Introduction

An inherent consequence of the replacement of SiO2 and SiOxNy as the gate dielectrics in the future generations of CMOS devices is that a new method for the dielectric deposition will be needed too. Among the various candidates, atomic layer deposition (ALD, also known by the names atomic layer epitaxy (ALE) and atomic layer chemical vapour deposition (ALCVD), for example) offers certain important characteristics like excellent large area uniformity, outstanding conformality, and atomic level control of film composition and thickness [14]. As a consequence, ALD of high-k oxides has been a subject of increasingly intense research during the past few years. On the other hand, while new in the gate oxide application, the ALD method has been examined and developed continuously since its introduction in the late 1970s [58]. Most importantly, in thin film electroluminescent (TFEL) display devices [1], which were the original motivation for developing ALD and remained the only industrial application of ALD for a long time, one uses insulator films that are required to have quite similar properties as the high-k gate dielectrics. Therefore, ALD processes for many potential high-k gate oxide materials were developed and characterized already before the current high-k research began [1]. This chapter makes an overview of ALD and, in particular, its application to high-k gate oxide deposition. The chapter begins with the introduction of the basic principle of ALD, followed by a discussion on its advantages and limitations. Precursor chemistry and ALD reactors, the two important requirements for a successful utilization of ALD, complete the introductory part. Next, the special issues related to the high-k gate oxide deposition on silicon by ALD are discussed. The rest of the chapter is devoted to a survey of high-k ALD oxide processes, mainly focusing on those processes that have dominated the research but also introducing alternative 17 processes available. Because device integration issues are discussed elsewhere in the book (see the chapter by E. Young and V. Kaushik), they are covered in this chapter only when directly related to ALD, the most important one being the compatibility of the ALD oxide processes with silicon.

Atomic layer deposition

Basic principle Like CVD, ALD is a chemical gas phase thin film deposition method. The distinct feature of ALDis that the film is grown through sequential saturative surface reactions that are realized by pulsing the two (or more) precursors into the reactor alternately, one at a time, separated by purging or evacuation steps. As an example, figure 2.1.1 demonstrates one ALD cycle in deposition of ZrO2 from ZrCl4 and H2O, which is one of the most extensively examined high-k gate oxide ALD processes. The film surface left from the previous cycle is terminated with hydroxyl groups. When dosed upon this surface, ZrCl4 reacts with the hydroxyl groups forming OZrCl3 and/or (O)2ZrCl2 surface groups. Under ideal ALD conditions, each reaction step is saturative, which in this case means that all the hydroxyl groups, and any other possibly existing adsorption sites like bare oxide ions, become consumed from the surface. The following purge (or evacuation) step removes the excess ZrCl4 molecules and HCl formed as a reaction by-product. When dosed upon this surface, water reacts with the ZrClx species converting them into ZrO2 covered by hydroxyl groups. Again the reaction is saturative so that all the chlorides are removed. Finally, the second purge/evacuation step completes the cycle leaving the surface covered by the same number of hydroxyl groups as at the beginning of the cycle. The outcome of this one ALD cycle is a deposition of a fixed amount, most often a part of a monolayer, of ZrO2 on the surface. In order to grow a thicker film, the ALD cycle is repeated as many times as it is necessary to reach the target thickness.