† Corresponding author. E-mail:
‡ Corresponding author. E-mail:
Project supported by the State Key Project of Fundamental Research of China (Grant No. 2012CB933004), the National Natural Science Foundation of China (Grant Nos. 11474295, 51571208, 51525103, and 11274322), Overseas, Hong Kong & Macao Scholars Collaborated Researching Fund (Grant No. 51428201), the Instrument Developing Project of the Chinese Academy of Sciences (Grant No. YZ201327), Ningbo Major Project for Science and Technology (Grant No. 2014B11011), Ningbo International Cooperation Projects (Grant Nos. 2012D10018 and 2014D10005), the Fund for Ningbo Science and Technology Innovation Team (Grant No. 2015B11001), the Youth Innovation Promotion Association of the Chinese Academy of Sciences, and the Key Research Program of the Chinese Academy of Sciences (Grant No. KJZD-EW-M05).
Recent studies of the modulation of physical properties in oxide thin films by multiple fields are reviewed. Some of the key issues and prospects of this area of study are also addressed. Oxide thin films exhibit versatile physical properties such as magnetism, ferroelectricity, piezoelectricity, metal–insulator transition (MIT), multiferroicity, colossal magnetoresistivity, switchable resistivity. More importantly, the exhibited multifunctionality can be tuned by various external fields, which has enabled demonstration of novel electronic devices.
Oxides are a class of materials that are particularly attractive due to their remarkable physical properties and multifunctionality.[1–4] For example, a diversity of physical properties exhibited in thin film oxides, such as magnetism, ferroelectricity, piezoelectricity, and superconductivity, have been intensively studied in the past several decades,[5–10] and the interplay between them has become a hot topic in condensed matter physics.[11–15] Intriguing phenomena including MIT,[16–24] colossal magnetoresistivity,[25–29] resistive switching,[30–38] ferroelectricity,[39–45] multiferroicity,[46–56] etc., make oxides appealing candidates for both electronic and spintronic devices.[57–63] From a fundamental perspective, the multifunctionality in oxides provides a playground for investigating the interplay between spin, charge, orbital and lattice degrees of freedom.[24,64–67] A number of interesting phenomena such as charge order, orbital order, multiferroicity, and interactions such as the electron correlation effect, Jahn–Teller interaction, and spin-orbit coupling, have been frequently discussed to understand the fundamental physics.[51,64,68–73] In addition, the advent of atomically tailored oxide heterostructures has enabled the observation of emergent phenomena, and raised excitement in the study of novel phenomena due to the symmetry breaking and charge transfer across the oxide interface.[67,73–76]
The interplay between spin, charge, orbital, and lattice degrees of freedom in oxides (especially complex oxides) reveals strong composition-structure-property relationships, and it enables study of the effects of various types of fields in various combinations on the physical properties of thin film oxides. As shown in Fig.
In many cases, combined external stimuli could enable fine tuning of physical properties in thin film oxides, which could benefit practical applications. In the following paragraphs, we will discuss the response of thin film oxides to an external stimulus such as electrical field, strain field, magnetic field or photo illumination. We have focused special concern on multiferroics, perovskite manganites, and oxides with resistive switching (RS) properties.
