An atomic layer deposition (ALD) process for SrTiO 3 (STO) thin film growth was developed using a newly designed and synthesized heteroleptic Sr-precursor, {Sr(demamp)(tmhd)} 2 (demampH = 1-{[2-(dimethylamino)ethyl](methyl)amino}-2-methylpropan-2-ol, tmhdH = 2,2,6,6-tetramethyl-3,5-heptanedione), which offered an intermediate reactivity toward oxygen between Sr(tmhd) 2 and Sr( i Pr 3 Cp) 2 . Because of the appropriate reactivity of {Sr(demamp)(tmhd)} 2 toward oxygen, the abnormal initial growth behavior (due to interaction between the Sr-precursor and active oxygen contained in the underlying oxidized Ru layer) became negligible during the growth of the SrO and STO films on the Ru electrode, which allowed the growth of the SrO and STO films to be highly controllable with a moderate growth rate. Using Ti(CpMe 5 )(OMe) 3 as the Ti-precursor and O 3 as the oxygen source in the TiO 2 ALD subcycle, the ALD process of the STO film revealed a growth rate of 0.05 nm/cycle and ∼85% of step coverage in terms of the thickness and cation composition on a capacitor hole structure with an aspect ratio of 10 (opening diameter of 100 nm and depth of 1 μm). The minimum achievable equivalent oxide thickness (t ox ) with a low leakage current (<10 −7 A/cm 2 at 0.8 V) was limited to 0.46 nm. The damage effect on the underlying Ru electrode by the prolonged ALD process time appears to affect the limited scalability of t ox . ■ INTRODUCTIONSrTiO 3 (STO) has been considered to be a promising candidate for a dielectric layer in the next-generation dynamic random access memory (DRAM) capacitors because of its high permittivity (∼300 in bulk material) compared with that of other dielectric materials, such as HfO 2 and ZrO 2 . Many studies have reported a high dielectric constant of >100 for metal− insulator−metal (MIM) capacitors that contain an STO insulator, in which the insulators are thinner than 20 nm. 1−6 Considering the extremely tiny three-dimensional (3D) structure of the DRAM capacitors, 7 atomic layer deposition (ALD) appears to be the only feasible thin film growth technique that can fulfill the stringent requirements of thickness and composition step coverage in the DRAM capacitors. Despite the acute requirement for a suitable ALD process of the STO films, the development has been hindered for two main reasons: first, the lack of a suitable Sr-precursor for feasible STO ALD, although that for Ti is abundant; second, because of the low temperature of the ALD, ensuring a suitable crystalline quality of the STO film is challenging in general. Because such problems and possible solutions have already been extensively reviewed in previous reports from the authors' group, 3,7,8 more recent reports that are directly related to the present work are described in this section.The first viable report in this field was published by the Helsinki group in the late 1990s. Vehkamaki et al. deposited STO films with Sr( i Pr 3 Cp) 2 (Pr and Cp are propyl and cyclopentadienyl group, respectively) and Ti(O i Pr) 4 [TTIP] as Sr-and Ti-precursors,...

The effects of Pt and RuO2 top electrodes on the electrical properties of capacitors with Al-doped TiO2 (ATO) films grown on the RuO2 bottom electrode by an atomic layer deposition method were examined. The rutile phase ATO films with high bulk dielectric constant (>80) were well-grown because of the local epitaxial relationship with the rutile structured RuO2 bottom electrode. However, the interface between top electrode and ATO was damaged during the sputtering process of the top electrode, resulting in the decrease in the dielectric constant. Postmetallization annealing at 400 °C was performed to mitigate the sputtering damage. During the postmetallization annealing, the ATO layer near the RuO2 top electrode/ATO interface was well-crystallized because of the structural compatibility between RuO2 and rutile ATO, while the ATO layer near the Pt top electrode/ATO interface still exhibited an amorphous-like structure. Despite the same thickness of the ATO films, therefore, the capacitors with RuO2 top electrodes showed higher capacitance compared to the capacitors with Pt top electrodes. Eventually, an extremely low equivalent oxide thickness of 0.37 nm with low enough leakage current density (<1 × 10(-7) A/cm(2) at 0.8 V) and physical thickness of 8.7 nm for the next-generation dynamic random access memory was achieved from ATO films with RuO2 top electrodes.

