Thomas S. Bischof

Next-generation in vivo optical imaging with short-wave infrared quantum dots

For in vivo imaging, the short-wavelength infrared region (SWIR; 1000–2000 nm) provides several advantages over the visible and near-infrared regions: general lack of autofluorescence, low light absorption by blood and tissue, and reduced scattering. However, the lack of versatile and functional SWIR emitters has prevented the general adoption of SWIR imaging by the biomedical research community. Here, we introduce a class of high-quality SWIR-emissive indium-arsenide-based quantum dots (QDs) that are readily modifiable for various functional imaging applications, and that exhibit narrow and size-tunable emission and a dramatically higher emission quantum yield than previously described SWIR probes. To demonstrate the unprecedented combination of deep penetration, high spatial resolution, multicolor imaging and fast-acquisition-speed afforded by the SWIR QDs, we quantified, in mice, the metabolic turnover rates of lipoproteins in several organs simultaneously and in real time as well as heartbeat and breathing rates in awake and unrestrained animals, and generated detailed three-dimensional quantitative flow maps of the mouse brain vasculature.

Measurement of Emission Lifetime Dynamics and Biexciton Emission Quantum Yield of Individual InAs Colloidal Nanocrystals

The understanding of the photophysics of visible-emitting colloidal nanocrystals (NCs) has long been aided by single-molecule studies of their emission. Until recently, no suitable detection technologies have existed for corresponding studies of shortwave-infrared (SWIR) emitters. Now, the use of superconducting nanowire single-photon detectors (SNSPDs) enables the detailed study of SWIR NC emission dynamics at the single-emitter level. Here, we report a detailed analysis of the emission dynamics of individual InAs/CdZnS NCs emitting in the SWIR region. We observe blinking akin to the type A and type B blinking previously observed in visible-emitting CdSe NCs. We determine the intrinsic radiative lifetime of several InAs/CdZnS NCs and find examples ranging from 50–200 ns, indicative of a quasi-type-II electronic structure. We also measure g0(2) for several of these NCs and find that their biexciton emission quantum yields vary from <1% up to 43%.

Sample-Averaged Biexciton Quantum Yield Measured by Solution-Phase Photon Correlation

The brightness of nanoscale optical materials such as semiconductor nanocrystals is currently limited in high excitation flux applications by inefficient multiexciton fluorescence. We have devised a solution-phase photon correlation measurement that can conveniently and reliably measure the average biexciton-to-exciton quantum yield ratio of an entire sample without user selection bias. This technique can be used to investigate the multiexciton recombination dynamics of a broad scope of synthetically underdeveloped materials, including those with low exciton quantum yields and poor fluorescence stability. Here, we have applied this method to measure weak biexciton fluorescence in samples of visible-emitting InP/ZnS and InAs/ZnS core/shell nanocrystals, and to demonstrate that a rapid CdS shell growth procedure can markedly increase the biexciton fluorescence of CdSe nanocrystals.

Optical trapping of a colloidal quantum dot

Bowtie apertures fabricated by lift-off were used to optically trap a 30-nm silica coated quantum dot (scQD) with 1.56-MW/cm2 intensity at 1064-nm wavelength. The trapped scQD emitted fluorescence by two photon excitation from the trapping laser.

Multiexciton Lifetimes Reveal Triexciton Emission Pathway in CdSe Nanocrystals

Multiexcitons in emerging semiconducting nanomaterials play a critical role in potential optoelectronic and quantum computational devices. We describe photon resolved single molecule methods to directly probe the dynamics of biexcitons and triexcitons in colloidal CdSe quantum dots. We confirm that biexcitons emit from a spin-correlated state, consistent with statistical scaling. Contrary to current understanding, we find that triexciton emission is dominated by band-edge 1Se1S3/2 recombination rather than the higher energy 1Pe1P3/2 recombination.

Extracting the average single-molecule biexciton photoluminescence lifetime from a solution of chromophores

We present a method for obtaining the average single-molecule biexciton lifetime from an ensemble of chromophores in solution. We apply this analysis to a series of core/shell CdSe/CdS quantum dot heterostructures with increasing shell thickness and find that the lifetime of the biexciton increases with increasing shell thickness, consistent with a simultaneous measurement of biexciton quantum yield.