Electric field has been recognized as an efficient and scalable way to tune the physical properties in various materials and structures. For example, in magnetic tunneling junctions, a spin polarized current can induce spin transfer torque effect, which has been intensively studied in MRAM devices[79–82] and microwave devices.[83] Upon the application of electric field, the polarization direction of ferroelectrics can be switched. This can result in either a large electroresistance effect in ferroelectric tunnel junctions[84,85] or a switchable diode effect in ferroelectric diodes.[86] Noticeable strain effect associated with electric-field-induced ferroelastic domain switching has also been intensively studied in magnetoelectric heterostructures.[87,88] In multiferroic materials where the electric polarization couples with the magnetization, applying an electric field modifies the electric polarization and tunes its magnetization through the magnetoelectrical (ME) coupling effect.[11,89,90] In RRAM devices, applying an electric field induces the RS effect by associating with several electric-field-induced effects: electric field induced ion transport,[35] electric field induced phase transition,[91] and the Joule heating effect.[92]
The interplay between electric polarization and magnetization has attracted wide interest for applications such as spintronic devices.[48,93] The presence of multiferroicity in some materials and structures has enabled several ways for the magnetic properties to be manipulated by applying an electric field:[94] (i) In single phase multiferroics where magnetic order and ferroelectricity are coupled, applying an electric field can alter the electric polarization along with the magnetization, owing to intrinsic ME coupling.[11] (ii) Many multiferroics are antiferromagnets; by attaching a multiferroic layer to a ferromagnetic layer, it is possible to construct an exchange bias system that can be controlled by applying electric field to the multiferroic layer, which is known as exchange-mediated ME coupling effect.[12] (iii) In magnetoelectric composites composed of ferroelectric (FE)/ferromagnetic (FM) heterostructures,[95] applying an electric field in the FE layer induces strain that is transmitted in to the FM layer and changes its magnetic properties through inverse magnetostrictive effect. (iv) In FE/FM heterostructures, the electric field can also switch the polarization direction of the FE layer, which may tune the carrier density and hence the magnetic properties of the FM layer, a phenomenon called charge-mediated ME coupling effect.[96]
In single phase multiferroic materials, a tempting idea is to design multiferroics that combine both ferromagnetism and ferroelectricity, and the manipulation of its magnetization by an electric field would be essential for the magnetoelectric control of spintronic devices. However, the exploration of ferromagnetism and ferroelectricity together in a single phase multiferroic has been found unexpectedly difficult.[46] One promising single phase multiferroic that could be utilized is BiFeO3 (BFO) — a material that unambiguously shows ferroelectricity and anti-ferromagnetism above room temperature.[97] The principle that BFO can be utilized for efficient magnetoelectric control of spintronic devices relies on the possibility of electric field controlled interfacial coupling composed of a BFO layer and a ferromagnetic layer.[12,98,99]
Recently, Heron et al. demonstrated deterministic magnetization reversal in BFO based heterostructures,[99] by utilizing the coupling between its weak magnetization arising from the Dzyaloshinskii–Moriya (DM) interaction and the ferroelectric polarization,[100,101] as well as the strong interfacial magnetic coupling.[102] Earlier, theory had predicted[103] that the direct reversal of ferroelectric polarization in BFO will leave the orientation of the canted magnetic moment unchanged, Heron et al. found that ferroelectric-polarization reversal in a strained BFO film actually follows an indirect pathway, and proposed that the indirect switching path reverses the canted magnetic moment [Fig.
Progress in strain-mediated and charge-mediated ME effect will be further discussed in later sections.
RRAM has been widely investigated for next-generation nonvolatile memory devices due to its simple structure, high density, low power consumption and compatibility with complementary metal oxide semiconductor technology.[61,104–106] Up to now, a large variety of materials have been investigated for RS, including solid electrolytes,[107] perovskite oxides,[32,108–110] binary oxides,[33,35,37,111] organic materials,[112–114] amorphous silicon,[115] and amorphous carbon.[116] Although the underlying mechanism is still controversial due to the diversity of RS behaviors, the conductive filament (CF) model has gained much success and has been accepted extensively.[34]
RRAM devices have a simple metal-insulator-metal sandwiched structure. For filament model based RRAMs, a sufficiently large electrical field between the two metallic electrodes can induce a soft dielectric breakdown in the insulator and set the device to a conductive state (also called an ON-state). In this process, due to the electrically induced ion migration, a large number of defects are formed inside the film and form CFs that connect the two terminal electrodes. The ON-state can also be electrically reset, leading to the OFF-state that corresponds to disruption of the CFs. In the CF model, the formation and rupture of local conducting paths connecting the two-terminal electrodes dominates the RS process.[36,38,117,118] Liu et al. have performed real-time characterizations of the CF formation and dissolution processes of an oxide-electrolyte-based RRAM device[36] that is based on a vertical Ag(Cu)/ZrO2/Pt structure with both small lateral sizes and ZrO2 thickness to facilitate direct TEM studies. During the SET process, a dark nano-bridge region appears, signifying the formation of CF [Fig.
