Ultrathin Polypyrrole Nanosheets via Space-Confined Synthesis for Efficient Photothermal Therapy in the Second Near-Infrared Window

Extensive efforts have been devoted to synthesizing photothermal agents (PTAs) that are active in the first near-infrared (NIR) region (650–950 nm). However, PTAs for photothermal therapy in the second NIR window (1000–1350 nm) are still rare. Here, it is shown that two-dimensional ultrathin polypyrrole (PPy) nanosheets prepared via a novel space-confined synthesis method could exhibit unique broadband absorption with a large extinction coefficient of 27.8 L g^–1 cm^–1 at 1064 nm and can be used as an efficient PTA in the second NIR window. This unique optical property is attributed to the formation of bipolaron bands in highly doped PPy nanosheets. The measured prominent photothermal conversion efficiency could achieve 64.6%, surpassing previous PTAs that are active in the second NIR window. Both in vitro and in vivo studies reveal that these ultrathin PPy nanosheets possess good biocompatibility and notable tumor ablation ability in the second NIR window. Our study highlights the potential of ultrathin two-dimensional polymers with unique optical properties in biomedical applications

Nonimaging Optical Gain in Luminescent Concentration through Photonic Control of Emission Étendue

Luminescent and nonimaging optical concentration constitute two fundamentally different ways of collecting and intensifying light. Whereas nonimaging concentrators based on reflective, refractive, or diffractive optics operate most effectively for collimated light, luminescent concentrators (LCs) rely on absorption, re-emission, and waveguiding to concentrate diffuse light incident from any direction. LCs have been explored in many different shapes and sizes but have so far been unable to exploit the power of nonimaging optics to further increase their concentration ratio because their emission is angularly isotropic. Here, we use a luminescent thin film bilayer to create sharply directed conical emission in an LC and derive a nonimaging optical solution to leverage this directionality for secondary geometric gain ranging up to an order of magnitude or higher. We demonstrate this concept experimentally using a custom compound parabolic optical element index-matched to the LC surface and show that it delivers three times more luminescent power to an opposing GaAs photovoltaic cell when the emission profile is conically directed than when it is isotropic or the nonimaging optic is absent. These results open up a significant and general opportunity to improve LC performance for a variety of applications including photovoltaics, photobioreactors, and scintillator-based radiation detection

Transfer-Printing of Tunable Porous Silicon Microcavities with Embedded Emitters

Here we demonstrate, via a modified transfer-printing technique, that electrochemically fabricated porous silicon (PSi) distributed Bragg reflectors (DBRs) can serve as the basis of high-quality hybrid microcavities compatible with most forms of photoemitters. Vertical microcavities consisting of an emitter layer sandwiched between 11- and 15-period PSi DBRs were constructed. The emitter layer included a polymer doped with PbS quantum dots, as well as a heterogeneous GaAs thin film. In this structure, the PbS emission was significantly redistributed to a 2.1 nm full-width at half-maximum around 1198 nm, while the PSi/GaAs hybrid microcavity emitted at 902 nm with a sub-nanometer full-width at half-maximum and quality-factor of 1058. Modification of PSi DBRs to include a PSi cavity coupling layer enabled tuning of the total cavity optical thickness. Infiltration of the PSi with Al₂O₃ by atomic layer deposition globally red-shifted the emission peak of PbS quantum dots up to ∼18 nm (∼0.9 nm per cycle), while introducing a cavity coupling layer with a gradient optical thickness spatially modulated the cavity resonance of the PSi/GaAs hybrid such that there was an ∼30 nm spectral variation in the emission of separate GaAs modules printed ∼3 mm apart