Two‐Photon Up‐Conversion Photoluminescence Realized through Spatially Extended Gap States in Quasi‐2D Perovskite Films

A new approach to generate a two‐photon up‐conversion photoluminescence (PL) by directly exciting the gap states with continuous‐wave (CW) infrared photoexcitation in solution‐processing quasi‐2D perovskite films [(PEA)₂(MA)₄Pb₅Br₁₆ with n = 5] is reported. Specifically, a visible PL peaked at 520 nm is observed with the quadratic power dependence by exciting the gap states with CW 980 nm laser excitation, indicating a two‐photon up‐conversion PL occurring in quasi‐2D perovskite films. Decreasing the gap states by reducing the n value leads to a dramatic decrease in the two‐photon up‐conversion PL signal. This confirms that the gap states are indeed responsible for generating the two‐photon up‐conversion PL in quasi‐2D perovskites. Furthermore, mechanical scratching indicates that the different‐n‐value nanoplates are essentially uniformly formed in the quasi‐2D perovskite films toward generating multi‐photon up‐conversion light emission. More importantly, the two‐photon up‐conversion PL is found to be sensitive to an external magnetic field, indicating that the gap states are essentially formed as spatially extended states ready for multi‐photon excitation. Polarization‐dependent up‐conversion PL studies reveal that the gap states experience the orbit–orbit interaction through Coulomb polarization to form spatially extended states toward developing multi‐photon up‐conversion light emission in quasi‐2D perovskites.     

Revealing the Cooperative Relationship between Spin,Energy, and Polarization Parameters toward Developing High‐Efficiency Exciplex Light‐Emitting Diodes

Experimental studies to reveal the cooperative relationship between spin, energy, and polarization through intermolecular charge‐transfer dipoles to harvest nonradiative triplets into radiative singlets in exciplex light‐emitting diodes are reported. Magneto‐photoluminescence studies reveal that the triplet‐to‐singlet conversion in exciplexes involves an artificially generated spin‐orbital coupling (SOC). The photoinduced electron parametric resonance measurements indicate that the intermolecular charge‐transfer occurs with forming electric dipoles (D^+?→A^??), providing the ionic polarization to generate SOC in exciplexes. By having different singlet‐triplet energy differences (ΔE_ST) in 9,9′‐diphenyl‐9H,9′H‐3,3′‐bicarbazole (BCzPh):3′,3′″,3′″″‐(1,3,5‐triazine‐2,4,6‐triyl)tris(([1,1′‐biphenyl]‐3‐carbonitrile)) (CN‐T2T) (ΔE_ST = 30 meV) and BCzPh:bis‐4,6‐(3,5‐di‐3‐pyridylphenyl)‐2‐methyl‐pyrimidine (B3PYMPM) (ΔE_ST = 130 meV) exciplexes, the SOC generated by the intermolecular charge‐transfer states shows large and small values (reflected by different internal magnetic parameters: 274 vs 17 mT) with high and low external quantum efficiency maximum, EQE_max (21.05% vs 4.89%), respectively. To further explore the cooperative relationship of spin, energy, and polarization parameters, different photoluminescence wavelengths are selected to concurrently change SOC, ΔE_ST, and polarization while monitoring delayed fluorescence. When the electron clouds become more deformed at a longer emitting wavelength due to reduced dipole (D^+?→A^??) size, enhanced SOC, increased orbital polarization, and decreased ΔE_ST can simultaneously occur to cooperatively operate the triplet‐to‐singlet conversion.     

UV–Vis–NIR Full‐Range Responsive Carbon Dots with Large Multiphoton Absorption Cross Sections and Deep‐Red Fluorescence at Nucleoli and In Vivo

