Two-dimensional Halide Perovskites Research Articles

Strain propagation in layered two-dimensional halide perovskites.

Impulsive light excitation presents a powerful tool for investigating the interdependent structural and electronic responses in layered two-dimensional (2D) halide perovskites. However, detailed understanding of the nonlinear lattice dynamics in these soft hybrid materials remains limited. Here, we explicate the intrinsic strain propagation mechanisms in 2D perovskite single crystals using transient reflection spectroscopy. Ultrafast photoexcitation leads to the generation of strain pulses via thermoelastic (TE) stress and deformation potential (DP) interaction whence their detection proceed via Brillouin scattering. Using a two-temperature model together with strain wave propagation, we discern the TE and DP contributions in strain generation. Hot carrier cooling plays a dominant role in effecting the weak modulation amplitude. Out-of-plane lattice stiffness is reduced by the weak van der Waals bond between organic layers, resulting in a slow strain propagation velocity. Our findings inject fresh insights into the basic strain properties of layered perovskites critical for manipulating their functional properties for new applications.

Switchable Color Semiconductors: Methylamine Intercalation, Deintercalation, and Retention in Two-Dimensional Halide Perovskites

The low formation energy of metal halide perovskites (MHPs) and their high performance in optoelectronic applications make them rather interesting semiconductor materials. In this work, we take advantage of the tunability of two-dimensional (2D) halide perovskites of the type A2PbI4 to explore a chromogenic mechanism in these materials where methylamine is allowed to intercalate into and deintercalate from the halide perovskite films. Methylamine intercalation results in a change in color from the initial yellow/orange color of the A2PbI4 films to visibly transparent films, while deintercalation leads to a return of a colored film. The reversibility of this solvatochromic mechanism was found to be highly dependent on the nature of the A-site cation used. We observe the formation of iodoplumbate phases, mixed 2D/three-dimensional (3D) perovskites, and/or 3D perovskites as secondary phases formed in some systems and, by exploring a wide array of A2PbI4 materials, we identify key design rules for the A-site cation to limit secondary phase formation and structural changes associated with methylamine intercalation/deintercalation. Specifically, the effects of changing cation–cation, cation “head”-inorganic, and cation “tail”-inorganic interactions in this system are demonstrated. By carefully controlling these interactions, more robust solvatochromic systems are realized. These initial explorations of metal halide solvatochromism improve the understanding of A-site cation design in A2PbI4 MHPs and show that these are a promising class of solvatochromic semiconductors.

First-principles investigation on adsorption of anchors on two-dimensional halide perovskite material

Anchoring groups are important to immobilize the organic species on emerging energy materials such as the halide perovskite material surfaces to tailor their optoelectronic performance. In this manuscript, we employ first-principles calculations to closely examine the interfacial atomic structures, electronic and optical properties of the anchor/perovskite system, using Cs2PbBr4 as an example. 13 small molecular anchors with various functional anchoring groups, including halogen species (-F, -Cl, -Br and –I) and Lewis acids/bases (–COOH, –NH2, –NO2, –OH, -SH and thiophene) are investigated to comprehensively understand the fundamental interactions between the anchors and the two-dimensional halide perovskite surface. The hydrogen bonds play predominant role in the anchor/perovskite interfacial structural stabilization, while the halogen bonds are suggested to initiate weak interactions. These anchoring groups initiate disparate charge transfer characters at the halide perovskite surface, and the nitrobenzene anchor containing the –NO2 group presents perovskite → molecule surface charge transfer direction while most other anchors cause charge transfer in the reverse direction. In addition, the adsorption of the anchors causes blue-shifts in the UV–vis absorption spectra and optical bleaching effects in the resulting halide perovskite systems. The present study facilitates the fundamental understanding on the basic interactions between the anchoring species and the halide perovskite materials toward the photovoltaic applications.

Rapidly expanding spin-polarized exciton halo in a two-dimensional halide perovskite at room temperature.

Monitoring of the spatially resolved exciton spin dynamics in two-dimensional semiconductors has revealed the formation of a spatial pattern and long-range transport of the spin-polarized excitons, which holds promise for exciton-based spin-optoelectronic applications. However, the spatial evolution has been restricted to cryogenic temperatures because of the short exciton spin relaxation times at room temperature. Here, we report that two-dimensional halide perovskites can overcome this limitation owing to their relatively long exciton spin relaxation times and substantial exciton-exciton interactions. We demonstrate the emergence of a halo-like spatial profile in spin-polarized exciton population and its ultrafast expansion at room temperature by performing time-resolved Faraday rotation imaging of spin-polarized excitons in two-dimensional perovskite (C4H9NH3)2(CH3NH3)3Pb4I13. Exciton-exciton exchange interactions induce density-dependent nonlinear relaxation and ultrafast transport of exciton spins and give rise to a rapidly expanding halo-like spatial pattern. The density-dependent spatial control suggests the potential of using two-dimensional halide perovskites for spin-optoelectronic applications.

