Switchable Photovoltaic Effect Research Articles

Octahedral Distortion and Displacement-Type Ferroelectricity with Switchable Photovoltaic Effect in a 3d^{3}-Electron Perovskite System.

Because of the half-filled t_{2g}-electron configuration, the BO_{6} octahedral distortion in a 3d^{3} perovskite system is usually very limited. In this Letter, a perovskitelike oxide Hg_{0.75}Pb_{0.25}MnO_{3} (HPMO) with a 3d^{3} Mn^{4+} state was synthesized by using high pressure and high temperature methods. This compound exhibits an unusually large octahedral distortion enhanced by approximately 2 orders of magnitude compared with that observed in other 3d^{3} perovskite systems like RCr^{3+}O_{3} (R=rare earth). Essentially different from centrosymmetric HgMnO_{3} and PbMnO_{3}, the A-site doped HPMO presents a polar crystal structure with the space group Ama2 and a substantial spontaneous electric polarization (26.5 μC/cm^{2} in theory) arising from the off-center displacements of A- and B-site ions. More interestingly, a prominent net photocurrent and switchable photovoltaic effect with a sustainable photoresponse were observed in the current polycrystalline HPMO. This Letter provides an exceptional d^{3} material system which shows unusually large octahedral distortion and displacement-type ferroelectricity violating the "d^{0}-ness" rule.

Optical reading of multistate nonvolatile oxide memories based on the switchable ferroelectric photovoltaic effect

Intensive research into functional oxides has been triggered by the quest for a solid-state universal memory with high-storage density, non-volatility, high read/write speed, and random access. The ferroelectric random-access memory (FeRAM), in which the information is stored in the spontaneous ferroelectric polarization of the material, offers great promise as nonvolatile and multistate memory, but its destructive electrical reading step requires a rewrite step after each reading, increasing energy consumption. As an alternative, optical nondestructive readout is based on the ferroelectric polarization dependence of the photovoltaic response in materials and has been reported in two-states ferroelectric memories and multistate devices with limited photocurrent switchability due to asymmetric interfacial effects. In this work, we report a nonvolatile oxide memory device based on a symmetric heterostructure with eight stable and well-controlled remanent polarization (Pr) states, written electrically by voltage pulse and read optically through polarization-dependent short-circuit photocurrent Isc or open circuit photovoltage Voc. This symmetric capacitor demonstrates a clear proportionality between Isc (Voc) and Pr, allowing to achieve a 100% switchability of the photovoltaic response. The memory devices based on 3-bit data storage show good performance in terms of data retention, fatigue behavior, and repeatability of writing and reading cycles. Thanks to the very high sensitivity of the optical reading method, the number of states could largely exceed eight, being limited only by the electrical writing step precision. These results are particularly exciting for the development of next-generation ferroelectric memory devices with increased memory storage density and lower power consumption.

Quantitative investigation of polarization-dependent photocurrent in ferroelectric thin films

Ferroelectric thin films are investigated for their potential in photovoltaic (PV) applications, owing to their high open-circuit voltage and switchable photovoltaic effect. The direction of the ferroelectric polarization can control the sign of the photocurrent through the ferroelectric layer, theoretically allowing for 100% switchability of the photocurrent with the polarization, which is particularly interesting for photo-ferroelectric memories. However, the quantitative relationship between photocurrent and polarization remains little studied. In this work, a careful investigation of the polarization-dependent photocurrent of epitaxial Pb(Zr, Ti)O3 thin films has been carried out, and has provided a quantitative determination of the unswitchable part of ferroelectric polarization. These results represent a systematic approach to study and optimize the switchability of photocurrent, and more broadly to get important insights on the ferroelectric behavior in all types of ferroelectric layers in which pinned polarization is difficult to investigate.

Switchable photovoltaic and enhanced photoelectricity in a single PbS@CH3NH3PbI3 hybrid composite micro/nanowire

