High permittivity (high-k) materials have received considerable attention as alternatives to SiO 2 for CMOS and low-power flexible electronics applications. In this study, we have grown high-quality ZrO 2 by using atmospheric-pressure plasma-enhanced spatial ALD (PE-sALD), which, compared to temporal ALD, offers higher effective deposition rates and uses atmospheric-pressure plasma to activate surface reactions at lower temperatures. We used tetrakis(ethylmethylamino)zirconium (TEMAZ) as precursor and O 2 plasma as co-reactant at temperatures between 150 and 250 • C. Deposition rates as high as 0.17 nm/cycle were achieved with N-and C-contents as low as 0.4% and 1.5%, respectively. Growth rate, film crystallinity and impurity contents in the films were found to improve with increasing deposition temperature. The measured relative permittivity lying between 18 and 28 with leakage currents in the order of 5 × 10 −8 A/cm 2 demonstrates that atmospheric PE-sALD is a powerful technique to deposit ultrathin, high-quality dielectrics for low-temperature, large-scale microelectronic applications. The continuous improvement in performance of integrated circuits has been based on miniaturization of components. The effective gate length in field-effect transistors shrinks to smaller and smaller sizes and, consequently, the thickness of the gate oxide decreases.1 SiO 2 has been the most popular gate oxide material used in microelectronic manufacturing due to its thermal stability and ideal interface quality on Si. However, during the past fifty years the thickness of the SiO 2 gate oxide has already been reduced to its physical limit of 1.2 nm, below which a critical gate leakage of 1 A/cm 2 is exceeded. 2 To overcome this problem, dielectrics with a high permittivity (high-k materials) have been extensively investigated as promising substitutes of the conventional SiO 2 for CMOS and DRAM technology. The high permittivity (k > 10) ensures high capacitance for thicker gate oxide layers while greatly reducing tunneling and gate leakage currents. 3,4 Among high-k oxides, ZrO 2 is considered one of the most promising SiO 2 alternatives due to its high dielectric constant (k = 20-25), large bandgap (5.1-7.8 eV) and thermodynamical stability. 5,6 ZrO 2 proved to be a good dielectric in transistor applications with leakage current of the order of 10 −6 -10 −9 A/cm 2 and in DRAM capacitor applications especially when present in ZrO 2 /Al 2 O 3 /ZrO 2 nanolaminate structures.7 High-k materials are also relevant for low-power applications of flexible electronics. 5,8-11High-k materials are deposited in a variety of chemical and physical deposition techniques including metallorganic chemical vapor deposition (MOCVD), atomic layer deposition (ALD), sol-gel and sputtering. ALD has proven to be the most suitable technique for high-k deposition due to its unique nanoscale thickness and layer uniformity control. In its conventional time-sequenced mode, ALD is a gas phase deposition technique in which the substrate surface is exposed altern...

An atmospheric-pressure plasma-enhanced spatial atomic layer deposition (PE-s-ALD) process for SiO2 using bisdiethylaminosilane (BDEAS, SiH2[NEt2]2) and O2 plasma is reported along with an investigation of its underlying growth mechanism. Within the temperature range of 100–250 °C, the process demonstrates self-limiting growth with a growth per cycle (GPC) between 0.12 and 0.14 nm and SiO2 films exhibiting material properties on par with those reported for low-pressure PEALD. Gas-phase infrared spectroscopy on the reactant exhaust gases and optical emission spectroscopy (OES) on the plasma region are used to identify the species that are involved in the ALD process. Based on the identified species, we propose a reaction mechanism where BDEAS molecules adsorb on −OH surface sites through the exchange of one of the amine ligands upon desorption of diethylamine (DEA). The remaining amine ligand is removed through combustion reactions activated by the O2 plasma species leading to the release of H2O, CO2, and CO in addition to products such as N2O, NO2, and CH-containing species. These volatile species can undergo further gas-phase reactions in the plasma as indicated by the observation of OH*, CN*, and NH* excited fragments in OES. Furthermore, the infrared analysis of the precursor exhaust gas indicated the release of CO2 during precursor adsorption. Moreover, this analysis has allowed the quantification of the precursor depletion yielding values between 10 and 50% depending on the processing parameters. Besides providing insights into the chemistry of atmospheric-pressure PE-s-ALD of SiO2, our results demonstrate that infrared spectroscopy performed on exhaust gases is a valuable approach to quantify relevant process parameters, which can ultimately help evaluate and improve process performance.

Atmospheric-pressure plasma-enhanced spatial atomic layer deposition (PE-s-ALD) is considered a promising technique for high-throughput and low-temperature deposition of ultrathin films for applications where volume and costs are particularly relevant. The number of atmospheric-pressure PE-s-ALD processes developed so far is rather limited, and the fundamental aspects of their growth mechanisms are largely unexplored. This work presents a study of the atmospheric-pressure PE-s-ALD process of Al2O3 using trimethylaluminum [TMA, Al(CH3)3] and Ar–O2 plasma within the temperature range of 80–200 °C. Thin-film analysis revealed low impurity contents and a decreasing growth-per-cycle (GPC) with increasing temperature. The underlying chemistry of the process was studied with a combination of gas-phase infrared spectroscopy on the exhaust plasma gas and optical emission spectroscopy (OES) on the plasma zone. Among the chemical species formed in the plasma half-cycle, CO2, H2O, CH4, and CH2O were identified. The formation of these products confirms that the removal of CH3 ligands during the plasma half-cycle occurs through two reaction pathways that have a different temperature dependences: (i) combustion reactions initiated by O2 plasma species and leading to CO2 and H2O formation and (ii) thermal ALD-like reactions initiated by the H2O molecules formed in pathway (i) and resulting in CH4 production. With increasing temperature, the dehydroxylation of OH groups cause less TMA adsorption which leads to less CO2 and H2O from the combustion reactions in the plasma step. At the same time, the higher reactivity of H2O at higher temperatures initiates more thermal ALD-like reactions, thus producing relatively more CH4. The CH4 can also undergo further gas-phase reactions leading to the formation of CH2O as was theoretically predicted. Another observation is that O3, which is naturally produced in the atmospheric-pressure O2 plasma, decomposes at higher temperatures mainly due to an increase of gas-phase collisions. In addition to the new insights into the growth mechanism of atmospheric-pressure PE-s-ALD of Al2O3, this work presents a method to study both the surface chemistry during spatial ALD to further extend our fundamental understanding of the method.

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