Dion-Jacobson Phases Research Articles

Single Crystal Ruddlesden-Popper and Dion-Jacobson Metal Halide Perovskites for Visible Light Photodetectors: Present Status and Future Perspectives.

2D metal halide perovskites (MHPs), mainly the studied Ruddlesden-Popper (RP) and Dion-Jacobson (DJ) phases, have gained enormous popularity as optoelectronic materials owing to their self-assembled multiple quantum well structures, tunable semiconducting properties, and improved structural stability compared to their bulk 3D counterparts. The performance of polycrystalline thin film devices is limited due to the formation of defects and trap states. However, as studied so far, single crystal-based devices can provide a better platform to improve device performance and investigate their fundamental properties more reliably. This Review provides the first comprehensive report on the emerging field of RP and DJ perovskite single crystals and their use in visible light photodetectors of varied device configurations. This Review structurally summarizes the 2D MHP single crystal growth methods and the parameters that control the crystal growth process. In addition, the characterization techniques used to investigate their crystal properties are discussed. The review further provides detailed insights into the working mechanisms as well as the operational performance of 2D MHP single crystal photodetector devices. In the end, to outline the present status and future directions, this Review provides a forward-looking perspective concerning the technical challenges and bottlenecks associated with the developing field of RP and DJ perovskite single crystals. Therefore, this timely review will provide a detailed overview of the fast-growing field of 2D MHP single crystal-based photodetectors as well as ignite new concepts for a wide range of applications including solar cells, photocatalysts, solar H2 production, neuromorphic bioelectronics, memory devices, etc.

Halide Ion Mobility in Paired 2D Halide Perovskites: Ruddlesden–Popper Versus Dion–Jacobson Phases

Abstract2D lead halide perovskites with tunable optoelectronic properties through modulating inorganic components and organic spacer ligands represent a promising candidate in perovskite optoelectronics. However, an intrinsic soft lattice of perovskites gives rise to a vacancy‐mediated halide ion migration, which further affects the long‐term stability of materials as well as devices. Here, halide ion mobility is evaluated using two different 2D perovskites yielded with butylammonium (BA) for the Ruddlesden–Popper (RP) phase and butane‐1,4‐diamine (BDA) for the Dion–Jacobson (DJ) phase, respectively. By probing the halide ion migration kinetics in the physically paired 2D bromide and iodide perovskite films, the softer lattice (RP) shows a lower activation energy of 50.9 kJ mol−1 as compared to that of more rigid lattice (DJ) of 60.8 kJ mol−1. Given similar halide diffusion pathlength and halide mixing chemical potential, the binding mode (RP and DJ) can indeed dictate the overall halide ion stability. Understanding such halide ion mobility is important in designing perovskites with increased stability and performances at material and device levels.

Synthesis, Ion-Exchange and Photocatalytic Properties of Layered Perovskite-Like Niobate CsBa2Nb3O10: Comparative Analysis with Related Dion–Jacobson Phases A$${\text{A}}_{2}^{'}$$Nb3O10 (A = K, Rb, Cs; A' = Ca, Sr, Pb)

Synthesis, Ion-Exchange and Photocatalytic Properties of Layered Perovskite-Like Niobate CsBa2Nb3O10: Comparative Analysis with Related Dion–Jacobson Phases A$${\text{A}}_{2}^{'}$$Nb3O10 (A = K, Rb, Cs; A' = Ca, Sr, Pb)

Layered Low-Dimensional Ruddlesden-Popper and Dion-Jacobson Perovskites: From Material Properties to Photovoltaic Device Performance.

