Publications

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The understanding and control of charge carrier interactions with defects at buried insulator/semiconductor interfaces is essential for achieving optimum performance in modern electronics. Here, we report on the use of scanning ultrafast electron microscopy (SUEM) to remotely probe the dynamics of excited carriers at a Si surface buried below a thick thermal oxide. Our measurements illustrate a previously unidentified SUEM contrast mechanism, whereby optical modulation of the space-charge field in the semiconductor modulates the electric field in the thick oxide, thus affecting its secondary electron yield. By analyzing the SUEM contrast as a function of time and laser fluence we demonstrate the diffusion mediated capture of excited carriers by interfacial traps.

This LDRD supported efforts to significantly advance the scanning ultrafast electron microscope (SUEM) for spatial-temporal mapping of charge carrier dynamics in semiconductor materials and microelectronic devices. Sandia's SUEM capability in Livermore, CA, was built and demonstrated with previous LDRD funding; however, the stability and usability of the tool limited the throughput for analyzing samples. A new laser alignment strategy improved the stability of the SUEM, and the design and characterization of a new micro-channel plate (MCP)- based detector improved the signal-to-noise of the SUEM signal detection. These enhancements to the SUEM system improved throughput by over two orders of magnitude (before, a single time series of SUEM measurements would take several days to several weeks to acquire; now, the same measurements can be completed in~90 minutes in an automated fashion). The SUEM system can now be routinely used as an analytical instrument and will be a central part of several multi-year projects starting in FY22.

This project aimed to identify the performance-limiting mechanisms in mid- to far infrared (IR) sensors by probing photogenerated free carrier dynamics in model detector materials using scanning ultrafast electron microscopy (SUEM). SUEM is a recently developed method based on using ultrafast electron pulses in combination with optical excitations in a pump- probe configuration to examine charge dynamics with high spatial and temporal resolution and without the need for microfabrication. Five material systems were examined using SUEM in this project: polycrystalline lead zirconium titanate (a pyroelectric), polycrystalline vanadium dioxide (a bolometric material), GaAs (near IR), InAs (mid IR), and Si/SiO 2 system as a prototypical system for interface charge dynamics. The report provides detailed results for the Si/SiO 2 and the lead zirconium titanate systems.

In this LDRD project, we developed a versatile capability for high-resolution measurements of electron scattering processes in gas-phase molecules, such as ionization, dissociation, and electron attachment/detachment. This apparatus is designed to advance fundamental understanding of these processes and to inform predictions of plasmas associated with applications such as plasma-assisted combustion, neutron generation, re-entry vehicles, and arcing that are critical to national security. We use innovative coupling of electron-generation and electron-imaging techniques that leverages Sandia’s expertise in ion/electron imaging methods. Velocity map imaging provides a measure of the kinetic energies of electrons or ion products from electron scattering in an atomic or molecular beam. We designed, constructed, and tested the apparatus. Tests include dissociative electron attachment to O2 and SO2, as well as a new method for studying laser-initiated plasmas. This capability sets the stage for new studies in dynamics of electron scattering processes, including scattering from excited-state atoms and molecules.

The predictive understanding of catalytic surface reactions requires accurate microkinetic models, and while decades of work has been devoted to the elucidation of the reaction steps in these models, many open questions remain. One key issue is a lack of approaches enabling the local spatially resolved assessment of catalytic activity over a surface. In this report, we detail efforts to develop a new diagnostic approach to solve this problem. The approach is based upon laser resonance enhanced multiphoton ionization of reaction products emitted into the gas phase followed by spatially resolved imaging of the resultant ions or electrons. Ion imaging is pursued with a velocity-selected spatially resolved ion imaging microscope, while electron imaging was attempted in a low energy electron microscope. Successful demonstration of the ion imaging microscope coupled with the development of transport simulations shows promise for a revolutionary new tool to assess local catalytic activity

