All-Inorganic CsPbBr3 Perovskite Nanocrystals/2D Non-Layered Cadmium Sulfide Selenide for High-Performance Photodetectors by Energy Band Alignment Engineering

Perovskites have attracted intensive attention as promising materials for the application in various optoelectronic devices due to their large light absorption coefficient, high carrier mobility, and long charge carrier diffusion length. However, the performance of the pure perovskite nanocrystals-based device is extremely restricted by the limited charge transport capability due to the existence of a large number of the grain boundary between perovskite nanocrystals. To address these issues, a high-performance photodetector based on all-inorganic CsPbBr₃ perovskite nanocrystals/2D non-layered cadmium sulfide selenide heterostructure has been demonstrated through energy band engineering with designed typed-II heterostructure. The photodetector exhibits an ultra-high light-to-dark current ratio of 1.36 × 10⁵, a high responsivity of 2.89 × 10² A W⁻¹, a large detectivity of 1.28 × 10¹⁴ Jones, and the response/recovery time of 0.53s/0.62 s. The enhancement of the optoelectronic performance of the heterostructure photodetector is mainly attributed to the efficient charge carrier transfer ability between the all-inorganic CsPbBr₃ perovskites and 2D cadmium sulfide selenide resulting from energy band alignment engineering. The charge carriers’ transfer dynamics and the mechanism of the CsPbBr₃ perovskites/2D non-layered nanosheets interfaces have also been studied by state-state PL spectra, fluorescence lifetime imaging microscopy, time-resolved photoluminescence spectroscopy, and Kelvin probe force microscopy measurements.     

Low-Temperature Crystallized and Flexible 1D/3D Perovskite Heterostructure with Robust Flexibility and High EQE-Bandwidth Product

All-inorganic perovskite cesium lead triiodide (CsPbI₃) has attracted much attention among the perovskite family due to its excellent optoelectronic properties and chemical stability. However, the high-temperature crystallization process makes CsPbI₃ less compatible with commercially flexible substrates, limiting its application into flexible optoelectronics. Here, a cation of 1-(3-aminopropyl)-2pyrrolidinone (APP) is reported that can form 1D (APP)PbI₃ perovskite as templates, and significantly reduce the CsPbI₃ black-phase transition energy with a low annealing temperature of 75 °C, which further enables a flexible (APP)PbI₃/γ-CsPbI₃ (1D/3D) heterostructure photodetector on ITO/PET substrate. A high external quantum efficiency (EQE) greater than 2377% is observed along the orientated 1D/3D heterostructure. The high gain and low noise result in a high specific detectivity (D*) over 10¹² Jones under −0.6 V low bias. The optimized device structure brings a high EQE × bandwidth product of 119 kHz under a low driving bias. Due to the high toughness of orientated APP⁺ ions and the face-connected [PbI₃]⁻ chains structure as a strong energy absorber, the flexible photodetector also shows excellent phase stability and impressive flexibility, remaining >90% initial responsivity after over 20 000 times bending with potential flexible imaging application in harsh environments.     

High-Performing Quasi-2D Perovskite Photodetectors with Efficient Charge Transport Network Built from Vertically Orientated and Evenly Distributed 3D-Like Phases

Quasi-two-dimensional (Q-2D) perovskites are emerging as one of the most promising materials for photodetectors. However, a significant challenge to Q-2D perovskites for photodetection is their insufficient charge transport ability, which is mainly attributed to their hybrid low-dimensional n-phase structure. This study demonstrates that evenly-distributed 3D-like phases with vertical orientation throughout the film can greatly facilitate charge transport and suppress charge recombination, outperforming the prevalent phase structure with a vertical dimension gradient. Based on such a phase structure, a Q-2D Ruddlesden−Popper perovskite self-powered photodetector achieving a combination of exceptional figures-of-merit is realized, including a responsivity of 0.45 AW⁻¹, a peak specific detectivity of 2.3 × 10¹³ Jones, a 156 dB linear dynamic range, and a rise/fall time of 2.89 µs/1.93 µs. The desired phase structure is obtained by utilizing a double-hole transport layer (HTL), combining hydrophobic PTAA and hydrophilic PEDOT: PSS. Besides, the dependence of the hybrid low-dimensional phase structure is also identified on the surface energy of the buried HTL substrate. This study gives insight into the correlation between Q-2D perovskites’ phase structure and performance, providing a valuable design guide for Q-2D perovskite-based photodetectors.     