Layered low-dimensional halide perovskites (LDPs) with multiple quantum well structure have shown increasing research interest in photovoltaic solar cell applications owing to their intrinsic moisture stability and favorable photophysical properties in comparison with their three-dimensional (3D) counterparts. The most common LDPs are Ruddlesden-Popper (RP) phases and Dion-Jacobson (DJ) phases, both of which have made significant research advances in efficiency and stability. However, distinct interlayer cations between RP and DJ phase lead to disparate chemical bonds and different perovskite structures, which endow RP and DJ perovskite with distinctive chemical and physical properties. Plenty of reviews have reported the research progress of LDPs but no summary has elaborated from the perspective of the merits and drawbacks of the RP and DJ phases. Herein, in this review, we offer a comprehensive expound on the merits and promises of RP and DJ LDPs from their chemical structure, physicochemical properties, and photovoltaic performance research progress aiming to provide a new insight into the dominance of RP and DJ phases. Then, we reviewed the recent progress on the synthesis and implementation of RP and DJ LDPs thin films and devices, as well as their optoelectronic properties. Finally, we discussed the possible strategies to resolve existing toughs to realize the desired high-performance LDPs solar cells.

The Impact of Spacer Size on Charge Transfer Excitons in Dion-Jacobson and Ruddlesden-Popper Layered Hybrid Perovskites.

Organic materials can tune the optical properties in layered (2D) hybrid perovskites, although their impact on photophysics is often overlooked. Here, we use transient absorption spectroscopy to probe the Dion-Jacobson (DJ) and Ruddlesden-Popper (RP) 2D perovskite phases. We show the formation of charge transfer excitons in DJ phases, resulting in a photoinduced Stark effect which is shown to be dependent on the spacer size. By using electroabsorption spectroscopy, we quantify the strength of the photoinduced electric field, while temperature-dependent measurements demonstrate new features in the transient spectra of RP phases at low temperatures resulting from the quantum-confined Stark effect. This study reveals the impact of spacer size and perovskite phase configuration on charge transfer excitons in 2D perovskites of interest to their advanced material design.

Recent developments in oxide ion conductors: focusing on Dion-Jacobson phases.

Oxide-ion conductors, also known as "oxygen ion conductors," have garnered significant attention in recent years due to their extensive applications in a variety of electrochemical devices, including oxygen concentrators, solid-oxide fuel cells (SOFCs), and solid oxide electrolysis cells. The key to improving the performance of these devices is the creation of novel oxide-ion conductors. In this feature article, we discuss the recent developments of new structural families of oxide-ion conductors and of the Dion-Jacobson-type layered oxide-ion conductors with a particular emphasis on CsM2Ti2NbO10-δ (M = Bi and lanthanoids; δ represents oxygen-vacancy content) and their solid solutions. CsBi2Ti2NbO10-δ is the first example of an oxide-ion conductor with a Dion-Jacobson-type layered perovskite structure, and the structural characteristics of these materials are extracted here. We have proposed an original concept that the large sized Cs+ cations and M3+ displacements yield the large bottlenecks for oxide-ion migration, which would facilitate the discovery of novel oxide-ion conductors. This article presents evidence that Dion-Jacobson-type layered perovskites are superior oxide-ion conductors. We also demonstrate how the information gleaned from these studies can be applied to the design of novel oxide-ion conductors.

Machine learning assisted synthetic acceleration of Ruddlesden-Popper and Dion-Jacobson 2D lead halide perovskites

Two-dimensional lead halide perovskites (2D LHPs) can be generally categorized into the Ruddlesden-Popper (RP) and Dion-Jacobson (DJ) phases, with unbiased and biased structural packing manners, respectively. To distinguish the two different phases during materials discovery, the synthesis has heavily relied on the traditional trial-and-error methods which severely delay the rapid development of these emerging 2D materials. In this work, we applied machine learning (ML) to accelerate the synthetic development of (100)-oriented 2D A2BX4 and ABX4 LHPs (A = organic amine cation, B = Pb, X = halide). The experimentally available 264 crystal structures were used as training data for our ML model to identify the descriptors influencing the formation of the RP- and DJ-phases. The number of nitrogen atoms able to be protonated, the heteroatom type, and the nitrogen content of the organic amine are identified as the most influential factors. To validate our model, three organic amines were tested by growing single crystals and two of the three new structures are consistent with our ML results. This study takes one step further toward the rational synthesis of RP- and DJ-phase hybrid 2D LHPs via an approach of ML.

