Perovskite Nanowire Laser for Hydrogen Chloride Gas Sensing

Abstract

Detection of hazardous volatile organic and inorganic species is a crucial task for addressing human safety in the chemical industry. Among these species, there are hydrogen halides (HX, X = Cl, Br, I) vastly exploited in numerous technological processes. Therefore, the development of a cost-effective, highly sensitive detector selective to any HX gas is of particular interest. Herein, we demonstrate the optical detection of hydrogen chloride gas with solution-processed halide perovskite nanowire lasers grown on a nanostructured alumina substrate. An anion exchange reaction between a CsPbBr3 nanowire and vaporized HCl molecules results in the formation of a structure consisting of a bromide core and thin mixed-halide CsPb(Cl,Br)3 shell. The shell has a lower refractive index than the core does. Therefore, the formation and further expansion of the shell reduce the field confinement for experimentally observed laser modes and provokes an increase in their frequency. This phenomenon is confirmed by the coherency of the data derived from XPS spectroscopy, EDX analysis, in situ XRD experiments, HRTEM images, and fluorescent microspectroscopy, as well as numerical modeling for Cl– ion diffusion and the shell-thickness-dependent spectral position of eigenmodes in a core–shell perovskite nanowire. The revealed optical response allows the detection of HCl molecules in the 5–500 ppm range. The observed spectral tunability of the perovskite nanowire lasers can be employed not only for sensing but also for their precise spectral tuning.

Giant and Tunable Excitonic Optical Anisotropy in Single-Crystal Halide Perovskites

“…Amorphous Al 2 O 3 substrate with island morphology was fabricated according to the protocol reported elsewhere. 48 Perovskite microplates on the substrate were synthesized by utilizing the same precursor solution in which 20 μL of deionized water was added (Supplementary Figure 5). The protocol is the same to the abovementioned.…”

Ultrahigh-Q Lead Halide Perovskite Microlasers

“…On the other hand, the exceptional gain coefficients (hundreds to thousands), large refractive index (2.2–2.5), and controllable emission wavelengths of perovskite enable the possibility to confine light for a very long time, thereby reducing the overall power consumption of micro- and nanolasers. Soon after the pioneering work on amplified spontaneous emission, − lead halide perovskite-based micro- and nanolasers have been intensively explored in the past decade. − A variety of high-performance lead halide perovskite lasers has been successfully achieved in various perovskites and nanostructures, and the corresponding applications in sensing, subdiffraction imaging, and ultrafast control have also been demonstrated. − Despite their remarkable and continuous progress, perovskite laser sources face severe challenges in nanostructure fabrication and integration due to their inherent fragility. Although photolithography and electron-beam (E-beam) lithography can precisely define the laser cavity, ,− they also inevitably introduce extra defects in the perovskite nanostructures and significantly spoil the device quality.…”

Non-stoichiometric hybrid halide perovskite film for gaseous NH3and HCl sensing

“…8 In general, halide perovskites are sensitive to external environment stimuli, which also provides an opportunity to be used as sensing materials for gas/vapor detection. 9 Recently, several types of lead halide perovskites were utilized as gas sensors toward various chemical gases/vapors, such as NH 3 , 10–15 NO, 16,17 O 3 , 18 HCl, 19,20 and volatile organic compounds, 21,22 etc.…”

“…20 Recently, Markina et al designed optical perovskite HCl sensors based on CsPbBr 3 nanowires, in which the mechanism is due to an anion exchange reaction between perovskite crystals and volatile HCl molecules. 19 Although the NH 3 and HCl sensing mechanisms are investigated extensively, the gas sensitivities of perovskites still need to be improved. Moreover, to the best of our knowledge, there is no report on the selective detection of both NH 3 and HCl in a halide perovskite-based sensor.…”

“…In the case of HCl, the response value versus HCl concentration could be ideally fitted to a linear relationship, similar to that of the previously reported CsPbBr 3 -based HCl sensor. 19 Finally, we determined the limit of detection (LOD) according to the equation LOD = 3 σ/S , where σ is the relative standard deviation and S is the slope of the calibration curve. The LODs of NH 3 and HCl were calculated as 0.08 ppm and 0.11 ppm, respectively.…”