Switchable and Reversible p+/n+ Doping in 2D Semiconductors by Ionic 2D Minerals

2D semiconductors are promising for fabricating miniaturized and flexible electronic devices. The manipulation of polarities in 2D semiconductors is key to fabricate functional devices and circuits. However, the switchable and reversible control of polarity in 2D semiconductors is challenging due to their ultrathin body. Herein, a reversible and non-destructive method is developed to dope 2D semiconductors by using ionic 2D minerals as the electrostatic gating. The 2D semiconductor channel can be reversibly transformed between n⁺ and p⁺ types with carrier concentrations of 1.59 × 10¹³ and 6.82 × 10¹² cm⁻², respectively. With the ability to in situ control carrier type and concentration in 2D semiconductors by ionic gating, a reversible PN/NP junction and programmable logic gate are demonstrated in such devices. This 2D mineral materials-based ionic doping approach provides an alternative method for achieving multi-functional and complex circuits in an all-2D material flatform.     

Highly Sensitive Self-Powered 2D Perovskite Photodiodes with Dual Interface Passivations

2D perovskites have attracted intensive attention by virtue of their excellent optical and electrical properties along with good stabilities. Herein, a highly sensitive self-powered photodiode based on (PEA)₂(MA)₄Pb₅I₁₆ (PEA=C₆H₅(CH₂)NH₃, MA=CH₃NH₃) 2D perovskite is demonstrated by dual interface passivations. The Al₂O₃ bottom passivation can reduce the pinhole defects in the 2D perovskite film and suppress the trap-related recombination loss, bringing forward much reduced dark current and increased photocurrent. The poly (methyl methacrylate) (PMMA) top passivation can encapsulate the 2D perovskite film and thus improve the stability of the device. These results show that the 2D perovskite-based photodiode with dual interface passivations exhibits a large photo-to-dark current ratio of 10⁷, a fast response speed of 597 ns and a linear dynamic range of 160 dB without bias. Responsivity (R) and detectivity (D*) respectively reach 0.36 A W⁻¹ and 5.4 × 10¹² Jones under 532 nm laser illumination at a power density of 1.5 nW cm⁻². Moreover, the dual interface passivated device exhibits good stabilities. This study paves the road for developing low-cost, low-power, solution processed image sensors.     

3D/2D Perovskite Single Crystals Heterojunction for Suppressed Ions Migration in Hard X-Ray Detection

Halide perovskites exhibit diverse properties depending on their compositions. However, integrating desired properties into one material is still challenging. Here, a facile solution-processed epitaxial growth method to grow 2D perovskite single crystal on top of 3D perovskite single crystal, which can passivate the surface defects for improved device performance is reported. Short formamidine (FA⁺) ions are replaced by long organic cations, which can fully align and cover the single crystal surface to prevent the ions migration or short FA⁺ ions volatilization. The thickness of epitaxial layer can be finely adjusted by controlling the growth time. The defect density of single crystals heterojunction is only 3.18 × 10⁹ cm⁻³, and the carrier mobility is 80.43 cm² V⁻¹ s⁻¹, which is greater than that of the control 3D perovskite single crystal. This study for the first time realized large area 3D/2D perovskite single crystals heterojunction, which suppressed ions migration and exhibited advanced performance in hard X-rays detection applications. This strategy also provides a way to grow large area 2D perovskite single crystal from solution processes.     

High Q-Factor and Low Threshold Continuous-Wave Near-Infrared Lasing with Quasi-2D Perovskites

Quasi-2D perovskites have shown great potential in achieving solution-processed electrically pumped laser diodes due to their multiple-quantum-well structure, which induces a carrier cascade process that can significantly enhance population inversion. However, continuous-wave (CW) optically pumped lasing has yet to be achieved with near-infrared (NIR) quasi-2D perovskites due to the challenges in obtaining high-quality quasi-2D films with suitable phase distribution and morphology. This study regulates the crystallization of a NIR quasi-2D perovskite ((NMA)₂FA_n−1Pb_nI_3n+1) using an 18-crown-6 additive, resulting in a compact and smooth film with a largely improved carrier cascade efficiency. The amplified spontaneous emission threshold of the film is reduced from 47.2 to 35.9 µJ cm⁻². Furthermore, by combining the film with a high-quality distributed feedback grating, this study successfully realizes a CW NIR laser of 809 nm at 110 K, with a high Q-factor of 4794 and a low threshold of 911.6 W cm⁻². These findings provide an important foundation for achieving electrically pumped laser diodes based on the unique quasi-2D perovskites.     

