Imprinted Photonic Hydrogels for the Size- and Shell-Selective Recognition of Nanoparticles.

Sensors based on responsive photonic hydrogels have recently attracted considerable attention for visual medical diagnostics, pharmaceutical bioassays, and environmental monitoring. However, the use of these promising materials for the detection of nanoparticles (NPs) has never been explored so far, although the sensing of nanoobjects is a rapidly evolving area of research. To address this issue, we have combined the concepts of inverse-opal hydrogels and nanoparticle-imprinted polymers. In this way, we could obtain a NP-imprinted photonic hydrogel consisting of a three-dimensional, highly ordered poly(methacrylic acid) macroporous array, in which nanocavities complementary to the target NPs, in this case colloidal quantum dots, are distributed. This novel type of NP-imprinted photonic hydrogel sensor was shown to display high sensitivity and selectivity, thus opening new prospects for the development of equipment-free and cost-efficient sensing devices for NPs.

The size of the proton.

The proton is the primary building block of the visible Universe, but many of its properties-such as its charge radius and its anomalous magnetic moment-are not well understood. The root-mean-square charge radius, r(p), has been determined with an accuracy of 2 per cent (at best) by electron-proton scattering experiments. The present most accurate value of r(p) (with an uncertainty of 1 per cent) is given by the CODATA compilation of physical constants. This value is based mainly on precision spectroscopy of atomic hydrogen and calculations of bound-state quantum electrodynamics (QED; refs 8, 9). The accuracy of r(p) as deduced from electron-proton scattering limits the testing of bound-state QED in atomic hydrogen as well as the determination of the Rydberg constant (currently the most accurately measured fundamental physical constant). An attractive means to improve the accuracy in the measurement of r(p) is provided by muonic hydrogen (a proton orbited by a negative muon); its much smaller Bohr radius compared to ordinary atomic hydrogen causes enhancement of effects related to the finite size of the proton. In particular, the Lamb shift (the energy difference between the 2S(1/2) and 2P(1/2) states) is affected by as much as 2 per cent. Here we use pulsed laser spectroscopy to measure a muonic Lamb shift of 49,881.88(76) GHz. On the basis of present calculations of fine and hyperfine splittings and QED terms, we find r(p) = 0.84184(67) fm, which differs by 5.0 standard deviations from the CODATA value of 0.8768(69) fm. Our result implies that either the Rydberg constant has to be shifted by -110 kHz/c (4.9 standard deviations), or the calculations of the QED effects in atomic hydrogen or muonic hydrogen atoms are insufficient.

Models of light absorption enhancement in perovskite solar cells by plasmonic nanoparticles.

Numerous experiments have demonstrated improvements on the efficiency of perovskite solar cells by introducing plasmonic nanoparticles, however, the underlying mechanisms are still not clear: the particles may enhance light absorption and scattering, as well as charge separation and transfer, or the perovskite's crystalline quality. Eventually, it can still be debated whether unambiguous plasmonic increase of light absorption has indeed been achieved. Here, various optical models are employed to provide a physical understanding of the relevant parameters in plasmonic perovskite cells and the conditions under which light absorption may be enhanced by plasmonic mechanisms. By applying the recent generalized Mie theory to gold nanospheres in perovskite, it is shown that their plasmon resonance is conveniently located in the 650-800 nm wavelength range, where absorption enhancement is most needed. It is evaluated for which active layer thickness and nanoparticle concentration a significant enhancement can be expected. Finally, the experimental literature on plasmonic perovskite solar cells is analyzed in light of this theoretical description. It is estimated that only a tiny portion of these reports can be associated with light absorption and point out the importance of reporting the perovskite thickness and nanoparticle concentration in order to assess the presence of plasmonic effects.

Isotropic broadband absorption by a macroscopic self-organized plasmonic crystal.