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The dissociation of aligned, electronically excited H2 (E,F (Formula presented.)), followed by the ionisation of the produced H atom, is analysed via the velocity mapped imaging technique. The dissociation and ionisation processes are accomplished, respectively, by a two- and a one-photon absorption from a single 532-nm laser pulse, while the alignment is induced by a separate 1064-nm laser pulse. The velocity of the produced H+ photofragments shows a weak perpendicular alignment at low alignment laser field values, evolving to strongly parallel for larger fields. We modelled this alignment behaviour with a simple two-state model involving the Stark mixing of the initially-prepared J = 0 with the J = 2 rotational state. This model is able to reproduce all of the observed angular distribution and permits us to extract from the fit the polarisability anisotropy of H2 (E,F) electronic state. We determine this value to be (3.7 ± 1.2) × 103 a.u. As this value is extremely large in comparison to what one would expect from the pure H2 (E,F) electronic state, we hypothesise that this value comes from the 1064-nm laser beam mixing nearby electronic states with the initially laser prepared (E,F) state generating a mixed state (EF**) with an extremely large polarisability anisotropy.

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Alignment of the electronically excited E,F state of the H2 molecule is studied using the velocity mapping imaging technique. Photofragment images of H+ due to the dissociation mechanism that follows the 2-photon excitation into the (E,F; ν = 0, J = 0) electronic state show a strong dependence on laser intensity, which is attributed to the high polarizability anisotropy of the H2 (E,F) state. We observe a marked structure in the angular distribution, which we explain as the interference between the prepared J = 0 and Stark-mixed J = 2 rovibrational states of H2, as the laser intensity increases. Quantification of these effects allows us to extract the polarizability anisotropy of the H2 (E,F J = 0) state yielding a value of 312 ± 82 a.u. (46 Å3). By comparison, CS2 has 10 Å3, I2 has 7 Å3, and hydrochlorothiazide (C7H8ClN3O4S2) has about 25 Å3 meaning that we have created the most easily aligned molecule ever measured, by creating a mixed superposition state that is highly anisotropic in its polarizability.

Since the first ion imaging experiment [D. W. Chandler and P. L. Houston, J. Chem. Phys. 87, 1445-1447 (1987)], demonstrating the capability of collecting an image of the photofragments from a unimolecular dissociation event and analyzing that image to obtain the three-dimensional velocity distribution of the fragments, the efficacy and breadth of application of the ion imaging technique have continued to improve and grow. With the addition of velocity mapping, ion/electron centroiding, and slice imaging techniques, the versatility and velocity resolution have been unmatched. Recent improvements in molecular beam, laser, sensor, and computer technology are allowing even more advanced particle imaging experiments, and eventually we can expect multi-mass imaging with co-variance and full coincidence capability on a single shot basis with repetition rates in the kilohertz range. This progress should further enable “complete” experiments - the holy grail of molecular dynamics - where all quantum numbers of reactants and products of a bimolecular scattering event are fully determined and even under our control.

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Modern semiconductor devices rely on the transport of minority charge carriers. Direct examination of minority carrier lifetimes in real devices with nanometer-scale features requires a measurement method with simultaneously high spatial and temporal resolutions. Achieving nanometer spatial resolutions at sub-nanosecond temporal resolution is possible with pump-probe methods that utilize electrons as probes. Recently, a stroboscopic scanning electron microscope was developed at Caltech, and used to study carrier transport across a Si p-n junction [ 1 , 2 , 3 ] . In this report, we detail our development of a prototype scanning ultrafast electron microscope system at Sandia National Laboratories based on the original Caltech design. This effort represents Sandia's first exploration into ultrafast electron microscopy.

