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Metal halide perovskites (MHPs) have garnered significant attention due to their distinctive optical and electronic properties, coupled with excellent processability. However, the thermal characteristics of these materials are often overlooked, which can be harnessed to cater to diverse application scenarios. We showcase the efficacy of lowering the congruent melting temperature (Tm) of layered 2D MHPs by employing a strategy that involves the modification of flexible alkylammonium through N-methylation and I-substitution. Structural-property analysis reveals that the N-methylation and I-substitution play pivotal roles in reducing hydrogen bond interactions between the organic components and inorganic parts, lowering the rotational symmetry number of the cation and restricting the residual motion of the cations. Additional I···I interactions enhance intermolecular interactions and lead to improved molten stability, as evidenced by a higher viscosity. The 2D MHPs discussed in this study exhibit low Tm and wide melt-processable windows, e.g., (DMIPA)2PbI4 showcasing a low Tm of 98 °C and large melt-processable window of 145 °C. The efficacy of the strategy was further validated when applied to bromine-substituted 2D MHPs. Lowering the Tm and enhancing the molten stability of the MHPs hold great promise for various applications, including glass formation, preparation of high-quality films for photodetection, and fabrication of flexible devices.
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Tuning phase transition temperature is one of the central issues in phase transition materials. Herein, we report a case study of using enantiomer fraction engineering as a promising strategy to tune the Curie temperature (TC) and related properties of ferroelectrics. A series of metal-halide perovskite ferroelectrics (S-3AMP)x(R-3AMP)1-xPbBr4 was synthesized where 3AMP is the 3-(aminomethyl)piperidine divalent cation and enantiomer fraction x varies between 0 and 1 (0 and 1 = enantiomers; 0.5 = racemate). With the change of the enantiomer fraction, the TC, second-harmonic generation intensity, degree of circular polarization of photoluminescence, and photoluminescence intensity of the materials have been tuned. Particularly, when x = 0.70 - 1, a continuously linear tuning of the TC is achieved, showing a tunable temperature range of about 73 K. This strategy provides an effective means and insights for regulating the phase transition temperature and chiroptical properties of functional materials.
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Actuating materials convert different forms of energy into mechanical responses. To satisfy various application scenarios, they are desired to have rich categories, novel functionalities, clear structure-property relationships, fast responses, and, in particular, giant and reversible shape changes. Herein, we report a phase transition-driven ferroelectric crystal, (rac-3-HOPD)PbI3 (3-HOPD = 3-hydroxypiperidine cation), showing intriguingly large and anisotropic room-temperature actuating behaviors. The crystal consists of rigid one-dimensional [PbI3] anionic chains running along the a-axis and discrete disk-like cations loosely wrapping around the chains, leaving room for anisotropic shape changes in both the b- and c-axes. The shape change is switched by a ferroelectric phase transition occurring at around room temperature (294 K), driven by the exceptionally synergistic order-disorder and displacive phase transition. The rotation of the cations exerts internal pressure on the stacking structure to trigger an exceptionally large displacement of the inorganic chains, corresponding to a crystal lattice transformation with length changes of +24.6% and -17.5% along the b- and c-axis, respectively. Single crystal-based prototype devices of circuit switches and elevators have been fabricated by exploiting the unconventional negative temperature-dependent actuating behaviors. This work provides a new model for the development of multifunctional mechanically responsive materials.
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Hybrid metal halides (HMHs) based phase transition materials have received widespread attention due to their excellent performance and potential applications in energy harvesting, optoelectronics, ferroics, and actuators. Nevertheless, effectively regulating the properties of phase transitions is still a thorny problem. In this work, two chiral lead-free HMHs (R-3FP)2 SbCl5 (1; 3FP=3-fluoropyrrolidinium) and (R-3FP)2 SbBr5 (2) were synthesized. By replacing the halide ions in the inorganic skeleton, the phase transition temperature of 2 changes with an increase of about 20â K, compared with 1. Meanwhile, both compounds display reversible dielectric switching properties. Through crystal structure analysis and Hirshfeld surface analysis, their phase transitions are ascribed to the disorder of the cations and deformation of the inorganic chains.