Photoluminescent Properties of Two-Dimensional Manganese(II)-Based Perovskites with Different-Length Arylamine Cations.

The participation of organic cations plays an important role in tuning broad-spectra emissions. Herein, we synthesized a series of Mn(II)-based two-dimensional (2D) halide perovskites with arylamine cations of different lengths having the general formula (C6H5(CH2)xNH3)2MnCl4 (x = 1-4), with the x = 4 compound reported here for the first time. With the increase in the -(CH2)- in organic cations, the distance between adjacent inorganic layers increases, causing the title compounds to exhibit different structural distortions. As the Mn-Cl-Mn angular distortion increases, the experimental optical band gaps of the title compounds increase correspondingly. When the angle distortion between the octahedrons of the compounds is similar, the band gaps may also be affected by the distortion of the octahedron itself (the bond-length distortion of 2 is greater than that of 4). Under UV-light irradiation at 298 K, all of the compounds exhibit two emission peaks centered at 480-505 and 610 nm, corresponding to the organic-cation emission and the 4T1(G) to 6A1(S) radiative transition of Mn2+ ions, respectively. Among these title compounds, (PPA)2MnCl4 [(PPA)+ = C6H5(CH2)3NH3+] exhibits the strongest photoluminescence (PL). The study of the title compounds contributes to an in-depth understanding of the relationship between the structural distortion and optical properties of 2D Mn(II)-based perovskite materials.

Ordered Mixed-Spacer 2D Bromide Perovskites and the Dual Role of 1,2,4-Triazolium Cation

Two-dimensional (2D) halide perovskites exhibit extraordinary stability and structural diversity because they can incorporate different organic cations (both cage A-site cation and the spacers). Here, we report on the behavior of Tz = 1,2,4-triazolium as an A-site cation as well as a spacer cation in new perovskite compounds. We describe the synthesis and structure–property relationships of a new family of hydrogen-bonding stabilized 2D perovskites (IPA)2(Tz)n−1PbnBr3n+1 (n = 1–3) (IPA = isopropylammonium, Tz = 1,2,4-triazolium), which represents the rare example of 2D perovskites incorporating the large A-site cation (Tz) that can form both the n = 2 and 3 phases. However, excess of Tz cations can split the n = 2 layers to act as a spacer and combine with another spacer PA (PA = propylammonium) or BA (BA = butylammonium) to form n = 1 structures (PA)(Tz)PbBr4 and (BA)(Tz)PbBr4. These ordered mixed-spacer perovskites with different interlayer distances are unusual because the different spacers tend to stay in the same interlayer. (IPA)2(Tz)n−1PbnBr3n+1 all exhibit broad photoluminescence emission but for different reasons. For the n = 1 phase, the large octahedral tilting (small Pb–Br–Pb angle) gives rise to the broad emission, while for the n = 2 and 3 phases, the individual octahedral distortion (large distortion index) plays a more important role. For the mixed-spacer (PA)(Tz)PbBr4 and (BA)(Tz)PbBr4, their band gaps are in between the parent n = 1 compounds [(BA)2PbBr4 or (PA)2PbBr4, and (Tz)2PbBr4]. Density functional theory calculations suggest that the band structures of (PA)(Tz)PbBr4 and (BA)(Tz)PbBr4 combine features from both parent compounds yet differ from a simple superposition. This work demonstrates the dual role of Tz molecules as the A-site cation in multilayer 2D perovskites and as the spacer in ordered mixed-spacer 2D phases.

Light-Controlled Reconfigurable Optical Synapse Based on Carbon Nanotubes/2D Perovskite Heterostructure for Image Recognition.

Two-dimensional (2D) halide perovskite material is characterized by a mixed conducting behavior that possesses both electronic and ionic conductivity. The study on the influence of the light on ion migration in the 2D perovskite is helpful to improve the performance of perovskite-based optoelectronic devices. Here, we constructed an exfoliated 2D perovskite/carbon nanotubes (CNTs) heterostructure optical synapse, in which CNTs can be used as nanoprobes to qualitatively observe the ion aggregation or dissipation process in 2D perovskite, and found that light significantly changes the memory curve of the reconfigurable optical synapses. Through the molecular dynamic simulation, the dynamic process of ion migration in the heterostructure was simulated and the electrostatic interaction effect of nonequilibrium charge distribution of CNTs on iodide ion was demonstrated. Finally, an effective light-controlled process was realized through the synapses, which in situ regulated the performance of the weight-value discretized BP (WD-BP) neural network. This work lays a foundation for the future development of intelligent nano-optoelectronic devices.