We describe the plasmonic properties of a two-dimensional periodic metallic grating of macroscopic size obtained by gold deposition on a self-assembled silica opal. Structural characterization shows a transition from microscopic order to isotropy at macroscopic scale. Optical reflection spectra exhibit a dip of almost complete absorption due to coupling to surface-plasmon-polaritons (SPP). This is explained by theoretical calculations introducing a density of coupled SPP modes. We demonstrate, at a given incidence angle, a broad continuum of coupled wavelengths over the visible spectrum. This opens new possibilities in fields where light-plasmon coupling is required over a broad range of wavelengths and incidence orientations.

Controlled modification of single colloidal CdSe/ZnS nanocrystal fluorescence through interactions with a gold surface.

Single colloidal CdSe/ZnS nanocrystals are deposited at various distances from a gold film in order to improve their performance as single photon sources. Photon antibunching is demonstrated and the experimental curves are accurately fitted by theoretical equations. Emission lifetime and intensity are measured and found in excellent agreement with theoretical values. The various effects of a neighbouring gold film are discussed : interferences of the excitation beam, interferences of the fluorescence light, opening of plasmon and lossy-surface-wave modes, modification of the radiation pattern leading to a modified objective collection efficiency. At 80 nm from the gold film, when using an objective with 0.75 numerical aperture, about a 2.4-fold increase of the detected intensity is evidenced.

Fine tuning of emission through the engineering of colloidal crystals.

We describe the preparation and characterization of photonic colloidal crystals from silica spheres with incorporated luminescent [Mo(6)Br(14)](2-) cluster units. These structures exhibit strong angle-dependent luminescent properties. The incorporation of one or several planar defects in the periodic structures gives rise to the creation of a passband in the stopband. In the energy range of this passband, an increase of the emission intensity has been found.

Extreme multiexciton emission from deterministically assembled single-emitter subwavelength plasmonic patch antennas.

Coupling nano-emitters to plasmonic antennas is a key milestone for the development of nanoscale quantum light sources. One challenge, however, is the precise nanoscale positioning of the emitter in the structure. Here, we present a laser etching protocol that deterministically positions a single colloidal CdSe/CdS core/shell quantum dot emitter inside a subwavelength plasmonic patch antenna with three-dimensional nanoscale control. By exploiting the properties of metal-insulator-metal structures at the nanoscale, the fabricated single-emitter antenna exhibits a very high-Purcell factor (>72) and a brightness enhancement of a factor of 70. Due to the unprecedented quenching of Auger processes and the strong acceleration of the multiexciton emission, more than 4 photons per pulse can be emitted by a single quantum dot, thus increasing the device yield. Our technology can be applied to a wide range of photonic nanostructures and emitters, paving the way for scalable and reliable fabrication of ultra-compact light sources.

Laser spectroscopy of muonic deuterium.

The deuteron is the simplest compound nucleus, composed of one proton and one neutron. Deuteron properties such as the root-mean-square charge radius rd and the polarizability serve as important benchmarks for understanding the nuclear forces and structure. Muonic deuterium µd is the exotic atom formed by a deuteron and a negative muon µ(-). We measured three 2S-2P transitions in µd and obtain r(d) = 2.12562(78) fm, which is 2.7 times more accurate but 7.5σ smaller than the CODATA-2010 value r(d) = 2.1424(21) fm. The µd value is also 3.5σ smaller than the r(d) value from electronic deuterium spectroscopy. The smaller r(d), when combined with the electronic isotope shift, yields a "small" proton radius r(p), similar to the one from muonic hydrogen, amplifying the proton radius puzzle.

Proton structure from the measurement of 2S-2P transition frequencies of muonic hydrogen.

Accurate knowledge of the charge and Zemach radii of the proton is essential, not only for understanding its structure but also as input for tests of bound-state quantum electrodynamics and its predictions for the energy levels of hydrogen. These radii may be extracted from the laser spectroscopy of muonic hydrogen (µp, that is, a proton orbited by a muon). We measured the 2S(1/2)(F=0)-2P(3/2)(F=1) transition frequency in µp to be 54611.16(1.05) gigahertz (numbers in parentheses indicate one standard deviation of uncertainty) and reevaluated the 2S(1/2)(F=1)-2P(3/2)(F=2) transition frequency, yielding 49881.35(65) gigahertz. From the measurements, we determined the Zemach radius, r(Z) = 1.082(37) femtometers, and the magnetic radius, r(M) = 0.87(6) femtometer, of the proton. We also extracted the charge radius, r(E) = 0.84087(39) femtometer, with an order of magnitude more precision than the 2010-CODATA value and at 7σ variance with respect to it, thus reinforcing the proton radius puzzle.