Hybrid Improper Ferroelectricity: A Theoretical, Computational, and Synthetic Perspective

We review the theoretical, computational, and synthetic literature on hybrid improper ferroelectricity in layered perovskite oxides. Different ferroelectric mechanisms are described and compared, and their elucidation using theory and first-principles calculations is discussed. We also highlight the connections between crystal chemistry and the physical mechanisms of ferroelectricity. The experimental literature on hybrid improper ferroelectrics is surveyed, with a particular emphasis on cation-ordered double perovskites, Ruddlesden–Popper and Dion–Jacobson phases. We discuss preparative routes for synthesizing hybrid improper ferroelectrics in all three families and the conditions under which different phases can be stabilized. Finally, we survey some synthetic opportunities for expanding the family of hybrid improper ferroelectrics.

Improved oxide-ion conductivity by substitution of Sr for Bi in Dion-Jacobson phase CsBi2Ti2NbO10

Oxide ion conducting ceramics have attracted much attention due to their various applications such as solid oxide electrolysis cells (SOECs) and solid-oxide fuel cells (SOFCs). Herein, we present the first report on the preparation, electrical and structural properties of oxide-ion conducting Dion-Jacobson phases CsBi1.9M0.1Ti2NbO9.95 (M = Mg, Ca, Sr and Ba). It was found that partial substitution of Bi3+ by Sr2+ improves the conductivity of CsBi2Ti2NbO10. The electrical conductivity of CsBi1.9Sr0.1Ti2NbO9.95 is approximately 2 times higher than that of CsBi2Ti2NbO10 at 600–900 °C and is 1.65 × 10−2 S cm−1 at 900 °C. The improvement of oxide-ion conductivity in CsBi1.9Sr0.1Ti2NbO9.95 can be attributed to the increase of the carrier (oxygen vacancy) concentration and small size mismatch between the dopant Sr and host Bi cations. The electrical conductivities of CsBi1.9Sr0.1Ti2NbO9.95 are almost constant in the oxygen partial pressure region from 10−25 to 1 atm at 600 °C, indicating the predominant oxide-ion conduction and high chemical and electrical stability. Bond-valence-based energy landscapes of a test oxide ion in CsBi1.9Sr0.1Ti2NbO9.95 suggest that oxide ions migrate along the edges of the octahedra in the inner perovskite layers, leading to two-dimensional oxide-ion diffusion. This study demonstrates the successful improvement of oxide-ion conductivity by the substitution in Dion-Jacobson phase, which would develop the science and technology of Dion-Jacobson type oxide-ion conductors.

Tailoring the thermal conductivity of two-dimensional metal halide perovskites.

Proper thermal management of solar cells based on metal halide perovskites (MHPs) is key to increasing their efficiency as well as their durability. Although two-dimensional (2D) MHPs possess enhanced thermal stability as compared to their three-dimensional (3D) counterparts, the lack of comprehensive knowledge of the heat transfer mechanisms dictating their ultralow thermal conductivities is a bottleneck for further improvements in their thermal performance. Here, we experimentally and computationally study the Dion-Jacobson (DJ) and Ruddlesden-Popper (RP) phases of MHPs (n = 1) to demonstrate that the length of the organic spacers has a negligible influence on their thermal transport properties; we experimentally measure thermal conductivities of 0.19 ± 0.03 W m-1 K-1 and 0.18 ± 0.03 W m-1 K-1 for the RP and DJ phases with 13.6 Å and 6.3 Å interlayer inorganic separations, respectively. In contrast, we show that thermal conductivity is mainly dependent on the separation between the adjacent organic cations. Decreasing the intermolecular distance (by up to 40%) leads to drastically enhanced overall heat conduction (with monotonically increasing thermal conductivity by more than threefold) which is mainly driven by the vibrational hardening of the organic spacers. Although these 2D layered materials constitute a high density of hybrid organic-inorganic interfaces, our results also show that a substantial portion of heat is conducted through coherent phonon transport and that the thermal conductivity of these materials is not solely limited by incoherent interfacial scattering.

