High-quality integratable microlasers from scalable perovskite heterostructures enabled by solution-phase processing.

High-performance transferable and integratable microlasers hold great promise to construct the integrated photonics and optoelectronics. However, the qualified candidates are still being pursued. Herein, a mass-production of low-threshold and wavelength-tunable microlasers that is readily integratable with the optical fiber platform is realized by a two-step solution-phase approach. The demonstration is enabled by the formation of a novel semiconductor heterostructure from halide perovskites featuring the quasi-free-standing and highly emissive properties. Corroborated by the in-situ optical characterization, we reveal that the lateral perovskite heterostructures are constructed through a sequential reaction driven by the surface energy contrast. These perovskite heterostructures exhibit low-threshold and broadband tunable lasing action thanks to the efficient spatial light conversion nature and the facile composition tunability. Taking the merits together, the heterostructure microlasers can be the competitive applicants for photonic integration as demonstrated by the laser-on-fiber configuration.

3D-Assembled rutile TiO2 spheres with c-channels for efficient lithium-ion storage.

Three-dimensional (3D) TiO2 architectures have attracted significant attention recently as they can improve the electrochemical stability and realize the full potential of TiO2-based anodes in lithium ion batteries. Here, flower-like rutile TiO2 spheres with radially assembled nanorods (c-channels) were fabricated via a simple hydrothermal method. The 3D radial architecture affords massive active sites to fortify the lithium storage. Moreover, the presence of c-channels facilitates electrolyte infiltration and offers facile pathways for efficient Li+ transport. As a result, this flower-like rutile TiO2 anode gives significantly enhanced specific capacities (615 mA h g-1 at 1 C and 386 mA h g-1 at 2 C after 400 cycles) and a superior long-term cyclability (up to 10 000 cycles with a specific capacity of 67 mA h g-1 at 100 C). Kinetic analysis reveals that the enhanced diffusion-controlled and surface capacitive storage leads to the excellent electrochemical behavior. This work not only exhibits the enormous advantages of 3D architectures with c-channels, but also provides access to structural design and crystal phase selection for TiO2-based anode materials.

Deciphering the excited-state dynamics and multicarrier interactions in perovskite core-shell type hetero-nanocrystals.

Deciphering and modulating the carrier dynamics of perovskite nanocrystals (Pe-NCs) is crucial for their optoelectronic applications, which remains elusive to date. Herein, we, for the first time, explore the ultrafast dynamics of perovskite core-shell type NCs using CsPbBr3@ZnS as a model system. According to the transient spectroscopic characterization, a physical picture of the ultrafast dynamics in core-shell Pe-NCs is built. Specifically, we directly observed the "hot" hole transfer from CsPbBr3 to ZnS and confirmed the formation of charge-transfer state in CsPbBr3@ZnS NCs. Such ultrafast (<100 fs) hole rearrangement speeds up the carrier cooling and breaks the hot phonon bottleneck effect in Pe-NCs. Moreover, thanks to the charge separation in CsPbBr3@ZnS NCs, the Auger recombination is largely suppressed and the Auger lifetime is increased nearly 5-fold compared to that of "pure" CsPbBr3 NCs, which endows CsPbBr3@ZnS NCs with unique optical gain properties. These results are informative for halide perovskite-based applications, such as photocatalysis, hot-carrier photovoltaics and lasers.

Harnessing Hot Phonon Bottleneck in Metal Halide Perovskite Nanocrystals via Interfacial Electron-Phonon Coupling.

Slow hot carrier (HC) cooling resulting from hot phonon bottleneck has been widely demonstrated in metal halide perovskites. Although manipulating HC kinetics in these materials is of both fundamental and technological importance, this task remains a daunting challenge. Here, via interfacial engineering, i.e., epitaxial growth of Cs4PbBr6 on CsPbBr3 nanocrystals (NCs), we have revealed an obvious shortening of HC cooling times, evidenced by transient absorption and ultrafast PL spectra. Collaborated with the longitudinal optical (LO) phonon model, theoretical calculations verify the breaking of the hot phonon bottleneck in CsPbBr3@Cs4PbBr6 and identify the interfacial electron-LO phonon coupling as the leading mechanism for the observed large tuning of HC cooling times. Especially, the participation of LO phonons from Cs4PbBr6 enables the efficient Klemens channel for hot phonon decay. Our findings establish an effective method to tailor HC dynamics in perovskite NCs, which could be conducive to improving the performance of optoelectronic applications.

