Search Results (22)

Patterned lead-halide perovskite microstructures are promising for integrated optoelectronics, photonics, and polarization-sensitive devices, but the practical growth behavior of compositionally tunable microcrystals under simple static confinement remains insufficiently understood. Here, we investigate template-assisted confined crystallization of MAPbBr₃ and MAPbBr_3−xCl_x microstructures using patterned polydimethylsiloxane (PDMS) stamps. MAPbBr₃ was first examined as a reference system to evaluate pattern transfer, morphology, substrate compatibility, and characteristic growth imperfections. Periodic microstructures with template spacings from 0.8 to 10 μm were obtained on Si/SiO₂, ITO, PDMS, and MAPbBr₃ macrocrystal substrates. Static stamping creates strong edge–center morphological divergence: thick patterned microcrystals and coalesced domains formed preferentially near the sample edges, whereas thinner isolated microcrystal arrays were more common in central regions. XRD, AFM, SEM, SAED, EDX, HRTEM, PL microscopy, and TRPL analyses show that the method can generate well-crystallized and optically active perovskite domains while also producing multidomain aggregates, incomplete pattern transfer, pressure-induced wrinkling, and nanoscale secondary crystallites. Extension to MAPbBr_3−xCl_x demonstrates that patterned mixed-halide microstructures can be obtained with composition-dependent structural and optical properties. Nevertheless, XRD, EDX, PL, and TRPL results indicate that Cl-rich samples are not fully described by a simple homogeneous solid-solution model, likely involving compositionally heterogeneous crystallization and a Br-rich emissive component. Preliminary MAPbCl₃-on-MAPbBr₃ experiments further show that PDMS-confined patterning can be coupled with substrate-mediated halide exchange or interfacial recrystallization. Overall, static PDMS-confined crystallization is established as a simple exploratory platform for producing diverse patterned perovskite microstructures. This approach is well-suited for the manual selection of suitable crystals and the fabrication of individual microdevices; however, improved control over pressure, mass transport, nucleation localization, and composition will be required when the uniformity of produced patterned microcrystals is desired. Full article

Semiconductor photodetectors can work only in specific material-dependent light wavelength ranges, connected with the bandgaps and absorption capabilities of the utilized semiconductors. This limitation has driven the development of hybrid devices that exceed the capabilities of individual materials. In this study, for the first time, a hybrid heterojunction photodetector based on methylammonium lead bromide (MAPbBr₃) polycrystalline film deposited on gallium arsenide (GaAs) was presented, along with comprehensive morphological, structural, optical, and photoelectrical investigations. The MAPbBr₃/GaAs heterojunction photodetector exhibited wide spectral responsivity, from 540 to 900 nm. The fabrication steps of the prototype device, including a new preparation recipe for the MAPbBr₃ solution and spinning, will be disclosed and discussed. It will be shown that extending the soaking time and refining the precursor solution’s stoichiometry may enhance surface coverage, adhesion to the GaAs, and film uniformity, as well as provide a new way to integrate MAPbBr₃ on GaAs. Compared to the pristine MAPbBr₃, the enhanced structural purity of the perovskite on GaAs was confirmed by X-ray Diffraction (XRD) upon optimization compared to the conventional glass substrate. Scanning Electron Microscopy (SEM) revealed the formation of microcube-like structures on the top of an otherwise continuous MAPbBr₃ polycrystalline film, with increased grain size and reduced grain boundary effects pointed by Energy-Dispersive Spectroscopy (EDS) and cathodoluminescence (CL). Enhanced absorption was demonstrated in the visible range and broadened photoluminescence (PL) emission at room temperature, with traces of reduction in the orthorhombic tilting revealed by temperature-dependent PL. A reduced average carrier lifetime was reduced to 13.8 ns, revealed by time-resolved PL (TRPL). The dark current was typically around 8.8 × 10⁻⁸ A. Broad photoresponsivity between 540 and 875 nm reached a maximum of 3 mA/W and 16 mA/W, corresponding to a detectivity of 6 × 10¹⁰ and 1 × 10¹¹ Jones at −1 V and 50 V, respectively. In case of on/off measurements, the rise and fall times were 0.40 s and 0.61 s or 0.62 s and 0.89 s for illumination, with 500 nm or 875 nm photons, respectively. A long-term stability test at room temperature in air confirmed the optical and structural stability of the proposed hybrid structure. This work provides insights into the physical mechanisms of new hybrid junctions for high-performance photodetectors. Full article

