacancies toward the source respective reversely biased barrier to switch the PRM cell from side at a large applied voltage and their accumulation are hRS to lRS state within the time scale in the experimental setup considered as the cause of the hysteresis observed in I-Vcurve. (the sweeping frequency of the bias signal was 0. 1 Hz).The As the applied bias switches the polarity from point o to point characteristic of the PRM cells at different sweeping rates has C, the source side is now forward-biased and the bias voltage drops also been investigated primarily for two frequencies(0.1 and mainly at the reversely biased drain side with the total resistance of 0.01 Hz). It is interesting to notice that the hysteresis loop PRM cell RPRM N Ro, which is the new HRS state Oxygen shrinks for larger sweeping frequency, while no significant acancies near the drain side are attracted toward and accumulated variations can be observed for the turn-on threshold voltage at the reversely biased drain barrier to modify the interface contact,(Supporting Information Figure S8). hile oxygen vacancies previously piled up at the source side are The external mechanical perturbation-induced strain(E,)acts drifting away. Similar to the case in region O-A, the switch from as the programming input for modulating the hysteretic I-V hRS to lRS state occurs only after a larger bias beyond point C is characteristics of the PRM cell. A positive/negative strain is created applied. When the bias voltage sweeps from point C to point when the ZnO NW is stretched/compressed(see Supporting through point D, the In (I)-V curve for region D-o(empty Information for calculation of the strain in the PRM cell) triangle in Supporting Information Figure $4)can again be Interesting phenomena was observed when a PRM cell experi numerically fitted using the In(nw v/ relationship(blue line enced straining(Figure 3a). When the PRM cell was tensile in Supporting Information Figure S4), indicates che transport at toward lower voltage side by 1. 49 V(red line in Figure 3a);when ing that the ther stretched(E= 1.17%), the hysteretic switching curve shifted mionic emission-diffusion model also dominates the reverse-biased drain barrier the cell was compressively deformed(E=-0.76%), the hysteretic 2782 dx. dolora/0.102/n201074a| Nano Lert.2011l27792785
2782 dx.doi.org/10.1021/nl201074a |Nano Lett. 2011, 11, 2779–2785 Nano Letters LETTER reversely biased source side. The total resistance of PRM cell is RPRM ∼ RS (with RS . RNW, RD), which is the HRS state. The lower voltage at the source side attracts oxygen vacancies toward the interface to modify the contact barrier at the source. The switching from HRS to LRS state occurs at a larger bias beyond point A, in corresponding to a largely reduced SBH at the source side. When the bias voltage sweeps from point A to point O through point B, the ln(I)V curve for region BO (empty circle in Supporting Information Figure S4), shows that ln(I) relates to V1/4, as confirmed by the numerical fitting curve (purple line in Supporting Information Figure S4). This indicates that the thermionic emission-diffusion model dominates the transport at the reverse-biased source barrier.29 An accelerated diffusion of the oxygen vacancies toward the source side at a large applied voltage and their accumulation are considered as the cause of the hysteresis observed in IV curve. As the applied bias switches the polarity from point O to point C, the source side is now forward-biased and the bias voltage drops mainly at the reversely biased drain side with the total resistance of PRM cell RPRM ∼ RD, which is the new HRS state. Oxygen vacancies near the drain side are attracted toward and accumulated at the reversely biased drain barrier to modify the interface contact, while oxygen vacancies previously piled up at the source side are drifting away. Similar to the case in region OA, the switch from HRS to LRS state occurs only after a larger bias beyond point C is applied. When the bias voltage sweeps from point C to point O through point D, the ln(I)V curve for region DO (empty triangle in Supporting Information Figure S4) can again be numerically fitted using the ln(I) ∼ V1/4 relationship (blue line in Supporting Information Figure S4), indicating that the thermionic emissiondiffusion model also dominates the transport at the reverse-biased drain barrier. It can also be observed that both Vth,S and Vth,D and hence the width of the HRS window increased as the temperature decreased from 350 to 90 K (Figure 2b and Supporting Information Figure S3). Qualitatively, this can be understood since the drift/ diffusion of the charged ions/dopants and electrons are thermally activated processes. Employing the rigid point ion model derived by Mott and Gurney,30 the diffusion coefficient of oxygen vacancy is given by D = D0 3 exp(Ea/kT) and the drift velocity is v = af exp(Ea/kT)sinh(qEa/2kT), where Ea is the activation energy, k is the Boltzmann constant, a is the effective hopping distance for the ion to hop between potential wells, and f is the attempt-to-escape frequency. At decreased temperatures, larger bias is required to attract