Atomic layer deposition (ALD) processes for binary oxide (AO_y or BO_z) growth consist of a sequential introduction of metal precursor (precursor-A or precursor-B) and oxidant-O such that the respective surface reactions are self-limiting with respect to precursor and oxidant exposure times (t_A or t_B and t_O). This approach has been further extended for ternary oxide A_δB_1−δO_λ deposition with (i) super-cycle ALD method (where each super-cycle comprises of m-cycles of AO_y ALD followed by n-cycles of BO_z ALD), (ii) precursor co-dosing method (where precursor-A and precursor-B are simultaneously pulsed followed by an oxidant-O pulse), and (iii) 3-step ALD (where precursor-A, precursor-B, and oxidant-O are sequentially pulsed). In this Letter, we present a subsaturation pulse initiated 3-step process with A^pBO… pulsing sequence for ternary oxide A_δB_1−δO_λ deposition in showerhead ALD reactors. Here, the pulse-A^p reaction step is controlled in the subsaturation regime, while both pulse-B and pulse-O reaction steps are allowed to reach saturation as in a typical ALD. From kinetic simulations, we show that the chemisorbed –A^che surface coverage [A^che] could be controlled below its saturation limit [A^che]^sat with exposure time t_A and precursor impingement rate k_Aⁱⁿ in the pulse-A^p reaction step. Furthermore, with precursor transport model, we show that k_Aⁱⁿ could be varied with a better control using ampoule temperature T_amp^A and precursor-A carrier gas flow F_i^A together than using T_amp^A alone. As example, we report Zr^pHfO… pulsed deposition of Zr_xHf_1−xO₂ ternary oxide samples ZHO1–ZHO4 in a showerhead ALD reactor, and from quantitative XPS analysis, we show that the Zr-fraction (x) could be varied in the range of 0.094 ≤ x ≤ 0.159 with Zr-carrier gas flow F_Ar^Zr.

中文翻译：

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化学计量控制的喷淋头原子层沉积反应器中均匀三元氧化物的生长及其在ZrxHf1-xO2中的应用

用于二元氧化物（AO _y或BO _z）生长的原子层沉积（ALD）工艺包括依次引入金属前体（前体A或前体B）和氧化剂O，以使各自的表面反应具有自限性。关于前体和氧化剂的暴露时间（t _A或t _B和t _O）。这种方法已被进一步扩展为三元氧化物A _δ乙_1-δ ö _λ沉积与（i）超周期ALD法（其中AO的米周期的每个超级周期包括_ý ALD接着BO的正周期_žALD），（ii）前体共配量方法（其中前体-A和前体-B同时被脉冲，接着是氧化剂-O脉冲）和（iii）3步ALD（其中前体-A，前体-B，和氧化剂-O被顺序脉冲）。在这种信，我们提出了一个subsaturation脉冲引发的3步过程与甲^p BO ...为脉冲序列三元氧化物A _δ乙_1-δ Ö _λ沉积在喷头ALD反应器。在此，脉冲-A ^p反应步骤被控制在subsaturation制度，同时兼具脉冲-B和脉冲-O反应步骤被允许达到饱和如在典型的ALD。从动力学模拟，我们显示化学吸附的–A ^che表面覆盖率[A ^che]可以被控制低于其饱和极限[A^澈]^坐在与曝光时间t_甲和前体冲击率k_阿^中在脉冲-A ^p反应步骤。此外，通过前驱体传输模型，我们表明，与单独使用T _amp ^A相比，使用安瓿瓶温度T _amp ^A和前驱物A载气流F _i ^A可以更好地控制k _A ^in，从而可以进行控制。例如，我们报告Zr _x Hf _1-x O _2的Zr ^p HfO…脉冲沉积喷淋头ALD反应器中的三元氧化物样品ZHO1–ZHO4，并且通过定量XPS分析，我们发现，随着Zr载气流F _Ar ^Zr的存在，Zr分数（x）可以在0.094≤x≤0.159的范围内变化。