It has been found that the nanoscale conduction channel not only dominates the RS process but also shows some other effects, such as quantum size effects and exchange bias effect. For example, quantized conductance has been realized in zinc-oxide based sandwich devices.[35] As can be seen from Fig.
It has also been revealed that by controlling the migration of ions through electrical fields, the magnetism of some magnetic dielectrics can be modulated. For example, Chen et al. successfully modulated the magnetization and coercive field of Co-doped ZnO thin films.[123] Similar behavior has been reported in other materials such as Mn:ZnO[124] and Fe3O4.[125] In CoFe2O4 (CFO) thin films, nanoscale magnetization reversal via electrical ion-manipulation at room temperature has been reported.[126] As is shown in Fig.
In thin film oxides, besides the ionic transport process, the RS phenomenon is associated with other mechanisms such as self-Joule heating effect[92] and electric field induced electronic phase transition.[91] The electric field induced electronic phase transition has been predicted theoretically in charge-orbital ordered manganites, where applying an electric field may suppress the charge ordering and drive the system from the antiferromagnetic charge-ordered state to the ferromagnetic metallic state, resulting in the well-known MIT.[127] The electric field induced magnetism in manganites is a newly found way of realizing the electrical control over magnetism.[128,129] Another very interesting and widely studied correlated material with electric field induced MIT is vanadium dioxide (VO2). Bulk VO2 exhibits MIT at temperature ∼340 K.[130] The electric field was found to be able to drive MIT in VO2, accompanied by a structural change[131] and a large isothermal entropy change.[132] Various electronic devices have been proposed based on the electric field induced MIT in VO2.[133,134] However, the underlying mechanisms have not been fully clarified.[135–138]
The electronic structures of some functional oxides (such as manganites) depend critically on the doping level; hence doping enables electrostatic field tuning of their physical properties.[139,140] The charge-mediated tuning of functionality (such as electron transport and magnetization) in oxides has been studied both theoretically[141–144] and experimentally[96,145,146] in a number of heterostructures.
In perovskite manganites, the electrostatic field can modify the charge carrier concentration without affecting the lattice distortion, which is useful to study the influence of band filling on the electronic properties. The only challenge comes from the high carrier concentration in FM manganites (with carrier density as high as 1021 carriers per cm3), which results in an electronic screening length on the order of only 1 nm (the Thomas–Fermi screening limit), limiting the tunability of the electrostatic field imposed by utilizing conventional dielectrics, like SiO2, SrTiO3 (STO), and ferroelectrics such as lead zirconate titanate (PZT).[140,147] In recent years, the electric double-layer transistor (EDLT) has been used to achieve high electric fields, enabling charge accumulation in the channel surface at densities as high as 1015 per cm2.[148] This is almost two orders of magnitude larger than that in conventional field effect transitions, thus providing better access to electrostatic modulation of electronic phases. The effective tunability by using EDLT has been demonstrated in manganite transistors such as (La, Ca)MnO3 (LCMO) transistors,[149] (Pr,Sr)MnO3 (PSMO) thin films,[150] and (Pr,Ca,Sr)MnO3 (PCSMO) thin films.[151] For example, in PCSMO thin films, it is found that, consistent with the phase diagram, electrostatic modulation of the carrier concentration can effectively modify the phase transition temperature. Electrostatic modulation can also co-play with external magnetic field, resulting in the fine tuning of electronic phase and phase transitions.[150,151]
An MIT can be induced by a gating field in VO2, and the electrostatic effect caused by the gating field was found by Nakano et al. to overcome the Thomas–Fermi screening limit.[152] They suggested that the Thomas–Fermi screening limit does not apply to materials such as VO2, which is characterized by inherent collective interactions between electrons and the crystal lattice. Jeong et al.,[153] however, showed that the electrolyte gating of VO2 leads not to electrostatically induced carriers but instead to the electric field induced creation of oxygen vacancies. They found that by sweeping VG, the device can be reversibly switched between the insulating and metallic states. Hysteresis in the sheet conductance centered about VG = 0 V was observed [Fig.
