<p> Lithium niobate has interesting characteristics such as the electro-optic effect, the acousto-optic effect, piezoelectricity and large nonlinear optical coefficients. Potential applications in MEMS field could be explored if microstructures are fabricated in lithium niobate substrates,. This thesis presents the fabrication and characterization of a lithium niobate MEMS device. As lithium niobate crystal is difficult to process using standard semiconductor techniques including both wet etching and dry etching, new methods are required to process lithium niobate. In our project, picosecond laser pulses were chosen to produce bridges on lithium niobate. Fabrication of grooves with high aspect ratio were attempted and grooves with clean morphology were obtained when laser pulses with low cutting speed, medium pulse energy, and large number of passes were employed. This shows picosecond laser machining is a viable method to process lithium niobate.</p> <p> Waveguides in Z cut lithium niobate crystal were fabricated using Ti-indiffusion techniques. After the fabrication of waveguides in lithium niobate, a SiO2 film with a thickness of 0.3μm was deposited as a buffer layer. Ti-Pt-Au electrodes for actuation function were then deposited through lift-off technique. Finally a bridge structure (80um in width and 600um in length) with a waveguide embedded in it was fabricated with picosecond laser. The insertion loss before and after laser machining was 6.99dB and 5.01dB respectively.</p> <p> Optical and electrical tests were performed in an effort to determine the resonance frequency of bridge. In the optical test, many bulk piezoelectric resonance peaks were presented in the frequency spectrum. After damping the vibration of substrate, these spikes disappeared and only a background noise with small spikes were obtained. As those small spikes are not reproducible, the optical test is not a viable method to determine resonance frequency of the bridge structure in our device. The electrical test was then carried out in a vacuum environment in order to find the resonance frequency. The spectrum presents a spike with large amplitude. However, the phase and amplitude of the spike remained the same when the vacuum condition was removed, which indicates the spike is not related to the resonance of the bridge. In summary, the resonance frequency of bridge structure could not be determined by these two approaches.</p> <p> Future work could involve directly investigating the material properties surrounding the machining region to see whether the piezoelectricity of the material has been damaged from laser ablation process. New laser machining process of lithium niobate may also need to be studied to avoid this damage to the substrate structure. Even though our device could not be driven to vibrate at its resonance frequency, it is worth making microstructures in lithium niobate substrates. The combination of optical, mechanical and electrical elements will make lithium niobate a great potential material for optical MEMS applications.</p> / Thesis / Master of Applied Science (MASc)

We demonstrate four experimentally simple methods for measuring very complex ultrashort light pulses. Although each method is comprised of only a few optical elements, they permit the measurement of extremely complex pulses with time-bandwidth products greater than 65,000. First, we demonstrate an extremely simple frequency-resolved-optical gating (GRENOUILLE) device for measuring the intensity and phase of pulses up to ~20ps in length. In order to achieve the required high spectral resolution and large temporal range, it uses a few-cm-thick second harmonic-generation crystal in the shape of a pentagon. This has the additional advantage of reducing the device's total number of components to three. Secondly, we introduce a variation of spectral interferometry (SI) using a virtually imaged phased array and grating spectrometer for measuring long complex ultrashort pulses up to 80 ps in length. Next, we introduce a SI technique for measuring the complete intensity and phase of relatively long and very complex ultrashort pulses. It involves making multiple measurements using SI (in its SEA TADPOLE variation) at numerous delays, measuring many temporal pulselets within the pulse, and concatenating the resulting pulselets. Its spectral resolution is the inverse delay range--many times higher than that of the spectrometer used. The waveforms were measured with ~ fs temporal resolution over a temporal range of ~ns and had time-bandwidth products exceeding 65,000, which to our knowledge is the largest time-bandwidth product ever measured with ~fs temporal resolution. Finally, we demonstrate a single-shot measurement technique that temporally interleaves hundreds of measurements with ~fs temporal resolution. It is another variation of SI for measuring the complete intensity and phase of relatively long and complex ultrashort pulses in a single shot. It uses a grating to introduce a transverse time delay into a reference pulse which gates the unknown pulse by interfering it at the image plane of an imaging spectrometer. It provided ~125 fs temporal resolution and a temporal range of 70 ps using a low-resolution spectrometer.

