Perovskite Nanosheets Research Articles

Graded interface engineering of 3D/2D halide perovskite solar cells through ultrathin (PEA)2PbI4 nanosheets

2D halide perovskites have emerged as promising materials because of their stability and passivation effect in perovskite solar cells (PSCs). However, the introduction of bulky organic ammonium cations from 2D halide perovskites would decrease the device performance generally compared to the traditional 3D MAPbI3. Incorporation of ultrathin 2D halide perovskite nanosheets (NSs) with 3D MAPbI3 could address this issue. Herein, we report a rationally designed PSCs with dimensional graded 3D/2D MAPbI3/(PEA)2PbI4 heterojunction, in which 2D (PEA)2PbI4 NSs were synthesized and incorporated between 3D MAPbI3 and hole-transporting layer. Besides the significantly improved stability, a notable increasement in power conversion efficiency (PCE) of 20% was obtained for the 3D/2D perovskite solar cells due to the favourable band alignment among (PEA)2PbI4 NSs and the other components. The graded structure of MAPbI3/(PEA)2PbI4 would upshift the energy level continuously, which enhances the hole extraction efficiency thus reduces the interface charge recombination, leading to the increasements of VOC from 1.04 V to 1.07 V, JSC from 21.81 mA/cm2 to 23.15 mA/cm2 and the fill factor from 67.89% to 74.78%, and therefore an overall PCE of 18.53%.

Thickness dependent properties of ultrathin perovskite nanosheets with Ruddlesden-Popper-like atomic stackings.

Ruddlesden-Popper perovskites possess a rich variety of multiple phases due to their mixed organic cations and variable layer numbers. However, the direct observation of these phases and their optical performance in ultrathin nanosheets, have rarely been reported. Here we demonstrate, through a one-pot CVD synthesis method to incorporate MA+ and NMA+ cations into PbI2 simultaneously, that the stackings of Ruddlesden-Popper phases with a distribution of a number of layers 〈n〉 can be produced within a single perovskite nanosheet. As featured by the micro-, time-resolved and temperature-dependent photoluminescence measurements, the optical properties are highly dependent on the nanosheet thickness.

Continuous production of ultrathin organic-inorganic Ruddlesden-Popper perovskite nanoplatelets via a flow reactor.

Because of their enhanced quantum confinement, colloidal two-dimensional Ruddlesden-Popper (RP) perovskite nanosheets with a general formula L2[ABX3]n-1BX4 stand as a promising narrow-wavelength blue-emitting nanomaterial. Despite ample studies on batch synthesis, for RP perovskites to be broadly applied, continuous synthetic routes are needed. Herein, we design and optimize a flow reactor to continuously produce high-quality n = 1 RP perovskite nanoplatelets. The effects of antisolvent composition, reactor tube length, precursor solution injection rate, and antisolvent injection rate on the morphology and optical properties of the nanoplatelets are systematically examined. Our investigation suggests that flow reactors can be employed to synthesize high-quality L2PbX4 perovskite nanoplatelets (i.e., n = 1) at rates greater than 8 times that of batch synthesis. Mass-produced perovskite nanoplatelets promise a variety of potential applications in optoelectronics, including light emitting diodes, photodetectors, and solar cells.

A versatile approach for shape-controlled synthesis of ultrathin perovskite nanostructures.

Very recently, ultrathin perovskite nanostructures, with the advantages of perovskite and ultrathin properties, have received an enormous level of interest due to their many fascinating properties, such as a strong quantum confinement effect and a large specific surface area. In spite of this incredible success of perovskite nanocrystals (NCs), the development of perovskite NCs is still in its infancy, and the production of high-quality ultrathin perovskite nanostructures has been a hot topic in the fields of nanoscience and nanotechnology. Herein, we demonstrate that ultrathin CsPbBr3 perovskite nanosheets (NSs) can be obtained by a simple mixing of precursor-ligand complexes under ambient conditions. It was found that the formation of NSs is ascribed to the stepwise self-assembly of the initially formed different types of ultrathin nanostructures. Due to the disappearance of grain boundaries and protection of branched ligands, these NSs exhibit enhanced optical properties compared to other types of samples. This direct synthesis method opens up a promising road for the synthesis of ultrathin NSs and guides the fabrication of other ultrathin nanostructures.