The mechanism associated with electric field induced oxygen migration has also been suggested by Cui et al.[154,155] in ionic liquid gating experiments on (La,Sr)MnO3 (LSMO). Although oxygen vacancy migration has not been directly observed, the Mn valence variation in XPS and microstructure evolution in HRTEM under different gate voltages suggest the formation and annihilation of oxygen vacancies. The electric fields created by the electric double layer (EDL) on a manganite under VG will change the chemical composition, which is accompanied by changes in the effective doping level x [Fig.
Applying strain on thin film oxides has been proven to be an efficient way for tuning their physical properties. Exerting strain on thin films can induce distortions of the film unit cell, which changes the elastic energy and modifies the films’ electro–magnetic properties.[156] In some cases, applying strain can alter the ground state of thin film oxides and novel phases are disclosed. There are three ways to apply strain in thin films: mechanical strain,[157] epitaxial strain,[158] and strain that is due to the converse piezoelectric effect.[159] In recent years, inspired by the idea of wearable electronic devices, there has been increasing interest in the study of flexible electronic devices,[160–164] and the strain effect in these devices has been intensively investigated.
In some transition metal oxides, the electronic phases are very sensitive to external strain,[165,166] resulting in highly sensitive electrical and magnetic response to external strain field. For example, the strain effect on the electrical properties of manganite thin films has been studied by using the converse piezoelectric effect; the resistance of manganite thin films is found to change dramatically under small strain, resulting in very large strain gauge factor.[159,167–169] The electrical and magnetic response to external strain is essentially mediated by the piezostrain coupled orbital reoccupation[170] and electronic phase separation.[169] Zheng et al. investigated the influences of piezostrain on the electronic transport and magnetic properties of charge-ordered La0.5Ca0.5MnO3 thin films.[169] An unprecedented large strain-induced resistance change is found to be magnetic-field tunable [Fig.
The substrate strain can sometimes induce new phases with dramatic electron transport properties. For example, it has been predicted theoretically that in a half-doped manganite, the ferromagnetic charge ordered insulating state, previously inaccessible to experiments, becomes stable under tensile strain.[173] A recent report on LSMO thin films deposited on DyScO3 (DSO) substrate evidences a new phase at low temperature with dramatic anisotropic transport properties [Figs.
In ferroelectric materials, the formation of ferroelectric domain structures is a consequence of minimizing the elastic and electrostatic energy of the ferroelectric system. Hence applying strain can effectively tune the ferroelectric domain structures, which could be useful for further exploring the ME properties in multiferroic systems. Both theoretical and experimental studies have been performed on controlling the ferroelectric domain structures of BFO thin films, and strain constraints have been found to be an effective way of controlling the domain structures of BFO thin films. Zhang et al.[40] have been trying to understand how the strain state can affect the polarization variants and to predict the domain structures in epitaxial BFO thin films with different orientations. Their findings suggest that the domain structures of BFO thin films can be controlled by selecting the proper film orientations and strain constraints. Chu et al.[174] have demonstrated the realization of one-dimensional nanoscale arrays of domain walls in epitaxial BFO/ SrRuO3 (SRO)/DSO structures. This quasi-periodic structure results from the strain induced by the anisotropic in-plane lattice parameters of DSO (a1 = 3.951 Å and a2 = 3.946 Å); it pins the structure of the SRO layer and, eventually, the ferroelectric domain structure of BFO. Through the careful control of electrostatic boundary conditions, such as the thickness of the underlying SRO layer, Chu et al.[175] demonstrated the creation of ordered arrays of the prototypical domain structures predicted before.[176] The selection between the 71° and 109° domain patterns depends on the electrostatic boundary conditions, such as the existence of an SRO conducting layer and its thickness. When the bottom electrode SRO layer is thick enough to be a good metal, the elastic energy dominates the system, and the domain is fully out-of-plane polarized downward toward the SRO layer, forming ordered arrays of 71° domain walls. On the other hand, when the SRO layer is very thin, electrostatic energy becomes the dominant energy and the domains are alternately pointing up and down, with arrays of 109° domain walls favored.