Le caractère entièrement sans contact de la technique d'Ultrasons-Laser en fait un outil de premier choix pour étudier la propagation des ondes acoustiques dans diverses géométries. Les problèmes rencontrés lors du couplage de transducteurs piézoélectriques sur une surface courbe sont ainsi évités et l'étude de structures cylindriques de diverses tailles, notamment à l'échelle du micron, peut être envisagée. Le développement de l'acoustique picoseconde dans les années 80 a permis, en effet, de générer des ultrasons de très haute fréquences (>GHz) présentant des longueurs d'onde de l'ordre de quelques nanomètres. Il devient alors possible de sonder des couches minces de tailles microniques à sub-microniques. Une extension de ces travaux au cas de fibres de diamètres micrométriques est ici proposée. Le mécanisme de génération acoustique par laser nécessite quel'échantillon soit optiquement absorbant. Plusieurs régimes de génération sont abordés suivant la fluence laser et la longueur de pénétration optique. Des modèles semi-analytiques de la génération acoustique dans des structures cylindriques optiquement absorbantes sont ainsi proposés. Une première approche, s'intéresse à la modélisation de la propagation dans un multi-couche cylindrique pour lequel la source acoustique est distribuée selon un profil d'intensité imposée par l'absorption de l'impulsion optique. Une seconde approche consiste à rechercher la fonction de Green d'une source enfouie. Une convolution par la distribution de source permet ensuite de calculer la réponse du cylindre. Une validation expérimentale est menée sur un barreau de verre de 5 mm de diamètre à l'aide d'un laser Nd:Yag délivrant des impulsions de 5ns. Une confrontation expérience/théorie est enfin proposée pour une fibre de tungstène de 5 microns de diamètre étudiée par un dispositif d'acoustique picoseconde. Enfin, des expériences similaires ont été réalisées sur des fibres de carbone d'un diamètre de 5 et 10 microns et ont permis d'évaluer localement leur indice optique complexe ainsi que leur élasticité transverse. / Having emerged in the 80s, the laser ultrasonics technique with its non-contact generation and detection process overpasses the difficulties of coupling piezoelectric transducers with curved surfaces. With the picosecond ultrasonics technique it is now possible to generate acoustic waves with very high frequency (>GHz) and very short wavelengths of few nanometers giving access to micrometric and sub-micrometric samples probing. To date, the acoustic generation for cylinders opaque at a given laser wavelength where the acoustic source is located at the cylinder surface was investigated. In this PhD thesis, an extension of this work is proposed in the case of micro-fibers where taking into account the optical penetration depth becomes essential. Semi-analytical models for acoustic waves generation and propagation in a optically absorptive cylinder are derived. In a first way, we adapt modelling techniques used to calculate the response of elastically heterogeneous materials to the case of an homogeneous material with a radially distributed source imposed by the optical absorption. In a second model, the radial displacement for an inner point source is derived, in a 2D Fourier domain. The response to a volume-source distribution along a radius is obtained as a convolution of the above Green function with the corresponding source distribution caused by optical absorption. Two inverse transforms are then applied. Picosecond ultrasonics experiments are performed for different micrometric fibers and compared with calculated waveforms for different optical absorptive properties. Experiments made on carbon micro-fibers have permitted to locally evaluate the transverse elasticity of the fibers as well as their complex optical index.

