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Electron beam induced etching (EBIE) is a high resolution, direct write, chemical dry etch process in which surface-adsorbed precursor molecules are activated by an electron beam. We show that nanoscale EBIE is rate limited through at least two mechanisms ascribed to adsorbate depletion and the transport of gaseous precursor molecules into an etch pit during etching, respectively. The latter has, to date, not been accounted for in models of EBIE and is needed to reproduce etch kinetics which govern the time-evolution of etch pits, EBIE throughput, and spatial resolution.

Focused ion beam ͑FIB͒ methodologies for successfully milling copper ͑U.S. Patent No. 6,322,672 B1͒ have been demonstrated. Approaches to milling copper ͑Cu͒ are required because standard FIB mill procedures produce rough, uneven cuts that are unsuitable for circuit edits, a principal FIB function. Efforts to develop gas assisted etching ͑GAE͒ processes which would smoothly mill Cu failed because Cu halides are not volatile and remain on the substrate as corrosive electrically conductive debris. Single crystal studies show that Cu grains with different crystal orientations vary in mill rate by as much as 4ϫ. Moreover, the ͑110͒ crystal orientation, which mills most slowly, forms a Cu 3 Ga phase when milled with a focused Ga ion beam. This phase is particularly resistant to milling and, in polycrystalline Cu, propagates during the milling operation, contributing to the uneven trench profiles. CoppeRx, a novel scan strategy, cleanly and uniformly removes polycrystalline Cu with minimal damage to the underlying dielectric. CoppeRx minimizes the formation and propagation of the Cu 3 Ga phase and equalizes the etch rates of the Cu crystal orientations. The CoppeRx strategy includes the milling of an ''egg crate'' topography to minimize the propagation of the Cu 3 Ga phase and the creation of a heavy atom sacrificial layer of the Cu surface ͑U.S. Patent Application No. 20010053605͒ which scatters the incident Ga ion beam, thereby reducing the channeling influence on Cu milling rates. This heavy atom layer is created by flowing W͑CO͒ 6 vapor during the FIB milling process. The CoppeRx scan strategy is especially beneficial for milling thick ͑Ͼ0.8 m͒ Cu structures with large, prominent grains. Because Cu interconnect lines are relatively thin ͑Ͻ0.4 -0.5 m͒, grain-related milling roughness is less of a problem. The CoppeRx egg crate topography and W scattering layer are not required. Instead, the successful cutting of 40 ohm Cu interconnect lines to produce Ͼ20 M ohm open circuits is achieved by flowing O 2 or H 2 O during the milling process ͑U.S. Patent No. 6,322,672B1͒. The O 2 /H 2 O flow smoothes the Cu milling by producing an amorphous surface oxide, thereby reducing channeling, and by enhancing the etch selectivity for Cu relative to the surrounding and underlying SiO 2 based dielectric. These interconnect cuts have been routinely done at the bottom of high aspect ratio holes ͑e.g., 1ϫ1ϫ9 m͒.

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Crystalline, perovskite-phase metal oxide materials AB03 such as PbTi03, PbZr03, and PbZri-,Ti,03 exhibit a variety of interesting properties such as ferroelectric, pyroelectric, and piezoelectric behavior.4-8 In order to take advantage of these properties, it is often necessary to develop low-temperature (<400 eC) synthetic routes to crystalline thin films. The preparation of these materials generally involves thermal decomposition of metal-organic lead, titanium, and zirconium compounds.8-11 However, these metal oxides are polymorphic and can crystallize in either the pyrochlore or perovskite phases.12 The formation * To whom correspondence should be addressed.(1) Butler University.