Multi-Length Scale Structure of 2D/3D Dion-Jacobson Hybrid Perovskites Based on an Aromatic Diammonium Spacer.

Dion-Jacobson (DJ) iodoplumbates based on 1,4-phenylenedimethanammonium (PDMA) have recently emerged as promising light absorbers for perovskite solar cells. While PDMA is one of the simplest aromatic spacers potentially capable of forming a DJ structure based on (PDMA)An-1 Pbn I3n+1 composition, the crystallographic proof has not been reported so far. Single crystal structure of a DJ phase based on PDMA is presented and high-field solid-state NMR spectroscopy is used to characterize the structure of PDMA-based iodoplumbates prepared as thin films and bulk microcrystalline powders. It is shown that their atomic-level structure does not depend on the method of synthesis and that it is ordered and similar for all iodoplumbate homologues. Moreover, the presence of lower (n) homologues in thin films is identified through UV-Vis spectroscopy, photoluminescence spectroscopy, and X-ray diffraction measurements, complemented by cathodoluminescence mapping. A closer look using cathodoluminescence shows that the micron-scale microstructure corresponds to a mixture of different layered homologues that are well distributed throughout the film and the presence of layer edge states which dominate the emission. This work therefore determines the formation of DJ phases based on PDMA as the spacer cation and reveals their properties on a multi-length scale, which is relevant for their application in optoelectronics.

The Role of Alkyl Chain Length and Halide Counter Ion in Layered Dion-Jacobson Perovskites with Aromatic Spacers.

Layered hybrid perovskites based on Dion-Jacobson phases are of interest to various optoelectronic applications. However, the understanding of their structure-property relationships remains limited. Here, we present a systematic study of Dion-Jacobson perovskites based on (S)PbX4 (n = 1) compositions incorporating phenylene-derived aromatic spacers (S) with different anchoring alkylammonium groups and halides (X = I, Br). We focus our study on 1,4-phenylenediammonium (PDA), 1,4-phenylenedimethylammonium (PDMA), and 1,4-phenylenediethylammonium (PDEA) spacers. Systems based on PDA did not form a well-defined layered structure, showing the formation of a 1D structure instead, whereas the extension of the alkyl chains to PDMA and PDEA rendered them compatible with the formation of a layered structure, as shown by X-ray diffraction and solid-state NMR spectroscopy. In addition, the control of the spacer length affects optical properties and environmental stability, which is enhanced for longer alkyl chains and bromide compositions. This provides insights into their design for optoelectronic applications.

Suppressed Phase Segregation in High‐Humidity‐Processed Dion–Jacobson Perovskite Solar Cells Toward High Efficiency and Stability

The Dion–Jacobson (DJ) perovskites solar cells (PSCs) demonstrate impressive humidity stability compared with 3D counterparts and have aroused extensive attention recently. However, it has not been investigated yet, how the humidity condition influences the photovoltaic performances. Herein, the effect of the humidity condition on the crystallization behavior, charge dynamics, photovoltaic and stability performances of BDAFAn‐1PbnI3n+1 DJ perovskite is systematically investigated. Humidity‐assisted annealing process can lead to reduced trap concentration and fast charge transfer process between different‐n DJ phases. The BDAFA5Pb6I19 PSC with the assistance of moisture achieves an efficiency as high as 17.17%, which is the highest value ever reported for methylammonium‐free DJ PSCs. In addition, the humidity‐, thermal‐, and photo‐stability properties of the DJ film and devices are significantly boosted. Further, first‐principles calculation indicates that water molecules occupy the iodide vacancies through a strong bonding with Pb ions during the crystallization process under humidity and increase the decomposition energy of the DJ phase, which corresponds to the improved photoelectronic and stability properties. These results show that humidity‐assisted deposition of 2D/3D multidimensional perovskite can be further explored to reduce the high demand of the production environment and enhance the performances.

Tuning between Proper and Hybrid-Improper Mechanisms for Polar Behavior in CsLn 2Ti2NbO10 Dion-Jacobson Phases.

