Nonradiative Relaxation Time Research Articles

Single-electron spin resonance detection by microwave photon counting.

Electron spin resonance spectroscopy is the method of choice for characterizing paramagnetic impurities, with applications ranging from chemistry to quantum computing1,2, but it gives access only to ensemble-averaged quantities owing to its limited signal-to-noise ratio. Single-electron spin sensitivity has, however, been reached using spin-dependent photoluminescence3-5, transport measurements6-9 and scanning-probe techniques10-12. These methods are system-specific or sensitive only in a small detection volume13,14, so that practical single-spin detection remains an open challenge. Here, we demonstrate single-electron magnetic resonance by spin fluorescence detection15, using a microwave photon counter at millikelvin temperatures16. We detect individual paramagnetic erbium ions in a scheelite crystal coupled to a high-quality-factor planar superconducting resonator to enhance their radiative decay rate17, with a signal-to-noise ratio of 1.9 in one second integration time. The fluorescence signal shows anti-bunching, proving that it comes from individual emitters. Coherence times up to 3 ms are measured, limited by the spin radiative lifetime. The method has the potential to be applied to arbitrary paramagnetic species with long enough non-radiative relaxation times, and allows single-spin detection in a volume as large as the resonator magnetic mode volume (approximately 10 μm3 in the present experiment), orders of magnitude larger than other single-spin detection techniques. As such, it may find applications in magnetic resonance and quantum computing.

Characterization of Cuban and Brazilian natural zeolites by photoacoustic spectroscopy and electron paramagnetic resonance.

This report describes the photoacoustic and electron paramagnetic resonance investigations of Brazilian and Cuban zeolites. Photoacoustic optical absorption measurements indicate the presence of iron (Fe3+) ions with their respective transition bands for both zeolites. Two species of manganese (Mn2+ and Mn3+) were identified in the Cuban sample and the electronic transitions assigned. Iron and manganese ions were confirmed through nonradiative relaxation (τ) and characteristic diffusion (τβ) times evaluation, whose values were found to be τBRA = 5.40 ms, τCUB = 4.60 ms, τβBRA = 387 μs and τβCUB = 305 μs. Crystal field (Dq-BRA/Dq-CUB = 1048 cm-1/945 cm-1) plus Racah (B-BRA/B-CUB = 457 cm-1/813 cm-1 and C-BRA/C-CUB = 3655 cm-1/2496 cm-1) parameters were assessed as well. Paramagnetic resonance corroborated Fe3+ ions present in the Brazilian zeolite occupying sites showing axial and/or rhombic symmetry distortions. For the Cuban sample, results reveal the characteristic hyperfine sextet lines of Mn2+ overlapping the Fe3+ line. Values of Landé factor and isotropic hyperfine splitting constant were found to be 2.0 and 9.7 mT, respectively. This tells us that the Mn2+ lies in octahedral symmetry probably replacing calcium ions and point towards an ionic bonding character of the Mn2+ and its surroundings.

Electron-phonon coupling in n -type Ge two-dimensional systems

Electron-optical phonon interaction is the dominant energy-loss mechanism in low-dimensional Ge/SiGe heterostructures and represents a key parameter for the design and realization of electronic and optoelectronic devices based on this material system compatible with the mainstream Si complementary metal-oxide semiconductor technology. Here we investigate the intersubband relaxation dynamics of $n$-type Ge/SiGe multiquantum wells with different symmetry and design by means of single-color pump-probe spectroscopy. By comparing the experimental differential transmittance data as a function of the pump-probe delay with numerical calculations based on an energy-balance rate-equation model, we could quantify an effective value for the optical phonon deformation potential describing the electron-phonon coupling in two-dimensional Ge-based systems. We found nonradiative relaxation times longer than 20 ps even in samples having intersubband energy separations larger than the optical phonon energy, evidencing the presence of a less effective electron-phonon coupling with respect to that estimated in bulk Ge.