Arterial diseases such as hypertension, carotid stenosis, and abdominal aortic aneurysm (AAA) may progress silently without symptoms and contribute to acute cardiovascular events such as heart attack, stroke, and aneurysm rupture, which are consistently among the leading causes of death worldwide. The arterial pulse wave, regarded as one of the fundamental vital signs of clinical medicine, originates from the heart and propagates throughout the arterial tree as a pressure, flow velocity, and wall displacement wave, giving rise to the natural pulsation of the arteries. The dynamic properties of the pulse wave are intimately related to the physical state of the cardiovascular system. Thus, the assessment of the arterial wall dynamics driven by the pulse wave may provide valuable insights into vascular mechanical properties for the early detection and characterization of arterial pathologies. The focus of this dissertation was to develop and clinically implement Pulse Wave Imaging (PWI), an ultrasound elasticity imaging-based method for the visualization and spatio-temporal mapping of the pulse wave propagation at any accessible arterial location. Motion estimation algorithms based on cross-correlation of the ultrasound radio-frequency (RF) signals were used to track the arterial walls and capture the pulse wave-induced displacements over the cardiac cycle. PWI facilitates the image-guided measurement of clinically relevant pulse wave features such as propagation speed (pulse wave velocity, or PWV), uniformity, and morphology as well as derivation of the pulse pressure waveform. A parametric study investigating the performance of PWI in two canine aortas ex vivo and 10 normal, healthy human arteries in vivo established the optimal image acquisition and signal processing parameters for reliable measurement of the PWV and wave propagation uniformity. Using this framework, three separate clinical feasibility studies were conducted in patients diagnosed with hypertension, AAA, and carotid stenosis. In a pilot study comparing hypertensive and aneurysmal abdominal aortas with normal controls, the AAA group exhibited significantly higher PWV and lower wave propagation uniformity. A “teetering” motion upon pulse wave arrival was detected in the smaller aneurysms (< 5 cm in diameter) but not in the larger aneurysms (> 5.5 cm in diameter). While no significant difference in PWV or propagation uniformity was observed between normal and hypertensive aortas, qualitative differences in the pulse wave morphology along the imaged aortic segment may be an indicator of increased wave reflection caused by elevated blood pressure and/or arterial stiffness. Pulse Wave Ultrasound Manometry (PWUM) was introduced as an extension of the PWI method for the derivation of the pulse pressure (PP) waveform in large central arteries. A feasibility study in 5 normotensive, 9 pre-hypertensive, and 5 hypertensive subjects indicated that a significantly higher PP in the hypertensive group was detected in the abdominal aorta by PWUM but not in the peripheral arteries by alternative devices (i.e. a radial applanation tonometer and the brachial sphygmomanometer cuff). A relatively strong positive correlation between aortic PP and both radial and brachial PP was observed in the hypertensive group but not in the normal and pre-hypertensive groups, confirming the notion that PP variation throughout the arterial tree may not be uniform in relatively compliant arteries. The application of PWI in 10 stenotic carotid arteries identified phenomenon such as wave convergence, elevated PWV, and decreased cumulative displacement around and/or within regions of atherosclerotic plaque. Intra-plaque mapping of the PWV and cumulative strain demonstrated the potential to quantitatively differentiate stable (i.e. calcified) and vulnerable (i.e. lipid) plaque components. The lack of correlation between quantitative measurements (PWV, modulus, displacement, and strain) and expected plaque stiffness illuminates to need to consider several physiological and imaging-related factors such as turbulent flow, wave reflection, imaging location, and the applicability of established theoretical models in vivo. PWI presents a highly translational method for visualization of the arterial pulse wave and the image-guided measurement of several clinically relevant pulse wave features. The aforementioned findings collectively demonstrated the potential of PWI to detect, diagnose, and characterize vascular disease based on qualitative and quantitative information about arterial wall dynamics under pathological conditions.

Further improvements to device performance are necessary to make solar energy conversion a compelling alternative to fossil fuels. Singlet exciton fission and charge separation are two processes that can heavily influence the power conversion efficiency of a solar cell. During exciton fission one singlet excitation converts into two triplet excitons, potentially doubling the photocurrent generated by higher energy photons. There is significant discord over the singlet fission mechanism and of particular interest is whether the process involves a multiexciton intermediate state. I used time-resolved two-photon photoemission to investigate singlet fission in hexacene thin films, a model system with strong electronic coupling. My results indicate that a multiexciton state forms within 40 fs of photoexcitation and loses singlet character on a 280 fs timescale, creating two triplet excitons. This is concordant with the transient absorption spectra of hexacene single crystals and definitively proves that exciton fission in hexacene proceeds through a multiexciton state. This state is likely common to all strongly-coupled systems and my results suggest that a reassessment of the generally-accepted singlet fission mechanism is required. Charge separation is the process of splitting neutral excitons into carriers that occurs at donor-acceptor heterojunctions in organic solar cells. Although this process is essential for device functionality, there are few compelling explanations for why it is highly efficient in certain organic photovoltaic systems. To investigate the charge separation process, I used the model system of charge transfer excitons at hexacene surfaces and time-resolved two-photon photoemission. Charge transfer excitons with sufficient energy spontaneously delocalize, growing from about 14 nm to over 50 nm within 200 fs. Entropy drives this delocalization, as the density of states within the Coulomb potential increases significantly with energy. This charge separation mechanism should occur at all donor-acceptor interfaces. My results show that entropy facilitates charge separation and indicate that the density of acceptor states should be a design consideration when constructing organic solar cells.