The Dion-Jacobson (DJ) family of perovskite-related materials have recently attracted interest due to their polar structures and properties, resulting from hybrid-improper mechanisms for ferroelectricity in n = 2 systems and from proper mechanisms in n = 3 CsBi2Ti2NbO10. We report here a combined experimental and computational study on analogous n = 3 CsLn2Ti2NbO10 (Ln = La, Nd) materials. Density functional theory calculations reveal the shallow energy landscape in these systems and give an understanding of the competing structural models suggested by neutron and electron diffraction studies. The structural disorder resulting from the shallow energy landscape breaks inversion symmetry at a local level, consistent with the observed second-harmonic generation. This study reveals the potential to tune between proper and hybrid-improper mechanisms by composition in the DJ family. The disorder and shallow energy landscape have implications for designing functional materials with properties reliant on competing low-energy phases such as relaxors and antiferroelectrics.

Phase transitions in RbPrNb2O7, a layer structured ferroelectric with a high Curie point

The development of lead-free ferroelectric ceramics exhibiting a high Curie point is regarded as a key aspect of improving the overall performance of high temperature sensing devices. Two-layer Dion-Jacobson phases have great potential for these applications, but the dielectric properties of many of these compounds have not been investigated and several are still erroneously considered to be non-polar. RbPrNb2O7, a two-layer Dion-Jacobson phase, has previously been identified as being non-polar at room temperature, with an orthorhombic crystal structure in space group Imma. Here, the structure of RbPrNb2O7 is re-examined and its ferroelectric (FE) character confirmed through ferroelectric, dielectric and piezoelectric measurements, using dense bulk ceramics. In addition, the microstructure and phase evolution of the compound were analysed by transmission electron microscopy, variable temperature X-ray powder diffraction and differential scanning calorimetry. RbPrNb2O7 is a ferroelectric at room temperature, exhibiting orthorhombic symmetry in space group I2cm. It undergoes a reversible FE ↔ FE phase transition at around 260 °C, with evidence for a diffuse apolar transition between 800 and 900 °C. Details of the subtle structural changes occurring at these transitions are discussed. RbPrNb2O7 possesses a high Curie point of ~1090 °C, making it a potential candidate for use in high temperature piezoelectric sensing.

Organic Cation Alloying on Intralayer A and Interlayer A' sites in 2D Hybrid Dion-Jacobson Lead Bromide Perovskites (A')(A)Pb2Br7.

Hybrid layered halide perovskites have achieved impressive performance in optoelectronics. New structural types in the two-dimensional (2D) halide system such as the Dion-Jacobson phases have attracted wide research attention due to the short interlayer distance and unique layer orientation that facilitate better charge-transport and higher stability in optoelectronic devices. Here, we report the first solid solution series incorporating both A and A' cations in the 2D Dion-Jacobson family, with the general formula (A')(A)Pb2Br7 ((A' = 3-(aminomethyl)piperidinium (3AMP) and 4-(aminomethyl)piperidinium) (4AMP); A = methylammonium (MA) and formamidinium (FA)). Mixing the spacing A' cations and perovskitizer A cations generates the new (3AMP)a(4AMP)1-a(FA)b(MA)1-bPb2Br7 perovskites. The crystallographically refined crystal structures using single-crystal X-ray diffraction data reveal that the distortion of the inorganic framework is heavily influenced by the degree of A' and A alloying. A rising fraction of 4AMP in the structure, decreases the Pb-Br-Pb angles, making the framework more distorted. On the contrary, higher FA fractions increase the Pb-Br-Pb angles. This structural evolution fine-tunes the optical properties where the larger the Pb-Br-Pb angle, the narrower the band gap. The photoluminescence emission energy mirrors this trend. Raman spectroscopy reveals a highly dynamical lattice similar to MAPbBr3 and consistent with the local distortion environment of the [Pb2Br7] framework. Density functional theory (DFT) calculations of the electronic structures reveal the same trend as the experimental results where (3AMP)(FA)Pb2Br7 has the smallest band gap while (4AMP)(MA)Pb2Br7 has the largest band gap. The structural effects from solely the organic cations in the 2D system highlight the importance of understanding the high sensitivity of the optoelectronic properties on the structural tuning in this broad class of materials.

