Laser-assisted deposition of tungsten by high-temperature decomposition of WF 6 , with only small amounts of H 2 present, has been studied. The kinetics of the process follows a different pathway than with standard chemical vapor deposition conditions, employing high H 2 partial pressures. The method allows rapid growth of single-crystal-like microtips with defined lateral borders, additionally self-termination of growth is achieved. 1 This technique has been applied to tungsten for applications such as the preparation of field emitters and needle-cathodes for use in microwave technology, medicine, and biology.
2-7Until now, single-crystal-like tungsten rods could be grown only at low rates.8 This is, at present, the main disadvantage of laser CVD. The low throughput makes it only suitable as a specialized technique for purposes where very high quality devices, which cannot be produced by other techniques, are required.1 Research directed at optimizing the single step laser fabrication of freestanding 3D objects for industrial application is currently in progress.
9This paper describes an attractive alternative to ultrahigh pressure performance and laser-assisted mask technologies, for the rapid deposition of single-crystal-like tungsten microtips from WF 6 : The classical CVD method for W deposition, thermal reduction of WF 6 by H 2 at partial pressure ratios p H 2 /p WF 6 ϵ ⌫ P ӷ 1is widely employed. This method is used for very large scale integrated metallization because of its ability to adequately coat high aspect ratio features. 10 Within the temperature limits in CVD it has been found that deposition ceases if too small H 2 partial pressure is employed.
11The mechanisms which influence the CVD process in the case of small partial pressures of H 2 can be described by the thermodynamics of pure WF 6 and solid W, taking into account the reactions W͑s͒ ϩ 5WF 6 6WF 5 ͓2͔WF 5 W͑s͒ ϩ 5F ͓3͔ Thermodynamic modeling of the reaction behavior of Eq. 2 and 3 has been performed following the approach outlined by McCarty et al. 12 and has been adapted to localized laser processing. Close to the laser-heated substrate area a reaction zone is defined, where constant pressure and constant temperature are assumed. Within this zone, equilibrium concentrations of the ͑homogeneous͒ reaction constituents are calculated from Eq. 2 and 3 for a given initial pressure, p WF 6 , and temperature, T. Far away from this zone, at room temperature, it is assumed that no reactions occur. Due to the different concentrations of species, i, inside and outside the reaction zone a flux of species J i will appear. From these fluxes the ͑heterogeneous͒ reaction rate, i.e., the rate of removal/deposition of W species at the solid surface can be estimated. The equilibrium concentrations of WF 6 , WF 5 , and F within the reaction zone are estimated from the law of mass action, taking the corresponding free energies of species either from 12 or from the JANAF tables.
13The etch/deposition rate is then obtained from the net flux of W atomsusing the ...