sufficient oxygen vacancies toward the respective reversely biased barrier to switch the PRM cell from HRS to LRS state within the time scale in the experimental setup (the sweeping frequency of the bias signal was 0.1 Hz). The characteristic of the PRM cells at different sweeping rates has also been investigated primarily for two frequencies (0.1 and 0.01 Hz). It is interesting to notice that the hysteresis loop shrinks for larger sweeping frequency, while no significant variations can be observed for the turn-on threshold voltage (Supporting Information Figure S8). The external mechanical perturbation-induced strain (εg) acts as the programming input for modulating the hysteretic IV characteristics ofthe PRM cell. A positive/negative strain is created when the ZnO NW is stretched/compressed (see Supporting Information for calculation of the strain in the PRM cell). Interesting phenomena was observed when a PRM cell experienced straining (Figure 3a). When the PRM cell was tensile stretched (ε = 1.17%), the hysteretic switching curve shifted toward lower voltage side by 1.49 V (red line in Figure 3a); when the cell was compressively deformed (ε = 0.76%), the hysteretic Figure 3. Stain-modulated hysteretic switching of PRM cell. (a) IV characteristics of ZnO PRM cells under tensile, zero, and compressive strains respectively. (b) Dependence of threshold voltages on applied strains. Both Vth,S (in red) and Vth,D (in black) almost linearly depends on strain applied to the PRM cell, while the width of the HRS window remains almost constant for different strain values. (c) Schematic of band-diagram of PRM cell under tensile strain. (c1) Schottky barrier at drain side is forward biased. (c2) Schottky barrier at drain side is reversely biased. Red solid lines represent banddiagrams after tensile strain is applied. Black dashed lines represent band-diagrams under strain free condition. The color gradient represents the distribution of piezopotential field
Nano Letters LETTER o Fhhh 且 B cele 8=0 0 C cell: a=-07B% 之 Figure 4. Write/read access of PRM cell as an electromechanical memory. A pulse train consisting of several write/read/erase pulses was applied to the PRM cell to record and read out the logic levels of the"stored"strain in the cell. Each write/erase pulse was followed by a read pulse with positive or negative polarity respectively. The following voltage amplitudes were applied: 6.44V (write 1), 1.sv(read 1),-535v(erase 1),-15V(read 2),5.37 (erase 2), and-6.42 V(write 2). Short current spikes occur in the output reading current with the write/erase pulses if the resistance states(HRs LRS)change in the PRM cell. switching curve shifted toward higher voltage side by 1.18 V (blue modified by shifting the local Fermi level. The change in SBH line in Figure 2a).VchS*, Vth.so, Vh s-and Vth, D+, Vuh, Do, Vt, D-are induced by piezoelectric polarization is given approximately by e threshold switching voltages for the PRM cell with tensile, ApB=polD(1+1/(2gswa)), where opol is the volume ro,and compressive strains, respectively. The same hystereti density of the polarization charge and directly related to the witching curves can then be plotted in a semilogarithmic current piezoelectric polarization P vector, D is the two-dimensional scale to illustrate and highlight the characteristics of the curves density of interface states at the Fermi level at the Schottky (Supporting Information Figure S5). The ratios of conductance barrier, as is the two-dimensional screening parameter, and wa between LRS and HRS for the PRM cell remain steady at high is the width of the depletion layer. Thus the mechanical strain values(10)under different strains( Supporting Information an effectively change the local contact characteristics as well as Figure S6), demonstrating the stable performance of the cell and e charge carrier transport process. On the basis of the above discussions, the modulation effect of strain on the hystereti operations. The intrinsic rectifying behavior of the PRM cell may switching behavior of the PRM cell, as shown in Figure 3a, b, solve the sneak path problem as well as reduce the static power can then be understood and explained using the band-diagrar consumption,which allows for construction of large passive of the working device(Figure 3c). If the PRM cell is under esistive-switching device arrays. The changes in threshold switching tensile strain with the Schottky barrier at drain side being ages of the PRM cell with different strains have been plotted in forward-biased(V>0 in Figure 3a), the positive piezoelectric Figure 3b. It can be seen that the change in both the Vuhs and Vad potential resulting from the positive strain-induced polariza almost linearly depends on strain applied to the PRM cell, while the tion charges reduced the SBH at the reverse-biased source width of the HRS window(Vohs-Voh D, where i=+, 0, - )remains barrier; while the negative piezoelectric potential resulting almost constant for different strain values. This strain-modulated from the negative strain-induced polarization charge hange in the threshold switching voltages was also observed for creased the SBH at the