Carbon dots (CDs), with excellent optical property and cytocompatibility, are an ideal class of nanomaterials applied in the field of biomedicine. However, the weak response of CDs in the near‐infrared (NIR) region impedes their practical applications. Here, UV–vis–NIR full‐range responsive fluorine and nitrogen doped CDs (N‐CDs‐F) are designed and synthesized that own a favorable donor‐π‐acceptor (D‐π‐A) configuration and exhibit excellent two‐photon (λ_ex = 1060 nm), three‐photon (λ_ex = 1600 nm), and four‐photon (λ_ex = 2000 nm) excitation upconversion fluorescence. D‐π‐A‐conjugated CDs prepared by solvothermal synthesis under the assistance of ammonia fluoride are reported and are endowed with larger multiphoton absorption (MPA) cross sections (3PA: 9.55 × 10^?80 cm⁶ s² photon^?2, 4PA: 6.32 × 10^?80 cm⁸ s³ photon^?3) than conventional organic compounds. Furthermore, the N‐CDs‐F show bright deep‐red to NIR fluorescence both in vitro and in vivo, and can even stain the nucleoli of tumor cells. A plausible mechanism is proposed on the basis of the strong inter‐dot and intra‐dot hydrogen bonds through N? H···F that can facilitate the expanding of conjugated sp² domains, and thus not only result in lower highest occupied molecular orbital‐lowest unoccupied molecular orbital energy level but also larger MPA cross sections than those of undoped CDs.     

Ultrahigh Photocatalytic Rate at a Single‐Metal‐Atom‐Oxide

Metal oxides, as one of the mostly abundant and widely utilized materials, are extensively investigated and applied in environmental remediation and protection, and in energy conversion and storage. Most of these diverse applications are the result of a large diversity of the electronic states of metal oxides. Noticeably, however, many metal oxides present obstacles for applications in catalysis, mainly due to the lack of efficient active sites with desired electronic states. Here, the fabrication of single‐tungsten‐atom‐oxide (STAO) is demonstrated, in which the metal oxide's volume reaches its minimum as a unit cell. The catalytic mechanism in the STAO is determined by a new single‐site physics mechanism, named as quasi‐atom physics. The photogenerated electron transfer process is enabled by an electron in the spin‐up channel excited from the highest occupied molecular orbital to the lowest unoccupied molecular orbital +1 state, which can only occur in STAO with W⁵⁺. STAO results in a record‐high and stable sunlight photocatalytic degradation rate of 0.24 s^?1, which exceeds the rates of available photocatalysts by two orders of magnitude. The fabrication of STAO and its unique quasi‐atom photocatalytic mechanism lays new ground for achieving novel physical and chemical properties using single‐metal‐atom oxides (SMAO).     

Rare‐Earth‐Element‐Ytterbium‐Substituted Lead‐Free Inorganic Perovskite Nanocrystals for Optoelectronic Applications

Lead‐(Pb‐) halide perovskite nanocrystals (NCs) are interesting nanomaterials due to their excellent optical properties, such as narrow‐band emission, high photoluminescence (PL) efficiency, and wide color gamut. However, these NCs have several critical problems, such as the high toxicity of Pb, its tendency to accumulate in the human body, and phase instability. Although Pb‐free metal (Bi, Sn, etc.) halide perovskite NCs have recently been reported as possible alternatives, they exhibit poor optical and electrical properties as well as abundant intrinsic defect sites. For the first time, the synthesis and optical characterization of cesium ytterbium triiodide (CsYbI₃) cubic perovskite NCs with highly uniform size distribution and high crystallinity using a simple hot‐injection method are reported. Strong excitation‐independent emission and high quantum yields for the prepared NCs are verified using photoluminescence measurements. Furthermore, these CsYbI₃ NCs exhibit potential for use in organic–inorganic hybrid photodetectors as a photoactive layer. The as‐prepared samples exhibit clear on–off switching behavior as well as high photoresponsivity (2.4 × 10³ A W^?1) and external quantum efficiency (EQE, 5.8 × 10⁵%) due to effective exciton dissociation and charge transport. These results suggest that CsYbI₃ NCs offer tremendous opportunities in electronic and optoelectronic applications, such as chemical sensors, light emitting diodes (LEDs), and energy conversion and storage devices.     