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Abstract Collisional energy transfer is an essential aspect of chemical reactivity and maintenance of thermal equilibrium. Here we report the shape (energy-dependence) of the collisional energy transfer probability function for collisions of vibrationally excited NO2 entrained in a molecular beam and photoexcited to within 40 cm-1 of its dissociation threshold. The internally excited molecules undergo collisions with Ar atoms in a crossed beam apparatus. Dissociative collisions rapidly produce the NO(J) fragment, which is observed by velocity-mapped ion imaging and REMPI techniques. The measured collisional energy transfer function is obtained via energy conservation and is compared with the results of classical trajectory calculations. Good agreement between the theory and experiment is found for collisions that transfer small amounts of energy, but the theory predicts a higher likelihood of energetic collisions than is observed experimentally. We explore possible explanations for this discrepancy in the dynamics of the collision excitation process.

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Experimental measurements of elementary reaction rate coefficients and product branching ratios are essential to our understanding of many fundamentally important processes in Combustion Chemistry. However, such measurements are often impossible because of a lack of adequate detection techniques. Some of the largest gaps in our knowledge concern some of the most important radical species, because their short lifetimes and low steady-state concentrations make them particularly difficult to detect. To address this challenge, we propose a novel general detection method for gas-phase chemical kinetics: time-resolved broadband cavity-enhanced absorption spectroscopy (TR-BB-CEAS). This all-optical, non-intrusive, multiplexed method enables sensitive direct probing of transient reaction intermediates in a simple, inexpensive, and robust experimental package.

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The 'dual etalon frequency comb spectrometer' is a novel low cost spectometer with limited moving parts. A broad band light source (pulsed laser, LED, lamp ...) is split into two beam paths. One travels through an etalon and a sample gas, while the second arm is just an etalon cavity, and the two beams are recombined onto a single detector. If the free spectral ranges (FSR) of the two cavities are not identical, the intensity pattern at the detector with consist of a series of heterodyne frequencies. Each mode out of the sample arm etalon with have a unique frequency in RF (radio-frequency) range, where modern electronics can easily record the signals. By monitoring these RF beat frequencies we can then determine when an optical frequencies is absorbed. The resolution is set by the FSR of the cavity, typically 10 MHz, with a bandwidth up to 100s of cm{sup -1}. In this report, the new spectrometer is described in detail and demonstration experiments on Iodine absorption are carried out. Further we discuss powerful potential next generation steps to developing this into a point sensor for monitoring combustion by-products, environmental pollutants, and warfare agents.

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We have developed a novel experimental technique for direct production of cold molecules using a combination of techniques from atomic optical and molecular physics and physical chemistry. The ability to produce samples of cold molecules has application in a broad spectrum of technical fields high-resolution spectroscopy, remote sensing, quantum computing, materials simulation, and understanding fundamental chemical dynamics. Researchers around the world are currently exploring many techniques for producing samples of cold molecules, but to-date these attempts have offered only limited success achieving milli-Kelvin temperatures with low densities. This Laboratory Directed Research and Development project is to develops a new experimental technique for producing micro-Kelvin temperature molecules via collisions with laser cooled samples of trapped atoms. The technique relies on near mass degenerate collisions between the molecule of interest and a laser cooled (micro-Kelvin) atom. A subset of collisions will transfer all (nearly all) of the kinetic energy from the 'hot' molecule, cooling the molecule at the expense of heating the atom. Further collisions with the remaining laser cooled atoms will thermally equilibrate the molecules to the micro-Kelvin temperature of the laser-cooled atoms.

A molecular fountain directs slowly moving molecules against gravity to further slow them to translational energies that they can be trapped and studied. If the molecules are initially slow enough they will return some time later to the position from which they were launched. Because this round trip time can be on the order of a second a single molecule can be observed for times sufficient to perform Hz level spectroscopy. The goal of this LDRD proposal was to construct a novel Molecular Fountain apparatus capable of producing dilute samples of molecules at near zero temperatures in well-defined user-selectable, quantum states. The slowly moving molecules used in this research are produced by the previously developed Kinematic Cooling technique, which uses a crossed atomic and molecular beam apparatus to generate single rotational level molecular samples moving slowly in the laboratory reference frame. The Kinematic Cooling technique produces cold molecules from a supersonic molecular beam via single collisions with a supersonic atomic beam. A single collision of an atom with a molecule occurring at the correct energy and relative velocity can cause a small fraction of the molecules to move very slowly vertically against gravity in the laboratory. These slowly moving molecules are captured by an electrostatic hexapole guiding field that both orients and focuses the molecules. The molecules are focused into the ionization region of a time-of-flight mass spectrometer and are ionized by laser radiation. The new molecular fountain apparatus was built utilizing a new design for molecular beam apparatus that has allowed us to miniaturize the apparatus. This new design minimizes the volumes and surface area of the machine allowing smaller pumps to maintain the necessary background pressures needed for these experiments.

