Morphological Evolution of Ag/Mica Films Grown by Pulsed Laser Deposition

Many vapor-deposited metal-on-insulator films exhibit a morphological progression with increasing thickness consisting of several distinct stages: (1) nucleation of 3-dimensional nanocrystalline islands; (2) elongation of the islands; (3) film percolation. Here we report a study of this progression during Pulsed Laser Deposition (PLD), a technique for film deposition that differs from thermal deposition in that the depositing species arrive in short energetic bursts, leading to instantaneous deposition fluxes orders of magnitude higher than can be achieved in thermal growth. Atomic Force Microscopy reveals that advancement through this same morphological progression occurs at lower thickness in PLD films relative to films grown under comparable conditions by thermal deposition, with PLD films having lower RMS roughness at a given thickness. We also observe that for a constant amount deposited per pulse, films deposited at higher laser pulse frequency are further advanced in morphological state. Kinetic Monte Carlo simulations reveal that PLD nucleation behavior differs from that of thermally deposited films, and this can account for the observed differences. Simulations also reveal a scaling of the percolation thickness with pulse frequency that is consistent with experiment.Engineering and Applied Science

Effect of deposition rate on morphology evolution of metal-on-insulator films grown by pulsed laser deposition

Ag films were grown by pulsed laser deposition on insulating SiO2 and mica substrates and exhibited a morphological progression beginning with nucleation of three-dimensional islands and culminating in a continuous, electrically conducting film. The rate of advancement through this progression with increasing pulse frequency was studied with experiments and with kinetic Monte Carlo (KMC) simulations. Experiments at 93 and 135 °C give exponents of −0.34 and −0.31, respectively, for the scaling of the electrical percolation thickness with pulse frequency. Simulations predicted an exponent of −0.34, in excellent agreement with the experiments. Both of these values agree well with the previously reported analytic value of −0.33 for the scaling of the morphology transition thickness with average flux in continuous deposition. Simulations also predicted that data collapse for island density vs amount deposited would be observed for experiments run at the same value of the parameter B/f at constant amount deposited per pulse, where B is the kinetic rate constant for coalescence and f is the pulse frequency. Measurements of the percolation transition were consistent with this prediction. These findings indicate that the elementary processes included in the KMC simulation—substrate terrace diffusion, irreversible aggregation of hemispherical islands, and two-island coalescence, but neglecting the effects of kinetic energy—are sufficient to explain the behavior observed when the pulse rate is varied at constant kinetic energy.Engineering and Applied Science

Fabrication and subband gap optical properties of silicon supersaturated with chalcogens by ion implantation and pulsed laser melting

Topographically flat, single crystal silicon supersaturated with the chalcogens S, Se, and Te was prepared by ion implantation followed by pulsed laser melting and rapid solidification. The influences of the number of laser shots on the atomic and carrier concentration-depth profiles were measured with secondary ion mass spectrometry and spreading resistance profiling, respectively. We found good agreement between the atomic concentration-depth profiles obtained from experiments and a one-dimensional model for plane-front melting, solidification, liquid-phase diffusion, with kinetic solute trapping, and surface evaporation. Broadband subband gap absorption is exhibited by all dopants over a wavelength range from 1 to 2.5 microns. The absorption did not change appreciably with increasing number of laser shots, despite a measurable loss of chalcogen and of electronic carriers after each shot.One of the authors M.T. acknowledges the financial support of the Fulbright Program. This research was supported in part by the U.S. Army ARDEC under Contract No. W15QKN-07- P-0092

Morphological stability during solidification of silicon incorporating metallic impurities

We study the stability of a planar solidification front during pulsed laser melting-induced rapid solidification of silicon containing high concentrations of ion-implated metallic impurities. We calculate the critical impurity concentration for destabilizing plane-front solidification, and introduce the "amplification coefficient", which is an empirical parameter describing the degree of amplification that must accord between the time the planar liquid-solid interface first becomes unstable, and the time of formation of morphological features of interface breakdown that are later observed in the microstructure. By connecting our calculations to experimental observations from the literature we determine this parameter for Au, Co, Cr, Fe, Ga, In, and Zn in (100) Si and Ti in (111) Si, and find that it increases with impurity diffusive speed vd approximately as vd^.56. We present an approximate but simple method of estimating the maximum impurity concentration that may be incorporated in a surface layer of a given thickness without the appearance of cellular breakdown.Engineering and Applied Science