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A two-dimensional (2D) organic-inorganic hybrid perovskite (OIHP) material with out-of-plane ferroelectricity is the key to the miniaturization of vertical-sandwich-type ferroelectric optoelectronic devices. However, 2D OIHP ferroelectrics with out-of-plane polarization are still scarce, and effective design strategies are lacking. Herein, we report a novel 2D Dion-Jacobson perovskite ferroelectric semiconductor synthesized by a rigid-to-flexible cationic tailoring strategy, achieving an out-of-plane polarization of 1.7 µC/cm2 and high photoresponse. Integrating out-of-plane ferroelectricity with excellent photoelectric properties affords a promising platform to investigate ferroelectricity-related effects in vertical optoelectronic devices.
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Materials emitting circularly polarized luminescence (CPL) have been intensively studied for their promising applications in various fields. However, developing tunable and responsive CPL materials in a wide wavelength range remains a great challenge. Here, a pair of chiral (R,R/S,S-DCDA)3Sb2Cl12 (DCDA = dimethyl-1,2-cyclohexanediamine divalent cation) shows efficient broadband yellow emission with a photoluminescence (PL) quantum yield of 27.6% with a CPL asymmetry factor of 3 × 10-3. The associated chiroptical activity is attributed to the efficient chiral transfer as well as the self-trapped exciton emission originating from the large distortion of the inorganic blocks. Notably, (R,R/S,S-DCDA)3Sb2Cl12 exhibits a large red-shift emission exceeding 100 nm upon lowering temperature. An excellent linear correlation of the PL wavelength on temperature indicates that the compounds can be used as PL thermometers, which originates from a temperature-dependent linear structural distortion of the [SbCl6] emitter. This work inspires the potential utilization of CPL-emitting materials as responsive light sources.
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Martensitic transformation, usually accompanied by ferroelastic and thermoelastic behaviors, is an interesting and useful mechanical-related property upon external stimuli. For molecular crystals, however, martensitic systems to show reversible stimuli-actuation behaviors are still limited because of a lack of designability and frequent crystal collapse due to large stress releases during the transformations. Here, a one-dimensional hybrid perovskite semiconductor (NMEA)PbI3 (NMEA = N-methylethylammonium) was prepared by following a dimensionality reduction design principle. The crystal undergoes reversible ferroelastic and thermoelastic martensitic transformations, which are attributed to weak intermolecular interactions among the chains that easily trigger the interchain shearing movement. The actuation behavior occurring during the phase transition is very close to room temperature and demonstrated to behave as a mechanical actuator for switching. This work provides an effective approach to designing molecular actuators with promising applications in next-generation intelligence devices.
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Metal-halide perovskites have been extensively investigated due to their fascinating structural diversity and outstanding optoelectronic properties. We report the photoluminescence and photoelectric response behavior of a nontypical Dion-Jacobson perovskite [(4AMTP)PbBr2]2PbBr4 (4AMTP = 4-aminomethyltetrahydropyran cation), featuring neutral PbBr2 layers incorporated into the cationic layers between the anionic [PbBr4]2- layers. A 4AMTP-coordinated PbBr2 unit constitutes the unique nontypical dication layer. The seven-coordinated PbBr6O unit forms a largely distorted decahedron with a short distance from the inorganic [PbBr4]2- layer. The photoluminescence behavior of [(4AMTP)PbBr2]2PbBr4 shows crystal size dependence. Larger crystals show purplish-blue emission with two peaks at 414 and 431 nm, whereas smaller grain size (<50 µm) crystals demonstrate a single emission peak at 425 nm. Meanwhile, it shows a blue-light photoelectric response under the illumination of 405 nm with an on/off ratio of 175 for single-crystal devices and 97 for thin-film devices. The photoresponse performance is proportional to the molar extinction coefficient of the absorption band edge.
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Direct detection of circularly polarized light (CPL) is a challenging task due to limited materials and ambiguous structure-property relationships that lead to low distinguishability of the light helicities. Perovskite ferroelectric semiconductors incorporating chirality provide new opportunities in dealing with this issue. Herein, a pair of 2D chiral perovskite ferroelectrics is reported, which have enhanced CPL detection performance due to interplays among lattice, photon, charge, spin, and orbit. The chirality-transfer-induced chiral&polar ferroelectric phase enhances the asymmetric nature of the photoactive sublattice and achieves a switchable self-powered detection via the bulk photovoltaic effect. The single-crystal-based device exhibits a CPL-sensitive detection performance under 430 nm with an asymmetric factor of 0.20 for left- and right-CPL differentiation, about two times that of the pure chiral counterparts. The enhanced CPL detection performance is ascribed to the Rashba-Dresselhaus effect that originates from the bulk inversion asymmetry and strong spin-orbit coupling, shown with a large Rashba coefficient, which is demonstrated by density functional theory calculation and circularly polarized light excited photoluminescence measurement. These results provide new perspectives on chiral Rashba ferroelectric semiconductors for direct CPL detection and ferroelectrics-based chiroptics and spintronics.
