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1.
Ferroelectricity and X-ray detection property have been recently implemented for the first time in hybrid bromide double perovskites. It sheds a light on achieving photosensitive and ferroelectric multifunctional materials based on 2D lead-free hybrid halide double perovskites. However, the low Tc, small Ps, and relatively low X-ray sensitivity in the reported bromide double perovskites hinder practical applications. Herein, the authors demonstrate a novel 2D lead-free iodide double perovskite (4,4-difluoropiperidinium)4AgBiI8 (1) for high-performance X-ray sensitive ferroelectric devices. Centimeter-sized single crystal of 1 is obtained and exhibits an excellent ferroelectricity including a high Tc up to 422 K and a large Ps of 10.5 μC cm−2. Moreover, due to a large X-ray attenuation and efficient charge carrier mobility (μ)–charge carrier lifetime (τ) product, the crystal 1 also exhibits promising X-ray response with a high sensitivity up to 188 μC·Gyair−1 cm−2 and a detection limit below 3.13 μGyair·s−1. Therefore, this finding is a step further toward practical applications of lead-free halide perovskite in high-performance photoelectronic devices. It will afford a promising platform for exploring novel photosensitive ferroelectric multifunctional materials based on lead-free double perovskites.  相似文献   

2.
Luminescent ferroelectrics have attracted considerable attention in terms of integrated photoelectronic devices, most of which are focused on the multicomponent systems of rare‐earth doping ferroelectric ceramics. However, bulk ferroelectricity with coexistence of strong white‐light emission, especially in the single‐component system, remains quite rare. Here, a new organic–inorganic hybrid ferroelectric of (C4H9NH3)2PbCl4 ( 1 ) is reported, adopting a 2D layered perovskite architecture, which exhibits an unprecedented coexistence of notable ferroelectricity and intrinsic white‐light emission. Decent above‐room‐temperature spontaneous polarization of ≈2.1 µC cm?2 is confirmed for 1 . Particularly, it also exhibits brilliant broadband white‐light emission with a high color‐rendering‐index up to 86 under UV excitation. Structural analyses indicate that ferroelectricity of 1 originates from molecular reorientation of dynamic organic cations, as well as significant structural distortion of PbCl6 octahedra that also contribute to its white‐light emission. This work paves an avenue to design new hybrid ferroelectrics for multifunctional application in the photoelectronic field.  相似文献   

3.
High‐density memory is integral in solid‐state electronics. 2D ferroelectrics offer a new platform for developing ultrathin electronic devices with nonvolatile functionality. Recent experiments on layered α‐In2Se3 confirm its room‐temperature out‐of‐plane ferroelectricity under ambient conditions. Here, a nonvolatile memory effect in a hybrid 2D ferroelectric field‐effect transistor (FeFET) made of ultrathin α‐In2Se3 and graphene is demonstrated. The resistance of the graphene channel in the FeFET is effectively controllable and retentive due to the electrostatic doping, which stems from the electric polarization of the ferroelectric α‐In2Se3. The electronic logic bit can be represented and stored with different orientations of electric dipoles in the top‐gate ferroelectric. The 2D FeFET can be randomly rewritten over more than 105 cycles without losing the nonvolatility. The approach demonstrates a prototype of rewritable nonvolatile memory with ferroelectricity in van der Waals 2D materials.  相似文献   

4.
In contrast to polar cation displacements driving oxides into noncentrosymmetric and ferroelectric states, inversion‐preserving anion displacements, such as rotations or tilts of oxygen octahedra about cation coordination centers, are exceedingly common. More than one nonpolar rotational mode in layered perovskites can lift inversion symmetry and combine to induce an electric polarization through a hybrid improper ferroelectric (HIF) mechanism. This form of ferroelectricity expands the compositional palette to new ferroelectric oxides because its activity derives from geometric rather than electronic origins. Here, the new Ruddlesden–Popper HIF Sr3Zr2O7, which is the first ternary lead‐free zirconate ferroelectric, is reported and room‐temperature polarization switching is demonstrated. This compound undergoes a first‐order ferroelectric‐to‐paraelectric transition, involving an unusual change in the “sense” of octahedral rotation while the octahedral tilt remains unchanged. Our experimental and first‐principles study shows that the paraelectric polymorph competes with the polar phase and emerges from a trilinear coupling of rotation and tilt modes interacting with an antipolar mode. This form of hybrid improper “antiferroelectricity” is recently predicted theoretically but has remained undetected. This work establishes the importance of understanding anharmonic interactions among lattice degrees of freedom, which is important for the discovery of new ferroelectrics and likely to influence the design of next‐generation thermoelectrics.  相似文献   