forward-biased drain barrier(red line other PRM cells with oxygen plasma treatment. in Figure 3c1). Since the I-V characteristic in this situation is It is well-known that ionic polarization in ZnO can be dictated by the reversely biased source barrier, the existence of induced by strain owing to the lacking of center symmetry in strain-induced piezoelectric potential results in the shift ZnO, which can strongly affect the charge transpor Novel switching threshold voltage from Vuh. so to Vth. + indicatin effects and applications9, 27, 32 have been observed and im- only a smaller bias is required to switch the PRM cell from HRS plemented utilizing the piezotronic effect in ZnO. The to LRS state. Alternatively, if the Schottky barrier at drain side ndamental concept of the piezotronic effect is that the is reverse-biased(V <0 in Figure 3a), the SBH is still reduced SBH at the metal-semiconductor contact can be effectively at the source barrier while it is increased at the drain barrier tuned by the strain-induced piezoelectric polarization charges Figure 3c2)since the polarity of the strain did not change, at the interface. The local conduction band profile can then be and hence the piezoelectric potential remained negative and 2783 dx. dolora/0.102/n201074a| Nano Lert.2011l27792785
2783 dx.doi.org/10.1021/nl201074a |Nano Lett. 2011, 11, 2779–2785 Nano Letters LETTER switching curve shifted toward higher voltage side by 1.18 V (blue line in Figure 2a). Vth,S+, Vth,S0, Vth,S and Vth,D+, Vth,D0, Vth,D are the threshold switching voltages for the PRM cell with tensile, zero, and compressive strains, respectively. The same hysteretic switching curves can then be plotted in a semilogarithmic current scale to illustrate and highlight the characteristics of the curves (Supporting Information Figure S5). The ratios of conductance between LRS and HRS for the PRM cell remain steady at high values (∼105 ) under different strains (Supporting Information Figure S6), demonstrating the stable performance of the cell and its potential feasibility for applications in flexible memory and logic operations.19The intrinsic rectifying behavior of the PRM cell may solve the sneak path problem as well as reduce the static power consumption,23 which allows for construction of large passive resistive-switching device arrays. The changes in threshold switching voltages of the PRM cell with different strains have been plotted in Figure 3b. It can be seen that the change in both the Vth,S and Vth,D almost linearly depends on strain applied to the PRM cell, while the width of the HRS window (Vth,Si Vth,Di , where i = +, 0, ) remains almost constant for different strain values. This strain-modulated change in the threshold switching voltages was also observed for other PRM cells with oxygen plasma treatment. It is well-known that ionic polarization in ZnO can be induced by strain owing to the lacking of center symmetry in ZnO, which can strongly affect the charge transport.18 Novel effects31 and applications19,27,32 have been observed and implemented utilizing the piezotronic effect in ZnO.18 The fundamental concept of the piezotronic effect is that the SBH at the metalsemiconductor contact can be effectively tuned by the strain-induced piezoelectric polarization charges at the interface. The local conduction band profile can then be modified by shifting the local Fermi level. The change in SBH induced by piezoelectric polarization is given approximately by ΔϕB = σpolD1 (1 + 1/ (2qswd))1 , where σpol is the volume density of the polarization charge and directly related to the piezoelectric polarization P vector, D is the two-dimensional density of interface states at the Fermi level at the Schottky barrier, qs is the two-dimensional screening parameter, and wd is the width of the depletion layer.33 Thus the mechanical strain can effectively change the local contact characteristics as well as the charge carrier transport process. On the basis of the above discussions, the modulation effect of strain on the hysteretic switching behavior of the PRM cell, as shown in Figure 3a,b, can then be understood and explained using the band-diagram of the working device (Figure 3c). If the PRM cell is under tensile strain with the Schottky barrier at drain side being forward-biased (V > 0 in Figure 3a), the positive piezoelectric potential resulting from the positive strain-induced polarization charges reduced the SBH at the reverse-biased source barrier; while the negative piezoelectric potential resulting from the negative strain-induced polarization charges increased the SBH at the forward-biased drain barrier (red line in Figure 3c1). Since the IV characteristic in this situation is dictated by the reversely biased source barrier, the existence of strain-induced piezoelectric potential results in the shift of switching threshold voltage from Vth,S0 to Vth,S+, indicating only a smaller bias is required to switch the PRM cell from HRS to LRS state. Alternatively, if the Schottky barrier at drain side is reverse-biased (V < 0 in Figure 3a), the SBH is still reduced at the source barrier while it is increased at the drain barrier (Figure 3c2) since the polarity of the strain did not change, and hence the piezoelectric potential remained negative and Figure 4. Write/read access of PRM cell as an electromechanical memory. A pulse train consisting of several write/read/erase pulses was applied to the PRM cell to record and read out the logic levels of the “stored” strain in the cell. Each write/erase pulse was followed by a read pulse with positive or negative polarity respectively. The following voltage amplitudes were applied: 6.44 V (write 1), 1.5 V (read 1), 5.35 V (erase 1), 1.5 V (read 2), 5.37 V (erase 2), and 6.42 V (write 2). Short current spikes occur in the output reading current with the write/erase pulses if the resistance states (HRS to LRS) change in the PRM cell