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The atomic layer deposition (ALD) of multication oxide films is complicated because the deposition behaviors of the component oxides are not independent of one another. In this study, the Ti and Sr atom incorporation behaviors during the ALD of SrTiO films were quantitatively examined via the carefully designed ALD process sequences. HO and O were adopted as the oxygen sources of the SrO subcycles, whereas only O was used for the TiO ALD subcycles. Apart from the general conjecture on the roles of the different types of oxygen sources, the oxygen source that was adopted for the subcycles of the other component oxide had almost complete control of the metal atom incorporation behaviors. This means that the first half-cycle of ALD played a dominant role in determining the metal incorporation rate, which revealed the critical role of the steric hindrance effect during the metal precursor injection for the ALD rate. O had almost doubled its reactivity toward the Ti and Sr precursors compared with HO. Although these are the expected results from the common knowledge on ALD, the quantitative analysis of the incorporation behaviors of each metal atom provided insightful viewpoints for the ALD process of this technically important oxide material. Furthermore, the SrTiO films with a bulk dielectric constant as high as 236 were obtained by the Ru-SrTiO-RuO capacitor structure.

To improve the electrical properties of metal/insulator/metal capacitors for dynamic random access memory, the effects of the top electrode materials and their structures on the capacitor performance are examined. Three kinds of top electrode types (TiN, Ru, and TiN/Ru) are sputter-deposited on ZrO 2 / Al 2 O 3 /ZrO 2 (ZAZ) dielectric layers grown via atomic layer deposition (ALD) on TiN bottom electrodes. The TiN/Ru top electrode samples show the highest capacitance density among the three types of top electrodes, and the Ru and TiN/Ru top electrodes show less leakage current density than the TiN top electrode. The interface property is optimized when the Ru directly contacts the insulating layer due to its higher work function. The TiN layer on the 2 nm-thick Ru top electrode decreases the adverse interfacial reaction layer (TiO x N y ) of the dielectric/TiN bottom electrode through the scavenging oxygen atoms.The major electrical properties required for the capacitors in dynamic random access memory (DRAM) is a sufficiently high capacitance density with a controlled leakage current in the metal/insulator/metal (MIM) structure. The current capacitor structure in mass production is based on the ZrO 2 /Al 2 O 3 /ZrO 2 (ZAZ) dielectric layer and TiN bottom and top electrodes, which have provided DRAM with an appropriate charge storage capacity down to the %20 nm technology node. To pursue further scaling down to the 15 nm DRAM node, however, a certain material innovation is required because the simple decrease in the physical thickness of the ZAZ dielectric layer may induce the critical risk of leakage current density (J) increase. To resolve these issues, various kinds of dielectric materials with a higher dielectric constant (k) than ZrO 2 , such as TiO 2 , Al-doped TiO 2 , SrTiO 3 , and (Ba,Sr)TiO 3 , have been exploited. These new higher-k dielectrics, however, have shown optimum performance on the noble metal electrodes, such as Ru and RuO 2 , which are premature as the capacitor node electrode or bottom electrode in mass production lines compared with the current TiN. Also, their $3.0-3.3 eV bandgap energy is much smaller than the 5.1-5.5 eV bandgap energy of ZrO 2 and the %7.0 eV bandgap energy of amorphous Al 2 O 3 , making them much more vulnerable to the leakage current problem as long as the capacitor voltage remains at %1 V. [1][2][3][4] Therefore, for a more immediate solution to the problem, a new top electrode material possessing a higher work function than TiN could be sought, which may suppress the leakage current even at a thinner ZAZ thickness. It should be noted that the top electrode in DRAM is structured into the shape of a large plate, making its application