Rational Assembly of Two-Dimensional Perovskite Nanosheets as Building Blocks for New Ferroelectrics.

Artificial materials in the form of superlattices have been studied actively in quest of new engineering methods or design rules for the development of desired functionalities, in particular high-k ferroelectricity, ferromagnetism, and high mobility electron gas. This work presents a controlled assembly strategy for fabricating atomically precise interfaces of two-dimensional (2D) homologous perovskite nanosheets (Ca2Nam-3NbmO3m+1-; m = 3-6) to construct artificial superlattices. The distinctive thickness of each 2D homologous perovskite nanosheets attributed to the presence of different number of NbO6 octahedra provides an exquisite control to engineer interfacial properties for tailored design of superior high-k properties and emergence of ferroelectricity. The higher dielectric constant (εr = 427) and development of ferroelectricity for (Ca2Nb3O10-/Ca2Na2Nb5O16-)6 superlattice indicate that superlattice films with both odd number of NbO6 octahedra possess extended polarization due to the potential effect of heterointerface and ferroelectric instabilities. Furthermore, the increased discontinuities/offsets in Ca2Nb3O10- and Ca2Na3Nb6O19- nanosheets band alignment results in superior insulating properties (∼1 × 10-11 A cm-2 at 1 V) for (Ca2Nb3O10-/Ca2Na3Nb6O19-)6 superlattice. These findings exhibit new research opportunities for the development of novel artificial high-k dielectric/ferroelectric via precise control of interfaces at the atomic level and can be extended to the large family of 2D perovskite compounds.

Pressure-Driven Transformation of CsPbBrI2 Nanoparticles into Stable Nanosheets in Solution through Self-Assembly.

Very recently, two-dimensional (2D) perovskite nanosheets (PNSs), taking the advantages of perovskite as well as the 2D structure properties, have received an enormous level of interest throughout the scientific community. In spite of this incredible success in perovskite nanocrystals (NCs), self-assembly of many nanostructures in metal halide perovskites has not yet been realized, and producing highly efficient red-emitting PNSs remains challenging. In this Letter, we show that by using CsPbBrI2 perovskite nanoparticles (NPs) as a building block, PNSs can emerge spontaneously under high ambient pressure via template-free self-assembly without additional complicated operation. It is found that the formation of PNSs is ascribed to the high pressure that provides the driving force for the alignment of NPs in solution. Because of the disappearance of the grain boundaries between the adjacent NPs and increased crystallinity, these PNSs self-assembled from NPs exhibit enhanced properties compared to the initial NPs, including higher PL intensity and remarkable chemical stability toward light and water.

Probing the Dielectric Effects on the Colloidal 2D Perovskite Oxides by Eu3+ Luminescence.

Solution-processing technique of two-dimensional (2D) materials requires the knowledge of the dielectric effects on mutual interaction of each component and the layer structure variation. This research uses the magnetic dipole (MD) transition of intentionally doped Eu3+, which is dependent on the dielectric environments, as an optical probe to study the dielectric effects on the colloidal charge-bearing [Ca1.8Eu0.1Na0.1Nb3O10]- perovskite nanosheets (NSs) in various solvents. Results reveal that the solvent molecules with longer alkyl chain could more easily impact the ligands on the surface of the NSs, leading to a weaker interaction between the ligands and the NSs as well as less distortion of Eu3+ site (Ca2+ site) at the inner layer of the NSs. The large-sized ligands would impede the stacking of the NSs, while H+ would make the H+-modified NSs restack more easily. With the assistance of density functional theory (DFT) simulation, it is found that the ligands or the dielectric solvents could distort or relax the surface covalent polyhedra [NbO6]7- to a larger extent than the inner polyhedra. Small-sized ligands and a large thickness with more atomic layers of the NSs can resist structural variation caused by solvents. The acquired knowledge in this research benefits the understanding of the solution-processing technique for industrial application of 2D materials.