Organic-inorganic perovskite has an excellent response to visible light. For nanostructure perovskite, however, the fast recombination of photoexcited electron-hole pairs can be triggered by the affluent surface states, resulting in a decrease of photoresponsivity. Herein, PbS@CH3NH3PbI3 hybrid composite micro/nanowires, where PbS quantum dots (QDs) are uniformly dispersed in CH3NH3PbI3 matrix, are prepared by a fast liquid–solid growth of supersaturated solution with solvent evaporation. The hybrid composite structures noticeably improve the photoresponse to long wavelength light. For a single micro/nanowire-based device with a configuration of symmetrical two electrodes, more interestingly, a switchable photovoltaic effect can be successfully realized after being applied a relatively large fixed bias, and moreover the polarity of electrical signal can be reversed by inverting the direction of applied electric field, which stems from the reversible asymmetrical filling of QDs-related interface state traps near two electrodes by a large electric field-induced injection and extraction of holes. After being filled by holes, the ideal heterojunction of n-PbS and p-CH3NH3PbI3 can effectively separate photoexcited electron-hole pairs, resulting into an enhanced photoelectric response with rapid response and decay rate. Moreover, the emptied interface traps can induce a more obvious photovoltaic effect due to higher surface barrier. Based on the hybrid composite micro/nanostructures, not only photoelectric response can be improved, but also a switchable solar cell can be realized in the configuration of geometry symmetry with two-terminal electrodes.

Reviewing and understanding the stability mechanism of halide perovskite solar cells

AbstractFinding sustainable and renewable energy to replace traditional fossil fuel is critical for reducing greenhouse gas emission and avoiding environment pollution. Solar cells that convert energy of sunlight into electricity offer a viable route for solving this issue. At present, halide perovskites are the most potential candidate materials for solar cell with considerable power conversion efficiency, whereas their stability remains a challenge. In this work, we summarize four different key factors that influence the stability of halide perovskites: (a) effect of environmental moisture on the degradation of halide perovskites. The performance of halide perovskite solar cells is reduced due to hydrated crystal hinders the diffusion of photo‐generated carriers, which can be solved by materials encapsulation technique; (b) photo‐induced instability. Through uncovering the underlying physical mechanism, we note that materials engineering or novel device structure can extend the working life of halide perovskites under continuous light exposure; (c) thermal stability. Halide perovskites are rapidly degraded into PbI2 and volatile substances as heating due to lower formation energy, whereas hybrid perovskite is little changed; (d) electric field effect in the degradation of halide perovskites. The electric field impacts significantly on the carrier separation, changes direction of photo‐induced currents and generates switchable photovoltaic effect. For each key factor, we have shown in detail the underlying physical mechanisms and discussed the strategies to overcome this stability difficulty. We expect this review from both theoretical and experimental points of view can be beneficial for development of perovskite solar cell materials and promotes practical applications.image

Switchable ferroelectric diode and photovoltaic effects in polycrystalline BiFeO3 thin films grown on transparent substrates

Switchable ferroelectric diode and photovoltaic effects in epitaxial BiFeO3 (BFO) thin films have drawn intense attention for its potential applications in resistive memory and solar cell. However, both of these two effects were observed almost entirely in epitaxial BFO thin films or bulk crystal. In this paper, we demonstrate these effects in a polycrystalline BFO thin film grown on a transparent Indium Tin Oxide (ITO) covered quartz plate by the pulsed laser deposition technique. The BFO thin film shows good ferroelectricity with remanent polarization of around 60 μC/cm2 and has a direct band gap of 2.64 eV. The current-voltage curves measured at an Au/BFO/ITO configuration show diode-like rectifying characteristics, and the diode polarity can be reversed with polarization switching. The polycrystalline BFO thin film also exhibits a switchable photovoltaic effect with an open-circuit voltage of approximately 0.2 V and a short-circuit current of nearly 60 μA/cm2 under illumination. This study demonstrates that the polycrystalline BFO thin film on a transparent substrate also has the ferroelectric switchable diode and photovoltaic effects. Therefore, these results will be useful to expand the application of BFO thin films in optoelectronic devices.

Cubic NaSbS2 as an Ionic–Electronic Coupled Semiconductor for Switchable Photovoltaic and Neuromorphic Device Applications

The recent emergence of lead halide perovskites as ionic-electronic coupled semiconductors motivates the investigation of alternative solution-processable materials with similar modulatable ionic and electronic transport properties. Here, a novel semiconductor-cubic NaSbS2 -for ionic-electronic coupled transport is investigated through a combined theoretical and experimental approach. The material exhibits mixed ionic-electronic conductivity in inert atmosphere and superionic conductivity in humid air. It is shown that post deposition electronic reconfigurability in this material enabled by an electric field induces ionic segregation enabling a switchable photovoltaic effect. Utilizing post-perturbation of the ionic composition of the material via electrical biasing and persistent photoconductivity, multistate memristive synapses with higher-order weight modulations are realized for neuromorphic computing, opening up novel applications with such ionic-electronic coupled materials.