In this study, we fabricated deep ultraviolet (DUV) photodetectors based on perovskite thin films doped with halide materials using formamidinium bromide (FABr) and methylammonium iodide (MAI). The device was fabricated using a simple surface engineering technique by post-treating the MAPbI₃ perovskite film with an FABr solution. This film acts as a light absorption layer, like a depletion layer with a p-i-n (PIN) structure, with n-type of SnO₂-SDBS and p-type of spiro-OMeTAD. Adding 0.10 M MACl to the MAPbI3 precursor solution during the manufacturing process could effectively reduce the trap density compared with existing films. Films with MACl added in the two-step process can control a wide band gap and improve crystallinity. In addition, the Cl atom has a smaller atomic radius than iodine and a higher electronegativity of 3.16, which can improve phase stability, and the effect of the added Cl⁻ increases the electron mobility of the perovskite, showing a fast response. Full article

Perovskite solar cells are attracting more and more attention due to their higher absorption and low cost. However, fabricating the perovskite film with high crystallinity and ideal morphology, which presents large-size and uniform particles with fewer grain boundaries, still needs further improvement. Herein, we introduce MAPbCl₃ crystals into the PbI₂ film in the sequential deposition process, which obtained the controlled crystallization in perovskite films. The perovskite films induced by MAPbCl₃ have stronger crystallinity, fewer defect states, and larger grain size, reducing carrier recombination and improving carrier transfer. The optimized perovskite solar cell (PSC) has achieved a power conversion efficiency of 20.97%. Furthermore, the stability of PSCs has also been enhanced due to the reduced grain boundaries impeding moisture diffusion. This strategy can be applied in other solution-based fabrication processes to improve the photovoltaic performance of PSCs. Full article

In recent years, there have been intense studies on hybrid organic–inorganic compounds (HOIPs) due to their tunable and adaptable features. This present study reports the vibrational, structural, and elastic properties of mixed halide single crystals of MA_xFA_1-xPbCl₃ at room temperature by introducing the FA cation at the A-site of the perovskite crystal structure. Powder X-ray diffraction analysis confirmed that its cubic crystal symmetry is similar to that of MAPbCl₃ and FAPbCl₃ with no secondary phases, indicating a successful synthesis of the MA_xFA_1-xPbCl₃ mixed halide single crystals. Structural analysis confirmed that the FA substitution increases the lattice constant with increasing FA concentration. Raman spectroscopy provided insight into the vibrational modes, revealing the successful incorporation of the FA cation into the system. Brillouin spectroscopy was used to investigate the changes in the elastic properties induced via the FA substitution. A monotonic decrease in the sound velocity and the elastic constant suggests that the incorporation of large FA cations causes distortion within the inorganic framework, altering bond lengths and angles and ultimately resulting in decreased elastic constants. An analysis of the absorption coefficient revealed lower attenuation coefficients as the FA content increased, indicating reduced damping effects and internal friction. The current findings can facilitate the fundamental understanding of mixed lead chloride perovskite materials and pave the way for future investigations to exploit the unique properties of mixed halide perovskites for advanced optoelectronic applications. Full article

