The exceptional photophysical properties of 3D organic–inorganic lead halide hybrids (OILHs) endow their significant potential for usage in optoelectronics, which has sparked intense research on ...novel 3D OILHs and associated applications. However, constructing new 3D OILHs based on large organic cations suffers from tough challenges due to the limitation of the Goldschmidt tolerance factor rule, let alone further explorations of their practical applications. Herein, a brand‐new 3D lead chloride hybrid, (1MPZ)Pb4Cl10·H2O (1, 1MPZ = 1‐methylpiperazine) is reported, featuring a dense 3D lead chloride framework made of the corner‐, edge‐, and face‐shared lead chloride polyhedra. 1 presents a broadband white light emission with a large Stokes shift and a nanosecond photoluminescence lifetime, which originates from radiative recombination of self‐trapped excitons (STEs) induced by the highly distorted structure. Such a reabsorption‐free and fast‐decayed STEs emission coupling with the dense 3D architecture further enables 1 with effective X‐ray scintillation with good sensitivity. Impressively, 1 also shows superior environmental and radiation stability. This study provides a new 3D OILH with appealing luminescence, not only expanding the 3D OILH family but also inspiring the exploitation of their optoelectronic applications.
A stable and dense 3D lead chloride hybrid, (1‐methylpiperazine)Pb4Cl10·H2O, built from the corner‐, edge‐, and face‐shared lead chloride polyhedra is developed, featuring unusual self‐trapped excitons emission and effective X‐ray scintillation, which sheds light on the future exploration of new 3D organic–inorganic metal halide hybrids and their optoelectronic properties tunability.
2D chiral hybrid perovskites have recently emerged as outstanding semiconductor materials. However, most of the reported 2D chiral perovskites have limited structural types and contain high levels of ...toxic lead, which severely hinders their further applications. Herein, by using a mixed‐cation strategy, an unprecedented type of lead‐free cluster‐based 2D chiral hybrid double perovskite derivatives are successfully obtained, (R/S‐PPA)4(IPA)6Ag2Bi4I24·2H2O (1‐R and 1‐S), and (R/S‐PPA)4(n‐BA)6Ag2Bi4I24·2H2O (2‐R and 2‐S) (R/S‐PPA=R/S–1‐phenylpropylamine; IPA=isopentylamine; n‐BA=n‐butylamine). Their inorganic skeletons are linked by binuclear {Bi2I10} and infinite chain {Ag2Bi2I14}∞, in which bismuth clusters and multiple coordination modes (e.g., tetrahedral AgI4 and octahedral AgI6) are introduced into the double perovskite system for the first time. This introduction induces distortion of the inorganic layer, which may facilitate the transfer of chirality from the chiral cations into achiral double perovskite skeletons. Further, circular dichroism measurements and circularly polarized light detection confirm their inherent chiral optical activities. In addition, 1‐S exhibits an ultralow X‐ray detection limit of 129.5 nGy s−1, which is 42‐fold lower than that of demands in regular medical diagnosis (5.5 µGy s−1). This study provides a pathway to construct novel type of lead‐free cluster‐based double perovskite derivatives.
An unprecedented type of lead‐free cluster‐based chiral double perovskite materials are obtained, in which {Bi2I10} clusters and multiple coordination modes (tetrahedral AgI4 and octahedral AgI6) are first introduced into double perovskite system. Circular dichroism and circularly polarized light detection confirm their inherent chiral optical activities. Besides, 1‐S exhibits an ultralow X‐ray detection limit.
