Dimensionality Engineering of Organic-Inorganic Halide Perovskites for Next-Generation X-Ray Detector.

The next-generation X-ray detectors require novel semiconductors with low material/fabrication cost, excellent X-ray response characteristics, and robust operational stability. The family of organic-inorganic hybrid perovskites (OIHPs) materials comprises a range of crystal configuration (i.e., films, wafers, and single crystals) with tunable chemical composition, structures, and electronic properties, which can perfectly meet the multiple-stringent requirements of high-energy radiation detection, making them emerging as the cutting-edge candidate for next-generation X-ray detectors. From the perspective of molecular dimensionality, the physicochemical and optoelectronic characteristics of OIHPs exhibit dimensionality-dependent behavior, and thus the structural dimensionality is recognized as the key factor that determines the device performance of OIHPs-based X-ray detectors. Nevertheless, the correlation between dimensionality of OIHPs and performance of their X-ray detectors is still short of theoretical guidance, which become a bottleneck that impedes the development of efficient X-ray detectors. In the review, the advanced studies on the dimensionality engineering of OIHPs are critically assessed in X-ray detection application, discussing the current understanding on the "dimensionality-property" relationship of OIHPs and the state-of-the-art progresses on the dimensionality-engineered OIHPs-based X-ray detector, and highlight the open challenges and future outlook of this field.

Promoting Ruddlesden-Popper Perovskite Formation by Tailoring Spacer Intramolecular Interaction for Efficient and Stable Solar Cells.

Low-dimensional Ruddlesden-Popper phase (LDRP) perovskites are widely studied in the field of photovoltaics due to their tunable energy-band properties, enhanced photostability, and improved environmental stability compared to the 3D perovskites. However, the insulating spacers with weak intramolecular interaction used in LDRP materials limit the out-of-plane charge transport, leading to poor device performance of LDRP perovskite solar cells (PSCs). Here, a functional ligand, 3-guanidinopropanoic acid (GPA), which is capable of forming strong intramolecular hydrogen bonds through the carboxylic acid group, is employed as an organic spacer for LDRP PSCs. Owing to the strong interaction between GPA molecules, high-quality LDRP (GPA)2(MA)n-1PbnI3n+1 film with promoted formation of n = 5 phase, improved crystallinity, preferential vertical growth orientations, reduced trap-state density, and prolonged carrier lifetime is achieved using GPAI as the dimensionality regulator compared to butylamine hydroiodide (BAI). As a result, GPA-based LDRP PSC exhibits a champion power conversion efficiency of 18.16% that is much superior to the BA-based LDRP PSC (15.43%). Importantly, the optimized GPA-based LDRP PSCs without encapsulation show enhanced illumination, thermal, storage, and humidity stability compared to BA-based ones. This work provides new insights into producing high n value LDRP films and their efficient and stable PSCs.

In Situ Interface Engineering for Highly Efficient Electron-Transport-Layer-Free Perovskite Solar Cells.

Electron-transport-layer free perovskite solar cells (ETL-free PSCs) have attracted great attention due to their low cost and simple manufacturing process. However, an additional interface layer has to be introduced, and the currently achieved efficiency remains far from full-structure PSCs. Here, we report an in situ interface engineering strategy by the methylammonium acetate (MAAc) ionic liquid perovskite precursor. We found that a dipole layer was in situ constructed through the physical adsorption of the residual MAAc polar molecules on the indium tin oxide electrode, which is significantly different from the treatment by the interface layer in previous reports. This allows a decrease of the effective work function and enables in situ band bending in the perovskite semiconductor. The in situ band bending facilitates charge collection and hinders interfacial charge recombination, leading to ETL-free PSCs with a maximum power conversion efficiency of 21.08%, which is the highest report to date.

Defects in metal triiodide perovskite materials towards high-performance solar cells: origin, impact, characterization, and engineering.