Orthorhombically distorted perovskite SeZnO3 nanosheets as an electrocatalyst for lithium-oxygen batteries

Perovskite ABO3 provides higher catalytic activity than binary metal oxides owing to crystallographic defects and oxygen vacancies due to the multivalence of the A and B cations. In this study, perovskite SeZnO3 nanosheets were synthesized via a simple wet chemistry method with sodium dodecyl sulfate as the surfactant. Material surface analysis using O 1s X-ray photo-electron spectroscopy confirmed an Ovacancy concentration of 50%, confirming the presence of large amounts of defects on the surface of the SeZnO3 nanosheets. The lithium-oxygen batteries with SeZnO3 nanosheet as an oxygen-electrode electrocatalyst exhibited a high reversibility (140 cycles) and a stable rate capability (50–500 mA g−1). Additionally, electrochemical impedance spectroscopy measurements indicated that the electronic conductivity of a SeZnO3 nanosheet was higher than that of ZnO. Therefore, we propose that the unique SeZnO3 structure exhibits excellent catalytic activity and electrical conductivity and can serve as a route towards improved lithium-oxygen batteries.

All-Inorganic Perovskite CsPb2Br5 Nanosheets for Photodetector Application Based on Rapid Growth in Aqueous Phase

All-inorganic cesium lead-halide perovskites exhibit great development prospect in optoelectronic devices owning to their stability and remarkable optoelectronic properties. Herein, we investigate the solution-processed synthesis of perovskite CsPb2Br5 nanosheets by using aqueous and ethanol as solvent. The result shows that the aqueous environment ensures the phase formation of CsPb2Br5, and that the supersaturated solution in ethanol boosts nucleation of the nanosheets. The substrates temperature is the key factor for the evolution of morphology and the variation of the thickness of CsPb2Br5 nanosheets. Lower substrate temperature (<35 °C) is conducive to the formation of evenly distributed nanosheets with less stacking. The spatial and time-resolved fluorescence spectra indicate the heterogeneity of the defect density and the recombination process in different nanosheet regions. The photodetector based on the prepared CsPb2Br5 nanosheet displays excellent switching current ratio (9×102), short rise and decay time (43 ms and 83 ms respectively) and good stability (75% of initial current after 90 days in air). In addition, the mechanical stability and flexibility of photodetector on the flexible substrate are investigates for bending 500 cycles.

Solution-Processed Quasi-Two-Dimensional/Nanoscrystals Perovskite Composite Film Enhances the Efficiency and Stability of Perovskite Light-Emitting Diodes.

Solution-processed quasi-two-dimensional (Q-2D)/colloidal perovskite nanocrystals (PNCs) perovskite composite films are first prepared as the emitting layers of perovskite light-emitting diodes (PeLEDs). The subsequent multi-spin-coating of PNCs not only fills the gully-like fluctuations of the nanocrystal pinning-prepared Q-2D perovskite films and decreases their surface roughness but also transforms the bilayer perovskite nanosheets into multilayer ones, thus improving the charge transport and reducing the hole-injection barrier in the composite films. More importantly, the bromide vacancies and Pb defects in the Q-2D perovskites are removed via Br- supply and Pb-OOC-R interaction, in which the Br ions and COO- groups (from oleic acid) come from the PNC solution, and the radiation recombination is significantly enhanced. Based on the Q-2D/PNCs perovskite composite emitter, the PeLEDs achieve a maximum luminescence of ∼2.0 × 104 cd/m2 and a peak current efficiency of 27.5 cd/A, showing 175 and 337% enhancements compared to the control device with the pristine Q-2D perovskite emitter. The lifetime for the luminance decaying to 50% of the initial intensity increases by a factor of 13.8, demonstrating that the device stability is also improved by the Q-2D/PNCs perovskite composite film.

Silver Adsorption on Calcium Niobate(001) Nanosheets: Calorimetric Energies That Explain Sinter-Resistant Support.