Ultrafast photophysical and nonlinear optical properties of novel free base and axially substituted phosphorus (V) corroles

The progression in synthetic procedures over the last two decades gave admittance to a wide variety of corroles for suitable potential applications such as photovoltaics, photonics, and bio-imaging. In this communication, we present results from our investigations of ultrafast photophysical processes and third-order nonlinear optical properties of newly synthesized donor-acceptor based free-base [(C6F5)3] and phosphorus [P-(OH)2(C6F5)3] corroles. The global analysis of the femtosecond transient absorption data based on the compartmental model revealed the corresponding time constants of several photophysical processes such as (a) internal conversion (τIC) in the 260–280 fs range (b) vibrational relaxation (τVR) in the 2.5-5 ps range and (c) nonradiative relaxation times (τnr) in the 4.15–7.6 ns range and finally (d) triplet lifetimes in the range of 25–50 μs. The two-photon absorption (TPA) cross-section measurements were performed using the femtosecond, kHz pulse Z-Scan technique at 600 nm and 800 nm and the retrieved TPA cross-section values were in the range of ~102 GM. Degenerate four-wave mixing measurements illustrated a large third-order nonlinear optical susceptibility χ(3) with a magnitude of 6.9 × 10−14 esu and instantaneous (sub-picosecond) response, suggesting a pure electronic contribution to the nonlinearity of these corroles. The discoveries from this study may help further to extend the capability of corroles as NLO materials for photonic applications.

Blood optical absorption of rats with hepatic damage and turmeric treatment: Methemoglobin analysis

Photoacoustic spectroscopy (PAS) is singled out by its capability to resolve the optical absorption spectra of each element, of a multicomponent system, by the named phase resolved method. The possibility of the use of this method is due to the fact that the Photoacoustic signal is not only sensitive to the optical absorption of the sample as well as the non-radiative relaxation times of its elements. In the present study we compare and analyze, by phase resolved method, Fisher rat blood in four groups: healthy rat blood, liver cancer rat blood, healthy rat blood given by a daily dose of Curcuma longa, and liver cancer rat blood given by a daily dose of Curcuma longa (turmeric), where the optical absorption spectra of the analyzed blood samples was obtained by PAS, in a wavelength range from 350 nm to 650 nm. Three repetitions of 60 μl of blood for each group was done. By using the phase resolved method a new optical absorption band suggestive of methemoglobin was found, observing the benefits of the intake of turmeric due to the fact that the optical absorption spectrum of the Cancer + turmeric group diminish 14% with respect to the Cancer group, anticipating a lower concentration of methemoglobin in blood.

Random laser in Nd:YBO3 nanocrystalline powders presenting luminescence concentration quenching

Enhancement of the random laser (RL) performance in crystalline nanopowders of vaterite-type orthoborate NdxY1.000-xBO3 (0.015 ≤ x ≤ 0.040) was investigated by exciting the trivalent neodymium ions (Nd3+) at 806 nm in resonance with the ground state transitions 4I9/2→ {4F5/2, 2H9/2}. RL emission at 1056 nm, due to the Nd3+ transition 4F3/2 → 4I11/2, was observed and characterized. Although luminescence concentration quenching was detected for x > 0.007, an improvement of the RL performance was demonstrated for large Nd3+ concentrations. This feature was understood considering that the RL onset time is shorter than the nonradiative relaxation time of the 4F3/2 emitting state. The experimental results are supported by numerical simulations based on coupled rate-equations for the excited ions density and the number of photons participating in the random lasing process. The present results can motivate further RL studies with large concentration of trivalent rare-earth ions in glassy, ceramics, and crystalline matrices, which are normally avoided due to the concentration quenching.