The rapid development of solar cells (SCs) based on organic-inorganic hybrid metal triiodide perovskite (MTP) materials holds great promise for next-generation photovoltaic devices. The demonstrated power conversion efficiency of the SCs based on MTP (PSCs for short) has reached over 20%. An MTP material is a kind of soft ionic solid semiconductor. The intrinsic optoelectronic properties of MTP are greatly determined by several factors, such as the crystalline phase, doping type, impurities, elemental composition, and defects in its crystal structure. In the development of PSCs, a good understanding and smart engineering of the defects in MTP have been demonstrated to be a key factor for the fabrication of high-efficiency PSCs. In this review, we start with a brief introduction to the types of defects and the mechanisms for their formation in MTP. Then, the positive and negative impacts of defects on the important optoelectronic features of MTP are presented. The optoelectronic properties mainly include charge recombination, charge transport, ion migration, and structural stability. Moreover, commonly used techniques for the characterization of the defects in MTP are systematically summarized. Recent progress on the state-of-the-art defect engineering approaches for the optimization of PSC devices is also summarized, and we also provide some perspectives on the development of high-efficiency PSCs with long-term stability through the optimization of the defects in MTP.

High-Quality Cs2 AgBiBr6 Double Perovskite Film for Lead-Free Inverted Planar Heterojunction Solar Cells with 2.2 % Efficiency.

All-inorganic double-metal perovskite materials have recently gained much attention due to their three dimensionality (3D) and non-toxic nature to replace lead-based perovskite materials. Among all those double perovskite materials, theoretical works have demonstrated that Cs2 AgBiBr6 shows high stability and possesses a suitable band gap for solar-cell applications. However, the film-forming ability of Cs2 AgBiBr6 is found to be the utmost challenge hindering its development in thin-film solar-cell devices. In this work, a high-quality Cs2 AgBiBr6 film with ultra-smooth morphology, micro-sized grains, and high crystallinity is realized via anti-solvent dropping technology and post-annealing at high temperature. After optimization, the first example of an inverted planar heterojunction solar-cell device based on Cs2 AgBiBr6 exhibits a power conversion efficiency of 2.23 % with VOC =1.01 V, JSC =3.19 mA/cm2 , and FF=69.2 %. Besides, the device shows no hysteresis and a high stability.

Charge Transport between Coupling Colloidal Perovskite Quantum Dots Assisted by Functional Conjugated Ligands.

Long alkyl-chain capping ligands are indispensable for preparing stable colloidal quantum dots. However, its insulating feature blocks efficient carrier transport among QDs, leading to inferior performance in light-emitting diodes (LEDs). The trade-off between conductivity and colloidal stability of QDs has now been overcome. Methylamine lead bromide (MAPbBr3 ) QDs with a conjugated alkyl-amine, 3-phenyl-2-propen-1-amine (PPA), as ligands were prepared. Owing to electron cloud overlapping and the delocalization effect of conjugated molecules, the conductivity and carrier mobility of PPA-QDs films increased almost 22 times over that of OA-QD films without compromising colloidal stability and photoluminescence. PPA-QDs LEDs exhibit a maximum current efficiency of 9.08 cd A-1 , which is 8 times of that of OA-QDs LEDs (1.14 cd A-1 ). This work provides critical solution for the poor conductivity of QDs in applications of energy-related devices.

The role of reduction extent of graphene oxide in the photocatalytic performance of Ag/AgX (X = Cl, Br)/rGO composites and the pseudo-second-order kinetics reaction nature of the Ag/AgBr system.

Although reduced graphene oxide (rGO)-based photocatalyst composites have been intensively developed during the past few years, the influence of reduction extent of rGO on the photocatalytic performance of the rGO-based composite has virtually not been investigated due to some technical limitations, such as the poor water dispersibility of rGO and low reduction selectivity of the hydrothermal method, which make it difficult to control the reduction extent of rGO in these composites. Herein, we used a facile room-temperature method to synthesize Ag/AgX (X = Cl, Br)/rGO photocatalyst composites as a model to study the effect of reduction extent of rGO on the photocatalytic performance of the photocatalyst. It was found that the photocatalytic activities of both Ag/AgCl/PrGO and Ag/AgBr/PrGO systems had an optimized threshold of the reduction extent of photoreduced GO (PrGO). More importantly, due to the different conductive band values of AgCl and AgBr, the optimized thresholds in the two systems were at different PrGO reduction extents, based on which we proposed that the favorable energy band matching between AgX and PrGO in the two systems played a crucial role in obtaining high photocatalysis performance. Besides, the photocatalytic reaction of the Ag/AgBr based system was confirmed to be a pseudo-second-order kinetics reaction rather than pseudo-first-order kinetics reaction. The new insights presented in this work provided useful information on the design and development of a more sophisticated photocatalyst, and can also be applied to many other applications.