Nano Letters LETTER positive at source and drain barriers, respectively. The I-V out by a read pulse(2 s)with a small magnitude(Vreadl Vhs +) characteristic is now dictated by the reversely biased drain side Subsequently a negative erase pulse(10 ms )with Vh.Do VeraselVid)is applied to read the new By the same token, in the case of applying a compressive strain states of the cells. In the third step, a positive erase pulse(10 ms) to the PRM cell, the shift of switching threshold voltage from with Vth Verase2< Vth, so sets the A cell from the hRS to the Vuh, so to Vth,s and Veh, Do to Vth, D can be explained LRS state again, while keeps the B and C cells in the HRS state Under strain free condition and if the applied external bias The same Vreadi pulse is then applied to read the new states of the exceeds the threshold voltage, the device is in LRS, and the cells. Finally, a negative write pulse(10 ms)with Vah. D+<Vwritez< concentration of oxygen vacancies in the Nw can significantly Vah, Do resets the A cell into the HRS state, while sets the B and C influence the total conductance of the Nw as well as the SBHs at cells into the LRS state. The same Vread2 pulse is then applied to the source/drain(see Figure al-a3 and Supporting Information read the new states of the cells. After the above series of pulse train Figure S1). Now we consider the case that a strain is applied to is applied, the waveform of the output currents of the cells is the PRM cell. The effect of piezopotential can be equivalently monitored and analyzed( Figure 4). If the logic levels of the outp taken as applying a positive voltage at the barrier interface if the currents with positive, almost zero and negative values are labeled local piezoelectric polarization charges are positive, which in as"1,"0"and"-1", the logic pattem of"10 1 0" indicates the effect decreases the value of the external bias required to over ositive nature of the"stored"strain in A cell. The logic patterns of come the SBH at the interface. Alternatively, a negative voltage is 100-1"and"0-1 0-1"represent the zero and negative strain created to act on the interface if the polarization charges are status of the B and C cells, respectively. a quantitative analysis of negative, which increases the value of the external bias required to the magnitudes of the output currents can give the absolute values overcome the barrier at the interface. From the data shown in of the strains stored in the PRM cells. Although there have been Figure 3a, the HRS window remains almost constant regardless numerous research as well as commercial products on strain the magnitude and sign of the applied strain, indicating the shifts detection and measurements such as semiconductor MEMS, in the observed threshold voltages under different strains are NEMS piezoresistive strain gauges, 5.36 the PRM cells demon dictated by the piezoelectric polarization charges at the interfaces strated here are fundamentally different from the these devices. and the contribution from the diffusion of the oxygen vacancies Piezoresistance effect is a nonpolar and symmetric effect resulting has negligible effect. This is because the oxygen vacancies are from the band structure change, while the PRM cells are based on distributed in the entire NW, while the piezoelectric charges are the asymmetric piezotronic effect. ZnO is a polar structure along c- accumulated right at the very near barrier interface in a region less axis, straining in axial direction(c-axis) creates a polarization of than a subnanometer. The diffusion force contributed by the cations and anions in the nw growth direction, resulting in a piezoelectric charges on the oxygen vacancies is a long-range piezopotential drop from V to V along the NW, which produces nteraction force, thus a variation of the vacancy concentration at an asymmetric effect on the changes in the Schottky barrier heights the interface owing to piezoelectric effect is rather small. (SBHs) at the drain and source electrodes. The strain sensor based Furthermore, the entire I-v curves are, " translated for a on piezotronic effect has been reported to possess much higher sensitivity than previously reported devices caused by the piezoelectric charges. For the samples pretreated in In summary, by utilizing the strain-induced polarization charges oxygen plasma, the concentration of the oxygen vacancies was created at the semiconductor/metal