Near-ultraviolet photodetector based on hexagonal TmFeO3 ferroelectric semiconductor thin film with photovoltaic and pyroelectric effects

The switchable ferroelectric photovoltaic (FPV) effect facilitates application of multifunctional photoelectric devices. The drawback of the FPV effect is that it generates a very low photocurrent in highly insulated ferroelectric materials. In contrast, the light-induced pyroelectric effect enhances photoelectric performance. Both effects strongly depend on the ferroelectric polarization of the material. In this study, we fabricated and characterized a near-ultraviolet photodetector consisting of a Pt/hexagonal TmFeO3/Pt heterojunction. The switchable FPV and light-induced pyroelectric effects are both observed in a hexagonal TmFeO3 ferroelectric semiconductor film. An additional potential arises from the light-induced pyroelectric effect, which strongly depends on the light intensity. The Schottky barrier height can be modulated by both the poling electric field and light-induced pyroelectric potential. Increasing the power density above the threshold leads to switchable polarization via the light-induced pyroelectric potential. The coexistence of photovoltaic and pyroelectric effects in the hexagonal TmFeO3 ferroelectric semiconductor makes it possible to develop electronic, thermal, and optical sensors as well as energy conversion devices.

Electro and photon double-driven non-volatile and non-destructive readout memory in Pt/Bi0.9Eu0.1FeO3/Nb:SrTiO3 heterostructures

Ferroelectric resistive switching has recently attracted considerable attention as a promising candidate for next-generation non-volatile memory. In this work, we report an electro and photon double-driven bipolar resistive switching behavior in Pt /Bi0.9Eu0.1FeO3 (BEFO) /Nb-doped SrTiO3 (NSTO) heterostructures prepared via pulsed laser deposition. In addition to the polarization-based control of the resistive memory, a switchable photovoltaic effect is observed that can be used to detect the polarization direction non-destructively. Significantly, the electric field-modulated interfacial barrier can be further affected by photon-generated carriers. This phenomenon is attributed to the barrier modulation in the Pt /BEFO and BEFO /NSTO interfaces by electric field and photon excitation. These results indicate the feasibility of non-volatile and non-destructive readout from ferroelectric memory.

Manipulation of Oxygen Vacancy for High Photovoltaic Output in Bismuth Ferrite Films.

Very recently, the ferroelectric photovoltaic property of bismuth ferrite (BiFeO3, BFO) has attracted much attention. However, the physical mechanisms for its anomalous photovoltaic effect and switchable photovoltaic effect are still largely unclear. Herein, a novel design was proposed to realize a high photovoltaic output in BiFeO3 films by manipulating its oxygen vacancy concentration through the alteration of the Bi content. Subsequent results and analysis manifested that the highest photovoltaic output was achieved in Bi1.05FeO3 films, differing 1000 times from that of Bi0.95FeO3 films. Simultaneously, the origin of photovoltaic effect in all BiFeO3 films was suggested as the bulk photovoltaic mechanism instead of the Schottky effect. Moreover, oxygen vacancy migration should be the dominant factor determining the switchable photovoltaic effect rather than the ferroelectric polarization. A switchable Schottky-to-Ohmic interfacial contact model was proposed to illustrate the observed switchable photovoltaic or diodelike effect. Therefore, the present work may open a new way to realize the high power output and controllable photovoltaic switching behavior for the photovoltaic applications of BiFeO3 compounds.

Conduction mechanism and switchable photovoltaic effect in (1 1 1) oriented BiFe0.95Mn0.05O3 thin film

Epitaxial 200 nm BiFe0.95Mn0.05O3 (BFO) film was grown by pulsed laser deposition (PLD) on (1 1 1) oriented SrTiO3 substrate buffered with a 50 nm thick SrRuO3 electrode. The BFO thin film shows a rhombohedral structure and a large remnant polarization of Pr = 104 µC cm−2. By comparing I(V) characteristics with different conduction models we reveal the presence of both bulk limited Poole–Frenkel and Schottky interface mechanisms and each one dominates in a specific range of temperature. At room temperature (RT) and under 10 mW laser illumination, the as grown BFO film presents short-circuit current density (Jsc) and open circuit voltage (Voc) of 2.25 mA cm−2 and −0.55 V respectively. This PV effect can be switched by applying positive voltage pulses higher than the coercive field. For low temperatures a large Voc value of about −4.5 V (−225 kV cm−1) is observed which suggests a bulk non-centrosymmetric origin of the PV response.

Photovoltaic Effect of a Ferroelectric-Luminescent Heterostructure under Infrared Light Illumination.