Employing the plasmonic effect of the Ag-graphene composite for enhancing light harvesting and photoluminescence quenching efficiency of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-vinylene].

In this work, we report that the Ag-graphene composite (AGC) can effectively enhance the light harvesting and photoluminescence (PL) quenching efficiency of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-vinylene] (MEH-PPV). Loading the AGC on MEH-PPV leads to improved light absorption ability and PL quenching efficiency, which is due to the strong interaction between localized surface plasmon resonance (LSPR)-activated Ag nanoparticles and the MEH-PPV molecule. Control experiment reveals that the combination of graphene and Ag nanoparticles achieves superior light absorptivity and PL quenching ability compared with individual graphene and Ag NPs. The exponential shape of the Stern-Volmer plot implies that both Ag and graphene in the AGC can offer the quenching pathway for the PL quenching process. We also found that the AGC with a broader LSPR absorption range is competitive in enhancing the light absorption ability and PL quenching efficiency of the MEH-PPV-AGC composite, because it can expand LSPR-induced light harvesting and PL quenching response to a wider absorption range.

Air-Processed Efficient Cesium-Based Two-Dimensional Perovskite Solar Cells Based on Asymmetric Chiral Ammonium Salts.

Cesium-based two-dimensional (2D) perovskites with attractive phase and environmental stability have broad application prospects in single-junction and tandem perovskite solar cells (PSCs). However, the severe nonradiative recombination and significant energy losses due to disordered phase orientations and phase distributions greatly hinder the carrier transport performance of cesium-based 2D PSCs and severely limit their photovoltaic performance. Here, we employ an asymmetric chiral spacer cation source, (R)-α-phenylethylamine acrylate (R-α-PEAAA), to prepare high-quality 2D cesium-based films with uniform phase distribution and high out-of-plane orientation by air processing, resulting in efficient carrier transport. More importantly, the asymmetric chiral spacer R-α-PEA has a stronger dipole moment than its isomer (PEA), which can regulate the dielectric properties of cesium-based 2D perovskites and promote charge dissociation. In addition, the chiral R-α-PEA can optimize the morphology and out-of-plane orientation of perovskite films, reduce trap density and nonradiative recombination loss, and optimize energy level alignment, thus enhancing carrier transport. As a result, cesium-based 2D PSCs (R-α-PEA2Cs4Pb5I16, n = 5) achieved a record power conversion efficiency of 19.71% and the unencapsulated device maintained over 90% efficiency after 1500 h of continuous light exposure and ambient storage (35 ± 5% relative humidity). This study provides an idea for the development of chiral 2D perovskite with efficient charge carrier transport toward efficient and stable cesium-based 2D PSCs.

Molecule Anchoring Strategy Promotes Vertically Homogeneous Crystallization and Aligned Interfaces for Efficient Pb-Sn Perovskite Solar Cells and Tandem Device.

Narrow-bandgap (NBG) Pb-Sn perovskites are ideal candidates as rear subcell in all-perovskite tandem solar cells. Because Pb-Sn perovskites contain multiple components, the rational regulation of vertical structure and both interfaces of the film is primarily crucial to achieve high-performing NBG perovskite solar cells (PSCs). Herein, a molecule anchoring strategy is developed to in situ construct Cs0.1MA0.3FA0.6Pb0.5Sn0.5I3 perovskite film with vertically aligned crystals and optimized interfaces. Specifically, l-alanine methyl ester is developed as an anchoring additive to induce the vertical crystal growth, while PEA2PbI3SCN film is introduced to promote the homogeneous crystallization at the buried interface via SCN- anchoring with cations. Further ethylenediamine dihalides (EDA(I/Cl)2) post-treatment leads to the gradient energy level alignment on the film surface. Pb-Sn PSCs based on such film show efficient charge transport and extraction, producing a champion power conversion efficiency (PCE) of 22.3% with an impressive fill factor of 82.14%. Notably, combining with semitransparent 1.78 eV wide-bandgap PSCs, the four-terminal all-perovskite tandem device achieves a PCE of 27.1%. This work opens up a new pathway to boost the performance of Pb-Sn PSCs and their tandem devices.

