Influence of Increasing Deposition Temperature during Atomic Layer Deposition on Electrical Properties and Reliability in Al2O3 - Doped ZrO2 Based Two-Dimensional and Three-Dimensional Metal-Insulator-Metal Decoupling Capacitors
Authors: Falidas Konstantinos Efstathios , Kühnel Kati , Everding Maximilian Bernd , Rudolph Matthias , Czernohorsky Malte , Heitmann Johannes 
Published: February 2024

The influence of deposition temperature (TD) on thin film layers of high-k dielectrics used as insulators in embedded Metal-Insulator-Metal (MIM) decoupling capacitors is critical to their future behavior in terms of electrical properties and reliability. These layers are deposited via atomic layer deposition (ALD), which is known for its high uniformity in any type of structural topology. High-k dielectrics, such as Zr, inside high aspect ratio three-dimensional (3-D) structures are a challenging task even in the case of ALD processing. Al2O3 doping is often used within the high-k layer stack during ALD to optimize electrical performance of MIM structures with respect to leakage currents and reliability. In this context, appropriate atomic layer deposition temperature (TD) of the Al2O3-doped ZrO2 high-dielectric stack must be established to enable optimum electrical properties. Electrical data of decoupling capacitors must fulfill the industrial requirements, which demand that, for example, the leakage current density (J) must not exceed a certain level (<1µA/cm²) and that long-term lifetimes under different operating temperatures of a minimum of 10 years at accumulated fail rate of 10 ppm must be achieved.
In this work, we report on a study of the influence of ALD TD on Al2O3-doped ZrO2 thin films fabricated on 300mm wafers. We evaluate the impact of TD on high aspect ratio substrates based on electrical properties and reliability parameters. To achieve this, we use 3 different deposition temperatures (293°C, 313°C, and 333°C) and two physical topologies (planar and 3-D capacitors with cavities-trenches) without compromising the chemical stability of the ALD precursors. For metal precursors, TEMAZ (Tetrakis-ethylmethylamino-zirconium) and TMA (Tri-methyl-aluminum) are used for Zr and Al, respectively. Ozone is used as reactant agent and argon as carrier/purge gas. The ZrO2 cycle consists of pulsing with TEMAZ, purging with Ar gas, oxidizing with O3, and purging with Ar gas. In a similar way, the dopant (TMA) is added, followed by purging steps with Ar, O3 and Ar again. After a few ZrO2 cycles, an Al2O3 cycle is followed, so that nano-laminate films of Al2O3 are formed on top of ZrO2 films. By repeating the ZrO2 and the Al2O3 cycles several times, the desired film thickness is achieved. For the MIM stacks, TiN is used as an electrode material on both sides. There was no post deposition anneal to maintain the amorphous state of the insulator with low defect density and high structural uniformity.
The planar capacitors show minimal changes in terms of capacitance density with increasing TD. On the other hand, the 3-D samples show a 17% increase in capacitance density with a TD increase of 20°C from 293°C to 313°C. This increase becomes much smaller (2.3%) for a further TD increase of 20°C at 333°C. However, with increasing TD, the E-field linearity of 3-D samples, expressed by the quadratic E-field capacitor coefficient α, increases by 2% and 17% for TD=313°C and TD=333°C, respectively. The significant improvement in field linearity indicates the highest TD provides the best and most stable capacitance behavior. The J(E)-curves of planar and 3-D devices exhibit different behavior with respect to current density and dielectric breakdown. Specifically, planar devices show greater variation in J(E)-curves over temperature, with decreasing breakdown field (EBD) as TD increases. On the other hand, 3-D samples show little variation in EBD with temperature. Furthermore, planar devices show lower symmetry in their J(E)-curves over the field polarity compared to 3-D capacitors, which could be attributed to differences in conduction mechanisms. Despite having a lower EBD, planar devices reveal improved lifetime and reliability with increasing TD, possibly due to reduced carbon impurities during the insulator deposition. For instance, increasing TD from 293°C to 313°C leads to a 47% improvement in extrapolated lifetime, while a further increase in TD, improves lifetime by an additional 14%. A 10-year lifetime goal can only be achieved at 1MV/cm with TD=333°C and for samples exposed to any temperature conditions (25-150°C). In contrast, 3-D capacitors exhibit a better degradation slope at lower deposition temperatures but require the highest TD to achieve an 18% improvement in lifetime. However, due to their lower EBD, they cannot reach the 10-year lifetime goal at 1MV/cm, except at low applied temperatures (25°C-50°C).
In conclusion, the highest TD of 333°C without any chemical decomposition of the metal precursor (TEMAZ) is the optimal deposition temperature for both planar and 3-D Al2O3-doped ZrO2 based MIM decoupling capacitors, providing auspicious results in terms of all relevant parameters.

Figure 1