Ultrafast Photoinduced Multimode Antiferromagnetic Spin Dynamics in Exchange‐Coupled Fe/RFeO3 (R = Er or Dy) Heterostructures

Antiferromagnetic spin dynamics is important for both fundamental and applied antiferromagnetic spintronic devices; however, it is rarely explored by external fields because of the strong exchange interaction in antiferromagnetic materials. Here, the photoinduced excitation of ultrafast antiferromagnetic spin dynamics is achieved by capping antiferromagnetic RFeO₃ (R = Er or Dy) with an exchange‐coupled ferromagnetic Fe film. Compared with antiferromagnetic spin dynamics of bare RFeO₃ orthoferrite single crystals, which can be triggered effectively by ultrafast laser heating just below the phase transition temperature, the ultrafast photoinduced multimode antiferromagnetic spin dynamic modes, for exchange‐coupled Fe/RFeO₃ heterostructures, including quasiferromagnetic resonance, impurity, coherent phonon, and quasiantiferromagnetic modes, are observed in a temperature range of 10–300 K. These experimental results not only offer an effective means to trigger ultrafast antiferromagnetic spin dynamics of rare‐earth orthoferrites, but also shed light on the ultrafast manipulation of antiferromagnetic magnetization in Fe/RFeO₃ heterostructures.     

Super‐Exchange Interaction Induced Overall Optimization in Ferromagnetic Perovskite Oxides Enables Ultrafast Water Oxidation

Oxygen evolution reaction (OER) is crucial in many renewable electrochemical technologies including regenerative fuel cells, rechargeable metal–air batteries, and water splitting. It is found that abundant active sites with favorable electronic structure and high electrical conductivity play a dominant role in achieving high electrocatalytic efficiency of perovskites, thus efficient strategies need to be designed to generate multiple beneficial factors for OER. Here, highlighted is an unusual super‐exchange effect in ferromagnetic perovskite oxide to optimize active sites and enhance electrical conductivity. A systematic exploration about the composition‐dependent OER activity in SrCo_1x Ru_x O_3?δ (denoted as SCRx) (x = 0.0–1.0) perovskite is displayed with special attention on the role of super‐exchange interaction between high spin (HS) Co³⁺ and Ru⁵⁺ ions. Induced by the unique Co³⁺–O–Ru⁵⁺ super‐exchange interactions, the SCR0.1 is endowed with abundant OER active species including Co³⁺/Co⁴⁺, Ru⁵⁺, and O₂^2?/O^?, high electrical conductivity, and metal–oxygen covalency. Benefiting from these advantageous factors for OER electrocatalysis, the optimized SCR0.1 catalyst exhibits a remarkable activity with a low overpotential of 360 mV at 10 mA cm^?2, which exceeds the benchmark RuO₂ and most well‐known perovskite oxides reported so far, while maintaining excellent durability. This work provides a new pathway in developing perovskite catalysts for efficient catalysis.     

Enhancing Light Emission in Interface Engineered Spin‐OLEDs through Spin‐Polarized Injection at High Voltages

The quest for a spin‐polarized organic light‐emitting diode (spin‐OLED) is a common goal in the emerging fields of molecular electronics and spintronics. In this device, two ferromagnetic (FM) electrodes are used to enhance the electroluminescence intensity of the OLED through a magnetic control of the spin polarization of the injected carriers. The major difficulty is that the driving voltage of an OLED device exceeds a few volts, while spin injection in organic materials is only efficient at low voltages. The fabrication of a spin‐OLED that uses a conjugated polymer as bipolar spin collector layer and ferromagnetic electrodes is reported here. Through a careful engineering of the organic/inorganic interfaces, it is succeeded in obtaining a light‐emitting device showing spin‐valve effects at high voltages (up to 14 V). This allows the detection of a magneto‐electroluminescence (MEL) enhancement on the order of a 2.4% at 9 V for the antiparallel (AP) configuration of the magnetic electrodes. This observation provides evidence for the long‐standing fundamental issue of injecting spins from magnetic electrodes into the frontier levels of a molecular semiconductor. The finding opens the way for the design of multifunctional devices coupling the light and the spin degrees of freedom.     

