Stephen T. Palmacci

Detection of condensed-phase explosives via laser-induced vaporization, photodissociation, and resonant excitation

We investigate the remote detection of explosives via a technique that vaporizes and photodissociates the condensed-phase material and detects the resulting vibrationally excited NO fragments via laser-induced fluorescence. The technique utilizes a single 7 ns pulse of a tunable laser near 236.2 nm to perform these multiple processes. The resulting blue-shifted fluorescence (226 nm) is detected using a photomultiplier and narrowband filter that strongly block the scatter of the pump laser off the solid media while passing the shorter wavelength photons. Various nitro-bearing compounds, including 2,6-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT), pentaerythritol tetranitrate (PETN), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) were detected with a signal-to-noise of 25 dB. The effects of laser fluence, wavelength, and sample morphology were examined.

Noncontact detection of homemade explosive constituents via photodissociation followed by laser-induced fluorescence

Noncontact detection of the homemade explosive constituents urea nitrate, nitromethane and ammonium nitrate is achieved using photodissociation followed by laser-induced fluorescence (PD-LIF). Our technique utilizes a single ultraviolet laser pulse (approximately 7 ns) to vaporize and photodissociate the condensed-phase materials, and then to detect the resulting vibrationally-excited NO fragments via laser-induced fluorescence. PD-LIF excitation and emission spectra indicate the creation of NO in vibrationally-excited states with significant rotational energy, useful for low-background detection of the parent compound. The results for homemade explosives are compared to one another and 2,6-dinitrotoluene, a component present in many military explosives.

Noncontact optical detection of explosive particles via photodissociation followed by laser-induced fluorescence

High-sensitivity (ng/cm²) optical detection of the explosive 2,4,6-trinitrotoluene (TNT) is demonstrated using photodissociation followed by laser-induced fluorescence (PD-LIF). Detection occurs rapidly, within 6 laser pulses (~7 ns each) at a range of 15 cm. Dropcasting is used to create calibrated samples covering a wide range of TNT concentrations; and a correspondence between fractional area covered by TNT and PD-LIF signal strength is observed. Dropcast data are compared to that of an actual fingerprint. These results demonstrate that PD-LIF could be a viable means of rapidly and remotely scanning surfaces for trace explosive residues.

High-Index Immersion Lithography : Preventing Lens Photocontamination and Identifying Optical Behavior of LuAG

A potential extension of water-based 193-nm immersion lithography involves transition to a higher refractive index organic immersion fluid coupled with a higher index last lens element. While considerable progress has been made in improving the photo-durability of the immersion fluid itself, photo-induced contamination of the last lens element caused by laser exposure in the presence of such organic fluids remains a major concern. In this work, we study remediation strategies for such contamination, which would be compatible with conventional lithographic production environments. In general, surface photocontamination layers were found to be highly graphitic in nature, where the first monolayer is strongly bound to the substrate. We have attempted to develop a surface passivation treatment for altering the monolayer chemistry and preventing large-scale contamination, but found such treatments to be unstable under laser irradiation. On the other hand, using hydrogen peroxide as a in-situ cleaning solution has been shown to be extremely effective. We also present first laser-based durability results of LuAG, which is a leading candidate material for high index last element to be used with high index fluids.

Development and Evaluation of a 193nm Immersion Generation-Three Fluid Candidates

The need to extend 193nm immersion lithography necessitates the development of a third generation (Gen-3) of high refractive index (RI) fluids that will enable approximately 1.7 numerical aperture (NA) imaging. A multi-pronged approach was taken to develop these materials. One approach investigated the highest-index organic thus far discovered. The second approach used a very high refractive index nanoparticle to make a nanocomposite fluid. This report will describe the chemistry of the best Gen-3 fluid candidates and the systematic approach to their identification and synthesis. Images obtained with the Gen-3 fluid candidates will also be presented for a NA ≥ 1.7.

Laser Durability Studies of High Index Immersion Fluids : Fluid Degradation and Optics Contamination Effects

An extension of water-based immersion lithography involves replacing water with a higher index transparent oil. Understandably, potential lens contamination is a major concern for an all-organic immersion fluid. We have constructed an experimental system for controlled irradiation of high index fluids, including capabilities for in-situ cleaning of potential deposits. We present results of laser-irradiation of several high index immersion fluid candidates. Using properly developed exposure metrics, we discuss implications for fluid lifetimes in an immersion system, with and without in-situ purification. Using our in-situ metrology, we are able to decouple bulk fluid degradation from window photocontamination for several fluids. We find a significant variation in optics contamination rate depending on the fluid tested. Even the slowest observed contamination rates would require some remediation strategies to remove the built-up deposit from the final element surface. We also present results of irradiation of model hydrocarbon compound fluids. Irradiation of these materials leads to fundamental understanding of underlying photochemistry, and also provides guidance in designing future generation high index fluids.

