One of the main requirements for Si-based ultrasmall devices is atomic-order control of process technology. Here we show the concept of atomically controlled processing for group IV semiconductors based on atomic-order surface reaction control. By ultraclean low-pressure chemical vapor deposition using SiH 4 and GeH 4 gases, high-quality low-temperature epitaxial growth of Si, Ge, and Si 1Àx Ge x with atomically flat surfaces and interfaces on Si (100) is achieved, and atomic-order surface reaction processes on group IV semiconductor surface are formulated based on a Langmuir-type surface adsorption and reaction scheme. In in-situ doped Si 1Àx Ge x epitaxial growth on the (100) surface in a SiH 4 -GeH 4 -dopant (PH 3 , or B 2 H 6 or SiH 3 CH 3 )-H 2 gas mixture, the deposition rate, the Ge fraction and the dopant concentration are explained quantitatively assuming that the reactant gas adsorption/reaction depends on the surface site material and that the dopant incorporation in the grown film is determined by Henry's law. Self-limiting formation of 1-3 atomic layers of group IV or related atoms in the thermal adsorption and reaction of hydride gases on Si(100) and Ge (100) is generalized based on the Langmuir-type model. Si or SiGe epitaxial growth over N, P or B layer already-formed on Si(100) or SiGe(100) surface is achieved. Furthermore, the capability of atomically controlled processing for advanced devices is demonstrated. These results open the way to atomically controlled technology for ultralarge-scale integrations.

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Atomic‐order surface reaction processes on the group IV semiconductor surface are formulated based on the Langmuir‐type surface adsorption and reaction scheme. In in situ doped Si1−xGex epitaxial growth on the (100) surface in an SiH4–GeH4–dopant (PH3, B2H6 or SiH3CH3)–H2 gas mixture, the deposition rate, the Ge fraction and the dopant concentration are explained quantitatively by assuming that the reactant gas adsorption/reaction depends on the surface site materials and that the dopant incorporation in the grown film is conducted by Henry's law. The self‐limiting formation of 1–3 monolayers of group IV or related atoms in the thermal adsorption and reaction of hydride gases (SiH4, GeH4, NH3, PH3, CH4 and SiH3CH3) on Si(100) and Ge(100) is also generalized based on the Langmuir‐type model. The Si epitaxial growth over the phosphorus layer already formed on Si(100) by PH3 treatment is achieved. Moreover, atomic layer‐by‐layer etching of Si and Ge is achieved by alternate chlorine supply and irradiation of low‐energy Ar+ ions, where the chlorine adsorption is described by the Langmuir‐type model. Silicon nitride is also etched layer by layer via a role‐share method with an argon and hydrogen mixed plasma. These results open the way to atomically controlled processing for ultra‐large‐scale integration. Copyright © 2002 John Wiley & Sons, Ltd.