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Oxygen doping of HTSC and resistive switching in HTSC-based heterostructures


The studies of the bipolar resistive switching effect in thin film heterojunctions (YBa2Cu3O7−δ /Ag) and (Nd 2−x Ce x CuO4−y /Ag) have exhibited the role of oxygen as a doping element in hole- and electron-doped HTSC compounds.


Most HTSC materials are hole-doped compounds. Nd2−x Ce x CuO 4−y (NCCO), Pr2−x Ce x CuO 4−y (PCCO), as well as Ba1−x K x BiO 3−y and BaPb1−x Bi x O 3−y are few representatives of electron-doped ones. The hole- and electron-doped compounds differ by their physical properties and their phase diagrams (Dagotto1994). Nevertheless, they have a feature in common. It is strong dependence of the properties on oxygen stoichiometry, since oxygen plays significant role in formation of the basic (ground) state in these compounds. Influence of oxygen is well studiled for p-type HTSC, it is important as hole dopant. However, questions still remain concerning the role of oxygen in electron-doped HTSC cuprates (Orenstein and Wishwanath2010). The studies of Hall effect (Jiang et al.1994; Mao et al.1995) in oxygen-reduced NCCO and PCCO revealed presence of holelike states in these n-type materials. The question arises whether the presence of p-type carriers is crucial for superconductivity in HTSC.

The effect of bipolar resistive switching (BRS) observed in oxide-based heterostructures, including based on strongly correlated electron systems (SCES), such as HTSC (see, for instance, (Waser and Aono2007; Tulina2007; Sawa2008; Kang et al.2007;Yang et al.2008; Inoue et al.2008)), is sensitive to type of charge carriers in SCES. BRS is exhibited in SCES-normal metal heterocontacts at specific polarity of the electric field as a change of the phase composition of the SCES surface layer at the nanosize level. As a result, the metastable high resistance (OFF) and low resistance (ON) states of the heterocontact are realized leading to colossal electrical resistance (CER)(Tulina2007). CER is the ratio of the resistance on OFF state to the resistance in ON state and characterizes the memory effect. CER = ΔR/R = (R OFF (V = 0) − R ON (V = 0))/R ON (V = 0). Intensive fundamental and application studies of this phenomenon are underway since BRS-based devices are regarded as a new generation of alternative nonvolatile memory (Meijer2008). Besides, BRS effect allows to study the microscopic nature of SCES underlying such devices.

Recent studies of the BRS effect in various compounds revealed the essential role of the oxygen diffusion processes. Electric field of different polarity induces two resistive states of the degraded HTSC surface which is indicative of its separation into conducting and dielectric phases. The switching process gives rise to metastable states with different oxygen content in the interface area of the compound. It is this area that determines the resistive properties of the structure (Tulina et al.2001; Tulina and Sirotkin2004). Therefore, the BRS effect involves reproducible oxygen doping of a specific sample area. In (Tulina and Klinkova2007) we observed BRS inversion in heterojunctions based on electron-doped BaK0,6 Bi 0,4 O 3−y : the switching to the high resistance metastable phase takes place when the HTSC crystal has a negative potential with respect to the normal electrode. In this case the current field (J = σ E) is directed to the surface in contrast to switching observed in hole-doped compounds.


The aim of the work was to observe bipolar resistive switching effect in YBa2Cu3O7−δ /Ag and NCCO/Ag heterojunctions in order to trace the role of oxygen as doping element in p-type and n-type HTSC. Thin epitaxial films of YBCO(001) and NCCO(001) grown by pulse laser deposition were used to produce HTSC-based heterostructures. Figure1 shows a heterocontact scheme. Silver counterelectrodes were deposited on the as-grown surface to form a HTSC film/interface/Ag structure. The upper silver electrode was deposited through a mask as point electrodes 1 mm in diameter. The electric supply leads were attached to the silver contacts with conductive paste or a mechanical contact in a micromanipulator. The x-ray studies of the YBCO films has revealed that, besides the basic composition, sample contains surface regions with a smoothly decreasing oxygen content down to δ = 1,0 (Jorgensen et al.1990).

Figure 1
figure 1

XPS and UPS of the as grown and ion milled Nd 1.75 Ce 0.15 CuO 4− y films.(a) Initial stage of ion milling (up to 10-15 nm depth). XPS spectrum of the film surface (top), corresponding heterocontact scheme (bottom); (b) Ion milling at 30 nm depth. XPS spectrum (top) and UPS spectra (middle and bottom) together with the heterocontact scheme.