The low‐toxic and environmentally friendly 2D lead‐free perovskite has made significant progress in the exploration of “green” X‐ray detectors. However, the gap in detection performance between them ...and their lead‐based analogues remains a matter of concern that cannot be ignored. To reduce this gap, shortening the interlayer spacing to accelerate the migration and collection of X‐ray carriers is a promising strategy. Herein, a Dion‐Jacobson (DJ) lead‐free double perovskite (4‐AP)2AgBiBr8 (1, 4‐AP = 4‐amidinopyridine) with an ultra‐narrow interlayer spacing of 3.0 Å, is constructed by utilizing π‐conjugated aromatic spacers. Strikingly, the subsequent enhanced carrier transport and increased crystal density lead to X‐ray detectors based on bulk single crystals of 1 with a high sensitivity of 1117.3 µC Gy−1 cm−2, superior to the vast majority of similar double perovskites. In particular, the tight connection of the inorganic layers by the divalent cations enhances structural rigidity and stability, further endowing 1 detector with ultralow dark current drift (3.06 × 10−8 nA cm−1 s−1 V−1, 80 V), excellent multiple cycles switching X‐ray irradiation stability, as well as long‐term environmental stability (maintains over 94% photoresponse after 90 days). This work brings lead‐free double perovskites one step closer to realizing efficient practical green applications.
In this work, by utilizing π‐conjugated 4‐amidinopyridine (4‐AP) as an aromatic diammonium cation, a novel 2D DJ‐type double perovskite (4‐AP)2AgBiBr8 is constructed, with an ultra‐narrow interlayer spacing of 3.0 Å. The device based on bulk single crystal exhibits superior X‐ray detection performance with high sensitivity and high stability.
Polar photovoltaic effect (PPE) has attracted great attention in regulating desired optoelectronic properties, which can be driven by order–disorder and displacive phase transitions. Bond‐switching ...is also a feasible method to induce PPE, but such investigation is very rare. Lead‐halide hybrid perovskite (LHHP) is an outstanding photodetection material; lead atoms possess rich coordination modes to provide possibilities to construct switchable bonds. Here, a unique perovskitizer N─Pb bond‐switching is disclosed to induce polar photovoltage in the emerging LHHP, PA2MHy2Pb3Br10 (1, PA = n‐propylamine, MHy = methylhydrazine). Interestingly, the perovskitizer MHy+ provides 2s2 lone pair while the Pb atom affords empty d orbitals, which coordinate with each other to generate a flexible N─Pb bond. Further, the introduction of N─Pb bonds results in a high distortion of the PbBr6 octahedron to form local polarity and further orientation to induce spontaneous polarization. More importantly, such a flexible N─Pb bond switching mechanism drives a notable PPE and controllable polarized photo‐response, a polarization ratio up to 9.7 at the polar phase in striking contrast with the non‐polar phase (1.03). The work provides the first demonstration of bond‐switching to induce polar phase transition and polar photovoltage in the photoconductive hybrid perovskites for photoelectric applications.
The unique perovskitizer methylhydrazine (MHy) coordinate with the Pb atom to form a flexible N─Pb bond in the photoconductive hybrid perovskite, (n‐propylamine)2(MHy)2Pb3Br10. The cleavage and formation of the N─Pb bond lead to a polar phase transition. A single crystal photodetector is successfully developed for controllable polar photovoltage and switchable polarized photodetection. This research sheds light on polarization switching and multifunctional photoelectric applications.
2D multilayered organic‐inorganic hybrid perovskites (OIHPs) have exhibited bright prospects for high‐performance self‐driven X‐ray detection due to their strong radiation absorption and long carrier ...transport. However, as an effective tool for self‐driven X‐ray detection, radiation photovoltaics remain rare, and underdeveloped in multilayered OIHPs. Herein, chirality to induce radiation photovoltaics in 2D multilayered chiral OIHPs is first utilized for efficient self‐driven X‐ray detection. Specifically, under X‐ray irradiation, a multilayered chiral‐polar (S‐BPEA)2FAPb2I7 (1‐S, S‐BPEA = (S)‐1‐4‐Bromophenylethylammonium, FA = formamidinium) shows remarkable radiation photovoltaics of 0.85 V, which endows 1‐S excellent self‐driven X‐ray detection performance with a considerable sensitivity of 87.8 µC Gyair−1 cm−2 and a detection limit low to 161 nGyair s−1. Moreover, the sensitivity is high up to 1985.9 µC Gyair−1 cm−2 under 80 V bias, higher than most those of 2D OIHPs. These results demonstrate that chirality‐induced radiation photovoltaics is an efficient strategy for self‐driven X‐ray detection.
