Two-dimensional Hybrid Perovskites Research Articles

Structural and photophysical properties of two-dimensional lead bromide hybrid perovskite (C8H17NH3)2PbBr4

The structural versatility of organic compounds imparts manifold properties to hybrid organic−inorganic perovskites, where two-dimensional (2D) halide perovskites are potential future platforms for light-emitting devices because of their unique quantum well configuration and dielectric confinement. Notwithstanding the numerous studies on the organic−inorganic perovskites carried out to date, precisely charactering the structure and photoluminescence mechanism remain considerable challenges. Herein, by applying Rietveld refinement, we have obtained crystal structure and atomic sites of 2D layered OA2PbBr4 perovskite, which undergoes a phase transition at 190 K with activation energies of 29.6 and 3.8 meV for the two phases, respectively. The theoretical analysis based on the crystal structure were performed to understand the nature of vibrations and band structure. Steady-state PL shows a narrow emission and a broad emission located at 409 and 487 nm, respectively. With temperature cooling down to 118 K, narrow emission gradually narrowed and enhanced. Meanwhile, intensity of broad emission first weakens and then increases. The turning point occurs near 198 K. By applying time-resolved PL (TRPL) and transient absorption (TA) spectra experiment, we observed a rapid carrier transfer from the FE to the STE state, and demonstrated the narrow and broad bands originate from free exciton and self-trapped exciton emission, respectively. And the self-trapping depth is proved to be 26.3 meV by low-temperature PL. Our findings indicate the synthesized 2D perovskite has potential applications in optoelectronic and display devices.

Organic Ligand Engineering for Tailoring Electron-Phonon Coupling in 2D Hybrid Perovskites.

In the emerging two-dimensional organic-inorganic hybrid perovskites, the electronic structures and carrier behaviors are strongly impacted by intrinsic electron-phonon interactions, which have received inadequate attention. In this study, we report an intriguing phenomenon of negative carrier diffusion induced by electron-phonon coupling in (2T)2PbI4. Theoretical calculations reveal that the electron-phonon coupling drives the band alignment in (2T)2PbI4 to alternate between type I and type II heterostructures. As a consequence, photoexcited holes undergo transitions between the organic ligands and inorganic layers, resulting in abnormal carrier transport behavior compared to other two-dimensional hybrid perovskites. These findings provide valuable insights into the role of electron-phonon coupling in shaping the band alignments and carrier behaviors in two-dimensional hybrid perovskites. They also open up exciting avenues for designing and fabricating functional semiconductor heterostructures with tailored properties.

Unveiling the Influence of Organic Chain Length on the Physical Properties of Two-Dimensional Cobalt-Based Hybrid Perovskites

Unveiling the Influence of Organic Chain Length on the Physical Properties of Two-Dimensional Cobalt-Based Hybrid Perovskites

Research Progress on Rashba Effect in Two-Dimensional Organic-Inorganic Hybrid Lead Halide Perovskites.

The Rashba effect appears in the semiconductors with an inversion-asymmetric structure and strong spin-orbit coupling, which splits the spin-degenerated band into two sub-bands with opposite spin states. The Rashba effect can not only be used to regulate carrier relaxations, thereby improving the performance of photoelectric devices, but also used to expand the applications of semiconductors in spintronics. In this mini-review, recent research progress on the Rashba effect of two-dimensional (2D) organic-inorganic hybrid perovskites is summarized. The origin and magnitude of Rashba spin splitting, layer-dependent Rashba band splitting of 2D perovskites, the Rashba effect in 2D perovskite quantum dots, a 2D/3D perovskite composite, and 2D-perovskites-based van der Waals heterostructures are discussed. Moreover, applications of the 2D Rashba effect in circularly polarized light detection are reviewed. Finally, future research to modulate the Rashba strength in 2D perovskites is prospected, which is conceived to promote the optoelectronic and spintronic applications of 2D perovskites.