Photo de-mixing in Dion-Jacobson two-dimensional mixed halide perovskites

Two-dimensional (2D) halide perovskites feature a versatile structure, which not only enables the fine-tuning of their optoelectronic properties but also makes them appealing as model systems to investigate the fundamental properties of hybrid perovskites. In this study, we analyzed the changes in the optical absorption of 2D Dion-Jacobson mixed halide perovskite thin films (encapsulated) based on (PDMA)Pb(I0.5Br0.5)4 (PDMA: 1,4-phenylenedimethanammonium spacer) exposed to a constant illumination. We demonstrate that these 2D mixed-halide perovskites undergo photo de-mixing with direct transformation from the pristine phase to the de-mixed phases. Almost complete re-mixing of these phases occurs when the sample is left in the dark, showing that the process is reversible in terms of optical properties. On the other hand, exposure to light appears to induce structural changes in the thin film that are not reversible in the dark. We have further investigated temperature-dependent absorption measurements under light to extract the photo de-mixed compositions and to map the photo-miscibility-gap. This work thereby reveals that photo de-mixing occurs in Dion-Jacobson two-dimensional hybrid perovskites and provides strategies to address the role of light in the thermodynamic properties of these materials.

Designing Two-Dimensional Halide Perovskites Based on High-Throughput Calculations and Machine Learning.

The interactions between ions and the low-dimensional halide perovskites are critical to realizing the next-generation energy storage devices such as photorechargeable ion batteries and ion capacitors. In this study, we performed high-throughput calculations and machine-learning analysis for ion adsorption on two-dimensional A2BX4 halide perovskites. The first-principles calculations obtained an initial data set containing adsorption energies of 640 compositionally engineered ion/perovskite systems with diverse ions including Li+, Zn2+, K+, Na+, Al3+, Ca2+, Mg2+, and F-. The machine learning algorithms including k-nearest neighbors (KNN), Kriging, Random Forest, Rpart, SVM, and Xgboost algorithms were compared, and the Xgboost algorithm achieved the best accuracy (r = 0.97, R2 = 0.93) and was selected to predict the virtual design space consisting of 11 976 ion/perovskite systems. The features were then analyzed and ranked according to their Pearson correlations to the output values. In particular, to better understand the features, diverse feature selection methods were employed to comprehensively evaluate the features. The machine-learning-predicted virtual design space was subsequently screened to select stable lead-free ion/perovskite systems with suitable band gaps and halogen mixing features. The present study provides a theoretical foundation to design halide perovskite materials for ion-based energy storage applications such as secondary ion batteries, ion capacitors, and solar-rechargeable batteries.

Elucidating the Unique Hot Carrier Cooling in Two-Dimensional Inorganic Halide Perovskites: The Role of Out-of-Plane Carrier–Phonon Coupling

Two-dimensional (2D) halide perovskites represent the natural semiconductor quantum wells (QWs), which hold great promise for optoelectronics. However, due to the hybrid structure of Ruddlesden-Popper 2D perovskites, the intrinsic nature of hot-carrier kinetics remains shielded within. Herein, we adopt CsPbBr3 nanoplates as a model system to reveal the intrinsic carrier dynamics in inorganic perovskite QWs. Interestingly, we revealed an ultrafast and hot-phonon-bottleneck (HPB)-free carrier cooling in monodisperse CsPbBr3 QWs, which is in sharp contrast to the bulk and nanocrystalline perovskites. The absence of HPB was attributed to the efficient out-of-plane triplet-exciton-LO-phonon coupling in 2D perovskites because of the structural anisotropy. Accordingly, the HPB can be activated by shutting down the out-of-plane energy loss route through forming the layer-stacked perovskite superlattice. The controllable on and off of HPB may provide new possibilities in optoelectronic devices and these findings deepen the understanding of a hot-carrier cooling mechanism in 2D perovskites.

Electron-Hole Binding Governs Carrier Transport in Halide Perovskite Nanocrystal Thin Films.