Fluorinated Organic A-Cation Enabling High-Performance Hysteresis-Free 2D/3D Hybrid Tin Perovskite Transistors

2D tin-based perovskites have gained considerable attention for use in diverse optoelectronic applications, such as solar cells, lasers, and thin-film transistors (TFTs), owing to their good stability and optoelectronic properties. However, their intrinsic charge-transport properties are limited, and the insulating bulky organic ligands hinder the achievement of high-mobility electronics. Blending 3D counterparts into 2D perovskites to form 2D/3D hybrid structures is a synergistic approach that combine the high mobility and stability of 3D and 2D perovskites, respectively. In this study, reliable p-channel 2D/3D tin-based hybrid perovskite TFTs comprising 3D formamidinium tin iodide (FASnI₃) and 2D fluorinated 4-fluoro-phenethylammonium tin iodide ((4-FPEA)₂SnI₄) are reported. The optimized FPEA-incorporated TFTs show a high hole mobility of 12 cm² V⁻¹ s⁻¹, an on/off current ratio of over 10⁸, and a subthreshold swing of 0.09 V dec⁻¹ with negligible hysteresis. This excellent p-type characteristic is compatible with n-type metal-oxide TFT for constructing complementary electronics. Two procedures of antisolvent engineering and device patterning are further proposed to address the key concern of low-performance reproducibility of perovskite TFTs. This study provides an alternative A-cation engineering method for achieving high-performance and reliable tin-halide perovskite electronics.     

Multi-Site Intermolecular Interaction for In Situ Formation of Vertically Orientated 2D Passivation Layer in Highly Efficient Perovskite Solar Cells

Surface passivation via 2D perovskite is critical for perovskite solar cells (PSCs) to achieve remarkable performances, in which the applied spacer cations play an important role on structural templating. However, the random orientation of 2D perovskite always hinder the carrier transport. Herein, multiple nitrogen sites containing organic spacer molecule (1H-Pyrazole-1-carboxamidine hydrochloride, PAH) is introduced to form 2D passivation layer on the surface of formamidinium based (FAPbI₃) perovskite. Deriving from the interactions between PAH and PbI₂, the defects of FAPbI₃ perovskite are effectively passivated. Interestingly, due to the multiple-site interactions, the 2D nanosheets are found to grow perpendicularly to the substrate for promotion of charge transfer. Therefore, an impressive power conversion efficiency of 24.6% and outstanding long-term stability are achieved for the 2D/3D perovskite devices. The findings further provide a perspective in structure design of novel organic halide salts for the fabrication of efficient and stable PSCs.     

Junction Field-Effect Transistors Based on PdSe2/MoS2 Heterostructures for Photodetectors Showing High Responsivity and Detectivity

2D materials have shown great promise for next-generation high-performance photodetectors. However, the performance of photodetectors based on 2D materials is generally limited by the tradeoff between photoresponsivity and photodetectivity. Here, a novel junction field-effect transistor (JFET) photodetector consisting of a PdSe₂ gate and MoS₂ channel is constructed to realize high responsivity and high detectivity through effective modulation of top junction gate and back gate. The JFET exhibits high carrier mobility of 213 cm² V⁻¹ s⁻¹. What is more, the high responsivity of 6 × 10² A W⁻¹, as well as the high detectivity of 10¹¹ Jones, are achieved simultaneously through the dual-gate modulation. The high performance is attributed to the modulation of the depletion region by the dual-gate, which can effectively suppress the dark current and enhance the photocurrent, thereby realizing high detectivity and responsivity. The JFET photodetector provides a new approach to realize photodetectors with high responsivity and detectivity.     