Effect of magnetic coupling on non-radiative relaxation time of Fe3+ sites on LaAl1−x Fe x O3 pigments

Inorganic pigments of the system LaAl1–xFexO3 were prepared by the Pechini and the Solid State Reaction (SSR) methods. Magnetic interactions and non-radiative relaxation time were analyzed by means of phase-resolved photoacoustic spectroscopy and electron paramagnetic resonance (EPR) techniques. EPR results show a change in the magnetic behavior from paramagnetic (x = 0.2 and 0.4) to antiferromagnetic (x = 1.0), which is believed to be a result of the SSR preparation method. Trends in the optical absorption bands of the Fe3+ are attributed to their electronic transitions, and the increase in the band's intensity at 480 and 550 nm was assigned to the increase in the magnetic coupling between Fe–Fe. The phase-resolved method is capable of distinguishing between the two preparation methods, and it is possible to infer that SSR modifies the magnetic coupling of Fe–Fe with x.

Photoacoustic Determination of Non-radiative Relaxation Time of Absorbing Centers in Maize Seeds

Using non-destructive photothermal techniques, it is possible to characterize non-homogenous materials to obtain its optical and thermal properties through photoacoustic spectroscopy (PAS). In photoacoustic (PA) phenomena, there are transient states of thermal excitation, when samples absorb the incident light; these states manifest an excitation process that generates the PA signal, being in direct relation with the non-radiative relaxation times with the sample absorbent centers. The objective of this study was to determine the non-radiative relaxation times associated with different absorbent centers of corn seeds (Zea mays L.), by using PAS. A frequency scan was done at different wavelengths (350 nm, 470 nm and 650 nm) in order to obtain the non-radiative relaxation times with different types of maize seeds.

Temperature-dependent excitonic effects in the optical properties of single-layerMoS2

Temperature influences the performance of two-dimensional materials in optoelectronic devices. Indeed, the optical characterization of these materials is usually realized at room temperature. Nevertheless most {\it ab-initio} studies are yet performed without including any temperature effect. As a consequence, important features are thus overlooked, such as the relative intensity of the excitonic peaks and their broadening, directly related to the temperature and to the non-radiative exciton relaxation time. We present {\it ab-initio} calculations of the optical response of single-layer MoS$_2$, a prototype 2D material, as a function of temperature using density functional theory and many-body perturbation theory. We compute the electron-phonon interaction using the full spinorial wave functions, i.e., fully taking into account effects of spin-orbit interaction. We find that bound excitons ($A$ and $B$ peaks) and resonant excitons ($C$ peak) exhibit different behavior with temperature, displaying different non-radiative linewidths. We conclude that the inhomogeneous broadening of the absorption spectra is mainly due to electron-phonon scattering mechanisms. Our calculations explain the shortcomings of previous (zero-temperature) theoretical spectra and match well with the experimental spectra acquired at room temperature. Moreover, we disentangle the contributions of acoustic and optical phonon modes to the quasi-particles and exciton linewidths. Our model also allows to identify which phonon modes couple to each exciton state, useful for the interpretation of resonant Raman scattering experiments.

Thermal Effects of Laser Irradiation on Maize Seeds

Abstract It is important to know the temperature changes in seeds that have been irradiated with laser light because this could have substantial practical and theoretical importance. Thus, the thermal effects of low intensity laser irradiation on seeds was studied, showing variation of temperature produced by laser light applied during 60 s on two maize seed genotypes, ‘Toluqueño’ and ‘Cacahuazintle’: crystalline and floury, respectively, under two different conditions: natural colour and dyed black, evaluating the temperature changes by a thermal camera. The optical absorption spectra and the non-radiative relaxation time of the seeds were obtained using photoacoustic spectroscopy. The results indicate that it is possible to produce temperature changes, detected by an infrared camera, in crystalline and floury seeds when they are irradiated with a laser beam at a 650 nm wavelength and 27.4 mW power. The highest variation of temperature in the seeds was obtained for the black-dyed condition, these variations being 5.56 and 9.28°C for crystalline and floury seeds, respectively. Among the seeds, in the dyed condition, the floury seed had the lower non-radiative relaxation time, the higher optical absorption coefficient and a lower optical penetration length at the laser wavelength (650 nm).