Radiation photovoltaics are first explored in chiral multilayered hybrid perovskites for efficient self‐driven X‐ray detection. (S‐BPEA)2FAPb2I7 (S‐BPEA = (S)‐1‐4‐Bromophenylethylammonium, FA = formamidinium) combines the merits of radiation photovoltaics and multilayered structure, showing a high‐sensitivity and a low X‐ray detection limit.
Immune infiltration of tumors is closely associated with clinical outcome in renal cell carcinoma (RCC). Tumor‐infiltrating immune cells (TIICs) regulate cancer progression and are appealing ...therapeutic targets. The purpose of this study was to determine the composition of TIICs in RCC and further reveal the independent prognostic values of TIICs. CIBERSORT, an established algorithm, was applied to estimate the proportions of 22 immune cell types based on gene expression profiles of 891 tumors. Cox regression was used to evaluate the association of TIICs and immune checkpoint modulators with overall survival (OS). We found that CD8+ T cells were associated with prolonged OS (hazard ratio HR = 0.09, 95% confidence interval CI.01‐.53; P = 0.03) in chromophobe carcinoma (KICH). A higher proportion of regulatory T cells was associated with a worse outcome (HR = 1.59, 95% CI 1.23‐.06; P < 0.01) in renal clear cell carcinoma (KIRC). In renal papillary cell carcinoma (KIRP), M1 macrophages were associated with a favorable outcome (HR = .43, 95% CI .25‐.72; P < 0.01), while M2 macrophages indicated a worse outcome (HR = 2.55, 95% CI 1.45‐4.47; P < 0.01). Moreover, the immunomodulator molecules CTLA4 and LAG3 were associated with a poor prognosis in KIRC, and IDO1 and PD‐L2 were associated with a poor prognosis in KIRP. This study indicates TIICs are important determinants of prognosis in RCC meanwhile reveals potential targets and biomarkers for immunotherapy development.
We described the immune landscape in detail, revealing the distinct immune infiltration patterns of different subtypes and stages of RCC. We further revealed relationships between TIIC and molecular subtypes, tumor stages, recurrent genomic alterations and survival in RCC. Our work advances the understanding of immune response meanwhile reveals potential targets and biomarkers for immunotherapy development.
Lead halide hybrid perovskites have made great progress in direct X‐ray detection and broadband photodetection, but the existence of toxic Pb and the demand for external operating voltage have ...severely limited their further applications and operational stability improvements. Therefore, exploring “green” lead‐free hybrid perovskite that can both achieve X‐ray detection and broadband photodetection without external voltage is of great importance, but remains severely challenging. Herein, using centrosymmetric (BZA)3BiI6 (1, BZA = benzylamine) as a template, a pair of chiral‐polar lead‐free perovskites, (BZA)2(R/S‐PPA)BiI6 (2‐R/S, R/S‐PPA = (R/S)‐1‐Phenylpropylamine) are successfully obtained by introducing chiral aryl cations of (R/S)‐1‐Phenylpropylamine. Compared to 1, chiral‐polar 2‐R presents a significant irradiation‐responsive bulk photovoltaic effect (BPVE) with an open circuit photovoltage of 0.4 V, which enables it with self‐powered X‐ray, UV–vis‐NIR broadband photodetection. Specifically, 2‐R device exhibits an ultralow detection limit of 18.5 nGy s−1 and excellent operational stability. Furthermore, 2‐R as the first lead‐free perovskite achieves significant broad‐spectrum (377–940 nm) photodetection via light‐induced pyroelectric effect. This work sheds light on the rational crystal reconstruction engineering and design of “green” hybrid perovskite toward high‐demanded self‐powered radiation detection and broadband photodetection.
Two novel “green” lead‐free chiral‐polar perovskites are designed and obtained by chiral‐achiral cations intercalation methods, which can realize self‐powered X‐ray detection with the LoD of 18.5 nGy s−1. In addition, 2‐R is the first lead‐free perovskite to enable UV–vis–NIR photodetection via light‐induced pyroelectric effect.