The application of TiO₂ nanorods in the field of ultraviolet (UV) photodetectors is hindered by a high dark current, which is attributed to crystal surface defects and intrinsic excitation by carrier thermal diffusion. Here, a photodetector based on polycrystalline perovskite MAPbCl₃/TiO₂ nanorods heterojunctions has been fabricated to overcome the shortcoming. The structure was composed of horizontal MAPbCl₃ polycrystalline and vertically aligned TiO₂ nanorods array. Many localized depletion regions at the MAPbCl₃/TiO₂ interface can reduce the dark current. The TiO₂/MAPbCl₃ detector shows high performance including a high ratio of light-dark current of about six orders of magnitude, which is much larger than that of the TiO₂ detector. This study indicates the potential in the TiO₂/MAPbCl₃ heterojunction to fabricate high-performance UV detectors. Full article

The relationship between halogen content and the elastic/vibrational properties of MAPbBr_3−xCl_x mixed crystals (x = 1.5, 2, 2.5, and 3) with MA = CH₃NH₃⁺ has been studied using Brillouin and Raman spectroscopy at room temperature. The longitudinal and transverse sound velocities, the absorption coefficients and the two elastic constants C₁₁ and C₄₄ could be obtained and compared for the four mixed-halide perovskites. In particular, the elastic constants of the mixed crystals have been determined for the first time. A quasi-linear increase in the sound velocity and the elastic constant C₁₁ with increasing chlorine content was observed for the longitudinal acoustic waves. C₄₄ was insensitive to the Cl content and very low, indicating a low elasticity to shear stress in mixed perovskites regardless of the Cl content. The acoustic absorption of the LA mode increased with increasing heterogeneity in the mixed system, especially for the intermediate composition where the Br and Cl ratio was 1:1. In addition, a significant decrease in the Raman-mode frequency of the low-frequency lattice modes and the rotational and torsional modes of the MA cations was observed with decreasing Cl content. It clearly showed that the changes in the elastic properties as the halide composition changes were correlated with the lattice vibrations. The present findings may facilitate a deeper understanding of the complex interplay between halogen substitution, vibrational spectra and elastic properties, and may also pave the way for optimizing the operation of perovskite-based photovoltaic and optoelectronic devices by tailoring their chemical composition. Full article

Mechanical properties are among the crucial parameters for multilayer hybrid perovskite-based devices. Here, the mechanical properties of the high-quality single-crystalline MAPbX₃ (MA = CH₃NH₃, X = Cl, Br, I), including the hardness (H) and Young’s modulus (E), are systematically studied using the three-dimensional nanoindentation (3D nanoindentation) method. In the sequence of Cl, Br, and I, the hardness and Young’s modulus of MAPbX₃ decrease gradually. The hardness of MAPbX₃ ranges from 0.31 to 0.57 GPa, and Young’s modulus values are less than 30 GPa. The low hardness and Young’s modulus are attributed to the weak lattice framework composed of Pb-X and the weak hydrogen bond between CH₃NH₃⁺ and the octahedron. The relationship between the hardness and Young’s modulus of MAPbX₃ is also described. Generally, this work provides the favorable parameters required to further support the design and modification of investigations regarding perovskite-based devices. Full article

Deep-ultraviolet (UV) sensing has attracted significant interest because of its wide range of applications. A mixed-cation halide perovskite-based photodetector prepared by mixing CH₃NH₃PbX₃ (X = I, Br, and Cl) and HC(NH₂)PbX₃ (X = I, Br, and Cl) exhibits high stability and excellent light absorption. In this study, perovskite was prepared by mixing CH₃NH₃⁺ (FA⁺) and HC(NH₂)₂⁺ (MA⁺) cations using I⁻, Br⁻, and Cl⁻ halide anions. The bandgaps of the prepared perovskites increased to 1.48, 2.25, and 2.90 eV with I-, Br-, and Cl-, respectively, and the light absorption spectra shifted to shorter wavelengths. An increase in the redshift of the light absorption led to an increase in the photocurrent. The FAPbCl₃-MAPbCl₃-based photodetector showed a high responsivity of 5.64 mA/W, a detectivity of 4.03 × 10¹¹, and an external quantum efficiency of 27.3%. The results suggested that the FAPbCl₃-MAPbCl₃ perovskite is suitable for deep-UV light sensing and is an excellent candidate for the fabrication of a sensitive photodetector. Full article