Long-term 193-nm laser irradiation of thin-film-coated CaF2 in the presence of H2O

The final projection lens element in a 193-nm immersion-based lithographic tool will be in direct contact with water during irradiation. Thus, any lifetime considerations for the lens must include durability data of lens materials and thin films in a water ambient. We have previously shown that uncoated CaF2 is attacked by water in a matter of hours, as manifested by a substantial increase in AFM-measured surface roughness.1 Thus, CaF2 lenses must be protected, possibly by a thin film, and the coatings tested for laser durability in water. To address the above lifetime concerns, we have constructed a marathon laser-irradiation system for testing thin film exposure to water under long-term laser irradiation. Coated substrates are loaded into a custom water cell, made of stainless steel and Teflon parts. Ultrapure water is delivered from a water treatment testbed that includes particle filtration, deionization and degassing stages. In-situ metrology includes 193-nm laser ratiometry, UV spectrophotometry and spectroscopic ellipsometry, all with spatial profiling capabilities. In-situ results are coupled with off-line microscopy, AFM measurements and spatial surface mapping with spectroscopic ellipsometry at multiple incidence angles. A variety of laser-induced changes have been observed, from complete adhesion loss of protective coatings to more subtle changes, such as laser-induced index changes of the thin films or surface roughening. Implications of the study on expected lifetimes of the protective coatings in the system will be discussed.

Controlled contamination of optics under 157-nm laser irradiation

Contamination rates of CaF2 substrates in the presence of trace levels of toluene vapor and oxygen under 157-nm irradiation have been studied to determine conditions which prevent contamination films from depositing on optical elements in lithographic projection systems. A 2 - 3 monolayer thick deposit, causing a 1 - 2% transmission drop per surface, can readily form over a range of contaminant levels in the sub-ppm range and typical background oxygen levels. In addition, stable partial surface coverage can be supported with either lower concentrations of contaminant or conversely much higher levels of oxygen. Contamination rates are also higher at lower fluences, and thus contamination effects are expected to impact the projection optics more severely than beam delivery and illumination components. Finally, a permanent degradation in transmission of coated optics has been observed on anti-reflective coatings exposed to sub-ppm levels of toluene. Taken together, the results suggest that even with hydrocarbon based contaminants, where oxygen can be introduced into the beam-line in trace levels (i.e. hundreds of ppb) without significantly degrading transmission, toluene contaminant levels will have to be maintained in the ppb range or below.

Laser micromachining of silicon: A new technique for fabricating terahertz imaging arrays

One of the main obstacles encountered in designing low noise, high efficiency, heterodyne receivers and local oscillator sources at submillimeter wavelengths is the quality and cost of waveguide structures. At wavelengths shorter than 400 micrometers, rectangular waveguide structures, feed-horns, and backshorts become extremely difficult to fabricate using standard machining techniques. We have used a new laser milling technique to fabricate high quality, THz waveguide components and feedhorns. Once metallized, the structures have the properties of standard waveguide components. Unlike waveguide components made using silicon wet-etching techniques, laser-etched components can have almost any cross section, from rectangular to circular. Under computer control, the entire waveguide structure (including the corrugated feedhorn a submillimeter-wave mixer or multiplier can be fabricated to micrometer tolerances in a few hours. Laser etching permits the direct scaling of successful waveguide multiplier and mixer designs to THz frequencies. Since the entire process is computer controlled, the cost of fabricating submillimeter waveguide components is significantly reduced. With this new laser etching process, the construction of high performance waveguide array receivers at THz frequencies becomes tractable. In this paper we will describe the laser etching technique and discuss how it can be used to construct THz imaging arrays. We will also describe the construction of a prototype 810 GHz mixer which utilizes these new construction techniques.

Long-term laser durability testing of optical coatings and thin films for 157-nm lithography

Long-term durability tests of optical thin films and thin films designed for attenuating phase shifters have been performed in a chamber, which stresses clean protocols to eliminate extraneous effects of surface contamination. Most anti-reflective coatings tend to degrade several percent in transmission within 1 MJ/cm2 total dose. Attenuating phase shifting materials usually show an increase in transmission during 6 kJ/cm2. In both types of films there are exceptions, indicating that there are no fundamental causes that would limit the performance of such films. A new phenomenon of laser-induced surface damage in calcium fluoride has been observed, and is being studied.