Screen-Printing Technology for Scale Manufacturing of Perovskite Solar Cells.

As a key contender in the field of photovoltaics, third-generation thin-film perovskite solar cells (PSCs) have gained significant research and investment interest due to their superior power conversion efficiency (PCE) and great potential for large-scale production. For commercialization consideration, low-cost and scalable fabrication is of primary importance for PSCs, and the development of the applicable film-forming techniques that meet the above requirements plays a key role. Currently, large-area perovskite films are mainly produced by printing techniques, such as slot-die coating, inkjet printing, blade coating, and screen-printing. Among these techniques, screen printing offers a high degree of functional layer compatibility, pattern design flexibility, and large-scale ability, showing great promise. In this work, the advanced progress on applying screen-printing technology in fabricating PSCs from technique fundamentals to practical applications is presented. The fundamentals of screen-printing technique are introduced and the state-of-the-art studies on screen-printing different functional layers in PSCs and the control strategies to realize fully screen-printed PSCs are summarized. Moreover, the current challenges and opportunities faced by screen-printed perovskite devices are discussed. This work highlights the critical significance of high throughput screen-printing technology in accelerating the commercialization course of PSCs products.

Unraveling the Role of Chloride in Vertical Growth of Low-Dimensional Ruddlesden-Popper Perovskites for Efficient Perovskite Solar Cells.

Recently, low-dimensional Ruddlesden-Popper (LDRP) perovskite-based solar cells (PSCs) have been extensively studied because of their robust stability. However, because of the poor conductivity of the organic spacer, the charge transport across the spacers in the LDRP perovskite is considerably poor, and thus regulation of the growth orientation of LDRP cells is of primary importance. So far, the key role of organic cations in controlling the growth orientation of LDRP films has been widely studied, but the impact of halogens has not been sufficiently investigated. Herein, we demonstrate the important role of halogens in determining the characteristics of benzylamine (BZA)-based LDRP perovskite films, where different BZAX salts (X = Cl, Br, I) are adopted. Compared to Br and I, Cl is shown to prominently enlarge the grain size, promote the vertical orientation, reduce the trap state density, and prolong the carrier lifetime of LDRP film, and all these merits effectively accelerate the carrier transport within the film. As a result, a PSC device based on BZACl delivers a champion PCE of 17.25% with much improved device stability. This work unravels the vital role of Cl in regulating the crystallization process of LDRP films, which provides a facile approach for boosting the performance of LDRP-based PSCs.

Designing Ionic Liquids as the Solvent for Efficient and Stable Perovskite Solar Cells.

As a green solvent, ionic liquids (ILs) are considered as a promising alternative to conventional polar aprotic solvents for the production of efficient and stable perovskite solar cells (PSCs). Moreover, with the use of IL solvents, perovskite films can be prepared without antisolvent treatments in an ambient environment instead of in a glovebox with inert gases, which simplifies the film manufacturing process and is favorable for industrialization production. However, the type of IL solvents that have been studied is limited, and the influence of IL molecular structures on the perovskite-film crystallization and device performance is not completely understood. In this work, four different ILs, methylammonium formate (MAF), methylammonium acetate (MAAc), methylammonium propionate (MAP), and mthylammonium isobutyrate (MAIB), are synthesized as the perovskite precursor solvents. The interaction between the functional groups of the synthesized solvents and Pb2+ in the precursor solution is studied, which has a direct impact on the morphology and crystallization of the deposited perovskite film. It is found that MAP solvent gives a high-quality perovskite film, which leads to the best photovoltaic performance with a champion PCE of 20.56% compared to the devices based on the other IL solvents. Moreover, the MAP-based device maintains 88% of its original PCE after 1000 h of storage in a N2 atmosphere, demonstrating excellent device stability. Therefore, it is concluded that MAP is the most suitable solvent for MAPbI3 films with respect to photovoltaic applications as compared to the other ILs.