Photoluminescence kinetics of multiperiod GaAs/AlGaAs structures with asymmetric barriers promising for making unipolar lasers

Photoluminescence kinetics in multiperiod GaAs/AlGaAs quantum-well structures with asymmetric barrier heights has been investigated. Owing to the barrier asymmetry, a time constant of nonradiative recombination between the laser subbands of 9 ps has been achieved, which is record long for unipolar lasers and exceeds the nonradiative relaxation time constant of the lower laser subband. This provides population inversion in the system. Efficient suppression of an unwanted cascade transition between the laser subbands via quasi-continuum states has been demonstrated.

Detection of sonoluminescence signals in a gel phantom in the presence of Protoporphyrin IX conjugated to gold nanoparticles

The particles in a liquid decrease the ultrasonic intensity threshold required for cavitation onset. In this study, a new nanoconjugate composed of Protoporphyrin IX and gold nanoparticles (Au–PpIX) was used as a nucleation site for cavitation. The nonradiative relaxation time of Protoporphyrin IX in the presence of gold nanoparticles is longer than the similar time without gold nanoparticles. The acoustic cavitation activity was investigated via recording of the integrated sonoluminescence signal in the wavelength range of 220–700nm in a gel phantom by a cooled charge coupled device (CCD) at different intensities of 1MHz ultrasound. In order to confirm these results, a chemical dosimetric method was utilized, too. The recorded sonoluminescence signal in the gel phantom containing Au–PpIX was higher than the other phantoms. These records have been confirmed by the chemical dosimetric data. Therefore, we anticipate that a new nanoconjugate composed of Protoporphyrin IX and gold nanoparticles can act as an efficient sonoluminescence agent and could be introduced as a novel sonosensitizer for sonodynamic therapy.

Evaluation of Sonochemiluminescence in a Phantom in the Presence of Protoporphyrin IX Conjugated to Nanoparticles

Introduction When a liquid is irradiated with high-intensity and low-frequency ultrasound, acoustic cavitation occurs and there are some methods to determine and quantify this phenomenon. The existing methods for performing these experiments include sonochemiluminescence (SCL) and chemical dosimetric methods. The particles in a liquid decrease the ultrasonic intensity threshold needed for cavitation onset. In this study, a new nanoconjugate made up of Protoporphyrin IX (PpIX) and gold nanoparticles (GNP), i.e., Au-PpIX was used to provide nucleation sites for cavitation. The nonradiative relaxation time of PpIX in the presence of GNPs is longer than the similar time for PpIX without GNPs. This effect can be used in medical diagnostic and therapeutic applications. Materials and Methods The acoustic cavitation activity was investigated studying integrated SCL signal in the wavelength range of 400-500 nm in polyacrylamide gel phantom containing luminol using a cooled CCD spectrometer at different intensities of 1 MHz ultrasound. In order to confirm these results, a chemical dosimetric method was utilized, too. Results SCL signal level in gel phantom containing Au-PpIX was higher than the other phantoms. These results have been confirmed by the chemical dosimetric data. Conclusion This finding can be related to the existence of PpIX as a sensitizer and GNPs as cavitation nuclei. In other words, nanoparticles have acted as the sites for cavitation and have increased the cavitation rate. Another theory is that activation of PpIX has produced more free radicals and has enhanced the SCL signal level.

Sonodynamic Therapy Using Protoporphyrin IX Conjugated to Gold Nanoparticles: An In Vivo Study on a Colon Tumor Model.