Piezoelectric materials with large piezoelectric coefficients (such as lead-based perovskites PZT, PMN-PT, and PZN-PT) are typically characterized by the intimate coexistence of two phases across a morphotropic phase boundary,[177] and an electrically switching from one phase to the other.[178] By using a combination of epitaxial growth techniques in conjunction with theoretical approaches, Zeches et al. formed morphotropic phase boundaries through epitaxial constraints in lead-free piezoelectric BFO films.[41] The tetragonal-like phase can be reversibly converted into a rhombohedral-like phase, making this new lead-free system interesting for probe-based data storage and actuator applications. Ab initio calculations demonstrated that the strain-induced structural change in BFO [Figs.
A number of works have been devoted to the study of composite multiferroic films,[96,179,180] most of which are composed of ferroelectrics and magnetic materials with layered heterostructures. In these composite multiferroic films, changes in magnetic anisotropy and coercivity can be realized by applying a strain[181,182] caused by applying an electric field to the piezoelectric layer. Strain-mediated electric field control of magnetism has been observed in a number of epitaxial heterostructures, such as ferromagnetic LSMO films,[183] ferromagnetic CFO films[184] and metals grown on PMN-PT single crystal substrate, and ferromagnetic LSMO films[95] and metals[185] grown on BTO substrate. A giant electrical-field-induced magnetic anisotropy has been observed in these layered multiferroic heterostructures, and the strong ME coupling is used to control the orientation of magnetization and thus enable dynamically tuning magnetoresistance in giant magnetoresistance (GMR) and anisotropic magnetoresistance (AMR) devices.[186,187]
In most cases of strain mediated electrical control over magnetism, the M–E loop is butterfly-shaped, tracking the butterfly-shaped piezo-strain curve of the ferroelectric substrate, which clearly demonstrates the vital role of the elastic strains for the converse ME response in the heterostructure. For the application of information storage, tunable and nonvolatile converse ME effects are two important requirements; hence loop-like behavior of the magnetic response to electric field is desirable. Therefore great efforts have been devoted to non-volatile control over magnetism.[88,188–192] For ferroelectric materials with compositions near the morphotropic phase boundary, the electric-field-induced phase transitions are very prominent. For example, a rhombohedral-to-orthorhombic phase transition takes place in (011)-oriented PZN(6-7%)-PT under sufficient poling fields. Most of such phase transitions are non-volatile, and it is expected to display a hysteresis-type lattice change as a function of electric field. This effect can be used for realizing non-volatile spintronics and microwave devices based on multiferroic heterostructures.[180,190]
Yang et al. reported piezostrain-mediated nonvolatile rotations of the magnetic easy axis (MEA) in the Co/PMN-PT multiferroic heterostructure at room temperature.[193] They found a reversible and non-volatile 90° rotation of magnetization [Fig.
Another way of realizing non-volatile electric-field-controlled magnetization is by inducing two different remnant strain states in the single-crystal piezoelectric substrate.[194] However, such an approach is not practical for real applications, as the remnant strain states strongly depend on the history of applied electric fields.
In the (001)-oriented PMN-PT substrate, a bipolar loop-like non-volatile strain has been reported, and this is ascribed to the ferroelastic domain switching that provides a third way for realizing the non-volatile strain state.[87,88] Although much remains to be done to attain precise control of the ferroelastic domain switching process, the non-volatile strain associated with it has been proven to be promising for realizing the non-volatile control over magnetism. For example, Zhang and co-authors[195] reported a large and nonvolatile bipolar electric-field-controlled magnetization in Co40Fe40B20 on a (001)-oriented PMN-PT structure [Fig.
In recent years, flexible electronic devices, which offer advantages of being lightweight, foldable, and stretchable, has attracted special attention. Although a great many flexible electronic devices were made of organic materials, there has been an increasing trend in the exploration of flexible inorganic devices, such as thin-film transistors,[196–199] magnetoelectronics,[164,200,201] and memories.[202–205] In this part, we merely review the progress on flexible RRAM devices based on oxides.