interface under externally rgely reduced in the Nw, thus, the screening effect of the free applied deformation as a result of piezotronic effect, the switching ge carriers to the piezoelectric charges was significantly characteristics of the ZnO NW resistive switching devices can be reduced, and the effect of the piezoelectric charges is enhanced. modulated and controlled. We further demonstrated that the logi Therefore, the shifts in threshold switch voltages due to piezo- levels of the strain applied on the memory cell can be recorded and electric polarization at both drain and source sides for a fixed read out for the first time utilizing the piezotronic effect, which strain have the same magnitude but opposite polarities, provided has the potential for implementing novel nanoelectromechanical that the doping level is low. This indicates that the magnitude of memories and integrating with NEMS technology to achieve the piezopotential at the interface is as large as 1.2 V micro/nanosystems capable of intelligent and self-sufficient multi- 0.S-0.76% of strain. The oxygen plasma pretreatment to the dimensional operations. Taking advantage of the recently The fabra y also improve the output of the nanogenerator developed large-scale fabrication technique of ZnO NW arrays, nonvolatile resistive switching memories using ZnO NW array as memory, in which the write/read access can be programmed via the storage medium may be readily engineered and implemented mechanical actuation. A pulse train consisting of several write/ for applications such in flexible electronics and force/pressure d/erase pulses is applied to the PRM cell to record and read out imaging. Non-Boolean neuromorphic computing might also be the polarity/logic levels of the "stored strain in the cell, by realized by integrating arrays of high-density resistive memory monitoring the characteristic patterns in the output current cells",on flexible substrates ( Figure 4). The data shown in Figure 4 was obtained for the same PRM cell under different strain status, which is equivalent to the cases of three identical PRM cells under tensile strain(A cell),zero ■ METHODS SUMMARY strain(B cell), and compressive strain(C cell), for easy descrip- ee Supporting Information for details ion.First, a positive write pulse(10 ms)with Voh. so< Vwritel < Vth. The ZnO nanowires were synthesized via a physical vapor is applied to these three cells. This short pulse sets the a and B deposition process based on thermal evaporation of ZnO cells switch from the HRS to the LRS state, while the C cell powders without the presence of catalyst. Large-scale ZnO emains in the HRS state. The status of the three cells are then read NWs were subsequently transferred to the PET receiving 2784 dx. dolora/0.102/n201074a| Nano Lert.2011l27792785
2784 dx.doi.org/10.1021/nl201074a |Nano Lett. 2011, 11, 2779–2785 Nano Letters LETTER positive at source and drain barriers, respectively. The IV characteristic is now dictated by the reversely biased drain side in this case, and a shift of switching threshold voltage from Vth, D0 to Vth,D+ was observed, indicating a larger bias has to be applied in order to switch the PRM cell from HRS to LRS state. By the same token, in the case of applying a compressive strain to the PRM cell, the shift of switching threshold voltage from Vth,S0 to Vth,S_ and Vth,D0 to Vth,D_ can be explained. Under strain free condition and if the applied external bias exceeds the threshold voltage, the device is in LRS, and the concentration of oxygen vacancies in the NW can significantly influence the total conductance of the NW as well as the SBHs at the source/drain (see Figure a1a3 and Supporting Information Figure S1). Now we consider the case that a strain is applied to the PRM cell. The effect of piezopotential can be equivalently taken as applying a positive voltage at the barrier interface if the local piezoelectric polarization charges are positive, which in effect decreases the value of the external bias required to overcome the SBH at the interface. Alternatively, a negative voltage is created to act on the interface if the polarization charges are negative, which increases the value of the external bias required to overcome the barrier at the interface. From the data shown in Figure 3a, the HRS window remains almost constant regardless the magnitude and sign of the applied strain, indicating the shifts in the observed threshold voltages under different strains are dictated by the piezoelectric polarization charges at the interfaces and the contribution from the diffusion of the oxygen vacancies has negligible effect. This is because the oxygen vacancies are distributed in the entire NW, while the piezoelectric charges are accumulated right at the very near barrier interface in a region less than a subnanometer. The diffusion force contributed by the piezoelectric charges on the oxygen vacancies is a long-range interaction force, thus a variation of the vacancy concentration at the interface owing to piezoelectric effect is rather small. Furthermore, the entire IV curves are “translated” for a constant voltage that is the change of