Two-dimensional halide perovskite nanoplatelets (NPLs) have exceptional light-emitting properties, including wide spectral tunability, ultrafast radiative decays, high quantum yields (QY), and oriented emission. Due to the high binding energies of electron-hole pairs, excitons are generally considered the dominant species responsible for carrier transfer in NPL films. To realize efficient devices, it is imperative to understand how exciton transport progresses therein. We employ spatially and temporally resolved optical microscopy to map exciton diffusion in perovskite nanocrystal (NC) thin films between 15 °C and 55 °C. At room temperature (RT), we find the diffusion length to be inversely correlated to the thickness of the nanocrystals (NCs). With increasing temperatures, exciton diffusion declines for all NC films, but at different rates. This leads to specific temperature turnover points, at which thinner NPLs exhibit higher diffusion lengths. We attribute this anomalous diffusion behavior to the coexistence of excitons and free electron hole-pairs inside the individual NCs within our temperature range. The organic ligand shell surrounding the NCs prevents charge transfer. Accordingly, any time an electron-hole pair spends in the unbound state reduces the FRET-mediated inter-NC transfer rates and, consequently, the overall diffusion. These results clarify how exciton diffusion progresses in strongly confined halide perovskite NC films, emphasizing critical considerations for optoelectronic devices.

Calculation Of Gruneisen Parameter, Compressibility, And Bulk Modulus as Functions Of Pressure In (C6H5CH2NH3)2 PBI4

Hybrid organic-inorganic perovskites (HOIPs) exhibit multiple structural phase transitions, which result in enhanced mechanical and electronic properties of these perovskites. Order-disorder of organic components was thought to be the main factor to cause these phase transitions up to the last decade; however, recent research about HOIPs have shown that the structural phase transition also occurs with the induced pressure or temperature. The research studies related to the pressure have attracted a great deal of scholarly interest due to its contribution to the func-tionality of HOIPs in many current applications. Two-dimensional halide perovskites having been synthesized in the last few years have been increasingly studied thanks to its superior hysteresis in flexibility and mechanical properties under pressure. It is important to understand and model theoretically how induced pressure affects mechanical and electronic properties of (PMA)2PbI4 in order to develop new potential applications in optoelectronics. In this study, the isothermal mode-Grüneisen parameter, the isothermal compressibility, and the bulk modulus were calculated as functions of pressure at ambient temperature by using the calculated Raman frequencies and observed volume data for the selected IR modes in (PMA)2PbI4. These calculated parameters were compared with the observed measurements reported for the Pbca, Pccn and Pccn (isostructural) phases in the studied perovskites. The results obtained in the present study, which were highly compatible with the experimental measurements, showed that (PMA)2PbI4 is usable in optoelectronic applications.

Two-Dimensional Dion-Jacobson Perovskite (NH3C4H8NH3)CsPb2Br7 with High X-ray Sensitivity and Peak Discrimination of α-Particles.

Two-dimensional (2D) halide perovskites have attracted extensive interest because of their excellent optoelectronic properties, structural diversity, and promising stability. Herein, we grow a novel 2D Dion-Jacobson halide perovskite, (BDA)CsPb2Br7 (BDA = 1,4-butanediamine, NH3C4H8NH32+), which exhibits a large bandgap (∼2.76 eV), high resistivity (∼4.35 × 1010 Ω·cm), and considerable switching ratio (>700), indicating great potential for radiation detection. Both experimental and calculated results demonstrate that (BDA)CsPb2Br7 has a significantly improved mobility compared to those of Ruddlesden-Popper perovskites (BA)2CsPb2Br7 and (i-BA)2CsPb2Br7, which is attributed to the shorter interlayer distance leading to the enhanced orbital interactions. The resulting (BDA)CsPb2Br7 detector along the out-of-plane direction achieves a high X-ray sensitivity of 725.5 μC·Gy-1·cm-2. Another fascinating attribute is that the detector exhibits good peak discrimination with an energy resolution of ∼37% when illuminated by the 241Am@5.48 MeV α-particles under a negative bias of 260 V. These results provide a broad prospect for 2D Dion-Jacobson perovskites for future radiation detection applications.

Bond length alternation- and data mining-assisted exploration of molecular adsorbates with π-conjugation and amines for two-dimensional halide perovskite surface

Bond length alternation- and data mining-assisted exploration of molecular adsorbates with π-conjugation and amines for two-dimensional halide perovskite surface

High-Throughput Calculation and Machine Learning of Two-Dimensional Halide Perovskite Materials: Formation Energy and Band Gap

High-Throughput Calculation and Machine Learning of Two-Dimensional Halide Perovskite Materials: Formation Energy and Band Gap

Design of two-dimensional halide perovskite composites for optoelectronic applications and beyond

Two-dimensional halide perovskite composites exhibit enhanced performances not observed in their individual components for versatile optoelectronic applications and beyond, manifesting the positive “1 + 1 > 2” effect.