Sonodynamic therapy is a physical treatment which utilizes ultrasound waves with an appropriate sensitizer such as protoporphyrin IX (PpIX). The activation of sensitizer depends on cavitation, and therefore, high intensity ultrasound is an important necessity. Beside, high intensity ultrasound can induce side effects on the healthy tissues which have surrounded tumor. The particles in a liquid decrease the ultrasonic intensity threshold needed for onset of cavitation. The non-radiative relaxation time of PpIX in the presence of gold nanoparticles (GNP) is longer than the similar time without GNP. This study was conducted on colon carcinoma tumor in BALB/c mice. The tumors were induced by subcutaneous injection of CT26 cells. Ultrasound irradiation were performed on tumors 24 hr after the injection of PpIX into GNPs. Antitumor effects were estimated by measuring tumor relative volume, doubling time and time being five times of the tumors and by calculating the average survival time of tumor-bearing mice after treatment. There is no inhibitory effect in control group. Ultrasound irradiation alone showed a slight antitumor effect which was enhanced by ultrasound plus PpIX (SDT). The synergistic inhibitory effect was significant when ultrasound plus PpIX was conjugated to GNPs. Our experiments suggested a significant synergistic effect of ultrasound combined with Au-PpIX that reduced tumor relative volume and increased average animal survival fraction. This effect was obviously stronger than ultrasound alone and synergistic effect of ultrasound combined with PpIX.

Long intersubband relaxation times in n-type germanium quantum wells

We measured the non-radiative intersubband relaxation time in n-type modulation-doped Ge/SiGe multi-quantum wells of different thickness by means of degenerate pump-probe experiments. The photon energy was tuned to be resonant with the lowest conduction band intersubband transition energy (14-29 meV), as measured by terahertz absorption spectroscopy and in agreement with band structure calculations. Temperature-independent lifetimes in excess of 30 ps were observed.

A Novel Nanosonosensitizer for Sonodynamic Therapy

The particles in a liquid decrease the ultrasonic intensity threshold needed for cavitation onset. In this study, a new nanoconjugate composed of protoporphyrin IX and gold nanoparticles was used as a nucleation site for cavitation. The nonradiative relaxation time of protoporphyrin IX in the presence of gold nanoparticles is longer than the similar time without gold nanoparticles. This study was conducted on colon carcinoma tumors in BALB/c mice. The tumor-bearing mice were randomly divided into 6 groups (each containing 15 mice): (1) control, (2) protoporphyrin IX, (3) gold nanoparticle-protoporphyrin IX conjugate, (4) ultrasound alone, (5) ultrasound + protoporphyrin IX, and (6) ultrasound + gold nanoparticle-protoporphyrin IX conjugate. In the respective groups as indicated above, protoporphyrin IX or the gold nanoparticle-protoporphyrin IX conjugate was injected into the tumors. Ultrasound irradiation was performed on the tumors 24 hours after injection. Antitumor effects were estimated by evaluation of the relative tumor volume, doubling time, and 5-folding time for the tumors after treatment. The cumulative survival fraction of the mice and percentage of the lost tissue volume (treated) were also assessed in the different groups. A significant difference in the average relative volumes of the tumors 13 days after treatment was found between the ultrasound + gold nanoparticle-protoporphyrin IX group and the other groups (P < .05). The longest doubling and 5-folding times were observed in the ultrasound + gold nanoparticle-protoporphyrin IX and ultrasound + protoporphyrin IX groups. Protoporphyrin IX conjugated to gold nanoparticles has been introduced as a promising compound and a new sonosensitizer for improving the tumor response to sonodynamic therapy by reducing the relative tumor volume and increasing the cumulative survival fraction.

Measuring non-radiative relaxation time of fluorophores with biomedical applications by intensity-modulated laser-induced photoacoustic effect

Modulated tone-burst light was employed to measure non-radiative relaxation time of fluorophores with biomedical importance through photoacoustic effect. Non-radiative relaxation time was estimated through the frequency dependence of photoacoustic signal amplitude. Experiments were performed on solutions of new indocyanine green (IR-820), which is a near infrared dye and has biomedical applications, in two different solvents (water and dimethyl sulfoxide (DMSO)). A 1.5 times slower non-radiative relaxation for the solution of dye in DMSO was observed comparing with the aqueous solution. This result agrees well with general finding that non-radiative relaxation of molecules in triplet state depends on viscosity of solvents in which they are dissolved. Measurements of the non-radiative relaxation time can be used as a new source of contrast mechanism in photoacoustic imaging technique. The proposed method has potential applications such as imaging tissue oxygenation and mapping of other chemophysical differences in microenvironment of exogenous biomarkers.