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Over the past few years we have developed the ability to acquire images through a confocal microscope that contain, for each pixel, the simultaneous fluorescence lifetime and spectra of multiple fluorophores within that pixel. We have demonstrated that our system has the sensitivity to make these measurements on single molecules. The spectra and lifetimes of fluorophores bound to complex molecules contain a wealth of information on the conformational dynamics and local chemical environments of the molecules. However, the detailed record of spectral and temporal information our system provides from fluorophores in single molecules has not been previously available. Therefore, we have studied several fluorophores and simple fluorophore-molecule systems that are representative of the use of fluorophores in biological systems. Experiments include studies of a simple fluorescence resonance energy transfer (FRET) system, green fluorescent probe variants and quantum dots. This work is intended to provide a basis for understanding how fluorophores report on the chemistry of more complex biological molecules.

The production of Ultra-cold molecules is a goal of many laboratories through out the world. Here we are pursuing a unique technique that utilizes the kinematics of atomic and molecular collisions to achieve the goal of producing substantial numbers of sub Kelvin molecules confined in a trap. Here a trap is defined as an apparatus that spatially localizes, in a known location in the laboratory, a sample of molecules whose temperature is below one degree absolute Kelvin. Further, the storage time for the molecules must be sufficient to measure and possibly further cool the molecules. We utilize a technique unique to Sandia to form cold molecules from near mass degenerate collisions between atoms and molecules. This report describes the progress we have made using this novel technique and the further progress towards trapping molecules we have cooled.

Single molecule fluorophores were studied for the first time with a new confocal fluorescence microscope that allows the wavelength and emission time to be simultaneously measured with single molecule sensitivity. In this apparatus, the photons collected from the sample are imaged through a dispersive optical system onto a time and position sensitive detector. This detector records the wavelength and emission time of each detected photon relative to an excitation laser pulse. A histogram of many events for any selected spatial region or time interval can generate a full fluorescence spectrum and correlated decay plot for the given selection. At the single molecule level, this approach makes entirely new types of temporal and spectral correlation spectroscopy of possible. This report presents the results of simultaneous time- and frequency-resolved fluorescence measurements of single rhodamine 6G (R6G), tetramethylrhodamine (TMR), and Cy3 embedded in thin films of polymethylmethacrylate (PMMA).

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We report the cooling of nitric oxide molecules in a single collision between an argon atom and an NO molecule at collision energies of 5.65 ± 0.36 kJ/mol and 14.7 ± 0.9 kJ/mol in a crossed molecular beam apparatus. We have produced in significant numbers (∼108 molecules cm -3 per quantum state) translationally cold NO(2Π 1/2, v′ = 0, j′ = 7.5) molecules in a specific quantum state with an upper-limit laboratory-frame rms velocity of 14.8 ± 1.1 m/s, corresponding to a temperature of 406 ± 28 mK. The translational cooling results from the kinematic collapse of the velocity distribution of the NO molecules after collision. Increasing the collision energy by increasing the velocity of the argon atoms, as we do here, does shift the scattering angle at which the cold molecules appear, but does not result in an experimentally measurable change in the velocity spread of the cold NO. This is entirely consistent with our analysis of the kinematics of the scattering which predicts that the velocity spread will actually decrease with increasing argon atom velocity. © EDP Sciences, Società, Italiana di Fisica, Springer-Verlag 2004.