5.
X‐ray detectors with high sensitivity are of great significance in both civil and military fields. Over the past decades, great efforts have been made to improve the sensitivity in conventional inorganic materials, but mainly at the cost of increasing the energy consumption with a quite high operating voltage. Developing photosensitive ferroelectrics directly as detector materials may be a conceptually new strategy in view of the strong ferroelectric spontaneous polarization (Ps) that assists photoinduced carriers separation and transport. A high‐performance X‐ray detector in 2D hybrid halide perovskite ferroelectric (C4H9NH3)2(C2H5NH3)2Pb3Br10 ( BA2EA2Pb3Br10 ) (Ps = 5 µC cm?2) is fabricated and exhibits an ultrahigh X‐ray sensitivity up to 6.8 × 103 µC Gyair?1 cm?2 even at a relatively low operating voltage, which is over 300‐fold larger than that of state‐of‐the‐art α‐Se X‐ray detectors. Such a brilliant figure‐of‐merit is largely attributed to the superior mobility–lifetime products associated with the strong ferroelectric polarization of BA2EA2Pb3Br10 . As pioneering work, these findings inform the exploration of hybrid halide perovskite ferroelectrics toward high‐performance photoelectronic devices.  相似文献   

6.
With the advent of the post Moore era, modern electronics require further device miniaturization of all electronic components, particularly ferroelectric memories, due to the need for massive data storage. This demand stimulates the exploration of robust switchable ferroelectric polarizations at the atomic scale. In this scenario, van der Waals ferroelectrics have recently gained increasing attention because of their stable layered structure at nanometer thickness, offering the opportunity to realize two-dimensional ferroelectricity that is long-sought in conventional thin film ferroelectrics. In this review, recent advancements are summarized in layered ferroelectrics with highlights of the fundamentals of intrinsic two-dimensional ferroelectricity, the emergence of artificial stacking ferroelectricity, and related protype devices with exotic functions. In addition, the unique polarization control in van der Waals ferroelectrics is discussed. Although great challenges remain unsolved, these studies undoubtedly advance the integration of 2D ferroelectrics in electronics.  相似文献   

7.
GeTe is an interesting material presenting both spontaneous polarization (ferroelectrics) and outstanding electrical conductivity (ideal for thermoelectrics). Pristine GeTe exhibits classic 71° and 109° submicron ferroelectric domains, and near unity thermoelectric figure of merit ZT at 773 K. In this work, it is demonstrated that Bi2Te3 alloying in GeTe lattice can introduce vast Ge vacancies which can further evolve into nanoscale van der Waals gaps upon proper heat treatment, and that these vacancy gaps can induce 180° nanoscale ferroelectric domain boundaries. These microstructures eventually become a hierarchical ferroelectric domain structure, with size varying from submicron to nanoscale and polarization from 71°, 109° to 180°. The establishment of hierarchical ferroelectric domain structure, together with the nanoscale Ge vacancy van der Waals gaps, has profound effects on the electrical and thermal transport properties, resulting in a striking peak thermoelectric ZT ≈ 2.4 at 773 K. These findings might provide an alternative conception for thermoelectric optimization via microstructure modulation.  相似文献   

8.
Hybrid organic-inorganic perovskites (e.g. CH3NH3PbI3) have attracted tremendous attention due to their promise for achieving next-generation cost-effective and high performance optoelectronic devices. These hybrid organic-inorganic perovskites possess excellent optical and electronic properties, including strong light absorption, high carrier abilities, optimized charge diffusion lengths, and reduced charge recombination etc., leading to their widespread applications in advanced solar energy technologies (e.g. high efficiency perovskite solar cells). However, there is still a lack of investigations regarding fundamental properties such as ferroelectricity in these perovskites. As conventional ferroelectric ceramics are prepared at high temperature and have no mechanically flexibility, low-temperature proceed and flexible perovskite ferroelectrics have become promising candidates and should be exploited for future flexible ferroelectric applications. Here, ferroelectric properties in hybrid organic-inorganic perovskites and several state-of-the-art perovskite ferroelectrics are reviewed. Novel ferroelectric applications of hybrid organic-inorganic perovskites are discussed as well, providing guideline for realizing future high performance and flexible ferroelectric devices.  相似文献   