Vertically aligned two-dimensional halide perovskites for reliably operable artificial synapses

Halide perovskites, fascinating memristive materials owing to mixed ionic-electronic conductivity, have been attracting great attention as artificial synapses recently. However, polycrystalline nature in thin film form and instability under ambient air hamper them to be implemented in demonstrating reliable neuromorphic devices. Here, we successfully fabricated vertically aligned 2D halide perovskite films (V-HPs) for active layers of artificial synapses, showing moisture stability for several months. Unlike random-oriented HPs, which exhibit negligible current hysteresis, the V-HPs possess multilevel analog memristive characteristics, programmable potentiation and depression with distinguished multi-states, long-short-term plasticity, paired-pulse facilitation, and even spike-timing-dependent plasticity. Furthermore, high classification accuracy is obtained with implementation in deep neural networks. These remarkable improvements are attributed to the vertically well-aligned lead iodide octahedra acting as the ion transport channel, confirmed by first-principles calculations. This study paves the way for understanding HPs nanophysics and demonstrating their potential utility in neuromorphic computing systems.

Implementing an intermittent spin-coating strategy to enable bottom-up crystallization in layered halide perovskites

Two-dimensional halide perovskites (2D PVSKs) have drawn tremendous attentions owing to their outstanding ambient stability. However, the random orientation of layered crystals severely impedes the out-of-plane carrier transport and limits the solar cell performance. An in-depth understanding coupled with an effective control of the crystallization in 2D PVSKs is the crux for highly efficient and durable devices. In this contribution, we accidentally discovered that the crystallization of 2D PVSKs can be effectively regulated by so-called ′intermittent spin-coating (ISC)′ process. Combined analyses of in(ex)-situ grazing-incidence wide-angle X-ray scattering with time-of-flight secondary ion mass spectrometry distinguish the interface initialized bottom-up crystallization upon ISC treatment from the bi-directional one in the conventional spin-coating process, which results in significantly enhanced crystal orientation and thus facilitated carrier transport as confirmed by both electrical measurements and ultrafast spectroscopies. As a result, the p-i-n architecture planar solar cells based on ISC fabricated paradigm PEA2MA3Pb4I13 deliver a respectable efficiency of 11.2% without any treatment, which is three-fold improvement over their spin-coated counterparts and can be further boosted up to 14.0% by NH4Cl addition, demonstrating the compatibility of ISC method with other film optimization strategies.

Ligand-Driven Grain Engineering of High Mobility Two-Dimensional Perovskite Thin-Film Transistors

Controlling grain growth is of great importance in maximizing the charge carrier transport for polycrystalline thin-film electronic devices. The thin-film growth of halide perovskite materials has been manipulated via a number of approaches including solvent engineering, composition engineering, and post-treatment processes. However, none of these methods lead to large-scale atomically flat thin films with extremely large grain size and high charge carrier mobility. Here, we demonstrate a novel π-conjugated ligand design approach for controlling the thin-film nucleation and growth kinetics in two-dimensional (2D) halide perovskites. By extending the π-conjugation and increasing the planarity of the semiconducting ligand, nucleation density can be decreased by more than 5 orders of magnitude. As a result, wafer-scale 2D perovskite thin films with highly ordered crystalline structures and extremely large grain size are readily obtained. We demonstrate high-performance field-effect transistors with hole mobility approaching 10 cm2 V-1 s-1 with ON/OFF current ratios of ∼106 and excellent stability and reproducibility. Our modeling analysis further confirms the origin of enhanced charge transport and field and temperature dependence of the observed mobility, which allows for clear deciphering of the structure-property relationships in these nascent 2D semiconductor systems.

Thermoelectric Performance of Lead-Free Two-Dimensional Halide Perovskites Featuring Conjugated Ligands.

Sn-based halide perovskites are promising for thermoelectric (TE) device applications because of their high electrical conductivity as well as the low thermal conductivity associated with their soft lattices. However, conventional three-dimensional Sn-based perovskites are not stable under typical TE device operating conditions. Here, we report a stable two-dimensional Sn-based perovskite for thermoelectric energy conversion by incorporating bulky conjugated ligands. We demonstrate a thin film with a large power factor of 5.42 ± 3.07 (average) and 7.07 (champion) μW m-1 K-2 at 343 K with an electrical conductivity of 5.07 S cm-1 and a Seebeck coefficient of 118.1 μV K-1. Importantly, these thin films show excellent operational stability (i.e., for over 100 h) at 313 K. This work suggests that the novel hybrid two-dimensional perovskites are a promising platform for thermoelectric energy conversion applications.