Introduction of a planar defect in a molecularly imprinted photonic crystal sensor for the detection of bisphenol A.

This paper reports the preparation of a molecularly imprinted inverse opal hydrogel containing a 2D defect layer, by combining the Langmuir-Blodgett technique and the photonic crystal template method. By coupling the exceptional characteristics of molecularly imprinted polymers, sensitive to the presence of a target molecule, and those of photonic crystals in a single device, we could obtain a defect-embedded imprinted photonic polymer consisting in a three-dimensional, highly-ordered and interconnected macroporous array, where nanocavities complementary to analytes in shape and binding sites are distributed. As a proof of concept, we prepared a three-dimensional macroporous array of poly(methacrylic acid) (PMAA) containing molecular imprints of bisphenol A (BPA) and a planar defect layer consisting in macropores of different size. The optical properties of the resulting inverse opal were investigated using reflection spectroscopy. The defect layer was shown to enhance the sensitivity of the photonic crystal material, opening new possibilities towards the development smart optical sensing devices.

Experimental Determination of the Fluorescence Quantum Yield of Semiconductor Nanocrystals.

Many studies have considered the luminescence of colloidal II-VI nanocrystals, both in solution at a collective scale and at an individual scale by confocal microscopy. The quantum yield is an important figure of merit for the optical quality of a fluorophore. We detail here a simple method to determine the quantum yield of nanocrystals in solution as a function of the absorption. For this purpose, we choose rhodamine 101 as a reference dye to measure the nanocrystal fluorescence quantum yield. The influence of the concentration on quantum yield is therefore studied for both the reference and the solutions of nanocrystals and is found to be critical for the acuity of the method. Different types of nanocrystals are studied to illustrate different quantum yield evolutions with the concentration.

Combination of BLOCH oscillations with a Ramsey-Bordé interferometer: new determination of the fine structure constant.

We report a new experimental scheme which combines atom interferometry with Bloch oscillations to provide a new measurement of the ratio h/mRb. By using Bloch oscillations, we impart to the atoms up to 1600 recoil momenta and thus we improve the accuracy on the recoil velocity measurement. The deduced value of h/mRb leads to a new determination of the fine structure constant alpha(-1) =137.03599945 (62) with a relative uncertainty of 4.6 x 10(-9). The comparison of this result with the value deduced from the measurement of the electron anomaly provides the most stringent test of QED.

Determination of the fine structure constant based on BLOCH oscillations of ultracold atoms in a vertical optical lattice.

We report an accurate measurement of the recoil velocity of 87Rb atoms based on Bloch oscillations in a vertical accelerated optical lattice. We transfer about 900 recoil momenta with an efficiency of 99.97% per recoil. A set of 72 measurements of the recoil velocity, each one with a relative uncertainty of about 33 ppb in 20 min integration time, leads to a determination of the fine structure constant with a statistical relative uncertainty of 4.4 ppb. The detailed analysis of the different systematic errors yields to a relative uncertainty of 6.7 ppb. The deduced value of alpha-1 is 137.035 998 78(91).

Bloch oscillations of ultracold atoms: a tool for a metrological determination of h/m Rb.

We use Bloch oscillations in a horizontal moving standing wave to transfer a large number of photon recoils to atoms with a high efficiency (99.5% per cycle). By measuring the photon recoil of 87Rb, using velocity-selective Raman transitions to select a subrecoil velocity class and to measure the final accelerated velocity class, we have determined h/m(Rb) with a relative precision of 0.4 ppm. To exploit the high momentum transfer efficiency of our method, we are developing a vertical standing wave setup. This will allow us to measure h/m(Rb) better than 10(-8) and hence the fine structure constant alpha with an uncertainty close to the most accurate value coming from the (g-2) determination.