9.
Room temperature ferroelectric thin films are the key element of high-density nonvolatile memories in modern electronics. However, with the further miniaturization of the electronic devices beyond the Moore’s law, conventional ferroelectrics suffer great challenge arising from the critical thickness effect, where the ferroelectricity is unstable if the film thickness is reduced to nanometer or single atomic layer limit. Two-dimensional(2D) materials, thanks to their stable layered structure, saturate interfacial chemistry, weak interlayer couplings, and the benefit of preparing stable ultra-thin film at 2D limit, are promising for exploring 2D ferroelectricity and related device applications. Therefore, it provides an effective approach to overcome the limitation in conventional ferroelectrics with the study of 2D ferroelectricity in van der Waals(vdW) materials. In this review article,we briefly introduce recent progresses on 2D ferroelectricity in layered vdW materials. We will highlight the study on atomically thin α-In2Se3, which is an emergent ferroelectric semiconductor with the coupled in-plane and out-of-plane ferroelectricity. Furthermore, two prototype ferroelectric devices based on ferroelectric α-In2Se3 will also be reviewed.  相似文献   

10.
Incipient ferroelectricity is known to occur in perovskites such as SrTiO3, KTaO3, and CaTiO3. For the first time it is shown that the intensively researched HfO2 thin films (16 nm) also possess ferroelectric properties when aluminium is incorporated into the host lattice. Polarization measurements on Al:HfO2 based metal–insulator–metal capacitors show an antiferroelectric‐to‐ferroelectric phase transition depending on annealing conditions and aluminium content. Structural investigation of the electrically characterized capacitors by grazing incidence X‐ray diffraction is presented in order to gain further insight on the potential origin of ferroelectricity. The non‐centrosymmetry of the elementary cell, which is essential for ferroelectricity, is assumed to originate from an orthorhombic phase of space group Pbc21 stabilized for low Al doping in HfO2. The ferroelectric properties of the modified HfO2 thin films yield high potential for various ferroelectric, piezoelectric, and pyroelectric applications. Furthermore, due to the extensive knowledge accumulated by various research groups regarding the HfO2 dielectric, an immediate relevance of ferroelectric hafnium oxide thin films is anticipated by the authors.  相似文献   

11.
Photoexcited pyroelectricity in ferroelectrics allows the direct conversion of light radiation into electric signal without external power source, thus paving an avenue to promote optoelectronic device performances. However, it is urgently demanded to exploit new ferroelectrics with this attribute covering ultraviolet (UV)-to-infrared (IR) region for self-powered photodetection. Herein, broadband light-induced pyroelectric effects in a new 2D perovskite-type ferroelectric, (BBA)2(EA)2Pb3Br10 (1; BBA = p-bromobenzylammonium, EA = ethylammonium), showing a high Curie temperature of 425 K and notable pyroelectric coefficient (≈5.4 × 10−3 µC cm−2 K−1) is presented. Especially, photo-induced change of its electric polarization leads to ultraviolet-to-infrared pyroelectricity in a wide spectral region (377–1950 nm). Broadband photoactivities actualized by this property break the limitation of its optical bandgap. Thus, single-crystal detectors of 1 are sensitive to UV-to-IR light with a small temperature fluctuation of 0.3 K, exhibiting a high transient responsivity up to ≈0.28 mA W−1 and specific detectivity of 1.31 × 1010 Jones under zero bias (at 405 nm); such figure-of-merits are beyond than those self-powered photodetectors using oxide ferroelectrics. It is anticipated that the findings of light-induced pyroelectricity afford a feasible strategy to assemble newly-conceptual smart photoelectric devices, such as self-powered broadband detectors.  相似文献   

12.
Dielectric ceramics are fundamental for electronic systems, including energy storages, microwave applications, ultrasonics, and sensors. Relaxor ferroelectrics show superb performance among dielectrics due to their high efficiency and energy density by the nature of nanodomains. Here, a novel non-perovskite relaxor ferroelectric, Bi6Ti5WO22, with ultralow loss, ≈10−3, highly tunable permittivity, ≈2200 at room temperature with 40% tunability and the superparaelectric region at room temperature is presented. The actual crystal structure and the nanodomains of Bi6Ti5WO22 are demonstrat Various-temperature neutron powder diffraction and in situ high-resolution transmission-electron-microscopy illustrate the twinning effect, subtle structure change and micro-strain in the material influenced by temperature, manifesting the actual crystal structure of Bi6Ti5WO22. Compared with dielectric loss of BaTiO3-based dielectric tunable materials, the loss of Bi6Ti5WO22 is more than an order of magnitude lower, which makes it exhibit a figure of merit (≈240), much higher than that of conventional dielectric tunable materials (< 100), endorse the material great potential for direct applications. The present research offers a strategy for discovering novel relaxor ferroelectrics and a highly desirable material for fabricating energy storage capacitors, microwave dielectrics, and ultrasonics.  相似文献   

