Thermal atomic layer deposition (ALD) of noble metals is frequently performed using molecular oxygen as the nonmetal precursor to effect combustion-type chemistry at r e l a t i v e l y h i g h t e m p e r a t u r e s o f 3 0 0°C . B i s -(ethylcyclopentadienyl)ruthenium (Ru(EtCp) 2 ) is one of the commonly used metal precursors for Ru ALD. Using Ru(EtCp) 2 and oxygen as reactants, Ru ALD was achieved at near 300°C. Here, we demonstrate that Ru ALD can proceed at as low as 150°C by using successive exposures to oxygen and hydrogen as the coreactants. In situ quartz crystal microbalance (QCM) and quadrupole mass spectroscopy (QMS) measurements both suggest that this ABC-type ALD occurs through dissociative chemisorption, combustion, and reduction for the Ru(EtCp) 2 , oxygen, and hydrogen steps, respectively, in a similar manner to processes using ozone and hydrogen as coreactants reported previously. Moreover, we believe this molecular O 2 and H 2 based ABC-type ALD could be exploited for the ALD of other noble metals to decrease the deposition temperature and reduce oxygen impurities.
■ INTRODUCTIONUltrathin conformal Ru films have been used as electrodes in a variety of microelectronics applications including positivechannel metal oxide semiconductor (PMOS) metal gates and dynamic random access memory (DRAM) capacitors, due to the high work function (4.7 eV), low bulk resistivity (7.1 μΩ· cm), good thermal stability, and, more importantly, oxygen diffusion barrier property of Ru. 1−5 As the size of semiconductor devices decreases according to Moore's Law, complicated three-dimensional (3-D) nanostructures will be needed to achieve high storage capacities. 6−9 As a consequence, the requirements for conformality, thickness control, and low temperature of the Ru deposition process become more severe. Among the various thin film deposition techniques, atomic layer deposition (ALD) is considered to be the most promising for meeting these requirements. 10−12 Ruthenium ALD has been widely explored using a variety of Ru precursors including metallocenes, β-diketonates, and their derivatives. 13−21 In these studies, molecular oxygen is most often employed as the nonmetal precursor for thermal Ru ALD. As with similar noble metal ALD processes utilizing O 2 (e.g., Pt, Rh, and Ir), the Ru ALD is thought to follow a combustiontype mechanism in which the metal organic precursor first reacts with surface oxygen to burn off a fraction of the ligands, and then the rest of the ligands are further combusted in the subsequent oxygen exposure step. The oxygen exposure also serves to replenish the surface oxygen through dissociation on the noble metal surface. Carbon dioxide and water are the major gaseous products formed during the two half reactions, 13,22−25 while in some cases dehydrogenation can also occur. 24,26 This oxygen-based, combustion-type noble metal ALD typically requires relatively high temperature above 200°C (near 300°C in most cases), to burn off the organic ligands. [13][14][15][16][17][18][19][20]25,27,28 Th...