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Placing plasmonic nanoparticles (NPs) in close proximity to semiconductor nanostructures renders effective tuning of the optoelectronic properties of semiconductors through the localized surface plasmon resonance (LSPR)-induced enhancement of light absorption and/or promotion of carrier transport. Herein, we report on, for the first time, the scrutiny of carrier dynamics of perovskite solar cells (PSCs) via sandwiching monodisperse plasmonic/dielectric core/shell NPs with systematically varied dielectric shell thickness yet fixed plasmonic core diameter within an electron transport layer (ETL). Specifically, a set of Au NPs with precisely controlled dimensions ( i.e. , fixed Au core diameter and tunable SiO 2 shell thickness) and architectures (plain Au NPs and plasmonic/dielectric Au/SiO 2 core/shell NPs) are first crafted by capitalizing on the star-like block copolymer nanoreactor strategy. Subsequently, these monodisperse NPs are sandwiched between the two consecutive TiO 2 ETLs. Intriguingly, there exists a critical dielectric SiO 2 shell thickness, below which hot electrons from the Au core are readily injected to TiO 2 ( i.e. , hot electron transfer (HET)); this promotes local electron mobility in the TiO 2 ETL, leading to improved charge transport and increased short-circuit current density ( J sc ). It is also notable that the HET effect moves up the Fermi level of TiO 2 , resulting in an enhanced built-in potential and open-circuit voltage ( V oc ). Taken together, the PSCs constructed by employing a sandwich-like TiO 2 /Au NPs/TiO 2 ETL exhibit both greatly enhanced J sc and V oc , delivering champion PCEs of 18.81% and 19.42% in planar and mesostructured PSCs, respectively. As such, the judicious positioning of rationally designed monodisperse plasmonic NPs in the ETL affords effective tailoring of carrier dynamics, thereby providing a unique platform for developing high-performance PSCs. 

We report a viable route to plasmonic nanoparticles with well-controlled sizes, shapes, and compositions. A series of monodisperse Ag and Au nanoparticles capped with polystyrene chains ( i.e. , “hairy” nanoparticles) are crafted by capitalizing on star-like diblock copolymers as nanoreactors. Such monodisperse nanoparticles render an accurate absorption spectrum, providing a strong basis for theoretical investigation into their optical properties. By combining the experimental study with the three-dimensional finite element calculation of electromagnetic field distributions, the contributions of both intra-band and inter-band transitions to plasmonic absorption are revealed. The calculated absorption spectra perfectly reproduce the experimental observations, including the peak positions, shapes, and trends of peak shifting or broadening as a function of nanoparticle sizes. The influences of nanoparticle dimensions and surface ligands on plasmonic absorption of metallic nanoparticles are also systematically explored. 

The current trend in the miniaturization of electronic devices has driven the investigation into many nanostructured materials. The ferroelectric material barium titanate (BaTiO 3 ) has garnered considerable attention over the past decade owing to its excellent dielectric and ferroelectric properties. This has led to significant progress in synthetic techniques that yield high quality BaTiO 3 nanocrystals (NCs) with well-defined morphologies ( e.g. , nanoparticles, nanorods, nanocubes and nanowires) and controlled crystal phases ( e.g. , cubic, tetragonal and multi-phase). The ability to produce nanoscale BaTiO 3 with controlled properties enables theoretical and experimental studies on the intriguing yet complex dielectric properties of individual BaTiO 3 NCs as well as BaTiO 3 /polymer nanocomposites. Compared with polymer-free individual BaTiO 3 NCs, BaTiO 3 /polymer nanocomposites possess several advantages. The polymeric component enables simple solution processibility, high breakdown strength and light weight for device scalability. The BaTiO 3 component enables a high dielectric constant. In this review, we highlight recent advances in the synthesis of high-quality BaTiO 3 NCs via a variety of chemical approaches including organometallic, solvothermal/hydrothermal, templating, molten salt, and sol–gel methods. We also summarize the dielectric and ferroelectric properties of individual BaTiO 3 NCs and devices based on BaTiO 3 NCs via theoretical modeling and experimental piezoresponse force microscopy (PFM) studies. In addition, viable synthetic strategies for novel BaTiO 3 /polymer nanocomposites and their structure–composition–performance relationship are discussed. Lastly, a perspective on the future direction of nanostructured BaTiO 3 -based materials is presented. 

Thermoresponsive nanoparticles (NPs) represent an important hybrid material comprising functional NPs with temperature‐sensitive polymer ligands. Strikingly, significant discrepancies in optical and catalytic properties of thermoresponsive noble‐metal NPs have been reported, and have yet to be unraveled. Reported herein is the crafting of Au NPs, intimately and permanently ligated by thermoresponsive poly(N‐isopropylacrylamide) (PNIPAM), in situ using a starlike block copolymer nanoreactor as model system to resolve the paradox noted above. As temperature rises, plasmonic absorption of PNIPAM‐capped Au NPs red‐shifts with increased intensity in the absence of free linear PNIPAM, whereas a greater red‐shift with decreased intensity occurs in the presence of deliberately introduced linear PNIPAM. Remarkably, the absence or addition of free linear PNIPAM also accounts for non‐monotonic or switchable on/off catalytic performance, respectively, of PNIPAM‐capped Au NPs.

 

Thermoresponsive nanoparticles (NPs) represent an important hybrid material comprising functional NPs with temperature‐sensitive polymer ligands. Strikingly, significant discrepancies in optical and catalytic properties of thermoresponsive noble‐metal NPs have been reported, and have yet to be unraveled. Reported herein is the crafting of Au NPs, intimately and permanently ligated by thermoresponsive poly(N‐isopropylacrylamide) (PNIPAM), in situ using a starlike block copolymer nanoreactor as model system to resolve the paradox noted above. As temperature rises, plasmonic absorption of PNIPAM‐capped Au NPs red‐shifts with increased intensity in the absence of free linear PNIPAM, whereas a greater red‐shift with decreased intensity occurs in the presence of deliberately introduced linear PNIPAM. Remarkably, the absence or addition of free linear PNIPAM also accounts for non‐monotonic or switchable on/off catalytic performance, respectively, of PNIPAM‐capped Au NPs.