RESUMEN
Determining the factors that influence and can help predict energetic material sensitivity has long been a challenge in the explosives community. Decades of literature reports identify a multitude of factors both chemical and physical that influence explosive sensitivity; however no unifying theory has been observed. Recent work by our team has demonstrated that the kinetics of "trigger linkages" (i.e., the weakest bonds in the energetic material) showed strong correlations with experimental drop hammer impact sensitivity. These correlations suggest that the simple kinetics of the first bonds to break are good indicators for the reactivity observed in simple handling sensitivity tests. Herein we report the synthesis of derivatives of the explosive pentaerythritol tetranitrate (PETN) in which one, two or three of the nitrate ester functional groups are substituted with an inert group. Experimental and computational studies show that explosive sensitivity correlates well with Q (heat of explosion), due to the change in the number of trigger linkages removed from the starting material. In addition, this correlation appears more significant than other observed chemical or physical effects imparted on the material by different inert functional groups, such as heat of formation, heat of explosion, heat capacity, oxygen balance, and the crystal structure of the material.
RESUMEN
Spray drying has recently gained interest in the high explosives (HE) community for the production of novel nanocomposites and well-controlled particle size distributions. However, there is a dearth of information on spray-dried, neat energetic materials. In this work, we correlate the spray drying production parameters to the resulting microstructure and handling sensitivity properties of neat RDX. We demonstrate the capability to fine-tune the particle size distributions for "nanopowder" spray-dried RDX, as well as larger particle size distributions by simply changing the spray dryer setup. We also investigate other physical and chemical changes that RDX undergoes after being processed with spray drying. We characterize these changes with scanning electron microscopy, X-ray diffraction, ultrahigh-performance liquid chromatography, and small-scale sensitivity tests. Interestingly, although the phase and chemical properties are similar before and after spray drying, small-scale sensitivity testing reveals that size reduction of RDX does not follow the typical HE desensitization trends, generally observed for other energetic materials.
RESUMEN
Controlling the photoexcited properties and behavior of hybrid perovskites by halide doping has the potential to impact a wide range of emerging technologies, including solar cells and radiation detectors. Crystalline samples of methylammonium lead bromide substituted with chlorine (MAPbBr3-xClx) were examined by transient reflectivity spectroscopy and nonadiabatic molecular dynamics simulations. At picosecond time scales, the addition of chlorine to the perovskite crystal increased the observed rate of hot carrier cooling and the calculated electron-phonon coupling constants. Chlorine-doped samples also exhibit a slower surface recombination velocity and a smaller ambipolar mobility.
RESUMEN
Halide perovskites are promising optoelectronic semiconductors. For applications in solid-state detectors that operate in low photon flux counting mode, blocking interfaces are essential to minimize the dark current noise. Here, we investigate the interface between methylammonium lead tri-iodide (MAPbI3) single crystals and commonly used high and low work function metals to achieve photon counting capabilities in a solid-state detector. Using scanning photocurrent microscopy, we observe a large Schottky barrier at the MAPbI3/Pb interface, which efficiently blocks dark current. Moreover, the shape of the photocurrent profile indicates that the MAPbI3 single-crystal surface has a deep fermi level close to that of Au. Rationalized by first-principle calculations, we attribute this observation to the defects due to excess iodine on the surface underpinning emergence of deep band-edge states. The photocurrent decay profile yields a charge carrier diffusion length of 10-25 µm. Using this knowledge, we demonstrate a single-crystal MAPbI3 detector that can count single γ-ray photons by producing sharp electrical pulses with a fast rise time of <2 µs. Our study indicates that the interface plays a crucial role in solid-state detectors operating in photon counting mode.
RESUMEN
This letter reports optomechanical effects occurring in a hybrid metal-halide perovskite single crystal (MAPbBr3) based on resonant ultrasound spectroscopy (RUS) measurements under continuous wave (CW) laser illumination. The optomechanical effects are a new phenomenon in hybrid perovskite single crystals where the elastic constant of a single crystal is measured by RUS probed under varying excitation conditions. Our studies show that applying a CW laser (405 nm) to the single-crystal face shifts the RUS peaks to higher frequencies by about 1-4% in the perovskite single crystal at room temperature. The light-induced shift of the RUS peaks can be observed only when photoexcitation is occurring, rather than during heating, by positioning the laser wavelength within the optical absorption spectrum. In contrast, positioning the laser wavelength outside of the optical absorption spectrum leads to an absence of RUS peak shifting. Clearly, the laser-light-induced RUS peak shifts shows that the crystal elastic moduli can be changed by photoexcitation, leading to an optomechanical phenomenon via excited states. Essentially, the observed optomechanical phenomenon reflects the fact that the mechanical properties can be optically changed through internal repulsive and attractive force constants by external photoexcitation in a hybrid perovskite single crystal.