threshold switch voltage caused by the piezoelectric charges. For the samples pretreated in oxygen plasma, the concentration of the oxygen vacancies was largely reduced in the NW, thus, the screening effect of the free charge carriers to the piezoelectric charges was significantly reduced, and the effect of the piezoelectric charges is enhanced.34 Therefore, the shifts in threshold switch voltages due to piezoelectric polarization at both drain and source sides for a fixed strain have the same magnitude but opposite polarities, provided that the doping level is low. This indicates that the magnitude of the piezopotential at the interface is as large as 1.2 V at 0.50.76% of strain. The oxygen plasma pretreatment to the ZnO NWs may also improve the output of the nanogenerator.34 The fabricated PRM can function as an electromechanical memory, in which the write/read access can be programmed via mechanical actuation. A pulse train consisting of several write/ read/erase pulses is applied to the PRM cell to record and read out the polarity/logic levels of the “stored” strain in the cell, by monitoring the characteristic patterns in the output current (Figure 4). The data shown in Figure 4 was obtained for the same PRM cell under different strain status, which is equivalent to the cases of three identical PRM cells under tensile strain (A cell), zero strain (B cell), and compressive strain (C cell), for easy description. First, a positive write pulse (10 ms) with Vth,S0 Vth,D_) is applied to read the new states of the cells. In the third step, a positive erase pulse (10 ms) with Vth,S+ < Verase2 < Vth,S0 sets the A cell from the HRS to the LRS state again, while keeps the B and C cells in the HRS state. The same Vread1 pulse is then applied to read the new states of the cells. Finally, a negative write pulse (10 ms) with Vth,D+ < Vwrite2 < Vth,D0 resets the A cell into the HRS state, while sets the B and C cells into the LRS state. The same Vread2 pulse is then applied to read the new states of the cells. After the above series of pulse train is applied, the waveform of the output currents of the cells is monitored and analyzed (Figure 4). If the logic levels of the output currents with positive, almost zero and negative values are labeled as “1”, “0” and “-1”, the logic pattern of “1010” indicates the positive nature of the “stored”strain in A cell. The logic patterns of “100 1” and “0 1 0- 1” represent the zero and negative strain status of the B and C cells, respectively. A quantitative analysis of the magnitudes of the output currents can give the absolute values of the strains stored in the PRM cells. Although there have been numerous research as well as commercial products on strain detection and measurements such as semiconductor MEMS/ NEMS piezoresistive strain gauges,35,36 the PRM cells demonstrated here are fundamentally different from the these devices. Piezoresistance effect is a nonpolar and symmetric effect resulting from the band structure change, while the PRM cells are based on the asymmetric piezotronic effect. ZnO is a polar structure along caxis, straining in axial direction (c-axis) creates a polarization of cations and anions in the NW growth direction, resulting in a piezopotential drop from V+ to V along the NW, which produces an asymmetric effect on the changes in the Schottky barrier heights (SBHs) at the drain and source electrodes. The strain sensor based on piezotronic effect has been reported to possess much higher sensitivity than previously reported devices.27 In summary, by utilizing the strain-induced polarization charges created at the semiconductor/metal interface under externally applied deformation as a result of piezotronic effect, the switching characteristics of the ZnO NW resistive switching devices can be modulated and controlled. We further demonstrated that the logic levels of the strain applied on the memory cell can be recorded and read out for the first time utilizing the piezotronic effect,18 which has the potential for implementing novel nanoelectromechanical memories and integrating with NEMS technology to achieve micro/nanosystems capable of intelligent and self-sufficient multidimensional operations.18,20 Taking advantage of the recently developed large-scale fabrication technique of ZnO NW arrays,37 nonvolatile resistive switching memories using ZnO NW array as the storage medium may be readily engineered and implemented for applications such in flexible electronics and force/pressure imaging. Non-Boolean neuromorphic computing might also be realized by integrating arrays of high-density resistive memory cells38,39 on flexible substrates. ’METHODS SUMMARY (See Supporting Information for details.) The ZnO nanowires were synthesized via a physical vapor deposition process21 based on thermal evaporation of ZnO powders without the presence of catalyst. Large-scale ZnO NWs were subsequently transferred to the PET receiving