Metal nanoparticles deposited on oxide supports are essential to many technologies, including catalysts, fuel cells, and electronics. Therefore, understanding the chemical bonding strength between metal nanoparticles and oxide surfaces is of great interest. The adsorption energetics, adhesion energy, and adsorbate structure of Ag on dehydrated HCa2Nb3O10(001) nanosheets at 300 K have been studied using metal adsorption calorimetry and surface spectroscopies. These dehydrated ("dh") calcium niobate nanosheets (dh-HCa2Nb3O10(001)) have the stoichiometry Ca4Nb6O19. They impart unusual stability to metal nanoparticles when used as catalyst supports and are easy-to-prepare by Langmuir-Blodgett (LB) techniques, highly ordered, and essentially single-crystal surfaces of mixed oxides with a huge ratio of terrace to edge sites. Below the monolayer coverage, Ag grows on dh-HCa2Nb3O10(001) as 2D islands of thickness ∼2 layers. The differential heat of Ag adsorption is initially ∼303 kJ/mol, increasing slowly to ∼338 kJ/mol by 0.8 ML. At higher coverages, Ag atoms mainly add on top of these 2D islands, growing 3D nanoparticles of increasing thickness, as the heat decreases asymptotically toward silver's heat of sublimation (285 kJ/mol). The adhesion energy of Ag(s) to this Ca niobate surface is estimated to be 4.33 J/m2, larger than that on any oxide surface previously measured. This explains the sinter resistance reported for metal nanoparticles on this support. Electron transfer from Ag into the calcium niobate is also measured. These results demonstrate an easy way to do single-crystal-type surface science studies-and especially thermochemical measurements-on the complex surfaces of mixed oxides: using LB-deposited perovskite nanosheets and ultrahigh-vacuum annealing in O2.

Engineering the Phases and Heterostructures of Ultrathin Hybrid Perovskite Nanosheets.

Low-dimensional perovskites have gained increasing attention recently, and engineering their material phases, structural patterning and interfacial properties is crucial for future perovskite-based applications. Here a phase and heterostructure engineering on ultrathin perovskites, through the reversible cation exchange of hybrid perovskites and efficient surface functionalization of low-dimensional materials, is demonstrated. Using PbI2 as precursor and template, perovskite nanosheets of varying thickness and hexagonal shape on diverse substrates is obtained. Multiple phases, such as PbI2 , MAPbI3 and FAPbI3 , can be flexibly designed and transformed as a single nanosheet. A perovskite nanosheet can be patterned using masks made of 2D materials, fabricating lateral heterostructures of perovskite and PbI2 . Perovskite-based vertical heterostructures show strong interfacial coupling with 2D materials. As a demonstration, monolayer MoS2 /MAPbI3 stacks give a type-II heterojunction. The ability to combine the optically efficient perovskites with versatile 2D materials creates possibilities for new designs and functionalities.

Impact of excitation energy on the excitonic luminescence of cesium lead bromide perovskite nanosheets.

An excitation-energy-dependent luminescence phenomenon is reported in cesium lead bromide (CsPbBr3) perovskite nanosheets. At 10 K, the relative integrated luminescence intensity between the trapped exciton (TX) emission and the free exciton (FX) emission shows an interesting tendency with increasing the optical excitation energy from 2.431 eV (510 nm) to 3.758 eV (330 nm). To interpret such phenomenon, we develop a quantitative model on the basis of the biological population growth theory. A good agreement between experiment and theory is obtained. It is thus revealed that the lower capture coefficient of the TX level to the excited excitons via multiphonon emission relative to the FX level shall be the major cause of the observed phenomenon. These findings may help to deepen the current understanding of the complex luminescence mechanisms of these emerging light-emitting materials.

Flat Lenses Based on 2D Perovskite Nanosheets.