Silole‐Based Red Fluorescent Organic Dots for Bright Two‐Photon Fluorescence In vitro Cell and In vivo Blood Vessel Imaging

Robust luminescent dyes with efficient two‐photon fluorescence are highly desirable for biological imaging applications, but those suitable for organic dots fabrication are still rare because of aggregation‐caused quenching. In this work, a red fluorescent silole, 2,5‐bis[5‐(dimesitylboranyl)thiophen‐2‐yl]‐1‐methyl‐1,3,4‐triphenylsilole ((MesB)₂DTTPS), is synthesized and characterized. (MesB)₂DTTPS exhibits enhanced fluorescence efficiency in nanoaggregates, indicative of aggregation‐enhanced emission (AEE). The organic dots fabricated by encapsulating (MesB)₂DTTPS within lipid‐PEG show red fluorescence peaking at 598 nm and a high fluorescence quantum yield of 32%. Upon excitation at 820 nm, the dots show a large two‐photon absorption cross section of 3.43 × 10⁵ GM, which yields a two‐photon action cross section of 1.09 × 10⁵ GM. These (MesB)₂DTTPS dots show good biocompatibility and are successfully applied to one‐photon and two‐photon fluorescence imaging of MCF‐7 cells and two‐photon in vivo visualization of the blood vascular of mouse muscle in a high‐contrast and noninvasive manner. Moreover, the 3D blood vasculature located at the mouse ear skin with a depth of over 100 μm can also be visualized clearly, providing the spatiotemporal information about the whole blood vascular network.     

Multifunctional Gadolinium‐Doped Mesoporous TiO2 Nanobeads: Photoluminescence,Enhanced Spin Relaxation,and Reactive Oxygen Species Photogeneration,Beneficial for Cancer Diagnosis and Treatment

Materials with controllable multifunctional abilities for optical imaging (OI) and magnetic resonant imaging (MRI) that also can be used in photodynamic therapy are very interesting for future applications. Mesoporous TiO₂ sub‐micrometer particles are doped with gadolinium to improve photoluminescence functionality and spin relaxation for MRI, with the added benefit of enhanced generation of reactive oxygen species (ROS). The Gd‐doped TiO₂ exhibits red emission at 637 nm that is beneficial for OI and significantly improves MRI relaxation times, with a beneficial decrease in spin–lattice and spin–spin relaxation times. Density functional theory calculations show that Gd³⁺ ions introduce impurity energy levels inside the bandgap of anatase TiO₂, and also create dipoles that are beneficial for charge separation and decreased electron–hole recombination in the doped lattice. The Gd‐doped TiO₂ nanobeads (NBs) show enhanced ability for ROS monitored via ^?OH radical photogeneration, in comparison with undoped TiO₂ nanobeads and TiO₂ P25, for Gd‐doping up to 10%. Cellular internalization and biocompatibility of TiO₂@x Gd NBs are tested in vitro on MG‐63 human osteosarcoma cells, showing full biocompatibility. After photoactivation of the particles, anticancer trace by means of ROS photogeneration is observed just after 3 min irradiation.     

FA‐Assistant Iodide Coordination in Organic–Inorganic Wide‐Bandgap Perovskite with Mixed Halides

Mixed‐halide wide‐bandgap perovskites are key components for the development of high‐efficiency tandem structured devices. However, mixed‐halide perovskites usually suffer from phase‐impurity and high defect density issues, where the causes are still unclear. By using in situ photoluminescence (PL) spectroscopy, it is found that in methylammonium (MA⁺)‐based mixed‐halide perovskites, MAPb(I_0.6Br_0.4)₃, the halide composition of the spin‐coated perovskite films is preferentially dominated by the bromide ions (Br^?). Additional thermal energy is required to initiate the insertion of iodide ions (I^?) to achieve the stoichiometric balance. Notably, by incorporating a small amount of formamidinium ions (FA⁺) in the precursor solution, it can effectively facilitate the I^? coordination in the perovskite framework during the spin‐coating and improve the composition homogeneity of the initial small particles. The aggregation of these homogenous small particles is found to be essential to achieve uniform and high‐crystallinity perovskite film with high Br^? content. As a result, high‐quality MA_0.9FA_0.1Pb(I_0.6Br_0.4)₃ perovskite film with a bandgap (E_g) of 1.81 eV is achieved, along with an encouraging power‐conversion‐efficiency of 17.1% and open‐circuit voltage (V_oc) of 1.21 V. This work also demonstrates the in situ PL can provide a direct observation of the dynamic of ion coordination during the perovskite crystallization.     