Raman spectroscopy was applied to MAPbCl₃ single crystals in a wide frequency range from 10 to 3500 cm⁻¹ over a broad temperature range from −196 °C to 200 °C including both two structural phase transitions and a thermal degradation range. Low-frequency lattice modes of MAPbCl₃ were revealed for the first time, which showed discontinuous anomalies along with the change in the number of Raman modes at the transition points of −114 °C and −110 °C. Several Raman modes related to the C–N stretching and MA rocking modes in addition to the lattice modes displayed temperature dependences similar to those of MAPbBr₃ in both Raman shifts and half widths, indicating that the MA cation arrangement and H–halide bond interactions behave similarly in both systems during the phase transition. The substantial increase in the half widths of nearly all Raman modes especially suggests that the dynamic disorder caused by the free rotational motions of MA cations induces significant anharmonicity in the lattice and thus, reduces the phonon lifetimes. High-temperature Raman and Brillouin scattering measurements showed that the spectral features changed drastically at ~200 °C where the thermal decomposition of MAPbCl₃ into PbCl₂ began. This result exhibits that combined Raman and Brillouin spectroscopic techniques can be a useful tool in monitoring temperature-induced or temporal changes in lead-based halide perovskite materials. Full article

Three-dimensional lead halide perovskites are known for their excellent optoelectronic properties, making them suitable for photovoltaic and light-emitting applications. Here, we report for the first time the Raman spectra and photoluminescent (PL) properties of recently discovered three-dimensional aziridinium lead halide perovskites (AZPbX₃, X = Cl, Br, I), as well as assignment of vibrational modes. We also report diffuse reflection data, which revealed an extended absorption of light of AZPbX₃ compared to the MA and FA counterparts and are beneficial for solar cell application. We demonstrated that this behavior is correlated with the size of the organic cation, i.e., the energy band gap of the cubic lead halide perovskites decreases with the increasing size of the organic cation. All compounds show intense PL, which weakens on heating and shifts toward higher energies. This PL is red shifted compared to the FA and MA counterparts. An analysis of the PL data revealed the small exciton binding energy of AZPbX₃ compounds (29–56 meV). Overall, the properties of AZPbX₃ are very similar to those of the well-known MAPbX₃ and FAPbX₃ perovskites, indicating that the aziridinium analogues are also attractive materials for light-emitting and solar cell applications. Full article

Porous noble metal nanomaterials have attracted extensive attention due to their high specific surface area and surface plasmon resonance effect. However, it is difficult to form porous structures due to the high mobility and low reduction potential of noble metal precursors. In this article, we developed a facile method for preparing porous Ag with a controllable structure at room temperature. Two kinds of Ag crystals with different porous structures were successfully prepared by using AgCl cubes as sacrificial templates. Through the galvanic replacement reaction of Zn and AgCl, Ag crystals with a sponge-like porous structure were successfully prepared. Additionally, using NaBH₄ as the reducing agent, we prepared granular porous Ag cubes by optimizing the amount of reducing agent. Both the sponge-like and granular porous Ag cubes have clean and accessible surfaces. In addition, we used the prepared two porous Ag cubes as substrate materials for SERS detection of five kinds of methamphetamine analogs. The experimental results show that the enhancement effect of granular porous Ag is better than that of sponge-like porous Ag. Furthermore, we probed the hot spot distribution of granular porous Ag by Raman mapping. By using granular porous Ag as the substrate material, we have achieved trace detection of 5 kinds of methamphetamine analogs including Ephedrine, Amphetamine, N-Methyl-1-(benzofuran-5-yl)propan-2-amine (5-MAPB), N-Methyl-1-(4-methoxyphenyl)propan-2-amine (PMMA) and N-Methyl-1-(4-fluorophenyl)propan-2-amine (4-FMA). Furthermore, to achieve qualitative differentiation of analogs with similar structures we performed density functional theoretical (DFT) calculations on the Raman spectra of the above analogs. The DFT calculations provided the vibrational frequencies, Raman activities, and normal mode assignment for each analog, enabling the qualitative differentiation of the above analogs. Full article