In this report, a ferroelectric-luminescent heterostructure is designed to convert infrared light into electric power. We use BiFeO3 (BFO) as the ferroelectric layer and Y2O3:Yb,Tm (YOT) as the upconversion layer. Different from conventional ferroelectric materials, this heterostructure exhibits switchable and stable photovoltaic effects under 980 nm illumination, whose energy is much lower than the band gap of BFO. The energy transfer mechanism in this heterostructure is therefore studied carefully. It is found that a highly efficient nonradiative energy transfer process from YOT to BFO plays a critical role in achieving the below-band-gap photon-excited photovoltaic effects in this heterostructure. Our results also indicate that by introducing asymmetric electrodes, both the photovoltage and photocurrent are further enhanced when the built-in field and the depolarization field are aligned. The construction of ferroelectric-luminescent heterostructure is consequently proposed as a promising route to enhance the photovoltaic effects of ferroelectric materials by extending the absorption of the solar spectrum.

Ultrasensitive Heterojunctions of Graphene and 2D Perovskites Reveal Spontaneous Iodide Loss

Summary Despite the demonstrated high efficiency of perovskite solar cells and light-emitting devices, the understanding of the intrinsic stability of perovskites is far from complete. In this work, using an ultrasensitive, exfoliated 2D perovskite single-crystal sheet/graphene heterostructure device, we reveal spontaneous iodide loss as an important degradation pathway of 2D perovskite single crystals, which n-dopes the perovskite semiconductor by generating positively charged iodide vacancies. Furthermore, we show that covering perovskites with graphene can suppress the iodide loss, significantly improving perovskite stability. A perovskite phototransistor is demonstrated with a graphene/2D perovskite/graphene structure, which shows no degradation after 75 days. Our work not only provides important insights for future stable perovskite optoelectronic device development, but also demonstrates the potential of graphene as a promising sensitive diagnostic tool for device and material degradation studies.

Doping and Switchable Photovoltaic Effect in Lead-Free Perovskites Enabled by Metal Cation Transmutation.

Creating defect tolerant lead-free halide perovskites is the major challenge for development of high-performance photovoltaics with nontoxic absorbers. Few compounds of Sn, Sb, or Bi possess ns2 electronic configuration similar to lead, but their poor photovoltaic performances inspire us to evaluate other factors influencing defect tolerance properties. The effect of heavy metal cation (Bi) transmutation and ionic migration on the defects and carrier properties in a 2D layered perovskite (NH4 )3 (Sb(1-x) Bix )2 I9 system is investigated. It is shown, for the first time, the possibility of engineering the carriers in halide perovskites via metal cation transmutation to successfully form intrinsic p- and n-type materials. It is also shown that this material possesses a direct-indirect bandgap enabling high absorption coefficient, extended carrier lifetimes >100 ns, and low trap densities similar to lead halide perovskites. This study also demonstrates the possibility of electrical poling to induce switchable photovoltaic effect without additional electron and hole transport layers.

High-Performance Photovoltaic Readable Ferroelectric Nonvolatile Memory Based on La-Doped BiFeO3 Films.

Epitaxial La0.1Bi0.9FeO3 (LBFO) films with SrRuO3 (SRO) bottom electrodes were fabricated on SrTiO3(001) substrates by magnetron sputtering. The LBFO thin films exhibit strong ferroelectric properties. Nonvolatile reversible resistance switchings and switchable photovoltaic effects controlled by electric field have been observed in Pt/LBFO/SRO heterostructures. With the optimized LBFO film thickness, the observed room temperature pulsed-read resistance switching ratio can reach 105% magnitude by applying ±2.7 V pulse voltages. Besides, the observed ferroelectric switchable photovoltaic effect in the visible wavelength range shows a large tunable open-circuit photovoltage from -75 to -330 mV. The switching mechanisms in resistance and photovoltaic effects are demonstrated to be directly related to the ferroelectric reversal, which can be attributed to the polarization-modulated interfacial barriers and deep trap states.

Photoassisted Electric Field Modulation of Multiple Nonvolatile Resistance States in Highly Strained Epitaxial BiFeO3 Heterostructures

AbstractFor developing the high‐density and high‐speed nonvolatile memory storage, the photoassisted electric field modulation of resistive switching in ferroelectric heterostructures is studied. Highly strained epitaxial BiFeO3 heterostructures are fabricated on LaAlO3 substrates by magnetron sputtering. The electric field‐modulated wide range multilevel resistance and switchable photovoltaic effects are observed in these heterostructures. It is found that the electric field‐modulated interfacial barrier can be further affected by the photogenerated excitons. Therefore, a co‐modulation of light illumination and electric field on the resistive switching behavior is demonstrated, which generates four nonvolatile resistance states.

