Atomic layer deposition (ALD) has been studied for several decades now, but the interest in ALD of metal and nitride thin films has increased only recently, driven by the need for highly conformal nanoscale thin films in modern semiconductor device manufacturing technology. ALD is a very promising deposition technique with the ability to produce thin films with excellent conformality and compositional control with atomic scale dimensions. However, the applications of metals and nitrides ALD in semiconductor device processes require a deeper understanding about the underlying deposition process as well as the physical and electrical properties of the deposited films. This article reviews the current research efforts in ALD for metal and nitride films as well as their applications in modern semiconductor device fabrication.

Atomic layer deposition of metal and nitride thin films: Current research efforts and applications for semiconductor device processing

The move to implement metal oxide based gate dielectrics in a metal-oxide-semiconductor field effect transistor is considered one of the most dramatic advances in materials science since the invention of silicon based transistors. Metal oxides are superior to SiO 2 in terms of their higher dielectric constants that enable the required continuous down-scaling of the electrical thickness of the dielectric layer while providing a physically thicker layer to suppress the quantum mechanical tunneling through the dielectric layer. Over the last decade, hafnium based materials have emerged as the designated dielectrics for future generation of nano-electronics with a gate length less than 45 nm, though there exists no consensus on the exact composition of these materials, as evolving device architectures dictate different considerations when optimizing a gate dielectric material. In addition, the implementation of a non-silicon based gate dielectric means a paradigm shift from diffusion based thermal processes to atomic layer deposition processes. In this report, we review how HfO 2 emerges from all likely candidates to become the new gold standard in the microelectronics industry, its different phases, reported electrical properties, and materials processing techniques. Then we use specific examples to discuss the evolution in designing hafnium based materials, from binary to complex oxides and to non-oxide forms as gate dielectric, metal gates and diffusion barriers. To address the impact of these hafnium based materials, their interfaces with silicon as well as a variety of semiconductors are discussed. Finally, the integration issues are highlighted, including carrier scattering, interface state passivation, phonon engineering, and nano-scale patterning, which are essential to realize future generations of devices using hafnium-based high- k materials.

Development of hafnium based high-k materials—A review

The deposition of Al 2 O 3 by remote plasma atomic layer deposition (ALD) in the Oxford Instruments FlexAL reactor was studied and compared with results from thermal ALD in the same reactor. Trimethylaluminum [Al(CH 3 ) 3 ] was used as the metal precursor and O 2 plasma and H 2 O were used as oxidizing agents for the plasma and thermal processes, respectively. For remote plasma ALD with a total cycle time of 4 s, the growth per cycle decreased monotonically with substrate temperature, from 1.7 A/cycle at 25°C to 1.0 A/cycle at 300°C. This growth per cycle was consistently higher than that obtained for thermal ALD. For the latter a maximum growth per cycle of ∼ 1.0 A/cycle was found at 200°C. The film properties investigated were nearly independent of oxidant source for temperatures between 100 and 300°C, with a slightly higher mass density for the remote plasma ALD Al 2 O 3 films. Films deposited at 200 and 300°C were stoichiometric with a mass density of 3.0 g/cm 3 and low C (< 1 atom %) and H (<3 atom %) contents. At lower substrate temperatures, oxygen-rich films were obtained with a lower mass density and higher H-content. Remote plasma ALD produced uniform Al 2 O 3 films with nonuniformities of less than ±2% over 200 mm diam substrates. Excellent conformality was obtained for films deposited in macropores with an aspect ratio of ∼8 (2.0-2.5 μm diam). Preliminary results on electrical properties of remote plasma deposited films showed high dielectric constants of 7.8 and 8.9 for as-deposited and forming gas annealed Al 2 O 3 , respectively.

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Plasma and thermal ALD of Al2O3 in a commercial 200 mm ALD reactor

Methods of forming a capping layer over a metal wire structure of a semiconductor device are disclosed. In one embodiment, the method includes providing a partially fabricated semiconductor device having exposed surfaces of the metal (e.g., copper) wire structure and a dielectric around the metal wire structure. The exposed surface of the metal wire structure is then activated by forming a seed layer thereon. The capping layer is then formed over the exposed surface of the metal wire structure by performing a selective atomic layer deposition (ALD) of a capping layer material onto the metal wire structure. As an alternative, the dielectric may be masked off to further assist the selectivity of the ALD. The invention also includes a semiconductor structure including the metal wire structure having an atomic layer deposition capping layer over an upper surface thereof.

Forming capping layer over metal wire structure using selective atomic layer deposition

Atomic layer deposition of titanium nitride from TDMAT precursor

The architecture, materials choice and process technology for stacked-capacitors in embedded-DRAM applications are a crucial concern for each new technology node. An overview of the evolution of capacitor technology is presented from the early days of planar PIS (poly/insulator/silicon) capacitors to the MIM (metal/insulator/metal) capacitors used for todays 65 nm technology node. In comparing Ta2O5, HfO2 and Al2O3 as high-k dielectric for use in 65 nm eDRAM technology, Al2O3 is found to give a good compromise between capacitor performance and manufacturability. The use of atomic layer deposition (ALD) is identified to be an enabling technology for both high-k dielectrics and capacitor electrodes. � 2005 Elsevier Ltd. All rights reserved.

Steven Smith

Papers

Evolution of materials technology for stacked-capacitors in 65 nm embedded-DRAM

Low resistivity tungsten for contact metallization

Physical and electrical characterization of ALCVD TM TiN and WN x C y used as a copper diffusion barrier in dual damascene backend structures(08.2)