Boosting the internal electron transfer of two-dimensional hybrid perovskites via fluorination of organic cation towards enhanced photocatalytic hydrogen production

Two-dimensional (2D) organic-inorganic hybrid perovskites have emerged as promising candidates for photocatalytic hydrogen production due to their unique optoelectronic properties. However, the organic cations in the interlayer of 2D perovskites generally retard the internal charge transfer due to the large interlayer van der Waals barrier for electron transfer, which defines the imperative to engineering the organic entity. Herein, taking phenethylammonium lead iodide (PEA2PbI4) as a typical example, we show that by substituting the hydrogen with fluorine atom in the para-position of the phenyl group, the internal electron transfer was promoted remarkably. The improved electron transfer is ascribed to the introduction of fluorine with strong electronegativity, which leads to interlayer polarization and almost zero-potential barrier between the organic layers. Consequently, 4-FPEA2PbI4 exhibits ca. 8.2 times higher photocatalytic H2 evolution activity than PEA2PbI4. This work establishes a paradigm for optimizing the photocatalytic properties of 2D hybrid perovskites by engineering the organic cations.

Modelling iodine diffusion in 2D-Perovskites as a function of the length of the organic spacer molecules

Two-dimensional (2D) hybrid perovskites have emerged as promising materials for solar cell applications, offering increased stability and reduced ionic movements compared to the more commonly used 3D-perovskites. The atomistic mechanisms behind the lower ionic diffusion in these perovskites have remained rather underexplored. In this study, we have used density functional theory (DFT) to investigate the potential tunability of ionic movements in 2D-perovskites by varying the spacer molecules in the structure. We demonstrate that by changing the length of the spacer molecule, and thus the distance between the two-dimensional inorganic slabs of corner sharing lead halide octahedra, it is possible to significantly modulate the periodic potential distribution and long-range electrostatic interactions within these materials. This modulation has a distinct impact on the energy barriers for ionic movement. Notably, we find that longer spacer molecules decrease the energy barrier for in-plane iodine diffusion, while increasing the energy barrier for inter-layer diffusion. Furthermore, we observe a logarithmic relationship between the energy barrier for inter-layer diffusion and the inter-layer distance. These results clarify the mechanisms underlying the lower ionic movement in 2D-perovskites and open avenues for engineering ionic migration in novel 2D-perovskite structures, thus enhancing their applicability in optoelectronic technologies.

Two-Dimensional Hybrid Perovskite with High-Sensitivity Optical Thermometry Sensors.

Optical thermometry has gained significant attention due to its remarkable sensitivity and noninvasive, rapid response to temperature changes. However, achieving both high absolute and relative temperature sensitivity in two-dimensional perovskites presents a substantial challenge. Here, we propose a novel approach to address this issue by designing and synthesizing a new narrow-band blue light-emitting two-dimensional perovskite named (C8H12NO2)2PbBr4 using a straightforward solution-based method. Under excitation of near-ultraviolet light, (C8H12NO2)2PbBr4 shows an ultranarrow emission band with the full width at half-maximum (FWHM) of only 19 nm. Furthermore, its luminescence property can be efficiently tuned by incorporating energy transfer from host excitons to Mn2+. This energy transfer leads to dual emission, encompassing both blue and orange emissions, with an impressive energy transfer efficiency of 38.3%. Additionally, we investigated the temperature-dependent fluorescence intensity ratio between blue emission of (C8H12NO2)2PbBr4 and orange emission of Mn2+. Remarkably, (C8H12NO2)2PbBr4:Mn2+ exhibited maximum absolute sensitivity and relative sensitivity values of 0.055 K-1 and 3.207% K-1, respectively, within the temperature range of 80-360 K. This work highlights the potential of (C8H12NO2)2PbBr4:Mn2+ as a promising candidate for optical thermometry sensor application. Moreover, our findings provide valuable insights into the design of narrow-band blue light-emitting perovskites, enabling the achievement of single-component dual emission in optical thermometry sensors.

Modulation of active center distance of hybrid perovskite for boosting photocatalytic reduction of carbon dioxide to ethylene

Solar-driven photocatalytic CO2 reduction is an energy-efficient and sustainable strategy to mitigate CO2 levels in the atmosphere. However, efficient and selective conversion of CO2 into multi-carbon products, like C2H4, remains a great challenge due to slow multi-electron-proton transfer and sluggish C-C coupling. Herein, a two-dimensional thin-layered hybrid perovskite is fabricated through filling of oxygen into iodine vacancy in pristine DMASnI3 (DMA = dimethylammonium). The rational-designed DMASnI3(O) induces shrinkage of active sites distance and facilitates dimerization of C-C coupling of intermediates. Upon simulated solar irradiation, the DMASnI3(O) photocatalyst achieves a high selectivity of 74.5%, corresponding to an impressive electron selectivity of 94.6%, for CO2 to C2H4 conversion and an effective C2H4 yield of 11.2 μmol g-1 h-1. In addition, the DMASnI3(O) inherits excellent water stability and implements long-term photocatalytic CO2 reduction to C2H4 in a water medium. This work establishes a unique paradigm to convert CO2 to C2+ hydrocarbons in a perovskite-based photocatalytic system.

