Quantum Light-Enhanced Two-Photon Imaging of Breast Cancer Cells.

Correct biological interpretation from cell imaging can be achieved only if the observed phenomena proceed with negligible perturbation from the imaging system. Herein, we demonstrate microscopic images of breast cancer cells created by the fluorescence selectively excited in the process of entangled two-photon absorption in a scanning microscope at an excitation intensity orders of magnitude lower than that used for classical two-photon microscopy. Quantum enhanced entangled two-photon microscopy has shown cell imaging capabilities at an unprecedented low excitation intensity of ∼3.6 × 107 photons/s, which is a million times lower than the excitation level for the classical two-photon fluorescence image obtained in the same microscope. The extremely low light probe intensity demonstrated in entangled two-photon microscopy is of critical importance to minimize photobleaching during repetitive imaging and damage to cells in live-cell applications. This technology opens new avenues in cell investigations with light microscopy, such as enhanced selectivity and time-frequency resolution.

Origin of the "odd" behavior in the ultraviolet photochemistry of ozone.

The origin of the even-odd rotational state population alternation in the 16O2(a1Δg) fragments resulting from the ultraviolet (UV) photodissociation of 16O3, a phenomenon first observed over 30 years ago, has been elucidated using full quantum theory. The calculated 16O2(a1Δg) rotational state distribution following the 266-nm photolysis of 60 K ozone shows a strong even-odd propensity, in excellent agreement with the new experimental rotational state distribution measured under the same conditions. Theory indicates that the even rotational states are significantly more populated than the adjacent odd rotational states because of a preference for the formation of the A' Λ-doublet, which can only occupy even rotational states due to the exchange symmetry of the two bosonic 16O nuclei, and thus not as a result of parity-selective curve crossing as previously proposed. For nonrotating ozone, its dissociation on the excited B1A' state dictates that only A' Λ-doublets are populated, due to symmetry conservation. This selection rule is relaxed for rotating parent molecules, but a preference still persists for A' Λ-doublets. The A''/A' ratio increases with increasing ozone rotational quantum number, and thus with increasing temperature, explaining the previously observed temperature dependence of the even-odd population alternation. In light of these results, it is concluded that the previously proposed parity-selective curve-crossing mechanism cannot be a source of heavy isotopic enrichment in the atmosphere.

Evidence for lambda doublet propensity in the UV photodissociation of ozone.

The photodissociation of O3 at 266 nm has been studied using velocity mapped ion imaging. We report temperature-dependent vector correlations for the O2(a1Δg, v = 0, j = 18-20) fragments at molecular beam temperatures of 70 K, 115 K, and 170 K. Both the fragment spatial anisotropy and the v-j correlations are found to be increasingly depolarized with increasing beam temperature. At all temperatures, the v-j correlations for the j = 19 state were shown to be reduced compared to those of j = 18 and 20, while no such odd/even rotational state difference was observed for the spatial anisotropy, consistent with previous measurements. We find that temperature-dependent differences in the populations and v-j correlations between the odd and even rotational states can be explained by a Λ-doublet propensity model. Although symmetry conservation should lead to formation of only the A' Λ-doublet component, and only even rotational states, out-of-plane rotation of the parent molecule breaks the planar symmetry and permits the formation of the A″ Λ-doublet component and odd rotational states. A simple classical model to treat the effect of parent rotation on the v-j correlation and the odd/even rotational population alternation reproduces both the current measurements and previously reported rotational distributions, suggesting that the "odd" behavior originates from a Λ-doublet propensity, and not from a mass independent curve crossing effect, as previously proposed.

Nascent O2 (a 1Δg, v = 0, 1) rotational distributions from the photodissociation of jet-cooled O3 in the Hartley band.

We report rotational distributions for the O2 (a 1Δg) fragment from the photodissociation of jet-cooled O3 at 248, 266, and 282 nm. The rotational distributions show a population alternation that favors the even states, as previously reported for a 300 K sample by Valentini et al. [J. Chem. Phys. 86, 6745 (1987)]. The alternation from the jet-cooled precursor is much stronger than that observed by Valentini et al. and in contrast to their observations does not depend strongly on the O2 (a 1Δg) vibrational state or photolysis wavelength. The odd/even alternation diminishes substantially when the ozone beam temperature is increased from 60 to 200 K, confirming its dependence on parent internal energy. The magnitude of the even/odd alternation in product rotational states from the cold ozone sample, its temperature dependence, and other experimental and theoretical evidence reported since 1987 suggest that the alternation originates from a Λ-doublet propensity and not from a mass independent curve crossing effect, as previously proposed.