Four main aspects are studied and explored throughout this dissertation: (1) On-Package Multipolar antenna system design for integration with commercial wireless sensor nodes for machine-to-machine communication applications; (2) Development of a novel MMIC packaging process and subsequent antenna integration for chip-to-chip communication applications, (3) Design and characterization of additively manufactured lumped passive elements for integration with MMIC and hybrid circuits, (4) Design and characterization of antennas for on- and off-metal radio frequency identification (RFID) applications. This work presents the design of different 3-D printed tripolar antenna systems operating at 2.4 GHz. The antennas are designed for integration with commercial wireless nodes with the purpose of mitigating multipath and depolarization channel effects that might be present in many machine-to-machine (M2M) deployments. The antennas are fabricated utilizing an additive manufacturing (AM) approach that combines fused deposition modeling (FDM) of ABS plastic for dielectric parts and micro-dispensing of silver paste Du-Pont CB028 for conductive layers as the majority of the devices presented in this work. Over the air testing demonstrates a 1% channel improvement of up to 14 dB, achieved in a highly-reflective, Rayleigh-like fading environment by implementing selection diversity between three mutually orthogonal monopoles. This improvement leads to better bit error rate (BER) performance (as is also shown). Additionally, RSSI measurements show significant improvement when the prototype antenna system is integrated with commercial wireless sensor hardware. Implications of tripolar antenna integration on M2M systems include reduction in energy use, longer communication link distances, and/or greater link reliability. In order to incorporate the proposed multipolar selection diversity technique into short range wireless chip-to-chip communications, a novel and versatile 3D printed on-chip integration approach using laser machining is subsequently demonstrated for microwave and mm-wave systems in a process herein referred to as Laser Enhanced or Laser Assisted Direct Print Additive Manufacturing (LE-DPAM). The integration process extends interconnects laterally from a MMIC to a chip carrier. Picosecond laser machining is applied and characterized to enhance the 3D printing quality. Specifically, the width of micro-dispensed printed traces is accurately controlled within micrometer range (e.g. laser cuts ~12 μm wide), additionally, 150 μm probe pads are cut in order to facilitate RF measurement. The S-parameters of a distributed amplifier integrated into the package are simulated and measured from 2 to 30 GHz. It is seen how the overall performance is significantly better than a traditional wirebonded QFN package and previously reported AM MMIC interconnections. The attenuation of the microstrip line including interconnects is only 0.2 dB/mm at 20 GHz and return loss with the package is less than 10 dB throughout the operating frequency band A 17 GHz package integrated linearly polarized patch antenna, fabricated with a multi-layer and multi-material LE-DPAM process is then introduced for vertical interconnection with a MMIC die. Performance is successfully measured and characterized achieving a return loss greater than 19 dB at the desired design frequency. Good agreement between simulated and measured radiation patterns is also obtained with a peak gain of 4.2 dBi. Another section of this work utilizes LE-DPAM to fabricate lumped capacitors and inductors for coplanar waveguide (CPW) circuits, especially useful for filtering and matching network implementation. Laser machining is used to achieve ~12 µm slots on printed conductors, producing aspect ratios greater than 2:1, as well as to fabricate vertical interconnects or vias that allow for the fabrication of the multilayer inductors. Inductances in the range of 0.4-3 nH are achieved, with a maximum quality factor of 21, self-resonance frequencies up to 88 GHz, and an inductance per unit of area of 5.3 nH/mm2. Interdigital capacitors in the range of 0.05-0.5 pF are fabricated, having a maximum quality factor of 750 and self-resonances up to 120 GHz. All the components are made on the center line of a CPW that is 836 µm wide. The results show that LE-DPAM enables the fabrication of compact passive circuits that can be easily interconnected with MMIC dies, which at the same time, can be manufactured as part of a larger component. This enables the fabrication of structural electronics that are functional into the mm-wave frequency range. A final aspect of this work goes through antenna designs for specific RFID (radio frequency identification) applications. RFID tag design is generally focused specifically on either off-metal or on-metal configurations. In this work passive 2D and 3D RFID tags