Tunneling-Driven Marcus-Inverted Triplet Energy Transfer in a Two-Dimensional Perovskite.

Quantum tunneling, a phenomenon that allows particles to pass through potential barriers, can play a critical role in energy transfer processes. Here, we demonstrate that the proper design of organic-inorganic interfaces in two-dimensional (2D) hybrid perovskites allows for efficient triplet energy transfer (TET), where quantum tunneling of the excitons is the key driving force. By employing temperature-dependent and time-resolved photoluminescence and pump-probe spectroscopy techniques, we establish that triplet excitons can transfer from the inorganic lead-iodide sublattices to the pyrene ligands with rapid and weakly temperature-dependent characteristic times of approximately 50 ps. The energy transfer rates obtained based on the Marcus theory and first-principles calculations show good agreement with the experiments, indicating that the efficient tunneling of triplet excitons within the Marcus-inverted regime is facilitated by high-frequency molecular vibrations. These findings offer valuable insights into how one can effectively manipulate the energy landscape in 2D hybrid perovskites for energy transfer and the creation of diverse excitonic states.

Carrier Transport in 2D Hybrid Organic-Inorganic Perovskites: The Role of Spacer Molecules.

Two-dimensional organic-inorganic hybrid perovskites (2D HOIPs) have been widely used for various optoelectronics applications owing to their excellent photoelectric properties. However, the selection of organic spacer cations is mostly qualitative without quantitative guidance. Meanwhile, the fundamental mechanism of the carrier transport across the organic spacer layer is still unclear. Here, by using the first-principles nonadiabatic molecular dynamics (NAMD) method, we have studied the transport process of excited carriers between 2D HOIPs separated by a spacer cation layer in real time at atomic levels. We find that the excited electrons and holes can transfer from single-inorganic-layer 2D HOIP to bi-inorganic-layer 2D HOIP on a subpicosecond to picosecond scale. Moreover, we have developed a new method to capture the electron-hole interaction in the frame of NAMD. This work provides a promising direction to design new materials toward high-performance optoelectronics.

Dopant effect on the optical and thermal properties of the 2D organic-inorganic hybrid perovskite (HDA)2PbBr4.

Lead-based two-dimensional organic-inorganic hybrid perovskites (2D HOIPs) are popular materials with various optical properties, which can be tuned through metal ion doping. Due to the size and valence misfit, metal ion dopants in 2D lead-based HOIPs are still limited. In this work, Mn2+, Sb3+ and Bi3+ are doped into 2D (HDA)2PbBr4 (HDA = protonated dopamine) successfully. As a result, the dopants in 2D (HDA)2PbBr4 can induce their characteristic optical spectra, which is studied at different temperatures and excitation powers. The temperature-dependent energy transfer in the Mn-doped sample has been clarified, in which abnormal phenomena including negative thermal quenching have been observed. In addition, the dopant ions can impact the phase transition temperatures of the samples, especially lowering their crystallization temperatures greatly. The mussel-inspired organic cation, feasible metal ion regulation, and superior stability provide (HDA)2PbBr4 potential for further applications.