Photocarrier lifetime and transport in silicon supersaturated with sulfur

Doping of silicon-on-insulator layers with sulfur to concentrations far above equilibrium by ion implantation and pulsed laser melting can result in large concentration gradients. Photocarriers generated in and near the impurity gradient can separate into different coplanar transport layers, leading to enhanced photocarrier lifetimes in thin silicon-on-insulator films. The depth from which holes escape the heavily doped region places a lower limit on the minority carrier mobility-lifetime product of 10⁻⁸ cm²/V for heavily sulfur dopedsilicon. We conclude that the cross-section for recombination through S impurities at this concentration is significantly reduced relative to isolated impurities.Research at Rensselaer was supported by the Army Research Office under Contract No. W911NF0910470 and by the NSF REU program at Rensselaer. Research at Harvard was supported by US Army ARDEC under Contract No. W15QKN-07-P-0092. D.R. was supported in part by a National Defense Science and Engineering Graduate fellowship

Supersaturating silicon with transition metals by ion implantation and pulsed laser melting

We investigate the possibility of creating an intermediate band semiconductor by supersaturating Si with a range of transition metals (Au, Co, Cr, Cu, Fe, Pd, Pt, W, and Zn) using ion implantation followed by pulsed laser melting (PLM). Structural characterization shows evidence of either surface segregation or cellular breakdown in all transition metals investigated, preventing the formation of high supersaturations. However, concentration-depth profiling reveals that regions of Si supersaturated with Au and Zn are formed below the regions of cellular breakdown. Fits to the concentration-depth profile are used to estimate the diffusive speeds, v D, of Au and Zn, and put lower bounds on v D of the other metals ranging from 10² to 10⁴ m/s. Knowledge of v D is used to tailor the irradiation conditions and synthesize single-crystal Si supersaturated with 10¹⁹ Au/cm³ without cellular breakdown. Values of v D are compared to those for other elements in Si. Two independent thermophysical properties, the solute diffusivity at the melting temperature, D s(T m), and the equilibrium partition coefficient, k e, are shown to simultaneously affect v D. We demonstrate a correlation between v D and the ratio D s(T m)/k e ⁰·⁶⁷, which is exhibited for Group III, IV, and V solutes but not for the transition metals investigated. Nevertheless, comparison with experimental results suggests that D s(T m)/k e ⁰·⁶⁷ might serve as a metric for evaluating the potential to supersaturate Si with transition metals by PLM.Research at Harvard was supported by The U.S. Army Research Office under contracts W911NF-12-1-0196 and W911NF-09-1-0118. M.T.W. and T.B.’s work was supported by the U.S. Army Research Laboratory and the U.S. Army Research Office under Grant No. W911NF-10-1-0442, and the National Science Foundation (NSF) Faculty Early Career Development Program ECCS-1150878 (to T.B.). M.J.S., J.T.S., M.T.W., T.B., and S.G. acknowledge a generous gift from the Chesonis Family Foundation and support in part by the National Science Foundation (NSF) and the Department of Energy (DOE) under NSF CA No. EEC- 1041895. S.C. and J.S.W.’s work was supported by The Australian Research Council. J.M. was supported by a National Research Council Research Associateship

On the limits to Ti incorporation into Si using pulsed laser melting

Fabrication of p-Si(111) layers with Ti levels well above the solid solubility limit was achieved via ion implantation of 15 keV 48Ti+ at doses of 1012 to 1016 cm−2 followed by pulsed laser melting using a Nd:YAG laser (FWHM = 6 ns) operating at 355 nm. All implanted layers were examined using cross-sectional transmission electron microscopy, and only the 1016 cm−2 Ti implant dose showed evidence of Ti clustering in a microstructure with a pattern of Ti-rich zones. The liquid phase diffusivity and diffusive velocity of Ti in Si were estimated to be 9 × 10−4 cm2/s and (2 ± 0.5) × 104 m/s, respectively. Using these results the morphological stability limit for planar resolidification of Si:Ti was evaluated, and the results indicate that attaining sufficient concentrations of Ti in Si to reach the nominal Mott transition in morphologically stable plane-front solidification should occur only for velocities so high as to exceed the speed limits for crystalline regrowth in Si(111).Engineering and Applied Science