No abstract

Laser-induced breakdown spectrometry (LIBS) has been evaluated for depth profiling of phosphorus doping in silicon. Laser plasmas were formed by focusing a Nd:YAG laser (operating in the second harmonic, 532 nm) on the sample surface. Plasma emission was collected, dispersed, and detected with the use of a charge-coupled device (CCD). Experimental parameters, such as delay time and sample position relative to the laser focal point, were optimized to improve the signal-to-background ratio of phosphorus line emission. Diffusion profiles by LIBS of samples with different phosphorus diffusion steps are shown. Crater depth per pulse and ablated mass per pulse were measured to be 1.2 μm pulse−1 and 50 ng pulse−1, respectively. The knowledge of depth per pulse permitted the estimation of thickness of the P diffusion layer.

The sensitivity of vibronic calculations to electronic structure methods and basis sets is explored and compared to accurate relative intensities of the vibrational bands of phenylacetylene in the S(1)(A(1)B(2)) ← S(0)(X(1)A(1)) transition. To provide a better measure of vibrational band intensities, the spectrum was recorded by cavity ringdown absorption spectroscopy up to energies of 2000 cm(-1) above the band origin in a slit jet sample. The sample rotational temperature was estimated to be about 30 K, but the vibrational temperature was higher, permitting the assignment of many vibrational hot bands. The vibronic structure of the electronic transition was simulated using a combination of time-dependent density functional theory (TD-DFT) electronic structure codes, Franck-Condon integral calculations, and a second-order vibronic model developed previously [Johnson, P. M.; Xu, H. F.; Sears, T. J. J. Chem. Phys. 2006, 125, 164331]. The density functional theory (DFT) functionals B3LYP, CAM-B3LYP, and LC-BLYP were explored. The long-range-corrected functionals, CAM-B3LYP and LC-BLYP, produced better values for the equilibrium geometry transition moment, but overemphasized the vibronic coupling for some normal modes, while B3LYP provided better-balanced vibronic coupling but a poor equilibrium transition moment. Enlarging the basis set made very little difference. The cavity ringdown measurements show that earlier intensities derived from resonance-enhanced multiphoton ionization (REMPI) spectra have relative intensity errors.