Ultrasensitive and Fast All‐Inorganic Perovskite‐Based Photodetector via Fast Carrier Diffusion

Low trap‐state density, high carrier mobility, and efficient charge carrier collection are key parameters for photodetectors with high sensitivity and fast response time. This study demonstrates a simple solution growth method to prepare CsPbBr₃ microcrystals (MCs) with low trap‐state density. Time‐dependent photoluminescence study with one‐photon excitation (OPE) and two‐photon excitation (TPE) indicates that CsPbBr₃ MCs exhibit fast carrier diffusion with carrier mobility over 100 cm² V^?1 S^?1. Furthermore, CsPbBr₃ MC‐based photodetectors with high charge carriers' collection efficiency are fabricated. Such photodetectors show ultrahigh responsivity (R ) up to 6 × 10⁴ A W^?1 with OPE and high R up to 6 A W^?1 with TPE. The R for OPE is over one order of magnitude higher (the R for TPE is three orders of magnitude higher) than that of previously reported all‐inorganic perovskite‐based photodetectors. Moreover, the photodetectors exhibit fast response time of ≈1 ms, which corresponds to a gain ≈10⁵ and a gain‐ bandwidth product of 10⁸ Hz for OPE (a gain ≈10³ and a gain‐bandwidth product of 10⁶ Hz for TPE).     

Slow‐Photon‐Effect‐Induced Photoelectrical‐Conversion Efficiency Enhancement for Carbon‐Quantum‐Dot‐Sensitized Inorganic CsPbBr3 Inverse Opal Perovskite Solar Cells

All‐inorganic cesium lead halide perovskite is suggested as a promising candidate for perovskite solar cells due to its prominent thermal stability and comparable light absorption ability. Designing textured perovskite films rather than using planar‐architectural perovskites can indeed optimize the optical and photoelectrical conversion performance of perovskite photovoltaics. Herein, for the first time, this study demonstrates a rational strategy for fabricating carbon quantum dot (CQD‐) sensitized all‐inorganic CsPbBr₃ perovskite inverse opal (IO) films via a template‐assisted, spin‐coating method. CsPbBr₃ IO introduces slow‐photon effect from tunable photonic band gaps, displaying novel optical response property visible to naked eyes, while CQD inlaid among the IO frameworks not only broadens the light absorption range but also improves the charge transfer process. Applied in the perovskite solar cells, compared with planar CsPbBr₃, slow‐photon effect of CsPbBr₃ IO greatly enhances the light utilization, while CQD effectively facilitates the electron–hole extraction and injection process, prolongs the carrier lifetime, jointly contributing to a double‐boosted power conversion efficiency (PCE) of 8.29% and an increased incident photon‐to‐electron conversion efficiency of up to 76.9%. The present strategy on CsPbBr₃ IO to enhance perovskite PCE can be extended to rationally design other novel optoelectronic devices.     

Tailoring MoS2 Valley‐Polarized Photoluminescence with Super Chiral Near‐Field

Transition metal dichalcogenides with intrinsic spin–valley degrees of freedom hold great potentials for applications in spintronic and valleytronic devices. MoS₂ monolayer possesses two inequivalent valleys in the Brillouin zone, with each valley coupling selectively with circularly polarized photons. The degree of valley polarization (DVP) is a parameter to characterize the purity of valley‐polarized photoluminescence (PL) of MoS₂ monolayer. Usually, the detected values of DVP in MoS₂ monolayer show achiral property under optical excitation of opposite helicities due to reciprocal phonon‐assisted intervalley scattering process. Here, it is reported that valley‐polarized PL of MoS₂ can be tailored through near‐field interaction with plasmonic chiral metasurface. The resonant field of the chiral metasurface couples with valley‐polarized excitons, and tailors the measured PL spectra in the far‐field, resulting in observation of chiral DVP of MoS₂‐metasurface under opposite helicities excitations. Valley‐contrast PL in the chiral heterostructure is also observed when illuminated by linearly polarized light. The manipulation of valley‐polarized PL in 2D materials using chiral metasurface represents a viable route toward valley‐polaritonic devices.     