13.
Hafnium-based binary oxides have attracted considerable attention due to their robust ferroelectricity at the nanoscale and compatibility with silicon-based electronic technologies. To further promote the potential of Hafnium oxides for practical device applications, it is essential to effectively harness the interplay between structural symmetry, domain configuration, and ferroelectricity. Here, using Hf0.5Zr0.5O2/La0.67Sr0.33MnO3 (HZO/LSMO) heterostructures as a model system, the anisotropic strain-mediated symmetry engineering and ferroelectricity enhancement are systematically investigated. By growing the heterostructures on (110)-oriented perovskite substrates, considerable anisotropic strain is imposed on the LSMO bottom electrodes. Such an anisotropically-strained LSMO layer acts as a structural template and effectively tune the structural symmetry, polar/non-polar phase ratio, and ferroelectricity of the HZO top layer. Specifically, the anisotropic tensile strain stabilizes the ferroelectric rhombohedral and orthorhombic phases, thus enhancing the remnant polarization (Pr) up to 22 µC cm−2. In contrast, the anisotropic compressive strain facilitates the formation of non-ferroelectric tetragonal phases, leading to a suppressed Pr down to 8 µC cm−2. These findings provide a guideline for understanding and modulating the intrinsic structure-ferroelectricity relationship of HZO through anisotropic strain-mediated symmetry engineering, which may shed light on the development of hafnium-oxide-based electronic devices.  相似文献   

14.
The integration of thin-film ferroelectrics with reliable properties into oxide electronics requires accomplishing deterministic polarization states. Since ferroelectricity emerges during thin-film synthesis already, it is essential to elucidate how the interplay of different growth parameters affects the polarization. Here, the polarization of fully strained Pb(Zr0.2Ti0.8)O3 (PZT) films is accessed in situ, during epitaxial growth. Surprisingly, it is found that the orientation of the out-of-plane polarization during growth may differ from the one after growth completion and it strongly depends on the substrate temperature and the oxygen partial pressure. Increasing the growth temperature and/or the oxygen partial pressure favors a uniform downward-oriented polarization, independent of the direction of polarization during growth. Specifically, for films with an emerging upward-oriented polarization, a polarization reversal and a downward-oriented polarization after cool-down is observed. The in situ measurements obtained by optical second harmonic generation (SHG) in conjunction with ex situ piezoresponse force microscopy (PFM) and X-ray diffraction (XRD) measurements point to the temperature- and pressure-dependent formation of a charged Pb defect gradient toward the film surface as the responsible mechanism for the polarization reorientation.  相似文献   

15.
PbTiO3 (PTO) is explored as a versatile and tunable electron‐selective layer (ESL) for perovskite solar cells. To demonstrate effectiveness of PTO for electron–hole separation and charge transfer, perovskite solar cells are designed and fabricated in the laboratory with the PTO as the ESL. The cells achieve a power conversion efficiency (PCE) of ≈12.28% upon preliminary optimization. It is found that the PTO ferroelectric layer can not only increase the PCE, but also tune the photocurrent via tuning PTO's ferroelectric polarization. Moreover, to understand the physical mechanism underlying the carrier transport by the ferroelectric polarization, the electronic structure of PTO/CH3NH3PbI3 heterostructure is computed using the first‐principles methods, for which the triplet state is used to simulate charge transfer in the heterostructure. It is shown that the synergistic effect of type II band alignment and the specific ferroelectric polarization direction provide the effective extraction of electrons from the light absorber, while minimize recombination of photogenerated electron–hole pairs. Overall, the ferroelectric PTO is a promising and tunable ESL for optimizing electron transport in the perovskite solar cells. The design offers a different strategy for altering direction of carrier transport in solar cells.  相似文献   

16.
Metal halide perovskites are maturing as materials for efficient, yet low cost solar cells and light‐emitting diodes, with improving operational stability and reliability. To date however, most perovskite‐based devices contain Pb, which poses environmental concerns due to its toxicity; lead‐free alternatives are of importance to facilitate the development of perovskite‐based devices. Here, the germanium‐based Ruddledsen–Popper series (CH3(CH2)3NH3)2(CH3NH3)n?1GenBr3n+1 is investigated, derived from the parent 3D (n = ∞) CH3NH3GeBr3 perovskite. Divalent germanium is a promising, nontoxic alternative to Pb2+ and the layered, 2D structure appears promising to bolster light emission, long‐term durability, and moisture tolerance. The work, which combines experiments and first principle calculations, highlights that in germanium bromide perovskites the optical bandgap is weakly affected by 2D confinement and the highly stereochemically active 4s2 lone pair preludes to possible ferroelectricity, a topic still debated in Pb‐containing compounds.  相似文献   