All-Dielectric Nanostructure Fabry–Pérot-Enhanced Mie Resonances Coupled with Photogain Modulation toward Ultrasensitive In2S3 Photodetector

As the fresh blood of 2D family, non-layered 2D materials (2DNLMs) have demonstrated great potential in the application of next-generation optoelectronic devices. However, stemming from the weak light absorption brought by atomically thin thickness and the interfacial recombination brought by surface dangling bonds, traditional 2DNLM photodetectors are always accompanied by limited performance. Herein, a structure that integrates Si nanopillar array and non-layered 2D In₂S₃ to construct an ultrasensitive photodetector is designed. In particular, periodically Si nanopillars can act as Fabry–Pérot-enhanced Mie resonators that can effectively control and enhance the light absorption of 2D In₂S₃. On the other hand, a vertical built-in electric field is introduced in the In₂S₃ channel to capture photogenerated holes and leave electrons recycling in In₂S₃, obtaining a high photogain. Benefiting from these two mechanisms, this proposed photodetector presents a high responsivity of 4812 A W⁻¹ and short rise/decay time of 5.2/4.0 ms at the wavelength of 405 nm. Especially, a high light on–off ratio greater than 10⁶ and a record-high detectivity of 5.4 × 10¹⁵ Jones are achieved, representing one of the most sensitive photodetectors based on 2D materials. This deliberate device design concept suggests an effective scheme to construct high-performance 2DNLM optoelectronic devices.     

2D Antiferroelectric Hybrid Perovskite with a Large Breakdown Electric Field And Energy Storage Density

Energy conversion and storage devices are highly desirable for the sustainable development of human society. Hybrid organic–inorganic perovskites have shown great potential in energy conversion devices including solar cells and photodetectors. However, its potential in energy storage has seldom been explored. Here the crystal structure and electrical properties of the 2D hybrid perovskite (benzylammonium)₂PbBr₄ (PVK-Br) are investigated, and the consecutive ferroelectric-I (FE1) to ferroelectric-II (FE2) then to antiferroelectric (AFE) transitions that are driven by the orderly alignment of benzylamine and the distortion of [PbBr₆] octahedra are found. Furthermore, accompanied by field-induced AFE to FE transition near room temperature, a large energy storage density of ≈1.7 J cm⁻³ and a wide working temperature span of ≈70 K are obtained; both of which are among the best in hybrid AFEs. This good energy storage performance is attributed to the large polarization of ≈7.6 µC cm⁻² and the high maximum electric field of over 1000 kV cm⁻¹, which, as revealed by theoretical calculations, originate from the cooperative coupling between the [PbBr₆] octahedral framework and the benzylamine molecules. The research clarifies the discrepancy in the phase transition character of PVK-Br and shed light on developing high-performance energy storage devices based on 2D hybrid perovskite.     

Spacer Cation Tuning Enables Vertically Oriented and Graded Quasi-2D Perovskites for Efficient Solar Cells

Halide substitution in phenethylammonium spacer cations (X-PEA⁺, X  = F, Cl, Br) is a facile strategy to improve the performance of PEA based perovskite solar cells (PSCs). However, the power conversion efficiency (PCE) of X-PEA based quasi-2D (Q-2D) PSCs is still unsatisfactory and the underlying mechanisms are in debate. Here, the in-depth study on the impact of halide substitution on the crystal orientation and multi-phase distribution in PEA based perovskite films are reported. The halide substitution eliminates n  =  1 2D perovskite and thus leads to the perpendicular crystal orientation. Furthermore, nucleation competition exists between small-n and large-n phases in PEA and X-PEA based perovskites. This gives rise to the orderly distribution of different n-phases in the PEA and F-PEA based films, and random distribution in Cl-PEA and Br-PEA based films. As a result, (F-PEA)₂MA₃Pb₄I₁₂ (MA = CH₃NH₃⁺, n = 4) based PSCs achieve a PCE of 18.10%, significantly higher than those of PEA (12.23%), Cl-PEA (7.93%) and Br-PEA (6.08%) based PSCs. Moreover, the F-PEA based devices exhibit remarkably improved stability compared to their 3D counterparts.     