RESUMEN
Understanding the impact of environmental gaseous on the surface of organometal halide perovskites (OMHPs) couples to the electronic and ionic transport is critically important. Here, we explore the transport behavior and origins of the gas sensitivity in MAPbBr3 single crystals (SCs) devices using impedance spectroscopy and current relaxation measurements. Strong resistive response occurs when crystals are exposed to different environments. It was shown that SC response to the environment is extremely different at the surface as compared to the bulk due to the disorder surface chemistry. The nonlinear transport properties studied using ultrafast Kelvin probe force microscopy (G-KPFM) to unravel spatio-temporal charge dynamics at SC/electrode interface. The relaxation processes observed in pulse relaxation and G-KPFM measurements along with gas sensitivity of crystals suggest the presence of a triple-phase boundary between environment, electrode, and crystal. Results indicate that the environment is a nontrivial component in the operation of OMHP devices which is reminiscent of fuel cell systems. Furthermore, the triple-phase boundary can play a significant role in the transport properties of OMHPs due to the possibility of the redox processes coupled to the concentration of bulk ionic species. Although instrumental for understanding the device characteristics of perovskites, our studies suggest a new opportunity of coupling the redox chemistry of the Br2-Br- pair that defines the bulk ionic conductivity of MAPbBr3 with the redox chemistry of gaseous (or liquid) environment via a suitable electrocatalytic system to enable new class of energy storage devices and gas sensors.
RESUMEN
The spin on a ferromagnetic Co surface can interact with the asymmetric orbital on an organometal halide perovskite surface, leading to an anisotropic magnetodielectric effect. This study presents an opportunity to integrate ferromagnetic and semiconducting properties through the Rasbha effect for achieving spin-dependent electronic functionalities based on thin-film design.
RESUMEN
This paper reports Seebeck effects driven by both surface polarization difference and entropy difference by using photoinduced intramolecular charge-transfer states in n-type and p-type conjugated polymers, namely IIDT and IIDDT, respectively, based on vertical conductor/polymer/conductor thin-film devices. We obtain large Seebeck coefficients of -898 µV/K from n-type IIDT and 1300 µV/K from p-type IIDDT when the charge-transfer states are generated by a white light illumination of 100 mW/cm(2), compared with the values of 380 and 470 µV/K in dark condition, respectively. Simultaneously, the electrical conductivities are increased from almost insulating state in dark condition to conducting state under photoexcitation in both n-type IIDT and p-type IIDDT based devices. The large Seebeck effects can be attributed to the following two mechanisms. First, the intramolecular charge-transfer states exhibit strong electron-phonon coupling, which leads to a polarization difference between high and low temperature surfaces. This polarization difference essentially forms a temperature-dependent electric field, functioning as a new driving force additional to entropy difference, to drive the energetic carriers for the development of Seebeck effects under a temperature difference. Second, the intramolecular charge-transfer states generate negative or positive majority carriers (electrons or holes) in the n-type IIDT or p-type IIDDT, ready to be driven between high and low temperature surfaces for developing Seebeck effects. On the basis of coexisted polarization difference and entropy difference, the intramolecular charge-transfer states can largely enhance the Seebeck effects in both n-type IIDT and p-type IIDDT devices. Furthermore, we find that changing electrical conductivity can switch the Seebeck effects between polarization and entropy regimes when the charge-transfer states are generated upon applying photoexcitation. Therefore, using intramolecular charge-transfer states presents an approach to develop thermoelectric effects in organic materials-based vertical conductor/polymer/conductor thin-film devices.
RESUMEN
This article reports the magneto-dielectric studies on the coupling between optically generated CT states and magnetized CT states based on thin-film devices with the architecture of ITO/TPD:BBOT/TPD/Co/Al. The magnetized CT states are generated at the Co/TPD interface, generating a magneto-dielectric response with a broad, non-Lorentzian line-shape. The optically generated CT states are formed at the TPD:BBOT interfaces in the heterojunction under photoexcitation, leading to a magneto-dielectric signal with a narrow, Lorentzian line-shape. We find that combining the optically generated CT states and magnetized CT states yields a new magneto-dielectric signal with distinctive line-shape and amplitude in the ITO/TPD:BBOT/TPD/Co/Al device. The magneto-dielectric analysis indicates that there exists a coupling between optically generated CT states and magnetized CT states through the interactions between the magnetic Co/TPD interface and the optically excited TPD:BBOT heterojunction. Furthermore, we show that the coupling between optically generated CT states and magnetized CT states experiences Coulomb interactions and spin-orbital interaction by changing (i) the density of optically generated CT states and (ii) the separation distance between optically generated CT states and magnetized CT states. Clearly, this coupling provides a new approach to mutually tune magnetic and electronic properties through thin-film engineering by combining magnetic and organic materials.