17.
Dion–Jacobson (DJ)-type 2D halide perovskites present superior environmental stability and a narrower bandgap, yet a contradiction between charge transport and stability remains to be resolved. Herein, it is shown that both symmetry and substitution of the organic spacer in DJ perovskites synergistically direct the narrow interlayer spacing, staggered spacer alignment, and regular phase arrangement, thereby promoting out-of-plane carrier transport and ambient stability. Compared to its symmetric para-xylylenediamine (PDMA) counterpart, the asymmetric 2-(4-aminophenyl)ethylamine (PMEA) spacer largely aids in compressing the inorganic octahedra layer to form a non-confinement structure with decreased exciton binding energy, while stacked benzene rings enable a staggered alignment of spacers. Such non-confined structures are less remarkable in meta-substituted diamine-based DJ perovskites than those para-ones, which retard carrier transport from 2D to quasi-2D phases. The preferential PMEA spacer however requires a long relaxation time to form a dense and ordered staggered alignment, which is realized by a slight addition of strong-coordinating DMSO into the DMF solvent, thus decelerating crystallization and further optimizing lamellar orientation. As a result, a best efficiency of ≈ 12% is achieved in (PMEA)MA3Pb4I13 based p-i-n type planar solar cells. Importantly, such unencapsulated devices can maintain 81% initial efficiencies after storage in ambient conditions ( ≈ 60% relative humidity, ≈ 20 °C) for 700 h.  相似文献   

18.
Multiferroic heterostructures composed of complex oxide thin films and ferroelectric single crystals have aroused considerable interest due to the electrically switchable strain and charge elements of oxide films by the polarization reversal of ferroelectrics. Previous studies have demonstrated that the electric‐field‐control of physical properties of such heterostructures is exclusively due to the ferroelectric domain switching‐induced lattice strain effects. Here, the first successful integration of the hexagonal ZnO:Mn dilute magnetic semiconductor thin films with high performance (111)‐oriented perovskite Pb(Mg1/3Nb2/3)O3‐PbTiO3 (PMN‐PT) single crystals is reported, and unprecedented charge‐mediated electric‐field control of both electronic transport and ferromagnetism at room temperature for PMN‐PT single crystal‐based oxide heterostructures is realized. A significant carrier concentration‐tunability of resistance and magnetization by ≈400% and ≈257% is achieved at room temperature. The electric‐field controlled bistable resistance and ferromagnetism switching at room temperature via interfacial electric charge presents a potential strategy for designing prototype devices for information storage. The results also disclose that the relative importance of the strain effect and interfacial charge effect in oxide film/ferroelectric crystal heterostructures can be tuned by appropriately adjusting the charge carrier density of oxide films.  相似文献   

19.
Great progress has been made recently in molecular ferroelectrics with properties even comparable to those of inorganic ferroelectrics. However, it is difficult to develop basic thin films and devices for practical applications since most molecular ferroelectrics are uniaxial. The single polar axes of crystallites inside their films, if available, are usually oriented randomly. These can induce the components without contribution to ferroelectric polarization and a large depolarization electric field to suppress polarization. In this work, it is demonstrated that uniaxial croconic acid films in two‐terminal devices, deposited by thermal evaporation, can show effective ferroelectric polarization and nonvolatile memory switching behavior with small coercive fields of 11–30 kV cm?1. The polar c‐axes in thick crystalline films (>500 nm) are found to be self‐oriented nearly at a desired direction. With the assistance of trapped charges, stable ferroelectric polarization can be achieved, in spite of the existence of nonferroelectric components. These may pave a way to utilize uniaxial molecular ferroelectrics for various applications, such as gate dielectrics, electrets, and memory devices.  相似文献   

20.
The next-generation semiconductor memories are essentially required for the advancements in modern electronic devices. Ferroelectric memories by HfO2-based ferroelectric thin films (FE-HfO2) have opened promising directions in recent years. Nevertheless, improving the polarization switching speed of FE-HfO2 remains a critical task. In this study, it is demonstrated that the composition-graded Hf1-xZrxO2 (HZO) ferroelectric thin film has more than two times faster polarization switching speed than the conventional composition-uniform one. Meanwhile, it has excellent ferroelectricity and improved endurance characteristics. It is also discovered that when the HZO thin film has a gradient composition, the polarization-switching dynamics shifts from the nucleation-limited-switching mechanism to the domain-wall growth mechanism. Moreover, the transition of switching dynamics is responsible for the faster speed and better endurance of the composition-graded HZO thin film. These findings not only reveal the physical mechanisms of this material system but also provide a new strategy for memory devices having faster speed and higher endurance.  相似文献   

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