Suppressed Ion Migration along the In-Plane Direction in Layered Perovskites

Ion migration in a three-dimensional (3D) perovskite is the source of many unique phenomena such as photocurrent hysteresis and a giant switchable photovoltaic effect and can also accelerate the degradation of perovskite-based electronic devices. Here we report the observation of suppressed ion migration along the in-plane direction of layered perovskites by studying the conductivity of layered single-crystal perovskites at varied temperatures. Large-area layered perovskite thin single crystals are synthesized by the space-confined method. The absence of ion migration in these layered perovskites can be explained by an increase in the energy required to form an ion vacancy, compared to 3D perovskites. The suppressed ion migration in layered perovskites indicates that they have intrinsically better stability under an electric field and may contribute to the improved perovskite stability in devices made of layered perovskite through the reduction of ion diffusion-induced perovskite degradation or corrosion ...

Dipole pinning effect on photovoltaic characteristics of ferroelectric BiFeO3 films

Ferroelectric bismuth ferrite is an attractive candidate for switchable devices. The effect of dipole pinning due to the oxygen vacancy layer on the switching behavior of the BiFeO3 thin film fabricated by the chemical solution deposition method was studied after annealing under air, O2, and N2 environment. The air annealed film showed well defined and dense grains leading to a lower leakage current and superior electrical properties compared to the other two films. The photovoltage and transient photocurrent measured under positive and negative poling elucidated the switching nature of the films. Though the air and O2 annealed films showed a switchable photovoltaic response, the response was severely affected by oxygen vacancies in the N2 annealed film. In addition, the open circuit voltage was found to be mostly dependent on the polarization of BiFeO3 rather than the Schottky barriers at the interface. This work provides an important insight into the effect of dipole pinning caused by oxygen vacancies on the switchable photovoltaic effect of BiFeO3 thin films along with the importance of stoichiometric, defect free, and phase pure samples to facilitate meaningful practical applications.

Enhanced Switchable Ferroelectric Photovoltaic Effects in Hexagonal Ferrite Thin Films via Strain Engineering.

Ferroelectric photovoltaics (FPVs) are being extensively investigated by virtue of switchable photovoltaic responses and anomalously high photovoltages of ∼104 V. However, FPVs suffer from extremely low photocurrents due to their wide band gaps (Eg). Here, we present a promising FPV based on hexagonal YbFeO3 (h-YbFO) thin-film heterostructure by exploiting its narrow Eg. More importantly, we demonstrate enhanced FPV effects by suitably exploiting the substrate-induced film strain in these h-YbFO-based photovoltaics. A compressive-strained h-YbFO/Pt/MgO heterojunction device shows ∼3 times enhanced photovoltaic efficiency than that of a tensile-strained h-YbFO/Pt/Al2O3 device. We have shown that the enhanced photovoltaic efficiency mainly stems from the enhanced photon absorption over a wide range of the photon energy, coupled with the enhanced polarization under a compressive strain. Density functional theory studies indicate that the compressive strain reduces Eg substantially and enhances the strength of d-d transitions. This study will set a new standard for determining substrates toward thin-film photovoltaics and optoelectronic devices.

Switchable ferroelectric photovoltaic effects in epitaxial h-RFeO3 thin films.

Ferroelectric photovoltaics (FPVs) have drawn much attention owing to their high stability, environmental safety, and anomalously high photovoltages, coupled with reversibly switchable photovoltaic responses. However, FPVs suffer from extremely low photocurrents, which is primarily due to their wide band gaps. Here, we present a new class of FPVs by demonstrating switchable ferroelectric photovoltaic effects and narrow band-gap properties using hexagonal ferrite (h-RFeO3) thin films, where R denotes rare-earth ions. FPVs with narrow band gaps suggest their potential applicability as photovoltaic and optoelectronic devices. The h-RFeO3 films further exhibit reasonably large ferroelectric polarizations (4.7-8.5 μC cm-2), which possibly reduces a rapid recombination rate of the photo-generated electron-hole pairs. The power conversion efficiency (PCE) of h-RFeO3 thin-film devices is sensitive to the magnitude of polarization. In the case of the h-TmFeO3 (h-TFO) thin film, the measured PCE is twice as large as that of the BiFeO3 thin film, a prototypic FPV. The effect of electrical fatigue on FPV responses has been further investigated. This work thus demonstrates a new class of FPVs towards high-efficiency solar cell and optoelectronic applications.