are presented which perform similarly in both configurations. The presented tags operate in the ISM RFID UHF bands that cover 864-868 MHz and 902-928 MHz. A matching loop consisting of two parallel stubs to ground is used for impedance matching to a passive integrated circuit, which has -18 dBm sensitivity. A planar 2D tag with a footprint of 13126.5 mm2 is first introduced, showing a simulated gain of approximately 3 dBi and a measured read range of 10 m (for 31 dBm transmit power from the reader) in both on-metal and off-metal conditions. The tag is miniaturized into a 3D geometry with a footprint of 2524.25 mm2 (520% reduction) and achieves the same broadside simulated on-metal gain. The antennas are fabricated using a DPAM process, and a meshed ground configuration is explored in order to accomplish a 50% conductive paste reduction without disrupting the performance. The proposed tags are compared with commercially available tags as well as previously published tags in terms of read range and size. The tags in this work present an improvement in terms of read range, gain, and area with respect to previous designs covering the ISM RFID UHF bands. Moreover, the performance of these tags is maintained in on- and off-metal conditions, achieving comparable performance and a reduction in volume of 11482% with respect to the best tag reported.

L’adhésion et les propriétés mécaniques des cellules jouent un rôle crucial dans le fonctionnementcellulaire ainsi que dans l’apparition de maladies dégénératives. Pour mesurer ces quantités, nousavons développé dans ce travail un microscope opto-acoustique pour l’imagerie non-invasive de lamécanique de cellules individuelles avec une résolution sub-cellulaire. Ce microscope utilise latechnique d’acoustique picoseconde qui permet de générer et détecter optiquement des ondesacoustiques avec une large bande s’étendant jusqu’à 1 THz. Dans le but de reproduire lecomportement mécanique des cellules à des fréquences acoustiques supérieures à 10 GHz, uneétude sur des objets mous biomimétiques est menée dans une première partie. Les rigidité, viscositéet épaisseur de ces systèmes multicouches micrométriques sont caractérisées. Dans la deuxièmepartie de ce manuscrit, la technique d’acoustique picoseconde est employée pour imager le contactentre une cellule animale modèle et un biomatériau, ainsi que l’impédance acoustique de cette cellule.Un outil d’analyse nécessaire pour le traitement du signal acoustique est mis en place. Enfin, unmicroscope opto-acoustique opérationnel entre 10 et 100 GHz est présenté dans la dernière partie. Ilest basé sur un dispositif pompe-sonde asynchrone qui permet de produire des images acoustiquesen un temps court (4 pixels/min) avec une résolution axiale de l’ordre d’une dizaine de nm. Cetteapproche est comparable à une échographie mais à l’échelle cellulaire. L’étude de l’adhésion et despropriétés mécaniques de plusieurs types de cellules à différents stades de maturation est abordée.Des images topographiques des zones fines (< 50 nm) d’une cellule sont également analysées. Lemicroscope développé durant cette thèse offrira la possibilité d’explorer de nouvelles pistes derecherche dans les domaines de la biologie cellulaire et des biotechnologies. / Adhesion and mechanical properties of cells are key players in several cellular functions and areinvolved in the development of degenerative diseases. To characterize these quantities, we developedin this work an opto-acoustic microscope for the non-invasive imaging of the mechanics of individualcells with a sub-cell resolution. This microscope uses the Picosecond Ultrasonics (PU) technique thatallows optical generation and detection of acoustic waves with a large bandwidth up to 1 THz. In orderto reproduce the mechanical behaviour of cells at acoustic frequencies greater than 10 GHz, a studyof cell-mimicking micro-objects is first considered. The rigidity, viscosity and thickness of these microlayeredstructures are characterized. In the second part of this manuscript, the PU technique isapplied for imaging the contact between a simple animal cell and a biomaterial, as well as the acousticimpedance of this cell. An essential tool for analysing the acoustic signal is developed. In the thirdpart, the opto-acoustic microscope operating between 10 and 100 GHz is finally presented. It is basedon an asynchronous pump-probe setup that allows producing acoustic images within a short time (4pixels/min) and offering an axial resolution of about 10 nm. This is similar to cell ultrasonography. Thestudy of the adhesion and of the mechanical properties of different cell types at different stages of cellmaturation is then tackled. The topographic images of thin cell regions (< 50 nm) are also analysed.The microscope implemented during this thesis should offer the possibility of exploring new avenuesin the field of cellular biology.