Results of NCCO films structure study were reported elsewhere (Tulina et al.2011). There were detected reflexes of NCCO and Nd0.5 Ce 0.5 O 1.75(NCO) phase. Both phases were epitaxial and (001)-oriented. The obtained results are consistent with other evidences of two phases coexistence after oxygen reducing even in perfect single crystals (Mang et al.2004). Along with the main phase, the second phase can affect the behavior of the interface of the studied heterojunctions and lead to changes in the type of conductivity. Photoemission studies provided support for the X-ray data. After the film surface was milled with nitrogen ions at depth of 50 nm, it was shown using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy that the film surface was metallic and had an entire set of elements (Figure1). We thus obtained heterojunctions of two types on NCCO films: (a) with a surface buffer layer formed by NCO (Figure1a; see the XPS data above) and (b) without the NCO oxide layer, which was removed by ion milling to the main phase NCCO under photoemission control (Figure1).

The value of the BRS effect was insignificant in the heterocontacts formed immediately after the ion milling of NCCO surface, the switching pattern corresponded to the electron-doped systems (see Figure2). This fact can be understood considering weak influence of oxygen as a doping element on the properties of NCCO which has been already confirmed in some works (Higgins et al.2006;Gauthier et al.2007). Nonstoichiometric oxygen does not affect the number of carriers in NCCO and leads to disorder only. At the same time the BRS effect was considerably stronger in the YBCO/Ag heterocontacts, and the switching pattern corresponded to the hole-doped systems (Figure2). As it is seen from inset in the Figure, superconducting transition is observed in the On state. It means that the electric field has induced oxygen diffusion into the controlled region and the Tc value is close to optimal one for YBCO.

Figure 2
figure 2

Examples of the voltage-current characteristics of the YBa 2 Cu 3 O 7− δ /Ag (black points) and Nd 1,75 Ce 0,15 CuO 4− y / Ag (red points) heterocontacts with resistive switching. T = 300 K. Upper left corner - heterocontact scheme; Lower right corner - temperature dependences of YBa2Cu3O7−δ /Ag heterojunction resistance in Off and On states.


  •  The bipolar resistive switching has been experimentally observed in NCCO- and YBCO-based film heterojunctions.

  •  It has been shown that the surface layer of the studied HTSC films is oxygen degraded and can serve as an interface in HTSC perovskite-based heterostructures to create memory elements based on resistive switching.

  •  The switching polarity and the BRS effect value in the electron- and hole-doped compounds reflect the pattern of their oxygen doping.


  • Dagotto E: Correlated electrons in high-temperature superconductors. Rev Mod Phys 1994, 66: 763-840. 10.1103/RevModPhys.66.763

    Article  Google Scholar 

  • Gauthier J, Gagné S, Renaud J, Gosselin ME, Fournier P, Richard P: Different roles of cerium substitution and oxygen reduction in transport in Pr2-xCexCuO4 thin films. Phys. Rev. B 2007, 75: 024424.

    Article  Google Scholar 

  • Higgins JS, Dagan Y, Barr MC, Weaver BD, Greene RL: Role of oxygen in the electron-doped superconducting cuprates. Phys Rev B 2006, 73: 104510.

    Article  Google Scholar 

  • Inoue IH, Yasuda S, Akinaga H, Takagi H: Nonpolar resistance switching of metal/binary-transition-metal oxides/metal sandwiches: homogeneous/inhomogeneous transition of current distribution. Phys Rev B 2008, 77: 035105.

    Article  Google Scholar 

  • Jiang W, Mao SN, Xi XX, Jiang X, Peng JL, Venkatesan T, Lobb CJ, Greene RL: Anomalous Transport Properties in Superconducting Nd1.85Ce0.15CuO4-δ. Phys Rev Lett 1994, 73(9):1291-1294. 10.1103/PhysRevLett.73.1291

    Article  Google Scholar 

  • Jorgensen JD, Veal BW, Paulikas AP, Nowicki LJ, Crabtree GW, Claus H, Kwok WK: Structural properties of oxygen-deficient YBa2Cu3O7−δ. Phys Rev B 1990, 41: 1863-1877. 10.1103/PhysRevB.41.1863