Chiral three‐dimensional hybrid organic–inorganic perovskites (3D HOIPs) would show unique chiroptoelectronic performance due to the combination of chirality and 3D structure. However, the synthesis ...of 3D chiral HOIPs remains a significant challenge. Herein, we constructed a pair of unprecedented 3D chiral halide perovskitoids (R/S‐BPEA)EA6Pb4Cl15 (1‐R/S) (R/S‐BPEA=(R/S)‐1‐4‐Bromophenylethylammonium, EA=ethylammonium), in which the large chiral cations can be contained in the big “hollow” inorganic frameworks induced by mixing cations. Notably, 3D 1‐R/S shows natural chiroptical activity, as evidenced by its significant mirror circular dichroism spectra and the ability to distinguish circularly polarized light. Moreover, based on the unique 3D structure, 1‐S presents sensitive X‐ray detection performance with a low detection limit of 398 nGyair s−1, which is 14 times lower than the regular medical diagnosis of 5.5 μGyair s−1. In this work, 3D chiral halide perovskitoids provide a new route to develop chiral material in spintronics and optoelectronics.
A pair of unprecedented 3D chiral halide perovskitoids (R/S‐BPEA)EA6Pb4Cl15 (1‐R/S) (R‐/S‐BPEA=(R/S)‐1‐4‐Bromophenylethylamine, EA=Ethylamine) have been constructed by introducing chiral and achiral cations into the 3D “hollow” inorganic framework. The realization of 3D chiral halide perovskitoids provides a new route for developing chiral materials toward spintronics and chiroptoelectronics applications.
The combination of polyoxoniobates (PONbs) with 3d metal ions, azoles, and organoamines is a general synthetic procedure for making unprecedented PONb metal complex cage materials, including discrete ...molecular cages and extended cage frameworks. By this method, the first two PONb metal complex cages K4@{Cu29(OH)7(H2O)2(en)8(trz)21Nb24O67(OH)2(H2O)34} and Cu(en)2@{Cu2(en)2(trz)26(Nb68O188)} have been made. The former exhibits a huge tetrahedral cage with more than 120 metal centers, which is the largest inorganic–organic hybrid PONb known to date. The later shows a large cubic cage, which can act as building blocks for cage‐based extended assembly to form a 3D cage framework {Cu(en)2@{Cu2(trz)2(en)26H10Nb68O188}}. These materials exhibit visible‐light‐driven photocatalytic H2 evolution activity and high vapor adsorption capacity. The results hold promise for developing both novel cage materials and largely unexplored inorganic–organic hybrid PONb chemistry.
Hybrid polyoxoniobate cages: A series of polyoxoniobate (PONb) metal complex cage materials have been made, thus fusing two areas, namely PONbs and MOFs. The cage materials are by far the largest inorganic–organic hybrid PONbs and hold promise for the developments of both novel cage materials and largely unexplored inorganic–organic hybrid PONb chemistry.
The anomalous photovoltaic (APV) effect in organic–inorganic hybrid perovskites (OIHPs) has attracted massive interest for developing high‐performance optoelectronic devices. However, exploring the ...ionizing radiation responsive APV effect remains blank, let alone its potential applications. Herein, the unprecedented APV behavior in a 1D lead‐free OIHP, (4‐AMP)BiI5 (ABI, 4‐AMP = 4‐(aminomethyl)pyridine) under X‐ray irradiation is reported, exhibiting a large above‐bandgap bulk photovoltage of ≈10 V. Such a strong APV effect is closely related to the intrinsic electric polarization in polar ABI, which acts as the driving force for X‐ray‐generated carriers’ separation and transport, thus allowing it to be self‐powered. As a result, sensitive self‐powered X‐ray detectors based on high‐quality ABI single crystals are successfully fabricated, possessing a high sensitivity of 66.84 µC Gy−1 cm−2, a low detection limit of 482 nGy s−1, and superior operational stability. This work first demonstrates the ionizing radiation‐responsive APV effect in OIHPs, which further enables passive radiation detection.
The X‐ray responsive anomalous photovoltage is achieved in a 1D polar lead‐free hybrid perovskite, (4‐(aminomethyl)pyridine)BiI5, which further enables sensitive self‐powered X‐ray detection. Such a first demonstration of anomalous photovoltaic effect in organic–inorganic hybrid perovskites under ionizing radiation sheds light on future design of high‐performance passive radiation detectors.
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