(Invited) Atomic Imaging and Device Characterization of Molecularly Thin 2D Hybrid Perovskites

2D Organic-Inorganic Hybrid perovskites (OIHPs) possess alternating layers of organic molecules and inorganic quantum wells. By tuning the interaction between organic and inorganic layers, very interesting properties can be introduced. The successful isolation of hybrid perovskite monolayers with clean and flat surfaces are particularly suitable for atomic structure characterization and optoelectronic device fabrication. In this talk, I will present recent results on the excitonic properties and atomic structure of molecularly thin OIHPs1,2. We found that a reversible shift in excitonic energies can be induced upon laser irradiation in large-sized 2D hybrid perovskite monolayers which is attributed to the reversible structural reorientation of the surface BA cations in the easily deformable lattice3. The photodetection performance of monolayer, bilayer and thicker OIHPs were compared. The internal quantum efficiency was measured to be 34% for a monolayer (BA)2(MA)3Pb4I13 and 19% for the bulk crystal. In addition, 2D heterostructures of molecularly thin OIHPs/graphene were constructed which exhibited a lower barrier than gold for carrier injection, enabling applications in field effect transistors (FETs)4. Electron tunneling occurs across the interface of organic molecular layers on 2D perovskite and graphene, while photoinduced charge transfer occurs at femtosecond timescale (~50 fs).Resolving the atomic structure of 2D hybrid perovskite is a challenging task because it is easily damaged by electron beam. Here we use scanning tunneling microscopy (STM) & Qplus AFM to directly visualize surface octahedral tilt in freshly exfoliated 2D Ruddlesden-Popper perovskites (RPPs)5. The experimentally determined octahedral tilts from n = 1 to n = 4 RPPs from STM images are found to agree very well with out-of-plane surface octahedral tilts predicted by density functional theory calculations. The surface-enhanced octahedral tilt is correlated to excitonic redshift observed in photoluminescence (PL) and promotes Rashba spin splitting for n > 1. Our studies demonstrate a protocol to investigate structure-property correlations in low dimensional 2D OIHPs, which will pave the way to better material design and device performance.References Leng, W. Fu, Y. Liu, M. Chhowalla & KP Loh* “From Bulk to Molecularly Thin Hybrid Perovskites” Nature Reviews Materials , 5, 482-500 (2020).Zhao, KP Loh, K. Leng* “Organic-inorganic hybrid perovskites and their heterostructures” Matter , 5, 4153-4169 (2022).Leng, I. Abdelwaha, I. Verzhbitskiy, M. Telychko, L. Chu, W. Fu, X. Chi, N. Guo, Z. Chen, Z. Chen, C. Zhang, Q. Xu, J. Lu, M. Chhowalla, G. Eda, KP Loh* “Molecularly thin two-dimensional hybrid perovskites with tunable optoelectronic properties due to reversible surface relaxation” Nature Materials , 17, 908-914 (2018).Leng, L. Wang, Y. Shao, I. Abdelwahab, G. Grinblat, I. Verzhbitskiy, Y. Cai, X. Chi, W. Fu, P. Song, G. Eda, S. A. Maier & KP Loh* “Electron Tunneling at the Molecularly Thin 2D Perovskite and Graphene Van der Waals Interface” Nature Communications , 11, 5483 (2020).Y Shao, W. Gao, H. Yan, R. Li, I. Abdelwahab, L. Zhuang, W. Fu, SP Lau, SF YU, Y. Cai, KP Loh, K. Leng* “Unlocking Surface Octahedral Tilt in Two-dimensional Ruddlesden-Popper Perovskites” Nature Communications , 13, 138 (2022). AcknowledgementK.L. would like to acknowledge the Research Grants Council of the Hong Kong Special Administrative Region, China (Project No. PolyU15305221 for GRF project funded in 2021/22 Exercise and Project No. PolyU25305222 for ECS project funded in 2022/23 Exercise).

Enhancing photo and X-ray detection performance of (BDA)CsPb2Br7 perovskite single crystals by removing surface defects

Two-dimensional (2D) hybrid perovskite single crystals are promising photovoltaic materials. However, the single crystals grown from solution usually respond poorly to light and other charged particles. The 2D (BDA)CsPb2Br7 single crystals (BDA = 1,4-butanediamine) are grown from a supersaturated solution. The macroscopical growth steps are present on the surface, leading to a large leakage current during device operation. The surface defects are removed to expose a clean and flat surface. This well-defined crystallographic surface enables an Ohmic contact with the electrode, which minimized the dark current and baseline drift. Consequently, the assembled devices exhibit an enhanced response to LED light and X-rays, revealing the surface defect to be one of the culprits underneath the poor performance of solution-grown perovskite single crystals.

2D Hybrid Perovskites Employing an Organic Cation Paired with a Neutral Molecule.