    Article  Google Scholar 

  • Kang HJ, Dai P, Campbell BJ, Chupas PJ, Rozenkranz S, Lee PL, Huang Q, Li S, Komiya S, Ando Y: Microscopic annealing process and its impact on superconductivity in T’-structure electron-doped copper oxides. Nat Mater 2007, 6: 224-229. 10.1038/nmat1847

    Article  Google Scholar 

  • Mao SN, Jiang W, Xi XX, Li Q, Peng JL, Greene RL, Venkatesan T, Beesabathina DP, Salamanca-Riba L, Wu XD: Characteristics of oxygen over-reduced Nd1.85Ce0.15CuO4-y films. Appl Phys Lett 1995, 66(16):2137-2139. 10.1063/1.113928

    Article  Google Scholar 

  • Mang PK, Larochelle S, Mehta A, Vajk OP, Erickson AS, Lu L, Buyers WJL, Marshall AF, Prokes K, Greven M: Phase decomposition and chemical inhomogeneity in Nd2-xCexCuO4±δ. Phys Rev B 2004, 70: 094507.

    Article  Google Scholar 

  • Meijer GI: Who wins the nonvolatile memory race? Science 2008, 319: 1625-1626. 10.1126/science.1153909

    Article  Google Scholar 

  • Orenstein J, Wishwanath A: Breaking through to the other side. Nat Phys 2010, 6: 566-567. 10.1038/nphys1751

    Article  Google Scholar 

  • Sawa A: Resistive switching in transition metal oxides. Mater Today 2008, 11(6):28-36. 10.1016/S1369-7021(08)70119-6

    Article  Google Scholar 

  • Tulina NA: Colossal electroresistance and electron instability in strongly correlated electron systems. Phys-Uspekhi 2007, 50(11):1171-1178. 10.1070/PU2007v050n11ABEH006396

    Article  Google Scholar 

  • Tulina N, Borisenko I, Ivanov A, Ionov A, Shmytko I, Menushenkov A: Resistive switching effect in thin-film heterojunctions based on electron-doped Nd2-xCexCuO4-y superconductor. Bull Russ Acad Sci : Physics 2011, 75(5):605-608. 10.3103/S1062873811050480

    Article  Google Scholar 

  • Tulina NA, Ionov AM, Chaika AN: Reversible electrical switching at the Bi2Sr2CaCu2O8+y surface in the normal metal Bi2Sr2CaCu2O8+y single crystal heterojunction. Physica C 2001, 366: 23-30. 10.1016/S0921-4534(01)00631-1

    Article  Google Scholar 

  • Tulina NA, Klinkova: Reversal of the resistive switching effect in electron-doped Ba0.6K0.4BiO3-x. JETP 2007, 105: 238-240. 10.1134/S1063776107070527

    Article  Google Scholar 

  • Tulina NA, Sirotkin VV: Electron instability in doped-manganites-based heterojunctions. Physica C 2004, 400: 105-110. 10.1016/j.physc.2003.07.002

    Article  Google Scholar 

  • Waser R, Aono M: Nanoionics-based resistive switching memories. Nat Mat 2007, 6: 833-840. 10.1038/nmat2023

    Article  Google Scholar 

  • Yang JJ, Pickett MD, Li X, Ohlberg DAA, Stewart DR, Williams S: Memristive switching mechanism for metal/oxide/metal nanodevices. Nat Nanotechnol 2008, 3: 429-433. 10.1038/nnano.2008.160

    Article  Google Scholar 

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The work was financially supported by the Program of the Division of Physical Sciences RAS "Physics of Novel Materials and Structures", the program of the Presidium RAS "Quantum Condensed Matter Physics" and the Russian Foundation for Basic Research (project 11-02-01174a).

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Correspondence to Andrey A Ivanov.

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Authors’ contributions

NAT carried out out the bipolar resistive switching effect measurements and drafted the manuscript. IYB carried out bipolar resistive switching effect measurements and discussed results. AAI produced thin HTSC films by pulsed laser deposition, drafted the manuscript. AMI carried out photoelectron spectroscopy measurements and ion milling, discussed results. IMS carried out XRD measurements and discussed results. All authors read and approved the final manuscript.

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Tulina, N.A., Borisenko, I.Y., Ivanov, A.A. et al. Oxygen doping of HTSC and resistive switching in HTSC-based heterostructures. SpringerPlus 2, 384 (2013).

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