SnO2 Passivation and Enhanced Perovskite Charge Extraction with a Benzylamine Hydrochloric Interlayer.

Perovskite solar cells (PSCs) have gained much attention because of their expressive power conversion efficiency (PCE) of up to 25.5%. A good contact and a well-aligned energy level at the buried interfaces between electron transport layers (ETLs) and perovskite films play an essential role in promoting charge-carrier collection and suppressing nonradiative recombination. Currently, low-temperature-processed SnO2 thin films are widely used as the ETLs to achieve efficient and stable planar PSCs. However, fabricating proper SnO2/perovskite interfaces with a good contact and a well-aligned energy level is necessary but implies a great challenge. Herein, we modify the SnO2 ETL using benzylamine hydrochloride (BH), which is expected to facilitate the energy level alignment and to enhance perovskite crystallization. Moreover, the BH interlayer is found to effectively reduce the trap-state density and thereby improve the charge-carrier extraction between the ETL and the perovskite layer. Consequently, the PSC with BH modification yields a higher PCE, a lower hysteresis, and better stability than the device without a BH interlayer. This study highlights the key role of molecule modification of ETLs in designing efficient and stable PSCs.

Improving the Air Resistance of the Precursor Solution for Ambient-Air Coating of an Sn-Pb Perovskite Film with Superior Photovoltaic Performance.

Owing to narrow band gap and low toxicity, tin-lead (Sn-Pb) hybrid perovskites have shown great potential in photovoltaic applications, and the highest power conversion efficiency (PCE) of Sn-Pb perovskite solar cells (PSCs) has recently reached 23.6%. However, it is still challenging to prepare Sn-Pb films in open-air condition due to the Sn2+ oxidation of the precursor solution under this condition. In this work, we report the stabilizing of the Sn-Pb perovskite precursor solution by using ionic liquid methylammonium acetate (MAAc) as the solvent, which enables the fabrication of Sn-Pb films in air. MAAc is found to coordinate with the Sn-Pb precursor via abundant hydrogen bonding, which stabilizes the colloids and protects the Sn2+ stability in the precursor solution in air. Therefore, the durability of the Sn-Pb precursor solution based on the MAAc solvent is greatly improved, which enables the fabrication of efficient PSCs and achieves a champion PCE of ∼16% with robust device stability. Moreover, due to the chemical interactions of MAAc with Sn-Pb perovskites, the Pb leakage is also suppressed in the MAAc-based Sn-Pb PSCs. This work demonstrates a feasible strategy for reliable fabrication of Sn-Pb PSCs, which could also be applied in many other optoelectronic devices.

Solvent Engineering of the Precursor Solution toward Large-Area Production of Perovskite Solar Cells.

Solar cells based on emerging organic-inorganic hybrid perovskite materials have reached certified power conversion efficiency as high as 25.5%, showing great potential in the next generation of photovoltaics toward large-scale industrialization. The most competitive feature of perovskite solar cells (PSCs) is that the perovskite light absorber can be fabricated by a low-cost solution method. For the solution method, the characteristics of the solvent play a key role in determining the crystallization kinetics, growth orientation, and optoelectronic properties of the perovskite film. Although significant progress has been made in the field of solvent engineering in PSCs, it is still challenging for the solution method to sustainably produce industrial-scale PSCs for future commercialization applications. Herein, the advanced progress of solvent engineering of precursor solution in terms of coordination regulation and toxicity reduction is highlighted. The physical and chemical characteristics of different solvents in reducing the toxicity of the solvent system, regulating the coordination property of the precursor solution, controlling the film-forming process of the perovskite film, and adjusting the photovoltaic performance of the PSC are systematically discussed. Lastly, important perspectives on solvent engineering of the perovskite precursor solution toward future industrial production of high-performance PSCs are provided.

Polarization-Sensitive Halide Perovskites for Polarized Luminescence and Detection: Recent Advances and Perspectives.