2D Perovskites with Giant Excitonic Optical Nonlinearities for High‐Performance Sub‐Bandgap Photodetection

Two‐dimensional (2D) perovskites have proved to be promising semiconductors for photovoltaics, photonics, and optoelectronics. Here, a strategy is presented toward the realization of highly efficient, sub‐bandgap photodetection by employing excitonic effects in 2D Ruddlesden–Popper‐type halide perovskites (RPPs). On near resonance with 2D excitons, layered RPPs exhibit degenerate two‐photon absorption (D‐2PA) coefficients as giant as 0.2–0.64 cm MW^?1. 2D RPP‐based sub‐bandgap photodetectors show excellent detection performance in the near‐infrared (NIR): a two‐photon‐generated current responsivity up to 1.2 × 10⁴ cm² W^?2 s^?1, two orders of magnitude greater than InAsSbP‐pin photodiodes; and a dark current as low as 2 pA at room temperature. More intriguingly, layered‐RPP detectors are highly sensitive to the light polarization of incoming photons, showing a considerable anisotropy in their D‐2PA coefficients (β_[001]/β_[011] = 2.4, 70% larger than the ratios reported for zinc‐blende semiconductors). By controlling the thickness of the inorganic quantum well, it is found that layered RPPs of (C₄H₉NH₃)₂(CH₃NH₃)Pb₂I₇ can be utilized for three‐photon photodetection in the NIR region.     

Electrically Pumped White‐Light‐Emitting Diodes Based on Histidine‐Doped MoS2 Quantum Dots

MoS₂ quantum dots (QDs)‐based white‐light‐emitting diodes (QD‐WLEDs) are designed, fabricated, and demonstrated. The highly luminescent, histidine‐doped MoS₂ QDs synthesized by microwave induced fragmentation of 2D MoS₂ nanoflakes possess a wide distribution of available electronic states as inferred from the pronounced excitation‐wavelength‐dependent emission properties. Notably, the histidine‐doped MoS₂ QDs show a very strong emission intensity, which exceeds seven times of magnitude larger than that of pristine MoS₂ QDs. The strongly enhanced emission is mainly attributed to nitrogen acceptor bound excitons and passivation of defects by histidine‐doping, which can enhance the radiative recombination drastically. The enabled electroluminescence (EL) spectra of the QD‐WLEDs with the main peak around 500 nm are found to be consistent with the photoluminescence spectra of the histidine‐doped MoS₂ QDs. The enhanced intensity of EL spectra with the current increase shows the stability of histidine‐doped MoS₂ based QD‐WLEDs. The typical EL spectrum of the novel QD‐WLEDs has a Commission Internationale de l'Eclairage chromaticity coordinate of (0.30, 0.36) exhibiting an intrinsic broadband white‐light emission. The unprecedented and low‐toxicity QD‐WLEDs based on a single light‐emitting material can serve as an excellent alternative for using transition metal dichalcogenides QDs as next generation optoelectronic devices.     

Fused Tris(thienothiophene)‐Based Electron Acceptor with Strong Near‐Infrared Absorption for High‐Performance As‐Cast Solar Cells

A fused tris(thienothiophene) (3TT) building block is designed and synthesized with strong electron‐donating and molecular packing properties, where three thienothiophene units are condensed with two cyclopentadienyl rings. Based on 3TT, a fused octacylic electron acceptor (FOIC) is designed and synthesized, using strong electron‐withdrawing 2‐(5/6‐fluoro‐3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene)‐malononitrile as end groups. FOIC exhibits absorption in 600–950 nm region peaked at 836 nm with extinction coefficient of up to 2 × 10⁵m ^–1 cm^–1, low bandgap of 1.32 eV, and high electron mobility of 1.2 × 10^–3 cm² V^–1 s^–1. Compared with its counterpart ITIC3 based on indacenothienothiophene core, FOIC exhibits significantly upshifted highest occupied molecular orbital level, slightly downshifted lowest unoccupied molecular orbital level, significantly redshifted absorption, and higher mobility. The as‐cast organic solar cells (OSCs) based on blends of PTB7‐Th donor and FOIC acceptor without additional treatments exhibit power conversion efficiencies (PCEs) as high as 12.0%, which is much higher than that of PTB7‐Th: ITIC3 (8.09%). The as‐cast semitransparent OSCs based on the same blends show PCEs of up to 10.3% with an average visible transmittance of 37.4%.     