Nano Letters LETTER NWs were aligned on the PET substrate along the sweeping 2(12) Chen. L: Wang w2000, 77(8),1224-1228 Price, Dw-i substrate by sweeping the PEt substrate across the NWs. Zno Reed, M. A; Rawlett, A M our,J. M. AppL. Phys. Lett. direction due to the applied shear force. Drain/source electrodes (13)Baikalov, A; Wang, Y Q; Shen, B. Lorenz, B. Tsui, S. Sun, were defined and patterned over the transferred ZnO NWs by YY;Xue, YY; Chu, C W. AppL Phys. Lett. 2003, 83(5),957-959 photolithography and metal evaporation/lift off steps. After lift (14)Dong, Y ]; Yu, G H; McAlpine, M.C.; Lu,W;Lieber, C.M. off step, a substantial amount of the ZnO NWs was patterned Nano Lett.2008,8(2),386-391 ith ordered Au electrodes(Supporting Information Figure S7 (15)Seo, S. Lee, M. J; Seo, D H; Jeoung, E. J Suh, D S. Joung, Plasma treatment was performed to control and adjust th Y.S. Yoo, IK; Hwang, I R; Kim, S H; Byun, L.S. Kim, J S. Choi, J S Park, B. H. AppL. Phys. Lett. 2004, 85 (23), 5655-5657. electrical properties of the PRM cells by modulating the con (16)Szot, K; Speier, W; BihImayer, G. Waser, R. Nat. Mater. 2006, centration of oxygen vacancies in the ZnO NW. A custom 5(4),312-320 be card was used to access the (17)Sakamoto, T Sunamura, H; Kawaura, PRM cells in the temperature-dependence I-V characterization. Nakayama, T. Aono, M. Appl. Phys. Lett. 2003, 82 Electromechanical measurements were then carried out with a (18)Wang, Z. L Nano Today 2010, 5,$40-552. mputer-controlled data acquisition system and a 3-axis linear (19) Wu, W. Z; Wei, Y G; Wang, Z L. Adv. Mater. 2010, 22 (42), stage for investigating the stain-modulated resistive switching characteristics of the prm cells (20)Wang, Z L Nano Today 2010, 5, 512-514 (21)Pan, Z W; Dai, Z R; Wang, Z. L. Science 2001, 291(5510), ■ ASSOC| ATED CONTENT (22) Scott,J C. Science2004304(5667),62-63. (23)Linn, E; Rosezin, R; Kugeler, C Waser, R. Nat. Mater. 2010, 9 S Supporting Information. Additional information and (5),403-406 figures. This material is available free of charge via the Internet (24)Allen, M. W; Durbin, S M. AppL. Phys. Lett. 2008, 92(12), 12210 (25)Rhoderick, E H Williams, R H Metal-Semiconductor Contacts; ■ AUTHOR INFORMATION Clarendon: Oxford. 1988. (26)Schmidt-Mende, L; JL, M-D. Mater Today 2007, 10(5), Corresponding Author 40-48. E-mail: zlwang@gatech.edu. 27)Zhou, J. Nano Lett.208,8,3973-3977 (28)Zhang, Z Y; Yao, K; Liu, Y; Jin, C H; Liang, X L; Chen,Q. Peng, L M. Adv Funct. Mater. 2007, 17(14), 2478-2489 (29)Sze, S M. Physics of semiconductor devices; John Wiley & Sons ■ ACKNOWLEDGMENT New York, 1981. This work is supported by DARPA(HRO011-09-C-0142 )Mott, N F; Gurney, R W. Electronic processes in ionic crystals, Program manager, Dr. Daniel Wattendorf), Airforce, BES 2nd ed. Clarendon Press: Oxford, 1948 (31)Chung, KK; et al. AppL. Phys. Lett. 1991, 59(10), 1191-1193 DOE(DE-FGO2-07ER46394)and NSF(CMMI 0403671).(32)Liu, W H; Lee, M; Ding, L; Liu, J; Wang,ZLNano Lett. The authors thank Dr. Y. G. Wei for helpful discussions, Dr. M. B. Lee and C. Xu for assistance on cleanroom work, and T. J 2010,10,3084-3089 Chang for assistance on AFM imaging, Z L W. and w.Z. w (33)Zhang, Y; Hu, Y F; Xiang, S; Wang, Z. L. ApPL Phys. Let 2010,97,033509 designed the experiments. w.Z. W. performed the experiments (34)Gao, Y. Wang, Z. L. Nano Lett. 2009, 9(3),1103-1110. Z.L. W. and w.Z. W. analyzed the data and wrote the paper (35)Cao, L. Kim, T S. Mantell, S C Polla, D L Sens. Actuators, A 2000,80(3),273-279 ■ REFERENCES 6)Mile, E; Jourdan, G. Duraffourg L; Labarthe, S. Marcoux, C.; Mercier, D Robert, P; Andreucci, P. IEEE Sens. J. 2009, 1-3, (1)Waser, R; Aono, M. Nat. Mater. 2007, 6(11),833-840 1224-1226 (2)Sawa, A. Mater. Today 2008, 11(6),28-36 Wei, Y. G; Wu, W. Z; Guo, R; Yuan, D.J Das, S M. Wang (3)Strukov, D. B. Snider, G. S. Stewart, D. R; Williams, R.S. Z. L. Nano Lett.2010,10(9),3414-3419 Nature2008,453(7191),80-83 (38) Boahen,K.Sai.Am.2005,292(5),56-63 (4) Yang J- J Pickett, M. D Li, X. M; Ohlberg, D A. A; Stewart, (39) Jo, S H; Chang, T; Ebong, L; Bhadviya, BB; Mazumder, P DR; williams, R S. Nat. Nanotechnol. 2008, 3(7),429-433 Lu,W. Nano Lett.2010,10(4),1297-1301 (5)Choi, B J Jeong, D S; Kim, S K; Rohde, C; Choi, S. Oh, J.H. Kim, H.J.; Hwang, C. S. Szot, K; Waser, R; Reichenberg, B. Tiedke, S J. Appl. Phy2005,98(3)033715. )51mH1xm20909264 137-148 ( 8)Xia, Q F; Robinett, W; Cumbie, M. W; J Yang J J Wu, W; Li, X M Tong, W. M. Strukov, D B j Candidal, G.S.; Medeiros-Ribeiro, G; Williams, R.S. Nano Lett. 2009, 9(10) 3640-3645 (9)Borghetti, J; Snider, G. S; Kuekes, P J; Yang, ].J; Stewart, D.R; Williams,RS. Nature2010,464(7290),873-876 (10)Waser, R; Dittmann, R; Staikov, G. Szot, K. Adv. Mater. 2009, 21(25-26),2632-2663 (11) Kwon, D. H. Kim, K M; Jang, J H Jeon, ]. M; Lee, M. H. Kim,G.H. Li, X.S.; Park, G.S. Lee, B; Han, S. Kim, M Hwang, C.S. Nat. Nanotechnol. 2010, 5(2),148-153. dx. dolora/10.102/n201074 a Nano Lett.20111.27792785