Two-Dimensional Dion-Jacobson Hybrid Lead Iodide Perovskites with Aromatic Diammonium Cations.

Two-dimensional (2D) halide perovskites have extraordinary optoelectronic properties and structural tunability. Among them, the Dion-Jacobson phases with the inorganic layers stacking exactly on top of each other are less explored. Herein, we present the new series of 2D Dion-Jacobson halide perovskites, which adopt the general formula of A'An-1PbnI3n+1 (A' = 4-(aminomethyl)pyridinium (4AMPY), A = methylammonium (MA), n = 1-4). By modifying the position of the CH2NH3+ group from 4AMPY to 3AMPY (3AMPY = 3-(aminomethyl)pyridinium), the stacking of the inorganic layers changes from exactly eclipsed to slightly offset. The perovskite octahedra tilts are also different between the two series, with the 3AMPY series exhibiting smaller bandgaps than the 4AMPY series. Compared to the aliphatic cation of the same size (AMP = (aminomethyl)piperidinium), the aromatic spacers increase the rigidity of the cation, reduce the interlayer spacing, and decrease the dielectric mismatch between inorganic layer and the organic spacer, showing the indirect but powerful influence of the organic cations on the structure and consequently on the optical properties of the perovskite materials. All A'An-1PbnI3n+1 compounds exhibit strong photoluminescence (PL) at room temperature. Preliminary solar cell devices based on the n = 4 perovskites as absorbers of both series exhibit promising performances, with a champion power conversion efficiency (PCE) of 9.20% for (3AMPY)(MA)3Pb4I13-based devices, which is higher than the (4AMPY)(MA)3Pb4I13 and the corresponding aliphatic analogue (3AMP)(MA)3Pb4I13-based ones.

Cation Exchange as a Mechanism To Engineer Polarity in Layered Perovskites

Cation-exchange reactions performed on the n = 2 Dion–Jacobson phases RbNdNb2O7 and RbNdTa2O7, using LiNO3 and NaNO3, yield the corresponding LiNdM2O7 and NaNdM2O7 (M = Nb, Ta) phases. Synchrotron ...

Theory and Neutrons Combine To Reveal a Family of Layered Perovskites without Inversion Symmetry

A flurry of recent theoretical studies have predicted the existence of new polar materials among several families of layered perovskites, including the double-layered Dion–Jacobson phases. These predictions have opened up exciting new opportunities for both fundamental studies of the crystal chemistry of Dion–Jacobson phases and their application as components in next-generation memories and low-power electronic devices. However, with some rare exceptions, all known double-layered Dion–Jacobson phases are nonpolar. We use an integrated theoretical–experimental approach to show that several Dion–Jacobson phases that have previously been synthesized and characterized as nonpolar are in fact polar. Additional theoretical calculations reveal that the polar phases of these materials emerge through a hybrid improper or trilinear coupling mechanism. Finally, our work has highlighted the critical role of neutron diffraction in characterizing the structures of double-layered Dion–Jacobson phases, which are typifie...

Proper Ferroelectricity in the Dion–Jacobson Material CsBi2Ti2NbO10: Experiment and Theory

A diverse range of materials and properties are exhibited by layered perovskites. We report on the synthesis, characterization, and computational investigation of a new ferroelectric—CsBi2Ti2NbO10—an n = 3 member of the Dion–Jacobson (DJ) family. Structural studies using variable-temperature neutron powder diffraction indicate that a combination of octahedral rotations and polar displacements result in the polar structure. Density functional theory calculations reveal that the wider perovskite blocks in CsBi2Ti2NbO0 stabilize proper ferroelectricity, in contrast to the hybrid-improper ferroelectricity reported for all other DJ phases. Our results raise the possibility of a new class of proper ferroelectric materials analogous to the well-known Aurivillius phases.