While halide perovskites (HPs) have achieved enormous success in the field of optoelectronic applications, much attention has been recently drawn to the unique polarization sensitivity of HPs, either intrinsic or extrinsic, which makes HPs a potential candidate for innovative applications in directly polarized luminescence and detection. Herein, the research status in the field of polarization-sensitive HPs, including linear polarization and circular polarization, is comprehensively summarized. To evaluate the effectiveness of HPs in generating and detecting linearly or circularly polarized light, the principles and characterization methods of polarized luminescence and detection are introduced. Sequentially, the state-of-the-art development of the strategies that induce the linear or circular polarization characteristics of HPs is systematically reviewed, based on which the application of polarization-sensitive HPs in the field of polarization luminescence and detection are summarized. Moreover, the current challenges and opportunities are discussed, and prospects of the future development in this promising field are outlined.

In Situ Interfacial Passivation of Sn-Based Perovskite Films with a Bi-functional Ionic Salt for Enhanced Photovoltaic Performance.

Environment-friendly Tin (Sn)-based perovskite solar cells (PSCs) have lately made significant development, showing tremendous promise in addressing the hazardous problems associated with Pb-based PSCs. However, even in N2 atmospheres, the thermodynamic stability of Sn-based perovskite films and long-term stability of Sn-based PSCs are demonstrated to be poor due to the presence of interfacial defect trap states. Here, we demonstrate the post-treatment of Sn-based perovskite films with ethylenediamine formate (EDAFa2) ion salt, serving as a bi-functional interface layer to in situ passivate the interfacial defect and improve the stability of Sn2+ by creating a thermodynamic chemical environment pathway. Moreover, the presence of EDAFa2 is shown to promote the interfacial energy level alignment, which is beneficial for the charge extraction at the interface. As a result, PSC devices with a bi-functional interface achieve a champion power conversion efficiency (PCE) as high as 9.40% and enhanced stability, retaining ∼95% of the original PCE stored in a N2 environment after ∼1960 h without encapsulation. This work highlights the significant role of an interfacial design in efficient and stable Sn-based PSCs.

Stabilizing black-phase formamidinium perovskite formation at room temperature and high humidity.

The stabilization of black-phase formamidinium lead iodide (α-FAPbI3) perovskite under various environmental conditions is considered necessary for solar cells. However, challenges remain regarding the temperature sensitivity of α-FAPbI3 and the requirements for strict humidity control in its processing. Here we report the synthesis of stable α-FAPbI3, regardless of humidity and temperature, based on a vertically aligned lead iodide thin film grown from an ionic liquid, methylamine formate. The vertically grown structure has numerous nanometer-scale ion channels that facilitate the permeation of formamidinium iodide into the lead iodide thin films for fast and robust transformation to α-FAPbI3 A solar cell with a power-conversion efficiency of 24.1% was achieved. The unencapsulated cells retain 80 and 90% of their initial efficiencies for 500 hours at 85°C and continuous light stress, respectively.

All-inorganic Sn-based Perovskite Solar Cells: Status, Challenges, and Perspectives.

Recently, the power conversion efficiency (PCE) of perovskite solar cells (PSC) based on organic-inorganic hybrid Pb halide perovskites has reached 25.2 %. However, the toxicity of Pb has still been a main concern for the large-scale commercialization of Pb-based PSCs. Efforts have been made during the past few years to seek eco-friendly Pb-free perovskites, and it is a growing consensus that Sn is the best choice as Pb alternative over any other Pb-free metal elements. Among Sn-based perovskites, all-inorganic cells are promising candidates for PSCs owing to their more suitable bandgap, better stability, and higher charge mobility compared to the organic-inorganic hybrid counterparts. However, the poor phase stability of all-inorganic Sn-based perovskites (AISPs) and low PCE of their PSCs are most challenging in the field at present. Herein, recent developments on PSCs based on AISPs, including CsSnX3 and Cs2 SnX6 (X=Br, I), are comprehensively reviewed. Primarily, the intrinsic characteristics of the two AISPs are overviewed, including crystallographic property, band structure, charge carrier property, and defect property. Sequentially, state-of-the-art progress, regarding the photovoltaic application of AISPs as light absorber, is summarized. At last, current challenges and future opportunities of AISP-based PSCs are also discussed.