2785 dx.doi.org/10.1021/nl201074a |Nano Lett. 2011, 11, 2779–2785 Nano Letters LETTER substrate by sweeping the PET substrate across the NWs. ZnO NWs were aligned on the PET substrate along the sweeping direction due to the applied shear force. Drain/source electrodes were defined and patterned over the transferred ZnO NWs by photolithography and metal evaporation/lift off steps. After liftoff step, a substantial amount of the ZnO NWs was patterned with ordered Au electrodes (Supporting Information Figure S7). Plasma treatment was performed to control and adjust the electrical properties of the PRM cells by modulating the concentration of oxygen vacancies in the ZnO NW. A custom designed 10 pin probe card was used to electrically access the PRM cells in the temperature-dependence IV characterization. Electromechanical measurements were then carried out with a computer-controlled data acquisition system and a 3-axis linear stage for investigating the stain-modulated resistive switching characteristics of the PRM cells. ’ASSOCIATED CONTENT bS Supporting Information. Additional information and figures. This material is available free of charge via the Internet at http://pubs.acs.org. ’AUTHOR INFORMATION Corresponding Author *E-mail: zlwang@gatech.edu. ’ACKNOWLEDGMENT This work is supported by DARPA (HR0011-09-C-0142, Program manager, Dr. Daniel Wattendorf), Airforce, BES DOE (DE-FG02-07ER46394) and NSF (CMMI 0403671). The authors thank Dr. Y. G. Wei for helpful discussions, Dr. M. B. Lee and C. Xu for assistance on cleanroom work, and T. J. Zhang for assistance on AFM imaging. Z.L.W. and W.Z.W. designed the experiments. W.Z.W. performed the experiments. Z.L.W. and W.Z.W. analyzed the data and wrote the paper. ’REFERENCES (1) Waser, R.; Aono, M. Nat. Mater. 2007, 6 (11), 833–840. (2) Sawa, A. Mater. Today 2008, 11 (6), 28–36. (3) Strukov, D. B.; Snider, G. S.; Stewart, D. R.; Williams, R. S. Nature 2008, 453 (7191), 80–83. (4) Yang, J. J.; Pickett, M. D.; Li, X. M.; Ohlberg, D. A. A.; Stewart, D. R.; Williams, R. S. Nat. Nanotechnol. 2008, 3 (7), 429–433. (5) Choi, B. J.; Jeong, D. S.; Kim, S. K.; Rohde, C.; Choi, S.; Oh, J. H.; Kim, H. J.; Hwang, C. S.; Szot, K.; Waser, R.; Reichenberg, B.; Tiedke, S. J. Appl. Phys. 2005, 98 (3), 033715. (6) Jo, S. H.; Kim, K. H.; Lu, W. Nano Lett. 2009, 9 (2), 870–874. (7) Strukov, D. B.; Likharev, K. K. Nanotechnology 2005, 16 (1), 137–148. (8) Xia, Q. F.; Robinett, W.; Cumbie, M. W.; Banerjee, N.; Cardinali, T. J.; Yang, J. J.; Wu, W.; Li, X. M.; Tong, W. M.; Strukov, D. B.; Snider, G. S.; Medeiros-Ribeiro, G.; Williams, R. S. Nano Lett. 2009, 9 (10), 3640–3645. (9) Borghetti, J.; Snider, G. S.; Kuekes, P. J.; Yang, J. J.; Stewart, D. R.; Williams, R. S. Nature 2010, 464 (7290), 873–876. (10) Waser, R.; Dittmann, R.; Staikov, G.; Szot, K. Adv. Mater. 2009, 21 (2526), 2632–2663. (11) Kwon, D. H.; Kim, K. M.; Jang, J. H.; Jeon, J. M.; Lee, M. H.; Kim, G. H.; Li, X. S.; Park, G. S.; Lee, B.; Han, S.; Kim, M.; Hwang, C. S. Nat. Nanotechnol. 2010, 5 (2), 148–153. (12) Chen, J.; Wang, W.; Reed, M. A.; Rawlett, A. M.; Price, D. W.; Tour, J. M. Appl. Phys. Lett. 2000, 77 (8), 1224–1226. (13) Baikalov, A.; Wang, Y. Q.; Shen, B.; Lorenz, B.; Tsui, S.; Sun, Y. Y.; Xue, Y. Y.; Chu, C. W. Appl. Phys. Lett. 2003, 83 (5), 957–959. (14) Dong, Y. J.; Yu, G. H.; McAlpine, M. C.; Lu, W.; Lieber, C. M. Nano Lett. 2008, 8 (2), 386–391. (15) Seo, S.; Lee, M. J.; Seo, D. H.; Jeoung, E. J.; Suh, D. S.; Joung, Y. S.; Yoo, I. K.; Hwang, I. R.; Kim, S. H.; Byun, I. S.; Kim, J. S.; Choi, J. S.; Park, B. H. Appl. Phys. Lett. 2004, 85 (23), 5655–5657. (16) Szot, K.; Speier, W.; Bihlmayer, G.; Waser, R. Nat. Mater. 2006, 5 (4), 312–320. (17) Sakamoto, T.; Sunamura, H.; Kawaura, H.; Hasegawa, T.; Nakayama, T.; Aono, M. Appl. Phys. Lett. 2003, 82 (18), 3032–3034. (18) Wang, Z. L. Nano Today 2010, 5, 540–552. (19) Wu, W. Z.; Wei, Y. G.; Wang, Z. L. Adv. Mater. 2010, 22 (42), 4711–4715. (20) Wang, Z. L. Nano Today 2010, 5, 512–514. (21) Pan, Z. W.; Dai, Z. R.; Wang, Z. L. Science 2001, 291 (5510), 1947–1949. (22) Scott, J. C. Science 2004, 304 (5667), 62–63. (23) Linn, E.; Rosezin, R.; Kugeler, C.; Waser, R. Nat. Mater. 2010, 9 (5), 403–406. (24) Allen, M. W.; Durbin, S. M. Appl. Phys. Lett. 2008, 92 (12), 12210. (25) Rhoderick, E. H.; Williams, R. H. Metal-Semiconductor Contacts; Clarendon: Oxford, 1988. (26) Schmidt-Mende, L; JL, M.-D. Mater Today 2007, 10 (5), 40–48. (27) Zhou, J. Nano Lett. 2008, 8, 3973–3977. (28) Zhang, Z. Y.; Yao, K.; Liu, Y.; Jin, C. H.; Liang, X. L.; Chen, Q.; Peng, L. M. Adv. Funct. Mater. 2007, 17 (14), 2478–2489. (29) Sze, S. M. Physics of semiconductor devices; John Wiley & Sons: New York, 1981. (30) Mott, N. F.; Gurney, R. W. Electronic processes in ionic crystals, 2nd ed.; Clarendon Press: Oxford, 1948. (31) Chung, K. K.; et al. Appl. Phys. Lett. 1991, 59 (10), 1191–1193. (32) Liu, W. H.; Lee, M.; Ding, L.; Liu, J.; Wang, Z. L. Nano Lett. 2010, 10, 3084–3089. (33) Zhang, Y.; Hu, Y. F.; Xiang, S.; Wang, Z. L. Appl. Phys. Lett. 2010, 97, 033509. (34) Gao, Y.; Wang, Z. L. Nano Lett. 2009, 9 (3), 1103–1110. (35) Cao, L.; Kim, T. S.; Mantell, S. C.; Polla, D. L. Sens. Actuators, A 2000, 80 (3), 273–279. (36) Mile, E.; Jourdan, G.; Duraffourg, L.; Labarthe, S.; Marcoux, C.; Mercier, D.; Robert, P.; Andreucci, P. IEEE Sens. J. 2009, 13, 1224–1226. (37) Wei, Y. G.; Wu, W. Z.; Guo, R.; Yuan, D. J.; Das, S. M.; Wang, Z. L. Nano Lett. 2010, 10 (9), 3414–3419. (38) Boahen, K. Sci. Am. 2005, 292 (5), 56–63. (39) Jo, S. H.; Chang, T.; Ebong, I.; Bhadviya, B. B.; Mazumder, P.; Lu, W. Nano Lett. 2010, 10 (4), 1297–1301