Transferable High-Quality Inorganic Perovskites for Optoelectronic Devices by Weak Interaction Heteroepitaxy.

Transferable semiconductors with superior light-emitting properties are important for developing flexible and integrated optoelectronics. However, finding such a qualified candidate remains challenging. Here, we report the fabrication of transferable high-quality CsPbBr3 single crystals on a highly oriented pyrolytic graphite (HOPG) substrate via weak interaction heteroepitaxy for the first time. Semi-quantitative kinetic analysis based on the classical nucleation theory well accounts for the van der Waals (vdW) epitaxial growth process of perovskite on the HOPG substrate. The density functional theory calculations illustrate the bonding nature of the interface and predict the Volmer-Weber growth mode in vdW epitaxy, which is consistent with our experimental observations. Importantly, the extremely weak vdW interaction between the perovskite and HOPG not only enables the high quality of the crystals but also endows them with the facile transferability to any foreign substrate by the mechanical exfoliation technique. Leveraging on the transferred CsPbBr3 single crystals, the low-threshold microlasers and monolithic perovskite light-emitting diode devices are demonstrated. Our results represent a significant step toward advanced optoelectronic devices relying on the emerging perovskite semiconductors.

Probing the Reaction Mechanism in CO2 Hydrogenation on Bimetallic Ni/Cu(100) with Near-Ambient Pressure X-Ray Photoelectron Spectroscopy.

Bimetallic Ni-Cu catalysts feature high activity in CO2 hydrogenation. However, the primary surface intermediates during reaction are still elusive, making the understanding of the reaction mechanism inadequate. Herein, taking advantage of near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), we focused on the mechanistic exploration of CO2 hydrogenation on the Ni/Cu(100) model catalyst under millibar pressures. We show that CO2 dissociates into CO and atomic oxygen on the Ni/Cu(100) surface and gives rise to the formation of chemisorbed O and nickel oxide (NiO). The CO3* species is formed through the reaction of CO2 with surface oxygen during CO2 activation. With the presence of H2, the conversion of adsorbed CO3* into the formate intermediate, HCOO*, is unambiguously demonstrated by the C 1s and O 1s core-level spectra as well as ultraviolet photoelectron spectroscopy. Based on these observations, we conclude that the CO2 hydrogenation route via CO2 dissociation, the formation of CO3*, the conversion of CO3* to formate, and the ensuing hydrogenation of formate to methanol on the Ni-Cu catalyst are feasible.

Perovskite-Ion Beam Interactions: Toward Controllable Light Emission and Lasing.

Achieving controllable coherent and incoherent light sources is crucial to meet the requests of the constantly developing integrated optics, which, however, remains challenging for the existing semiconductor materials and techniques. All-inorganic lead halide perovskites (ILHPs) are emerging as the promising semiconductors, featuring the defect-tolerant nature and tunable band gap. Herein, an experimental design, based on the interaction between ILHPs and energetic ions, for achieving controllable light emitters and microlasers is reported. We reveal that the photoluminescence intensity from ILHPs can be modulated by more than 1 order of magnitude upon low-dose gallium ion (∼1015 ions/cm2) irradiation, which can be attributed to the generation of vacancy/interstitial defects, metallic lead, and crystal-to-amorphization transition. Such ion-dependent light emission can be exploited to make the colorful photopatterns and in situ tailor the lasing behavior from CsPbBr3 microplates. Further, a strong sputtering effect is observed with the increase of the ion dose (∼1017 ions/cm2), which enables the top-down fabrication of microlasers based on ILHPs. These findings represent a significant step toward controllable light sources leveraging on perovskite-ion interactions.

Laser induced ion migration in all-inorganic mixed halide perovskite micro-platelets.