L’acoustique picoseconde est un outil adapte a la mesure des proprietes mecaniques des films minces. la generation et la detection de phonons acoustiques de frequences voisines du thz sont effectuees a l'aide d'impulsions laser ultracourtes delivrees par des lasers femtosecondes. a cause de l’isotropie des transducteurs, les ondes acoustiques transverses ne peuvent etre thermo-elastiquement excitees que par conversion de mode d’ondes acoustiques longitudinales. ce travail propose comme alternative l’utilisation d’un reseau optique comme source d’excitation laser inhomogene pour generer et detecter des phonons plans transverses dans des materiaux isotropes. une etude theorique a montre que l'application d’un reseau optique transitoire a l’interface entre des materiaux isotropes induit l’excitation de reseaux acoustiques transverses par conversion de mode d’ondes acoustiques longitudinales en incidence oblique par rapport a l’interface. ces ondes sont inhomogenes car elles ont leur amplitude harmoniquement modulee selon l’interface. nous avons montre que la detection selective et heterodyne de ces ondes de cisaillement n’est possible que dans la configuration ou un reseau pompe 1d et sonde 2d sont associes. cela permet la depolarisation a travers l’interaction acousto-optique, de la sonde incidente par le reseau acoustique transverse. cela a ete realise en mettant le reseau sonde dans le plan perpendiculaire a celui de la pompe. de plus, l’adaptation et la mise en œuvre de methodes optiques de haute sensibilite, en particulier la polarimetrie et l’ellipsometrie nous ont permis d’evaluer et d’optimiser la sensibilite de la detection de ces ondes acoustiques transverses. / The picosecond acoustic technique which allows studies at picosecond characteristic time scale and nanometer space scale is a powerful tool for the diagnostic of elastic properties of sub-micrometer films. high frequency acoustic phonons (up to 1 thz) are generated and detected by the use of ultra-short femtosecond laser pulses. due to isotropy of most of opto-acoustic transducers, shear acoustic waves can be thermo-elastically excited only by mode conversion of longitudinal acoustic waves.this work suggests using optical gratings as inhomogeneous excitation laser source for the generation of shear acoustic phonons in isotropic media. the processes leading to excitation of inhomogeneous plane bulk compression/dilatation and shear acoustic modes following the creation of a transient laser interference pattern at an interface between an opaque and a transparent elastically isotropic media are analyzed. the developed theory predicts the excitation of shear acoustic grating by mode conversion of longitudinal waves obliquely incident to the interface. it is shown that only the association of 1d pump grating and 2d probe grating can allow selective and heterodyne detection of the excited shear acoustic gratings. in this configuration the incident probe is depolarized through the photo-elastic interaction by the shear acoustic gratings. this is experimentally realized by positioning the 2d probe grating perpendicularly to 1d pump grating plane. furthermore, the implementation and adaptation of high sensitive optical methods, particularly polarimetry and ellipsometry has permitted us to evaluate and to optimize the sensitivity of shear acoustic waves detection.