Unraveling the Raman Enhancement Mechanism on 1T′‐Phase ReS2 Nanosheets

2D transition metal dichalcogenides materials are explored as potential surface‐enhanced Raman spectroscopy substrates. Herein, a systematic study of the Raman enhancement mechanism on distorted 1T (1T′) rhenium disulfide (ReS₂) nanosheets is demonstrated. Combined Raman and photoluminescence studies with the introduction of an Al₂O₃ dielectric layer unambiguously reveal that Raman enhancement on ReS₂ materials is from a charge transfer process rather than from an energy transfer process, and Raman enhancement is inversely proportional while the photoluminescence quenching effect is proportional to the layer number (thickness) of ReS₂ nanosheets. On monolayer ReS₂ film, a strong resonance‐enhanced Raman scattering effect dependent on the laser excitation energy is detected, and a detection limit as low as 10^?9m can be reached from the studied dye molecules such as rhodamine 6G and methylene blue. Such a high enhancement factor achieved through enhanced charge interaction between target molecule and substrate suggests that with careful consideration of the layer‐number‐dependent feature and excitation‐energy‐related resonance effect, ReS₂ is a promising Raman enhancement platform for sensing applications.     

Highly Efficient 2D/3D Hybrid Perovskite Solar Cells via Low‐Pressure Vapor‐Assisted Solution Process

The fabrication of multidimensional organometallic halide perovskite via a low‐pressure vapor‐assisted solution process is demonstrated for the first time. Phenyl ethyl‐ammonium iodide (PEAI)‐doped lead iodide (PbI₂) is first spin‐coated onto the substrate and subsequently reacts with methyl‐ammonium iodide (MAI) vapor in a low‐pressure heating oven. The doping ratio of PEAI in MAI‐vapor‐treated perovskite has significant impact on the crystalline structure, surface morphology, grain size, UV–vis absorption and photoluminescence spectra, and the resultant device performance. Multiple photoluminescence spectra are observed in the perovskite film starting with high PEAI/PbI₂ ratio, which suggests the coexistence of low‐dimensional perovskite (PEA₂MA_n?1Pb_nI_3n+1) with various values of n after vapor reaction. The dimensionality of the as‐fabricated perovskite film reveals an evolution from 2D, hybrid 2D/3D to 3D structure when the doping level of PEAI/PbI₂ ratio varies from 2 to 0. Scanning electron microscopy images and Kelvin probe force microscopy mapping show that the PEAI‐containing perovskite grain is presumably formed around the MAPbI₃ perovskite grain to benefit MAPbI₃ grain growth. The device employing perovskite with PEAI/PbI₂ = 0.05 achieves a champion power conversion efficiency of 19.10% with an open‐circuit voltage of 1.08 V, a current density of 21.91 mA cm^?2, and a remarkable fill factor of 80.36%.     

Novel Mn3[Co(CN)6]2@SiO2@Ag Core–Shell Nanocube: Enhanced Two‐Photon Fluorescence and Magnetic Resonance Dual‐Modal Imaging‐Guided Photothermal and Chemo‐therapy

The versatile Mn₃[Co(CN)₆]₂@SiO₂@Ag core–shell NCs are prepared by a simple coprecipitation method. Ag nanoparticles with an average diameter of 12 nm deposited on the surface of Mn₃[Co(CN)₆]₂@SiO₂ through S–Ag bonding are fabricated in ethanol solution by reducing silver nitrate (AgNO₃) with NaBH₄. The NCs possess T₁–T₂ dual‐modal magnetic resonance imaging ability. The inner Prussian blue analogs (PBAs) Mn₃[Co(CN)₆]₂ exhibit bright two‐photon fluorescence (TPF) imaging when excited at 730 nm. Moreover, the TPF imaging intensity displays 1.85‐fold enhancement after loading of Ag nanoparticles. Besides, the sample also has multicolor fluorescence imaging ability under 403, 488, and 543 nm single photon excitation. The as‐synthesized Mn₃[Co(CN)₆]₂@SiO₂@Ag NCs show a DOX loading capacity of 600 mg g⁻¹ and exhibit an excellent ability of near‐infrared (NIR)‐responsive drug release and photothermal therapy (PTT) which is induced from the relative high absorbance in NIR region. The combined chemotherapy and PTT against cancer cells in vitro test shows high therapeutic efficiency. The multimodal treatment and imaging could lead to this material a potential multifunctional system for biomedical diagnosis and therapy.