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Cationic components in the organic-inorganic hybrid perovskites (OIHPs) play an important role in the arrangement and tilting of the inorganic part that is responsible for semiconducting, luminescent, and photoelectronic properties. Herein, we report two 2D OIHP compounds, (cis-4ACHO)2(H3OBr)PbBr4 (1) and (trans-4ACHO)2(H3OCl)PbBr4 (2) (4ACHO = 4-aminocyclohexanol), showing both photoluminescence (PL) and photodetection (PD) that are tuned by the cis- and trans configurational isomerism of 4ACHO. Crystals of 1 and 2 exhibit similar packing structures but with different crystallographic symmetries. Compound 2 displays a broadband white-light emission with a higher PL efficiency (6.6%) than 1 (2.1%) that emits narrowband blue light while the PD property of 1 is better than 2 with a higher on/off ratio under the same conditions. The PL and PD of the two compounds show a seesaw relationship, which provides a new perspective for understanding the PL and PD properties in OIHPs.
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Abnormal regulation of apoptosis can lead to carcinogenesis. Single nucleotide polymorphisms in apoptotic genes have been associated with cancer risk, such as the FAS rs2234767G/A polymorphism, which alters transcription of the FAS promoter. Downregulation of FAS, with resultant cellular resistance to death signals, has been found in many cancers. However, the association between the FAS rs2234767G/A polymorphism and cancer risk is still controversial. Here, we performed a meta-analysis including 41 articles (44 case-control studies, 17,814 cases and 24,307 controls) identified from PubMed and Chinese language (CNKI and WanFang) databases related to cancer susceptibility and the FAS rs2234767G/A polymorphism. We used odds ratios (ORs) and 95% confidence intervals (CIs) to assess the strength of the associations. We found that the rs2234767 G-allele was a protective factor for cancer risk (GG vs. AA: OR=0.88, 95% CI=0.79-0.98; GG+GA vs. AA: OR=0.87, 95% CI=0.79-0.96). Similar associations were detected in the "source of control", ethnicity, and cancer type subgroups. Further studies on a larger sample size and considering gene-environment interactions should be conducted to confirm the role of FAS polymorphisms, especially rs2234767G/A, in cancer risk.
Asunto(s)
Predisposición Genética a la Enfermedad , Neoplasias/genética , Polimorfismo de Nucleótido Simple , Receptor fas/genética , Estudios de Casos y Controles , HumanosRESUMEN
The cytochrome P450 1B1 (CYP1B1) gene plays a key role in the metabolism of various carcinogens. The CYP1B1 Leu432Val polymorphism leads to leucine to valine substitution at codon 432. A lot of studies have shown that the CYP1B1 Leu432Val polymorphism was associated with urinary system cancers, especially prostate cancer. However, the results were still inconclusive. In this meta-analysis, by searching online databases and references of related reviews, we identified 17 eligible studies to assess the relationship between CYP1B1 Leu432Val polymorphism and urinary system cancers, including 7,783 cancer cases and 7,238 controls. By pooling all eligible studies, we found that the CYP1B1 Leu432Val polymorphism was not associated with overall urinary system cancers. However, in subgroup analyses, we found that the variant 432Val allele significantly increased the risk of prostate cancer (Val vs. Leu, odds ratio (OR) = 1.064, 95% confidence interval (CI) 0.981-1.154; Pheterogeneity = 0.002), while no association was found for bladder cancer (Val vs. Leu, OR = 0.942, 95% CI 0.853-1.041; Pheterogeneity = 0.504). No evidence of publication bias was found (Begg's test, P = 0.053; Egger's test, P = 0.073). In conclusion, based on 17 eligible studies, we found that the CYP1B1 Leu432Val polymorphism was associated with an increased risk of prostate cancer, while no association of bladder cancer was observed.