Inelastic light scattering spectra of organic–inorganic halide perovskite MAPbCl₃ single crystals were investigated by using Brillouin spectroscopy. Sound velocities and acoustic absorption coefficients of longitudinal and transverse acoustic modes propagating along the cubic [100] direction were determined in a wide temperature range. The sound velocities exhibited softening upon cooling in the cubic phase, which was accompanied by the increasing acoustic damping. The obtained relaxation time showed a critical slowing-down behavior, revealing the order–disorder nature of the phase transition, which is consistent with the growth of strong central peaks upon cooling toward the phase transition point. The temperature dependences of the two elastic constants C₁₁ and C₄₄ were obtained in the cubic phase for the first time. The comparison of C₁₁ and C₄₄ with those of other halide perovskites showed that C₁₁ of MAPbCl₃ is larger and C₄₄ is slightly smaller compared to the values of MAPbBr₃ and MAPbI₃. It suggests that MAPbCl₃ has a more compact structure (smaller lattice constant) along with stronger binding forces, causing larger C₁₁ and bulk modulus in this compound, and that the shear rigidity is exceedingly small similar to other halide perovskites. The reported elastic constants in this study may serve as a testbed for theoretical and calculational approaches for MAPbCl₃. Full article

Halide perovskite based solar cells (PSC’s) have shown tremendous potential based on its facile fabrication technique, and the low cost of perovskite thin film formation with efficiency passing through an unmatched growth in recent years. High quality film along with morphology and crystallinity of the perovskite layer influences the efficiency and other properties of the perovskite solar cell (PSC). Furthermore, semitransparent perovskite solar cells (ST-PSC) are an area of attraction due to its application in tandem solar cells, although various factors like suitable transparent rear electrodes and optimized technique limit the power conversion efficiency (PCE). In this article, we fabricated perovskite film using a technique termed Double-sided sandwich evaporation technique (DS-SET) resulting in high quality perovskite film (MAPbI₃ and MAPbI_xCl_3−x). Using this fabrication approach as compared to the traditional spin-coating method, we reported an enhanced photovoltaic performance of the PSC with a better surface morphology and homogeneity. The best parameter via DS-SET was found to be SET 30 min, which demonstrated a PCE (%) up to 14.8% for MAPbI₃ and 16.25% for MAPbI_xCl_3−x, respectively. Addressing the tandem solar cell, incorporating thin Ag as a transparent electrode with a thickness of 20 nm onto the PSC’s as the top cell and further combining with the Si solar cell results in the four terminal (4T) tandem solar cell exhibiting a PCE (%) of 24.43%. Full article

In this article, we used a two-step chemical vapor deposition (CVD) method to synthesize methylammonium lead-tin triiodide perovskite films, MAPb_1−xSn_xI₃, with x varying from 0 to 1. We successfully controlled the concentration of Sn in the perovskite films and used Rutherford backscattering spectroscopy (RBS) to quantify the composition of the precursor films for conversion into perovskite films. According to the RBS results, increasing the SnCl₂ source amount in the reaction chamber translate into an increase in Sn concentration in the films. The crystal structure and the optical properties of perovskite films were examined by X-ray diffraction (XRD) and UV-Vis spectrometry. All the perovskite films depicted similar XRD patterns corresponding to a tetragonal structure with I4cm space group despite the precursor films having different crystal structures. The increasing concentration of Sn in the perovskite films linearly decreased the unit volume from about 988.4 ų for MAPbI₃ to about 983.3 ų for MAPb₀.₃₉Sn₀.₆₁I₃, which consequently influenced the optical properties of the films manifested by the decrease in energy bandgap (E_g) and an increase in the disorder in the band gap. The SEM micrographs depicted improvements in the grain size (0.3–1 µm) and surface coverage of the perovskite films compared with the precursor films. Full article