Despite intensive research on ion migration (IM) in organic-inorganic hybrid metal halide perovskites, much less is known about the irradiation effect on IM in all-inorganic perovskites, especially for those single crystals lacking complicated grain boundaries. Herein, the real-time IM process and the corresponding photoluminescence (PL) spectra induced by laser irradiation in all-inorganic CsPbBr x I(3-x) single crystals prepared by chemical vapor deposition (CVD) were investigated. We proposed that a local electric field acts as a driving force for IM and confirmed this by applying a bias to an indium tin oxide (ITO)/perovskite/ITO configuration. According to the control experiments on CsPbBr x I(3-x) micro-platelets with and without polymethyl methacrylate (PMMA) coating, it is concluded that the vacancy defect on the single crystal surface is the main pathway for IM. Our work is important for understanding and controlling light induced IM in all-inorganic perovskites.

Catalytic Intermediates of CO2 Hydrogenation on Cu(111) Probed by In Operando Near-Ambient Pressure Technique.

The in operando monitoring of catalytic intermediates is crucial for understanding the reaction mechanism and for optimizing the reaction conditions to improve the efficiency of the catalytic protocol; however, until now, this has remained a daunting challenge. Herein, we investigated the interaction of CO2 and H2 with the Cu(111) surface in a CO2 hydrogenation model system by using the in operando technique of near-ambient pressure X-ray photoelectron spectroscopy, which is further assisted by ultraviolet photoemission spectroscopy and low-energy electron diffraction (LEED) measurements. These techniques allowed the direct observation of CO2 dissociation into CO+O on the Cu(111) surface and the adsorption of O on the surface at room temperature. The intermediate HCOO- was unambiguously detected in the CO2 +H2 environment, which corroborated the formate pathway for methanol formation on the Cu(111) surface. We further found that O coverage can prevent the build up of graphitic carbon on the Cu surface. By taking advantage of the competitive interplay between Cu-O and graphitic carbon, we have proposed a feasible strategy for inhibition of the formation of graphitic carbon by tuning the CO2 and H2 partial pressures, which may contribute to sustaining the active Cu catalyst under the reaction conditions.

Water-Catalyzed Oxidation of Few-Layer Black Phosphorous in a Dark Environment.

Black phosphorus (BP) shows great potential in electronic and optoelectronic devices owing to its semiconducting properties, such as thickness-dependent direct bandgap and ambipolar transport characteristics. However, the poor stability of BP in air seriously limits its practical applications. To develop effective schemes to protect BP, it is crucial to reveal the degradation mechanism under various environments. To date, it is generally accepted that BP degrades in air via light-induced oxidation. Herein, we report a new degradation channel via water-catalyzed oxidation of BP in the dark. When oxygen co-adsorbs with highly polarized water molecules on BP surface, the polarization effect of water can significantly lower the energy levels of oxygen (i.e. enhanced electron affinity), thereby facilitating the electron transfer from BP to oxygen to trigger the BP oxidation even in the dark environment. This new degradation mechanism lays important foundation for the development of proper protecting schemes in black phosphorus-based devices.

Facile synthesis and strongly microstructure-dependent electrochemical properties of graphene/manganese dioxide composites for supercapacitors.

Graphene has attracted much attention since it was firstly stripped from graphite by two physicists in 2004, and the supercapacitor based on graphene has obtained wide attention and much investment as well. For practical applications of graphene-based supercapacitors, however, there are still many challenges to solve, for instance, to simplify the technological process, to lower the fabrication cost, and to improve the electrochemical performance. In this work, graphene/MnO2 composites are prepared by a microwave sintering method, and we report here a relatively simple method for the supercapacitor packaging, i.e., dipping Ni-foam into a graphene/MnO2 composite solution directly for a period of time to coat the active material on a current collector. It is found that the microwave reaction time has a significant effect on the microstructure of graphene/MnO2 composites, and consequently, the electrochemical properties of the supercapacitors based on graphene/MnO2 composites are strongly microstructure dependent. An appropriately longer microwave reaction time, namely, 15 min, facilitates a very dense and homogeneous microstructure of the graphene/MnO2 composites, and thus, excellent electrochemical performance is achieved in the supercapacitor device, including a high specific capacitance of 296 F/g and a high capacitance retention of 93% after 3,000 times of charging/discharging cycles. PACS: 81.05.ue; 78.67.Sc; 88.80.fh.