Assessment of nonradiative relaxation time and characteristic diffusion time of neodymium, erbium and cobalt doped low silica calcium aluminosilicate glasses

Nonradiative relaxation time ( τ) and characteristic diffusion time ( τ β ) of Nd, Er and Co doped low silica calcium aluminosilicate (LSCA) glasses were assessed by means of photoacoustic spectroscopy. The results are interpreted in terms of frequency dependence predicted by the theory of Rosencwaig and Gersho. Whereas τ varied between 7.2 ms and 36 ms, the values of τ β lied between 0.25 ms and 0.7 ms. For the neodymium doped LSCA glass, a decrease in τ β was observed as the ion concentration was increased. The results indicates that rare earth ion acts as network modifier, disrupting the glass lattice.

Investigation of doped calcium aluminosilicate glass: A coupling between thermal-expansion and thermal-diffusion models for assessment of nonradiative relaxation time and characteristic diffusion time

This paper discusses the use of photoacoustic models to obtain the nonradiative relaxation time (τ) and characteristic diffusion time (τβ) for a sample showing visible absorption bands from fluorescent ion-doped low-silica calcium aluminosilicate glass. Two models allowing phase shift analyses, the thermal-expansion and thermal-diffusion models, are briefly reviewed. These models have limitations when the photoacoustic signal depends on both factors, in a coupling mechanism. An alternative model is proposed to take both thermal expansion and thermal diffusion into account with a single temperature solution for the heat-coupled differential equation. This model is simulated for absorbing samples near the thermally thick region. The model is applied to Eu–V codoped glass showing intermediate signal dependence from ω−1.0 to ω−3/2. The nonradiative time and characteristic diffusion time are derived with 33&amp;lt;τ(ms)&amp;lt;39, and τβ(ms)∼70 ms for the Eu-ion and 340&amp;lt;τβ(ms)&amp;lt;710 for the V-ion. Four absorption bands were analyzed (280, 350, 420, and 600 nm), which showed a signal dependence from ω−1.1 to ω−1.52. Absorption coefficients were derived from τβ in the range of 15&amp;lt;β(cm−1)&amp;lt;51, which agreed fairly well with spectrophotometer data for the same ions.

Monitoring the non-radiative relaxation time of PpIX solution with Au nanoparticles using Photoacoustic Spectroscopy

In this work we have used the Photoacoustic Spectroscopy (PAS) to determine in vitro the non-radiative relaxation time (NRRT) of a protoporphyrin IX (PpIX) standard solution and samples of PpIX(1), PpIX(2) and PpIX(3) with Au nanoparticle concentrations of 0.001008, 0.00504 and 0.01008 mmol in 25 mL of water respectively. We have used PpIX disodium salt (DS) solution of 25% HCl. The results show that the NRRT average values, obtained for each one of the solution were: τ = 29 ± 0.001, 84 ± 0.001 and 62 ± 0.009 ms for PpIX(1), PpIX(2) and PpIX(3), respectively. These values were compared with some NRRT of triplet states reported in the literature for molecules with tetrapyrrolic structure, increasing the NRRT considerably. From each solution it was obtained its PAS signal phase as a function of the light modulation frequency from 17 to 80 Hz. UV–vis spectrophotometer, photoluminescence spectroscopy and Transmission Electron Microscopy (TEM) were used in order to obtain the optical absorption spectra, the photoluminescence intensities, and the gold nanoparticle sizes respectively. Our investigations are devoted to improve the thermal treatments of drugs the porphyrins as photosensitizers used in image photodynamic therapy.