In RRAM devices, the RS is dominated by the formation and rupture of the CF, as the CF is of small size and perpendicular to the film plane; hence the RS phenomenon can endure moderate strain along the film plane. There have been some reports of flexible memristive memories with a simple cross-point-type array based on various oxides such as GeOx/HfON,[206] aluminum oxide,[207] zinc oxide,[202,208] and TiO2.[209,210] These devices show good flexibility, and the performance of RS is not degraded by substrate bending. In order to overcome the cell-to-cell interference issue, Kim et al. developed the “NOR” type flexible RRAM with a one transistor-one memristor structure, and performed the first demonstration of random access memory operation of the RRAM on a flexible substrate.[211] Their device exhibited reliable and reproducible RS, good endurance and retention properties, along with excellent mechanical stability upon harsh bending. Liang et al. has demonstrated ultrathin WO3·H2O nanosheets as a promising material to construct a high performance and flexible RRAM device [Fig.
The study of magnetic field’s effects on the physical properties of oxide thin films is an important issue in condensed matter physics and has shown temping prospects of applications in spintronic devices and magnetic sensors. The discovery of the colossal magnetoresistance (CMR) effect and the investigation of all-oxide magnetic tunnel junctions (MTJ) have greatly promoted the study of magnetic field on thin film oxides. The effect of magnetic field on the electrical properties of oxide thin films has been studied in order to combine charge-tuning devices with spintronics devices.
In perovskite manganites, applying magnetic field usually facilitates double exchange interaction which favors metallic conductivity, inducing the well-known CMR effect.[213] The CMR effect has been widely studied in manganite,[26,28,29,214–216] and it always shows a peak value near the phase boundary, which reflects the fact that the phase competition is susceptible to external magnetic field.[27] In recent years, it has been found that despite the near-cubic structure of perovskite manganites, their electron transport behavior actually depends strongly on the magnetic field direction, resulting in a very large AMR effect in manganite single crystals[217–219] and thin films.[220–224] The AMR effect shows different magnetic-field and temperature dependence from that in 3d ferromagnetic alloys, suggesting different underlying mechanisms.[217,225,226] The AMR effect in manganite thin films can be tuned by epitaxial strain and has attracted lots of attention.[222,227–230]
Magnetic field couples with RRAM devices in two different ways. One is by the effective tuning of the resistance switching process, and the other is by realizing more resistance states through the magnetoresistance effect. Thakare et al.[231] reported a bipolar RRAM of CFO/LSMO that can be gated with high sensitivity by low magnetic fields. The switching shows a strong CFO thickness-dependence only under applied magnetic field, suggesting an effective coupling with the interfacial magnetoresistive LSMO layer. Li et al. demonstrated three-state RS in films combining a multiferroic CFO/PZT bilayer with a semiconducting ZnO layer.[232] The three states are distinguished by various stimuli combinations of electric voltage pulse and magnetic bias, and are attributed to changes in the charge carrier states modulated by magnetoelectric coupling between CFO and PZT layers, as well as interface polarization coupling between PZT and ZnO layers. In an Si–SiO2–MgO device, the nonvolatile RS effect can be controlled by applying a magnetic field.[233] The magnetic field delays the transition from HRS to LRS and can even suppress this transition. Das et al.[234] observed sharp switching between low and high conducting states having a large ratio of currents (∼107) in NiO film. Besides the switching effect, an extraordinarily large magnetoconductance (∼98% at 20 K) has been found in the device, signifying multifunctional applications.
The RS effect can be utilized as a simple and controllable way to produce nanoscale devices, such as an artificial MTJ.[235] The spin transport in memristive devices has also been reported in a number of MTJs,[236–239] it is found that applying an electric field may reversibly induce two stable resistance states, respectively, with a substantial magnetoresistance difference. Li et al. reported the use of composite barrier layers of CoO–ZnO to fabricate the spin memristive Co/CoO–ZnO/Co MTJ.[240] They found a high bipolar resistance switching ratio, up to 90 [Fig.