Field-Effect Transistors Based on Formamidinium Tin Triiodide Perovskite

To date, there are no reports of 3D tin perovskite being used as a semiconducting channel in field-effect transistors (FETs). This is probably due to the large amount of trap states and high p-doping typical of this material. Here, the first top-gate bottom-contact FET using formamidinium tin triiodide perovskite films is reported as a semiconducting channel. These FET devices show a hole mobility of up to 0.21 cm² V⁻¹ s⁻¹, an I_ON/OFF ratio of 10⁴, and a relatively small threshold voltage (V_TH) of 2.8 V. Besides the device geometry, the key factor explaining this performance is the reduced doping level of the active layer. In fact, by adding a small amount of the 2D material in the 3D tin perovskite, the crystallinity of FASnI₃ is enhanced, and the trap density and hole carrier density are reduced by one order of magnitude. Importantly, these transistors show enhanced parameters after 20 months of storage in a N₂ atmosphere.     

Introduction of Hydrophobic Ammonium Salts with Halogen Functional Groups for High‐Efficiency and Stable 2D/3D Perovskite Solar Cells

2D perovskites have attracted extensive attention due to their excellent stability compared with 3D perovskites. However, the intrinsic hydrophilicity of introduced alkylammonium salts effects the humidity stability of 2D/3D perovskites. Devices based on longer chain alkylammonium salts show improvement in hydrophobicity but lower efficiency due to the poorer charge transport among various layers. To solve this issue, two hydrophobic short‐chain alkylammonium salts with halogen functional groups (2‐chloroethylamine, CEA⁺ and 2‐bromoethylamine, BEA⁺) are introduced into (Cs_0.1FA_0.9)Pb(I_0.9Br_0.1)₃ 3D perovskites to form 2D/3D perovskite structure, which achieve high‐quality perovskite films with better crystallization and morphology. The optimal 2D/3D perovskite solar cells (PSCs) with 5% CEA⁺ display a power conversion efficiency (PCE) as high as 20.08% under 1 sun irradiation. Because of the notable hydrophobicity of alkylammonium cations with halogen functional groups and the formed 2D/3D perovskite structure, the optimal PSCs exhibit superior moisture resistance and retain 92% initial PCE after aging at 50 ± 5% relative humidity for 2400 h. This work opens up a new direction for the design of new‐type 2D/3D PSCs with improved performance by employing proper alkylammonium salts with different functional groups.     

Modifying Surface Termination of CsPbI3 Grain Boundaries by 2D Perovskite Layer for Efficient and Stable Photovoltaics

It is highly desirable for all-inorganic perovskite solar cells (PVSCs) to have reduced nonideal interfacial charge recombination in order to improve the performance. Although the construction of a 2D capping layer on 3D perovskite is an effective way to suppress interfacial nonradiative recombination, it is difficult to apply it to all-inorganic perovskites because of the resistance of Cs⁺ cesium ions in cation exchange reactions. To alleviate this problem, a simple approach using an ultra-thin 2D perovskite to terminate CsPbI₃ grain boundaries (GBs) without damaging the original 3D perovskite is developed. The 2D perovskite at the GBs not only enhances the charge-carrier extraction and transport but also effectively suppresses nonradiative recombination. In addition, because the 2D perovskite can prevent the moisture and oxygen from penetrating into the GBs and at the same time suppress the ion migration, the 2D terminated CsPbI₃ films exhibit significantly improved stability against humidity. Moreover, the devices without encapsulation can retain ≈81% of its initial power conversion efficiency (PCE) after being stored at 40 ± 5% relative humidity for 84 h. The 2D-based champion device exhibits a high PCE of 18.82% with a high open-circuit voltage of 1.16 V.     

A Spacer Cation Assisted Nucleation and Growth Strategy Enables Efficient and High-Luminance Quasi-2D Perovskite LEDs

Quasi-2D Ruddlesden-Popper perovskites receive tremendous attention for application in light-emitting diodes (LEDs). However, the role of organic ammonium spacers on perovskite film has not been fully-understood. Herein, a spacer cation assisted perovskite nucleation and growth strategy, where guanidinium (GA⁺) spacer is introduced into the perovskite precursor and at the interface between the hole transport layer (HTL) and the perovskite, to achieve dense and uniform perovskite films with enhanced optical and electrical performance is developed. A thin GABr interface pre-formed on HTL provides more nucleation sites for perovskite crystal; while the added GA⁺ in perovskite reduces the crystallization rate due to strong hydrogen bonding interacts with intermediates, which promotes the growth of enhanced-quality quasi-2D perovskite films. The ionized ammonium group ( NH₃⁺) of GA⁺ also favors formation of polydisperse domain distribution, and amine or imine ( NH₂ or NH) group interact with perovskite defects through coordination bonding. The spacer cation assisted nucleation and growth strategy is advantageous for producing efficient and high-luminance perovskite LEDs, with a peak external quantum efficiency of over 20% and a luminance up to 100 000 cd m⁻². This work can inform and underpin future development of high-performance perovskite LEDs with concurrent high efficiency and brightness.     