Charge-tunable quantum plasmons in colloidal semiconductor nanocrystals.

Nanomaterials exhibiting plasmonic optical responses are impacting sensing, information processing, catalysis, solar, and photonics technologies. Recent advances have expanded the portfolio of plasmonic nanostructures into doped semiconductor nanocrystals, which allow dynamic manipulation of carrier densities. Once interpreted as intraband single-electron transitions, the infrared absorption of doped semiconductor nanocrystals is now commonly attributed to localized surface plasmon resonances and analyzed using the classical Drude model to determine carrier densities. Here, we show that the experimental plasmon resonance energies of photodoped ZnO nanocrystals with controlled sizes and carrier densities diverge from classical Drude model predictions at small sizes, revealing quantum plasmons in these nanocrystals. A Lorentz oscillator model more adequately describes the data and illustrates a closer link between plasmon resonances and single-electron transitions in semiconductors than in metals, highlighting a fundamental contrast between these two classes of plasmonic materials.

Controlling carrier densities in photochemically reduced colloidal ZnO nanocrystals: size dependence and role of the hole quencher.

Photodoped colloidal ZnO nanocrystals are model systems for understanding the generation and physical or chemical properties of excess delocalized charge carriers in semiconductor nanocrystals. Typically, ZnO photodoping is achieved photochemically using ethanol (EtOH) as a sacrificial reductant. Curiously, different studies have reported over an order of magnitude spread in the maximum number of conduction-band electrons that can be accumulated by photochemical oxidation of EtOH. Here, we demonstrate that this apparent discrepancy results from a strong size dependence of the average maximum number of excess electrons per nanocrystal, . We demonstrate that increases in proportion to nanocrystal volume, such that the maximum carrier density remains constant for all nanocrystal sizes. is found to be largely insensitive to precise experimental conditions such as solvent, ligands, protons or other cations, photolysis conditions, and nanocrystal or EtOH concentrations. These results reconcile the broad range of literature results obtained with EtOH as the hole quencher. Furthermore, we demonstrate that depends on the identity of the hole quencher, and is thus not an intrinsic property of the multiply reduced ZnO nanocrystals themselves. Using a series of substituted borohydride hole quenchers, we show that it is possible to increase the nanocrystal carrier densities over 4-fold relative to previous photodoping reports. When excess lithium and potassium triethylborohydrides are used in the photodoping, formation of Zn(0) is observed. The relationship between metallic Zn(0) formation and ZnO surface electron traps is discussed.

Size-dependent trap-assisted Auger recombination in semiconductor nanocrystals.

The acceleration of Auger-type multicarrier recombination in semiconductor nanocrystals impedes the development of many quantum-dot photonics, solar-cell, lighting, and lasing technologies. To date, only multiexciton and charged-exciton Auger recombination channels are known to show strong size dependence in nanocrystals. Here, we report the first observation of strongly accelerated "trap-assisted" Auger recombination rates in semiconductor nanocrystals. Trap-assisted Auger recombination in ZnO nanocrystals, involving the recombination of conduction-band electrons with deeply trapped holes via nonradiative energy transfer to extra conduction-band electrons, has been probed using time-resolved photoluminescence and transient absorption spectroscopies. We demonstrate that this trap-assisted Auger recombination accelerates dramatically with decreasing nanocrystal size, having recombination times of >1 ns in the largest nanocrystals but only ~80 ps in the smallest. These trap-assisted Auger recombination rates are shown to scale with inverse nanocrystal radius squared (1/τ(Auger) ~ R(-2)). Because surface carrier traps are ubiquitous in colloidal semiconductor nanocrystals, such fast trap-assisted Auger recombination is likely more prevalent in semiconductor nanocrystal photophysics than previously recognized.