Abstract This thesis describes the development of a high precision time-to-digital converter (TDC) in which the conversion is based on a counter and three-stage stabilised delay line interpolation developed in this work. The biggest design challenges in the design of a TDC are related to the fact that the arrival moment of the hit signals (start and stop) is unknown and asynchronous with respect to the reference clock edges. Yet, the time interval measurement system must provide an immediate and unambiguous measurement result over the full dynamic range. It must be made sure that the readings from the counter and the interpolators are always consistent with very high probability. Therefore, the operation of the counter is controlled with a synchronising logic that is in turn controlled with the interpolation result. Another synchronising logic makes it possible to synchronise the timing signals with multiphase time-interleaved clock signals as if the synchronising was done with a GHz-level clock, and enables multi-stage interpolation. Multi-stage interpolation reduces the number of delay cells and registers needed. The delay line interpolators are stabilised with nested delay-locked loops, which leads to good stability and makes it possible to improve single-shot precision with a single look-up table containing the integral nonlinearities of the interpolators measured at the room temperature. A multi-channel prototype TDC was fabricated in a 0.6 μm digital CMOS process. The prototype reaches state-of-the-art rms single-shot precision of better than 20 ps and low power consumption of 50 mW as an integrated TDC.

Des mesures de radiolyse impulsionnelle avec des paquets d’électron de 7 picosecondes ont été effectuées dans des systèmes D₂O et D₂SO₄ / D₂O purs afin d'étudier l'effet isotopique sur la réactivité de l'électron solvaté (es⁻), du radical hydroxyle (OH•) et de son radical cation cationique (H₂O•⁺). Dans le système D₂O, le spectre d'absorption molaire de l’électron solvaté dans D₂O a été déterminé entre 250 et 1500 nm en utilisant la méthode du point isosbestique. Sur la base de ce coefficient d'extinction, le rendement radiolytique de es⁻ dans D₂O juste après l'impulsion d'électrons de 7 ps a été déterminé à (4,4 ± 0,2) × 10⁻⁷ mol J⁻¹, ce qui coïncide avec celui dans H₂O. Le rendement du radical OD• juste après l'impulsion d'électrons s'est révélée être (5,0 ± 0,2) × 10⁻⁷ mol J⁻¹. Dans le cas de l’électron solvaté la vitesse de déclin dans D₂O est plus lent que dans H₂O, tandis que la vitesse de déclin de OD• est similaire à celui de OH•. Dans le système D₂SO₄ /D₂O, la réactivité de D₂O•⁺ a été sondée dans des solutions d'acide sulfurique deutérées de diverses concentrations et comparée à celle de H₂O•⁺. Le soluté oxydé, le radical sulfate a été observé à 7 ps et des rendements plus élevés ont été trouvés dans les solutions deutérées. Les effets isotopiques révèlent la compétition entre deux réactions ultra-rapides : le transfert de protons vers H₂O (D₂O) et le transfert d'électrons de H₂O•⁺ (D₂O•⁺). Les simulations par la théorie de la densité fonctionnelle décryptent le mécanisme du transfert d’électrons : elles se font par migration de charge sub-femtoseconde et ne sont pas affectées par la substitution isotopique. / Picosecond pulse radiolysis measurements were performed in neat D₂O and D₂SO₄/D₂O system in order to study the isotopic effect on the reactivity of the solvated electron(es⁻), the hydroxyl radical (OH•) and its precursor—water cation radical (H₂O•⁺). In D₂O system, the molar absorption coefficient spectra of spectrum in D₂O was determined between 250 to 1500 nm using the isosbestic point method. Based on this extinction coefficient, the radiolytic yield of es⁻ in D₂O just after the 7 ps electron pulse was determined to be (4.4 ± 0.2) × 10⁻⁷ mol J⁻¹, which coincides with the one for in H₂O. The yield of the radical OD• just after the 7 ps electron pulse was found to be (5.0 ± 0.2) × 10⁻⁷ mol J⁻¹. In the spurs of ionization, the decay rate of es⁻ is slower in D₂O than that in H₂O, whereas the decay rate of OD• is similar to the one of OH•. In D₂SO₄/D₂O system, the reactivity of and D₂O•⁺ was probed in deuterated sulfuric acid solutions of various concentrations and compared with that of H2O•⁺. The oxidized solute sulfate radical was observed at 7 ps and remarkably higher yields are found in deuterated solutions. The isotopic effects reveal the competition between two ultrafast reactions: proton transfer toward H₂O (D₂O) and electron transfer from H₂SO4⁻ to H₂O•⁺ (D₂O•⁺). Density functional theory simulations decipher the electron transfer mechanism: it proceeds via sub-femtosecond charge migration and is not affected by isotopic substitution.