As mentioned above, the interplay between electric polarization and magnetization in multiferroic materials is very important for both fundamental physics and spintronic devices. Manipulation of magnetism by electric polarization has been demonstrated in both single-phase multiferroics and composites. Conversely, the possibility of electric polarization reversal induced by magnetic fields has been reported in multiferroics. Keeney et al. demonstrated switching of ferroelectric polarization by magnetic fields at room temperature in multiferroic Aurivillius phase thin films.[241] For practical applications, the weak ME coupling in single-phase multiferroics is always a big challenge.[242] Lu et al. reported a remarkable magnetically induced electric polarization in DyMnO3 thin films, and they found an enhancement of electric polarization up to 800% upon 2 Tesla at 2 K.[42]
An efficient coupling between magnetism and dielectric properties results in phenomena such as the magnetocapacitance effect. This phenomenon has been studied in both single phase materials[47,243–247] and composite systems.[248–251] For example, the magnetocapacitance effect has been found in perovskite heterostructures such as LCMO/BTO[248] and LCMO/Ba1−xSrxTiO3[252] superlattices, manifesting an effective ME coupling in these structures. Colossal magnetocapacitance has been reported in electronic phase-separated manganite thin films, and the competition of microscopic ferromagnetic metallic and charge ordered insulating clusters is believed to play a major role in the exhibited colossal magnetocapacitance effect.[246]
Photo-coupled phenomena have attracted wide interest due to the special advantages of light, such as high speed, low power consumption and “green” energy. In thin film oxides, photoinduced effects such as photostrictive effect,[77] photoinduced electronic phase transition,[253] photovoltaic effect[254] and photoinduced spin dynamics[255] indicate a diversity of degrees of freedom that couples effectively with light.
Light-controlled RS memory has photon-charge dual function. The resistance state can be modified not only by voltage pulses, but also by means of light. Ungureanu et al.[256] reported a new type of RS memory device with a simple metal/Al2O3/SiO2/Si structure. In verifying the performance of the devices when used as core of a binary memory cell, they observed that data can be accurately written, read, and erased only under illumination [Fig.
The change in the remnant current was interpreted as a modulation of the trapped electrons in the Al2O3 layer. Upon the introduction of electrons from the Si layer, the resistivity of this charge storage layer increases. For positive bias, a depletion region is generated in Si at the interface with the SiO2/Al2O3. The photogenerated electrons are injected into the Al2O3 layer when the electric field is high enough to overcome this energy barrier [Fig.
Recently, a multifunctional optoelectronic RS memory has been demonstrated in a simple ITO/CeO2−x/AlOy/Al structure [Fig.
Photoinduced phase transitions have attracted special interest because they can change the properties of complex materials on the ultrafast timescale.[260–263] In perovskite manganites, photoinduced insulator-to-metal transition has been frequently reported.[264–269] Photo illumination has been found to couple coherently in these materials, resulting in modifications of a variety of the physical properties due to the strong coupling between spin, charge, orbital and lattice. In PCSMO thin films, both photoinduced metal-to-insulator transition and photoinduced insulator-to-metal transition, have been confirmed.[270] This is a demonstration of photons as an effective way to overcome the large potential barrier due to the long-range elastic energy between the insulator and metallic phase. Possibly due to the high energies associated with photons, the photoinduced state can differ greatly from states produced with stimuli close to equilibrium. For example, in a charge-orbital ordered Nd0.5Sr0.5MnO3 thin film, the photoinduced state was found to be a structurally ordered, homogeneous, metastable insulating state with crystallographic parameters different from any thermodynamically accessible state.[271]
In vanadium dioxide (VO2), a first-order transition between a high-temperature metallic phase and a low-temperature semiconducting phase has been observed.[130] A non-thermally driven ultrafast phase transition can be achieved under photo illumination.[272] The transition takes place near room temperature and has been heavily studied for both fundamental physics and possible applications such as switching devices.[58,273] There has been hot debate regarding the driving force of this insulator-metal transition, and contributions of both electron-lattice interactions and electron-electron interactions have been proposed.[274,275] Advanced time-resolved methods have been developed to capture the phase transition processes, and much has been learned about the details during the transition processes.[275,276] For instance, Morrison et al. utilized ultrafast electron diffraction to monitor the crystal structure of VO2 and simultaneously measured its optical properties to monitor the electronic state, and they found an interesting metastable state that preserves the initial semiconducting crystal structure while showing metal-like properties.[276]