Two-dimensional (2D) hybrid perovskites harness the chemical and structural versatility of organic compounds. Here, we explore 2D perovskites that incorporate both a first organic component, a primary ammonium cation, and a second neutral organic module. Through the experimental examination of 42 organic pairs with a range of functional groups and organic backbones, we identify five crystallization scenarios that occur upon mixing. Only one leads to the cointercalation of the organic modules with distinct and extended interlayer spacing, which is observed with the aid of X-ray diffraction (XRD) pattern analysis combined with cross-sectional transmission electron microscopy (TEM) and elemental analysis. We present a picture in which complementary pairs, capable of forming intermolecular bonds, cocrystallize with multiple structural arrangements. These arrangements are a function of the ratio of organic content, annealing temperature, and substrate surface characteristics. We highlight how noncovalent bonds, particularly hydrogen and halogen bonding, enable the influence over the organic sublattice in hybrid halide perovskites.

Pioneering Two-Dimensional Perovskites Featuring Four-Layer Organic Spacers for Polarization-Sensitive Photodetection.

Hybrid perovskites have great potential in photovoltaics and photodetection. Specially, two-dimensional (2D) hybrid perovskites have been discovered to show distinctive applications in polarization-sensitive photodetection due to their intrinsic anisotropy. Herein, we designed a new type of 2D perovskite by introducing bifunctional alkylammonium as an organic spacer, (β-Ala)4PbBr4 (1, where β-Ala+ is 3-aminopropanoic), which has four organic spacers in adjacent inorganic layers and adjacent organic layers are linked by hydrogen bonding. The pioneering structure with four organic spacers enables an intrinsic high strong anisotropy, facilitating polarization-sensitive detection. The analysis of the crystal structure and optical properties further elucidates the natural anisotropic properties of 1. Strikingly, 1 has a strong optical dichroism (αc/αb ≈ 7.4 in 405 nm), and the polarization-sensitive detector on single crystals of 1 exhibits a large polarization ratio (Imax/Imin ≈ 2.0). This result highlights that the employment of bifunctional cations is efficient to explore new type 2D perovskites for potentially high-performance polarization-sensitive detection.

Stable two-dimensional tin-based perovskites for warm-white light emitters

Two-dimensional (2D) Sn-based organic-inorganic hybrid perovskites are useful materials for white light emitters due to their super high fluorescence efficiency and higher stability when compared to their three-dimensional (3D) counterparts. Herein, 2D Ruddlesden-Popper (RP) perovskites (BA)2Sn(Br1-x Ix)4 (BA = n-butylammonium, x: 0–1) were prepared and regulated using halogen doping. As iodine content increased, the band gap of (BA)2Sn(Br1-xIx)4 was finely regulated from 2.35 eV to 2.0 eV, thereby tuning the photoluminescence from yellow to red with relatively high PLQY exceeding 40 %. The use of small amounts of Pb2+ to stabilize Sn2+ through the addition of PbO in the precursor solution resulted in high air- and photo stable (BA)2Pb0.1Sn0.9(Br–I)4 phosphors with bright yellow to red light. The mixture with (BA)2PbBr4 (blue light phosphor) followed by excitement by UV LED chips (285 nm) resulted in cold and warm white Sn–Br–I perovskite LEDs. The CIE coordinates and correlated color temperature (CCT) indicated Br0.4I0.6 LED as an ideal warm-white emitter with suitable CIE (0.352, 0.330) and CCT (4376.3 K). The prepared white LEDs showed high photo and air stability without significant luminescence decay (<5 % relative) under continuous UV light excitation over 200 min and exposure to air for 3 months.

Luminescence properties of Mn-doped 2D organic-inorganic hybrid perovskites: Insights from (PPA)2PbBr4 perovskite

The incorporation of Mn2+ ions has been widely used to modulate optical properties of two-dimensional (2D) organic-inorganic hybrid perovskites (OIHPs). However, the luminescence mechanism of Mn2+ ions that is related to the A-site cations remains largely unexplored. Herein, we report the synthesis of a series of Mn-doped A2PbBr4 (A = C6H5(CH2)nNH3, n = 1,2,3,4,) 2D perovskites. The (C6H5(CH2)3NH3)2PbBr4 ((PPA)2PbBr4) 2D perovskite exhibited a maximum photoluminescence (PL) quantum yield of 67 %, a prolonged PL lifetime of 0.75 ms, and the highest energy transfer efficiency of 78.07 %. Furthermore, we systematically investigated the luminescence properties of Mn-doped (PPA)2PbBr4 perovskite with different Mn2+ concentrations. The temperature dependent PL spectra indicate a thermalized de-trap process of self-trapped exciton at high temperatures and the presence of permanently shallow defect states in highly doped samples with lower activation energy.