Ultrathin flat lenses based on metasurfaces or metamaterials have shown great promise in recent years as essential components in nano-optical system, with capability of abrupt changes of light wavefronts. However, such structural designs require complex nanopatterns and a time-consuming nanofabrication process. In this regard, flat lenses are developed based on 2D perovskite nanosheets, using a cost-effective mask-free femtosecond direct laser writing system. The optical properties of the 2D perovskite are rationally adjusted through facile composition engineering as well as thickness-dependent quantum-size confinement. A diffraction theory model is derived to understand the focusing mechanism of the 2D perovskite nanosheets flat lenses. The as-fabricated lenses exploit the tunable material property variations to effectively manipulate not only the amplitude but also the phase of the incident light to focus into a 3D focal spot with a sub-wavelength resolution in the range of 0.5-0.9λ. The results pave the way toward low-cost and large-scale high-resolution imaging applications in the future.

Noble-metal-free CoxP nanoparticles: modified perovskite oxide ultrathin nanosheet photocatalysts with significantly enhanced photocatalytic hydrogen evolution activity

The integration of semiconductor-based photocatalysts with noble-metal-free cocatalysts has great significance for practical applications. In this work, for the first time, novel CoxP/K+Ca2Nb3O10− nanostructures (abbreviated as CoxP/KCNOus) were synthesized by integrating noble-metal-free CoxP nanoparticles onto the surface of K+Ca2Nb3O10− ultrathin nanosheets (abbreviated as KCNOus), and exhibited enhanced photocatalytic hydrogen generation. Under the irradiation of xenon light, the hydrogen generation rate of the resulting optimal CoxP/KCNOus reached up to 90.4 μmol g−1 h−1, approximately 5.78 times higher than that of single-component KCNOus. The apparent quantum efficiency (AQE) of CoxP/KCNOus is 1.32% at 350 nm. Based on photoluminescence (PL), UV–vis diffuse reflectance spectroscopy (UV–vis DRS), and photo-electrochemical analyses, possible reasons for this improved photocatalytic activity can be ascribed to the enhanced light absorption capacity and strong separation efficiency of photoinduced carriers over CoxP/KCNOus owing to the formation of the interfaces between KCNOus and CoxP nanoparticles. It is believed that this work will provide a new insight into the development ofefficient and low-cost noble-metal-free cocatalysts for photocatalytic hydrogen evolution reactions.

Highly Efficient Surface Modification of Layered Perovskite Nanosheets with a Phosphorus Coupling Reagent Making Use of Microchannels.

Surface modification of niobate nanosheets in a double-Y-type microchannel was achieved for the first time using parallel flows of an aqueous dispersion of nanosheets derived from ion-exchangeable layered perovskite via delamination with a tetrabutylammonium hydroxide aqueous solution and a cyclohexane solution of oleyl phosphate. The surface modification was essentially completed within 4.6 s, and spectroscopic characterization (IR, solid-state 13C and 31P NMR) demonstrated the successful surface modification. The surface modification using a biphasic system in a vial using the same liquids required more than 4 h, indicating the extremely high efficiency of surface modification in the microchannel.

Quantum dots of two-dimensional Ruddlesden–Popper organic–inorganic hybrid perovskite with high optical limiting properties

Hybrid perovskites have been investigated for various potential applications because of their tunable optical properties. In this paper, we report the synthesis of quantum dots (QDs) of two-dimensional (2D) Ruddlesden–Popper (RP) hybrid perovskite using a top-down approach. The QDs of the developed 2D RP perovskite exhibit high and sharp photoluminescence in the ultraviolet region. The sharp peak in the absorption spectrum and the intense photoluminescence in the ultraviolet region indicate strong quantum confinement in these particles, which is further confirmed by x-ray photoelectron spectroscopy. These QDs show superior nonlinear optical scattering and absorption properties with the optical z-scan technique and strong nonlinear absorption property with the photoacoustic z-scan technique. Evaluating the nonlinear optical properties using two complementary techniques provides a deeper understanding of the nonlinear mechanism involved in the optical limiting process. The two-photon absorption coefficient obtained by optical z-scan is 7.2 × 102 cm/GW, which is larger than that of most perovskite nanocrystals and nanosheets. Our studies, therefore, reveal a new class of material, 2D RP perovskite QDs, which show important nonlinear properties that are important for optical limiting applications.