Synergy of Organic and Inorganic Sites in 2D Perovskite for Fast Neutron and X-Ray Imaging

Fast neutron and X-ray imaging are considered complementary nondestructive detection technologies. However, due to their opposite cross-sections, development of a scintillator that is sensitive to both fast neutrons and X-rays within a single-material framework remains challenging. Herein, an organic–inorganic hybrid perovskite (C₄H₉NH₃)₂PbBr₄ (BPB) is demonstrated as a scintillator that fully meets the requirements for both fast neutron and X-ray detection. The hydrogen-rich organic component acts as a fast neutron converter and produces detectable recoil protons. The heavy atom-rich inorganic fraction efficiently deposits the energy of charged recoil protons and directly provides a large X-ray cross-section. Due to the synergy of these organic and inorganic components, the BPB scintillator exhibits high light yields (86% of the brightness of a commercial ZnS (Ag)/⁶LiF scintillator for fast neutrons; 22 000 photons per MeV for X-rays) and fast response times (τ_decay = 10.3 ns). More importantly, energy-selective fast neutron and X-ray imaging are also demonstrated, with high resolutions of ≈1 lp mm⁻¹ for fast neutrons and 17.3 lp mm⁻¹ for X-rays; these are among the highest resolution levels for 2D perovskite scintillators. This study highlights the potential of 2D perovskite materials for use in combined fast neutron and X-ray imaging applications.     

3D HfO2 Thin Film MEMS Capacitor with Superior Energy Storage Properties

Capacitors are ubiquitous and crucial components in modern technologies. Future microelectronic devices require novel dielectric capacitors with higher energy storage density, higher efficiency, better frequency and temperature stabilities, and compatibility with integrated circuit (IC) processes. Here, in order to overcome these challenges, a novel 3D HfO₂ thin film capacitor is designed and fabricated by an integrated microelectromechanical system (MEMS) process. The energy storage density (ESD) of the capacitor reaches 28.94 J cm⁻³, and the energy storage efficiency of the capacitor is up to 91.3% under an applied electric field of 3.5 MV cm⁻¹. The ESD can be further improved by reducing the minimum period structure size of the 3D capacitor. Moreover, the 3D capacitor exhibits excellent temperature stability (up to 150 °C) and charge-discharge endurance (10⁷ cycles). The results indicate that the 3D HfO₂ thin film MEMS capacitor has enormous potential in energy storage applications in harsh environments, such as pulsed discharge and power conditioning electronics.     

Epitaxial 2D PbS Nanosheet-Formamidinium Lead Triiodide Heterostructure Enabling High-Performance Perovskite Solar Cells

Nanomaterials such as quantum dots and 2D materials have been widely used to improve the performance of perovskite solar cells due to their favorable optical properties, conductivity, and stability. Nevertheless, the interfacial crystal structures between perovskites and nanomaterials have always been ignored while large mismatches can result in a significant number of defects within solar cells. In this work, cubic PbS nanosheets with (200) preferred crystal planes are synthesized through anisotropy growth. Based on the similar crystal structure between cubic PbS (200) and cubic-phase formamidinium lead triiodide (α-FAPbI₃) (200), a nanoepitaxial PbS nanosheets-FAPbI₃ heterostructure with low defect density is observed. Attribute to the epitaxial growth, PbS nanosheets-FAPbI₃ hybrid polycrystalline films show decreased defects and better crystallization. Optimized perovskite solar cells perform both improved efficiency and stability, retaining 90% of initial photovoltaic conversion efficiency after being stored at 20 °C and 20% RH for 2500 h. Notably, the significantly improved stability is ascribed to the interfacial compression strain and chemical bonding between (200) planes of PbS nanosheets and α-FAPbI₃ (200). This study provides insight into high-performance perovskite solar cells achieved by manipulating nanomaterial surfaces.