Core/Shell Semiconductor Nanocrystals

Colloidal core/shell nanocrystals contain at least two semiconductor materials in an onionlike structure. The possibility to tune the basic optical properties of the core nanocrystals, for example, their fluorescence wavelength, quantum yield, and lifetime, by growing an epitaxial‐type shell of another semiconductor has fueled significant progress on the chemical synthesis of these systems. In such core/shell nanocrystals, the shell provides a physical barrier between the optically active core and the surrounding medium, thus making the nanocrystals less sensitive to environmental changes, surface chemistry, and photo‐oxidation. The shell further provides an efficient passivation of the surface trap states, giving rise to a strongly enhanced fluorescence quantum yield. This effect is a fundamental prerequisite for the use of nanocrystals in applications such as biological labeling and light‐emitting devices, which rely on their emission properties. Focusing on recent advances, this Review discusses the fundamental properties and synthesis methods of core/shell and core/multiple shell structures of II–VI, IV–VI, and III–V semiconductors.

     

核壳型复合半导体纳米粒子的研究

核壳型复合半导体纳米粒子,作为复合半导体纳米粒子材料的一个重要分支,凭借其优异的性质,受到了广泛关注.本文主要介绍了有机/无机和无机/无机核壳型复合半导体纳米微粒及其光学性质、分类、制备方法和应用.并对其发展做了展望.     

Selective Patterning of Gold Surfaces by Core/Shell,Semisoft Hybrid Nanoparticles

The generation of patterned surfaces with well‐defined nano‐ and microdomains is demonstrated by attaching core/shell, semisoft nanoparticles with narrow size distribution to microdomains of a gold‐coated silicon wafer. Near monodisperse nanoparticles are prepared using reversible addition‐fragmentation chain transfer (RAFT) polymerization, initiated from a silica surface, to prepare a polystyrene shell around a silica core. The particles are then used as‐prepared, or after aminolysis of the terminal thiocarbonyl group of the polystyrene shell, to give thiol‐terminated nanoparticles. When gold‐coated silicon wafers are immersed into very dilute suspensions of these particles (as low as 0.004 wt%), both types of particles are shown to adhere to the gold domains. The thiolated particles adhere selectively to the gold microdomains, allowing for microdomain patterning, while particles that contain the trithiocarbonate functionality lead to a much more even coverage of the gold surface with fewer particle aggregations.     

Enhanced Ultrafast Nonlinear Optical Response in Ferrite Core/Shell Nanostructures with Excellent Optical Limiting Performance

Nonlinear optical nanostructured materials are gaining increased interest as optical limiters for various applications, although many of them suffer from reduced efficiencies at high‐light fluences due to photoinduced deterioration. The nonlinear optical properties of ferrite core/shell nanoparticles showing their robustness for ultrafast optical limiting applications are reported. At 100 fs ultrashort laser pulses the effective two‐photon absorption (2PA) coefficient shows a nonmonotonic dependence on the shell thickness, with a maximum value obtained for thin shells. In view of the local electric field confinement, this indicates that core/shell is an advantageous morphology to improve the nonlinear optical parameters, exhibiting excellent optical limiting performance with effective 2PA coefficients in the range of 10^?12 cm W^?1 (100 fs excitation), and optical limiting threshold fluences in the range of 1.7 J cm^?2. These values are comparable to or better than most of the recently reported optical limiting materials. The quality of the open aperture Z‐scan data recorded from repeat measurements at intensities as high as 35 TW cm^?2, indicates their considerably high optical damage thresholds in a toluene dispersion, ensuring their robustness in practical applications. Thus, the high photostability combined with the remarkable nonlinear optical properties makes these nanoparticles excellent candidates for ultrafast optical limiting applications.     

Sequential Reactions Directed by Core/Shell Catalytic Reactors

Millimeter‐sized reactor particles made of permeable polymer doped with catalysts arranged in a core/shell fashion direct sequences of chemical reactions (e.g., alkyne coupling followed by hydrogenation or hydrosilylation followed by hydrogenation). Spatial compartmentalization of catalysts coupled with the diffusion of substrates controls reaction order and avoids formation of byproducts. The experimentally observed yields of reaction sequences are reproduced by a theoretical model, which accounts for the reaction kinetics and the diffusion of the species involved.     

Core/Shell ZnO/ZnS Nanoparticle Electron Transport Layers Enable Efficient All-Solution-Processed Perovskite Light-Emitting Diodes

Solution-processed perovskite-based light-emitting diodes (PeLEDs) are promising candidates for low-cost, large-area displays, while severe deterioration of the perovskite light-emitting layer occurs during deposition of electron transport layers from solution in an issue. Herein, core/shell ZnO/ZnS nanoparticles as a solution-processed electron transport layer in PeLED based on quasi-2D PEA₂Cs_n−1Pb_nBr_3n+1 (PEA = phenylethylammonium) perovskite are employed. The deposition of ZnS shell mitigates trap states on ZnO core by anchoring sulfur to oxygen vacancies, and at the same time removes residual hydroxyl groups, which helps to suppress the interfacial trap-assisted non-radiative recombination and the deprotonation reaction between the perovskite layer and ZnO. The core/shell ZnO/ZnS nanoparticles show comparably high electron mobility to pristine ZnO nanoparticles, combined with the reduced energy barrier between the electron transport layer and the perovskite layer, improving the charge injection balance in PeLEDs. As a result, the optimized PeLEDs employing core/shell ZnO/ZnS nanoparticles as a solution-processed electron transport layer exhibit high peak luminance reaching 32 400 cd m⁻², external quantum efficiency of 10.3%, and 20-fold extended longevity as compared to the devices utilizing ZnO nanoparticles, which represents one of the highest overall performances for solution-processed PeLEDs.     

Second‐Harmonic Generation from a Single Core/Shell Quantum Dot

Nanoparticles emitting two‐photon luminescence are broadly used as photostable emitters for nonlinear microscopy. Second‐harmonic generation (SHG) as another two‐photon mechanism offers complementary optical properties but the reported sizes of nanoparticles are still large, of a few tens of nanometers. Herein, coherent SHG from single core/shell CdTe/CdS nanocrystals with a diameter of 10 to 15 nm is reported. The nanocrystal excitation spectrum reveals resonances in the nonlinear efficiency with an overall maximum at about 970 nm. Polarization analysis of the second‐harmonic emission confirms the expected zinc blende symmetry, and allows extraction of the three‐dimensional nanocrystal orientation. The small size of these nonlinearly active quantum dots, together with the intrinsic coherence and orientation sensitivity of the SHG process, are well adapted for ultrafast probing of optical near‐fields with high resolution as well as for orientation tracking for bioimaging applications.