Quasi-2D organic cation-doped formamidinium lead bromide (FAPbBr3) perovskite light-emitting diodes by long alkyl chain

Abstract Organic-inorganic hybrid perovskites (OIHP) are promising materials for high efficiency light emitting diode (LEDs) due to their high color purity, their high photo-luminescence quantum yield and their bandgap tuneability. Introducing long chain ammonium halide in a perovskite films can result in energy funneling from a distribution of two-dimensional perovskite nanosheets to three-dimensional nanocrystals through energy cascade from high bandgap energy states (nanosheets) to lower bandgap energy states (nanocrystals), or enhance the passivation of the 3D nanocrystals. Thus, the electrical charge injection in the emitter site is enhanced or the non-radiative recombination rate is reduced. Here we report on the doping of a FAPbBr3 green-emitter with n-BABr (butyl ammonium bromide). Upon addition of a small amount of n-BABr (0.2 wt%) in a non-stoichiometric perovskite solution, the photoluminescence intensity of thin films and current efficiency of PeLEDs increase by about an order of magnitude, from 1.2 Cd/A without to 13.5 Cd/A with n-BABr doping.

Precise Tuning of the Thickness and Optical Properties of Highly Stable 2D Organometal Halide Perovskite Nanosheets through a Solvothermal Process and Their Applications as a White LED and a Fast Photodetector.

Precise control of the thickness of large-area two-dimensional (2D) organometal halide perovskite layers is extremely challenging owing to the inherent instability of the organic component. Herein, a novel, highly reproducible, and facile solvothermal route is reported to synthesize and tailor the thickness and optical band gap of the organic-inorganic halide perovskite nanosheets (NSs). Our study reveals that self-assembly of randomly oriented perovskite nanorods leads to the growth of multilayered perovskite NSs at ∼100 °C, while at higher temperature, large-area few-layer to bilayer 2D NSs (CH3NH3PbBr3) are obtained through lattice expansion and layer separation depending precisely on the temperature. Interestingly, the thickness of the 2D NSs shows a linear dependence on the reaction temperature and thus enables precise tuning of the thickness from 14 layers to 2 layers, giving rise to a systematic increase in the band gap and appearance of excitonic absorption bands. Quantitative analysis of the change in the band gap with thickness revealed a strong quantum confinement effect in the 2D layers. The perovskite 2D NSs exhibit tunable color and a high photoluminescence (PL) quantum yield (QY) up to 84%. Through a careful analysis of the steady-state and time-resolved PL spectra, the origin of the lower PL QY in thinner NSs is traced to surface defects in the 2D layers, for the first time. A white light converter was fabricated using the composition-tuned 2D CH3NH3PbBrI2 NS on a blue light-emitting diode chip. The 2D perovskite photodetector exhibits a stable and very fast rise/fall time (24 μs/103 μs) along with high responsivity and detectivity of ∼1.93 A/W and 1.04 × 1012 Jones, respectively. Storage, operational, and temperature-dependent stability studies reveal high stability of the 2D perovskite NSs under the ambient condition with high humidity. The reported method is highly promising for the development of large-area stable 2D perovskite layers for various cutting-edge optoelectronic applications.

Charge transfer from perovskite oxide nanosheets to N-doped carbon nanotubes to promote enhanced performance of a zinc-air battery.

Room temperature engineered spatially connected p-type double perovskite oxide (BaPrMn1.75Co0.25O5+δ, BPMC) nanosheets (NSs) with n-type nitrogen-doped multi-walled carbon nanotubes (NCNTs) show significant enhancement in bifunctional oxygen electrocatalytic activity. The optimization of the donor level by charge transfer from the perovskite to NCNTs is demonstrated to be a prodigious approach to facilitate redox oxygen activation. A proof-of-concept rechargeable zinc-air battery (ZAB) with BPMC containing a 10 wt% NCNT (BPMC/NCNT-10) cathode demonstrates the highest specific discharge capacity of 789.2 mA h gZn-1 and cyclic stability for 85 h at a current density of 5 mA cm-2.