A Two-Dimensional Hybrid Perovskite With Heat Switching Birefringence.

Birefringent crystals that can switch light polarization have important applications in optoelectronics. In the last decades, birefringence is mostly optimizedby chemical strategies. Recently, switching birefringence by physical means has attracted much attention. Here, this work reports the observation of heat switching birefringence in a 2D layered hybrid halide perovskite (C2N3H4)2PbCl4 ([C2N3H4]+ = 1,2,4-triazolium). This heat switching birefringence leads to a significant change in the interference color for the crystal plate under the illumination of orthogonal polarized light. Structure analyses reveal a heat dependent structure transition in (C2N3H4)2PbCl4, whose birefringence is switched by the change in the distortion degree of PbCl6 octahedron. This discovery may be beneficial to the further development of stimuli-responsive polarization optical devices.

Two-dimensional hybrid perovskite crystals for highly sensitive and stable UV light detector

Two-dimensional metal halide perovskites (2D MHPs) are promising candidates for ultraviolet (UV) light detection due to their narrow band gap and high stability in the air atmosphere. MHP crystals, with fewer defects and grain boundaries than polycrystalline films, are more suitable for photodetectors and other advanced semiconductor devices. In this paper, aimed to fabricate high-performance UV light detector, a series of high-quality and large-sized 2D perovskite crystals with the composition of (BA)2Pb(ClxBr1-x)4 were prepared and the best UV responsibility was found in the (BA)2Pb(Cl0.1Br0.9)4 crystal. Despite the detector was fabricated by the simple silver brushing method, it exhibits high responsivity of 3.19 mA/W, high detection rate of 3.87 × 1011 Jones, and fast response speed to UV light of 340 nm under the bias of 20 V. Moreover, the detector shows remarkable light sensitivity even under extremely weak UV illumination of 5.4 μW/cm2 and satisfactory stability during a long-duration switching operation. The excellent light response performance of the (BA)2Pb(Cl0.1Br0.9)4 detector was ascribed to the very low dark current (0.84 pA) of the detector, which highly relies on the crystal quality of the light-absorbing perovskites. The relationship between the structural and the compositional characteristics of (BA)2Pb(Cl0.1Br0.9)4 and its light response property was analyzed. This work provides a promising candidate material for sensitive UV detection and high-performance photodetectors.

Intrinsic Ferromagnetic Semiconductors with High Saturation Magnetization from Hybrid Perovskites.

Ferromagnetic semiconductors (FMS) enable simultaneous control of both charge and spin transport of charge carriers, which have emerged as a class of highly desirable but rare material for applications in spin field-effect transistors and quantum computing. Organic-inorganic hybrid perovskite with high compositional adjustability and structural versatility can offer unique benefits in the design of FMS but has not been fully explored. Here we demonstrate a series of molecular FMSs based on two-dimensional organic-inorganic hybrid perovskite structure, namely (2ampy)CuCl4 , (3ampy)CuCl4 and (4ampy)CuCl4 , which exhibits high saturation magnetization, dramatic temperature-dependent conductivity change and tunable ferromagnetic resonance. Magnetic measurements revealed high saturation magnetization up to 18.56 emu/g for (4ampy)CuCl4 , which is one of the highest value among reported hybrid FMSs to date. Conductivity studies of the three FMSs demonstrate that the smaller adjacent octahedron distance in the two-dimensional layer results in higher conductivity. Systematic ferromagnetic resonance investigation shows that the gyromagnetic ratio and Landau factor values are strongly dependent on the types of organic cations used. This work demonstrates that two-dimensional hybrid perovskite materials can simultaneously possess both tunable long-range ferromagnetic ordering and semiconductivity, providing a straightforward strategy for designing and synthesizing high-performance intrinsic FMSs. This article is protected by copyright. All rights reserved.