Another important consequence of photo illumination is the photovoltaic effect, which has been frequently studied in ferroelectric thin films. Ferroelectric–photovoltaic devices in which a homogeneous ferroelectric material is used as a light absorbing layer have been investigated with numerous ferroelectric oxides.[277–279] The ferroelectric–photovoltaic effect is distinctly different from the typical photovoltaic effect in semiconductor p–n junctions in that the polarization electric field is the driving force for the photocurrent in ferroelectric–photovoltaic devices.[280,281] In addition, the anomalous photovoltaic effect, in which the voltage output along the polarization direction can be significantly larger than the bandgap of the ferroelectric materials, has been frequently observed in ferroelectric–photovoltaic devices.[254,282] For most ferroelectric materials, the relatively wide band gap limits photovoltaic efficiency, and utilization of narrow-band-gap ferroelectrics is therefore a promising route toward their application in both novel optoelectronic and solar energy devices.[283,284] The multiferroic material BFO, which possesses a narrow band gap (∼2.2 eV), offers an exciting opportunity for such applications. A significant photovoltaic effect has already been observed in single crystalline BFO in both bulk[280,285,286] and thin film forms,[287–291] but it still needs improving.[254,292–294]
Yang et al.[254] studied the photovoltaic effect on BFO film with ordered domain strips and lateral device configuration [Fig.
In the ferroelectric based photovoltaic devices, it is suggested that the depolarization field may be the dominating driving force for the separation of photo-generated charge carrier-pairs. This depolarization field must be closely related to the degree of screening of the spontaneous polarization, which depends on the properties of both ferroelectric materials and electrode materials. Chen et al.[293] studied the anomalous photovoltaic effect in a device with a structure of Au/BFO/Au and found that the photocurrent output increased 25 times when the Au electrode was replaced by ITO. The great enhancement of photocurrent was attributed to the increased depolarizing field.
Furthermore, the photovoltaic effect in ferroelectric films has also provided a new method to sense the polarization direction non-destructively in ferroelectric memory. For example, Guo et al. reported a novel approach to create a non-volatile memory based on the ferroelectric polarization-dependent photovoltaic effect.[295] Recently, Wang et al. presented a new non-destructive readout by using photo-recovered surface potential contrast.[296] By introducing laser illumination, they found that the surface potential contrast between the adjacent oppositely polarized domains can be recovered, as has been revealed by Kelvin probe force microscopy (KPFM) measurement [Figs.
Oxide thin films exhibit interesting and sometimes unexpected property changes upon external stimulus. These novel phenomena provide the central concept for the next generation of nanodevices. Although much progress has been made in the systems, there are still many challenges and opportunities. As an example, the emergent phenomenon at oxide interface is an interesting subject, not yet well explored.[62,66,73] In multiferroic based devices, a central idea is the electric control of magnetism that would enable scalable, green-energy spintronic devices.[297] Although the electric field induced energy-efficient control of a spin-valve device at room temperature has been demonstrated in BFO based heterostructures,[99] improving reliability of the devices is a challenge, possibly due to oxidation of the ferromagnetic metal at the interface under the strong electric field. For this reason, full study of oxide spintronics is of importance to make the device robust.[98,298] In RRAM based devices, the study of ion transport has become a new direction toward nanoscale physics, and it could be useful in designing novel electronic devices with nanoscale sizes. Difficulties lie in effective characterizations of the ionic channels, and an effective way for improving the stability and uniformity of the nanoscale devices. Given the strong composition-structure-property relationship in many complex oxides, thin film oxides show sizable and sometimes unexpected responses to external stimuli, making them a wonderful playground for studying fundamental physics and exploring novel devices. In this case, in-situ structural and chemical characterizations during film growth are desirable.
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