Halide Perovskites for Nonlinear Optics.

Halide perovskites provide an ideal platform for engineering highly promising semiconductor materials for a wide range of applications in optoelectronic devices, such as photovoltaics, light-emitting diodes, photodetectors, and lasers. More recently, increasing research efforts have been directed toward the nonlinear optical properties of halide perovskites because of their unique chemical and electronic properties, which are of crucial importance for advancing their applications in next-generation photonic devices. Here, the current state of the art in the field of nonlinear optics (NLO) in halide perovskite materials is reviewed. Halide perovskites are categorized into hybrid organic/inorganic and pure inorganic ones, and their second-, third-, and higher-order NLO properties are summarized. The performance of halide perovskite materials in NLO devices such as upconversion lasers and ultrafast laser modulators is analyzed. Several potential perspectives and research directions of these promising materials for nonlinear optics are presented.

Crystallization growth rates and front propagation in amorphous solid water films.

The growth rate of crystalline ice (CI) in amorphous solid water (ASW) films was investigated using reflection absorption infrared spectroscopy. Two different experiments were set up to measure rates of the crystallization front propagation from the underlying crystalline template upward and from the vacuum interface downward. In one set of experiments, layers of ASW (5% D2O in H2O) were grown on a CI template and capped with a decane layer. In isothermal experiments from 140 to 150 K, crystallization was observed from the onset (no induction time) and the extent of crystallization increased linearly with time. In a second set of experiments, uncapped ASW films without a CI template were studied. The films were created by placing a 100 ML isotopic layer (5% D2O in H2O) at various positions in a 1000 ML ASW (H2O) film. The CI growth rates obtained from the two configurations (capped films with a CI template and uncapped films without a CI template) are in quantitative agreement. The results support the idea that for ASW films in a vacuum, a crystalline layer forms at the surface that then acts as a CI template for a growth front that moves downward into the film.

Chiral Lead Halide Perovskite Nanowires for Second-Order Nonlinear Optics.

Hybrid organic/inorganic lead halide perovskites (LHPs) have recently emerged as extremely promising photonic materials. However, the exploration of their optical nonlinearities has been mainly focused on the third- and higher-order nonlinear optical (NLO) effects. Strong second-order NLO responses are hardly expected from ordinary LHPs due to their intrinsic centrosymmetric structures, but are highly desirable for advancing their applications in the next generation integrated photonic circuits. Here we demonstrate the fabrication of a novel noncentrosymmetric LHP material by introducing chiral amines as the organic component. The nanowires grown from this new LHP material crystallize in a noncentrosymmetric P1 space group and demonstrate highly efficient second harmonic generation (SHG) with high polarization ratios and chiroptical NLO effects. Such a chiral perovskite skeleton could provide a new platform for future engineering of optoelectronic functionalities of hybrid perovskite materials.

Controlling the Growth of Molecular Crystal Aggregates with Distinct Linear and Nonlinear Optical Properties.

Two novel donor-acceptor molecules, 2,7-diphenylbenzo[1,2-b:4,3-b']difuran-4,5-dicarbonitrile and 2,7-bis(4-methoxyphenyl)benzo[1,2-b:4,3-b']difuran-4,5-dicarbonitrile containing cyano group as the electron acceptor, were synthesized. Their single-crystal structures, molecular packing, and self-assembly behaviors were also investigated. By simple solvent evaporation techniques, these compounds self-assemble into various low-dimensional microstructures that demonstrate distinctive nonlinear optical properties depending on the orientations of their transition dipoles. This study highlights the importance of the transition dipole moment in the construction of low-dimensional molecular materials with highly efficient nonlinear optical properties.

Communication: Distinguishing between bulk and interface-enhanced crystallization in nanoscale films of amorphous solid water.

The crystallization of amorphous solid water (ASW) nanoscale films was investigated using reflection absorption infrared spectroscopy. Two ASW film configurations were studied. In one case the ASW film was deposited on top of and capped with a decane layer ("sandwich" configuration). In the other case, the ASW film was deposited on top of a decane layer and not capped ("no cap" configuration). Crystallization of ASW films in the "sandwich" configuration is about eight times slower than in the "no cap." Selective placement of an isotopic layer (5% D2O in H2O) at various positions in an ASW (H2O) film was used to determine the crystallization mechanism. In the "sandwich" configuration, the crystallization kinetics were independent of the isotopic layer placement whereas in the "no cap" configuration the closer the isotopic layer was to the vacuum interface, the earlier the isotopic layer crystallized. These results are consistent with a mechanism whereby the decane overlayer suppresses surface nucleation and provide evidence that the observed ASW crystallization in "sandwich" films is the result of uniform bulk nucleation.

Isotope effect in the photochemical decomposition of CO2 (ice) by Lyman-α radiation.

The photochemical decomposition of CO2(ice) at 75 K by Lyman-α radiation (10.2 eV) has been studied using transmission infrared spectroscopy. An isotope effect in the decomposition of the CO2 molecule in the ice has been discovered, favoring (12)CO2 photodecomposition over (13)CO2 by about 10%. The effect is caused by electronic energy transfer from the excited CO2 molecule to the ice matrix, which favors quenching of the heavier electronically-excited (13)CO2 molecule over (12)CO2. The effect is similar to the Menzel-Gomer-Redhead isotope effect in desorption from adsorbed molecules on surfaces when electronically excited. An enhancement of the rate of formation of lattice-trapped CO and CO3 species is observed for the photolysis of the (12)CO2 molecule compared to the (13)CO2 molecule in the ice. Only 0.5% of the primary photoexcitation results in O-CO bond dissociation to produce trapped-CO and trapped-CO3 product molecules and the majority of the electronically-excited CO2 molecules return to the ground state. Here either vibrational relaxation occurs (majority process) or desorption of CO2 occurs (minority process) from highly vibrationally-excited CO2 molecules in the ice. The observation of the (12)C∕(13)C isotope effect in the Lyman-α induced photodecomposition of CO2 (ice) suggests that over astronomical time scales the isotope enrichment effect may distort historical information derived from isotope ratios in space wherever photochemistry can occur.

Lyman-α photodesorption from CO2(ice) at 75 K: role of CO2 vibrational relaxation on desorption rate.

The photodesorption of CO2 from CO2(ice) at 75 K when irradiated by Lyman-α light is strongly mediated by vibrational relaxation of highly vibrationally excited molecules produced from the electronically excited CO2 state. A vibrationally hot molecule can either relax (major process) in the ice or desorb (minor process). We find that isotopically pure CO2 ices photodesorb least efficiently due to efficient vibrational tuning between molecules in the ice. Isotopically impure CO2 ices are more poorly vibrationally relaxed and hence photodesorb more efficiently. Mixed CO2-Xe ices are still more efficiently photodesorbed due to the dilution of CO2, which further reduces the rate of vibrational relaxation. Resonant interactions as well as phonon-assisted interactions contribute to vibrational relaxation efficiency in ices, and inversely to photodesorption efficiency. The vibrational lifetime of hot CO2 in its ice at 75 K is of order of 10(-15) s. These results indicate that under astronomical conditions, the rate of photodesorption will depend inversely on the rate of vibrational quenching in the ice, which is dependent on the abundance and distance of like oscillators from each other in the ice. In rather isotopically pure ices, the minority isotopic species will photodesorb more rapidly.