Effectiveness of Different Ligands on Silane Precursors for Ligand Exchange to Etch Metal Fluorides
Effectiveness of Different Ligands on Silane Precursors for Ligand Exchange to Etch Metal Fluorides
复制标题
不同配体对硅烷前体进行配体交换蚀刻金属氟化物的有效性
DOI：
10.1021/acs.chemmater.2c01603
复制
发表时间：
2022
影响因子：
8.6
通讯作者：
George, Steven M.
中科院分区：
文献类型：
--
作者：
Lii-Rosales, Ann;Johnson, Virginia L.;Cavanagh, Andrew S.;Fischer, Andreas;Lill, Thorsten;Sharma, Sandeep;George, Steven M.
金属氟化物可以通过配体交换反应自发地蚀刻。在这些反应期间，进入的前体和金属氟化物之间的配体交换导致金属氟化物的挥发。这些配体交换反应在许多热原子层蚀刻（ALE）工艺中是重要的。为了测试不同配体对配体交换的有效性，采用原位四极杆质谱（QMS）研究了含不同配体的硅烷前驱体对金属氟化物的自发刻蚀。均配型和杂配型硅烷前体是SiCl 4、SiCl 2（CH 3）2、SiCl（CH 3）2 H和Si（CH 3）4。这些硅烷前体为配体交换反应提供Cl、CH 3或H配体。金属氟化物是GaF 3、InF 3、ZnF 2、ZrF 4、HfF 4和SnF 4。QMS结果表明，F/Cl配体交换观察到所有的金属氟化物与含氯硅烷前体。此外，所有挥发性金属蚀刻产物均为金属氯化物，即GaCl 3、InCl 3、ZnCl 2、ZrCl 4、HfCl 4和SnCl 4。没有检测到金属甲基络合物作为挥发性金属蚀刻产物，表明没有F/CH 3交换。对于SiCl（CH 3）2 H作为硅烷前体，SiF 2（CH 3）2的观察表明，除了F/Cl交换之外，F/H交换也是可能的。对于各种金属氟化物，占主导地位的F/Cl交换导致几乎相等的起始温度的配体交换和蚀刻产生金属氯化物。配体交换反应的热化学计算也预测了金属氯化物的形成。所有的F/Cl交换都是最有利的，如吉布斯自由能（ΔG）的负变化所证明的。这些实验和理论结果为热ALE工艺前驱体的设计提供了指导。
Metal fluorides can be spontaneously etched by ligand-exchange reactions. During these reactions, the exchange of ligands between the incoming precursor and the metal fluoride leads to the volatilization of the metal fluoride. These ligand-exchange reactions are important in many thermal atomic layer etching (ALE) processes. To test the effectiveness of different ligands for ligand exchange, the spontaneous etching of metal fluorides by silane precursors containing different ligands was investigated usingin situquadrupole mass spectrometry (QMS). The homoleptic and heteroleptic silane precursors were SiCl4, SiCl2(CH3)2, SiCl(CH3)2H, and Si(CH3)4. These silane precursors provide Cl, CH3, or H ligands for the ligand-exchange reaction. The metal fluorides were GaF3, InF3, ZnF2, ZrF4, HfF4, and SnF4. The QMS results showed that F/Cl ligand exchange was observed for all the metal fluorides with chlorine-containing silane precursors. In addition, all the volatile metal etch products were metal chlorides, namely, GaCl3, InCl3, ZnCl2, ZrCl4, HfCl4, and SnCl4. No metal methyl complexes were detected as volatile metal etch products indicating no F/CH3exchange. For SiCl(CH3)2H as the silane precursor, the observation of SiF2(CH3)2indicated that F/H exchange is also possible in addition to F/Cl exchange. For the various metal fluorides, the dominance of the F/Cl exchange led to nearly equivalent onset temperatures for ligand exchange and for etching to yield metal chlorides. Thermochemical calculations of the ligand-exchange reactions also predicted the formation of metal chlorides. All F/Cl exchanges were the most thermodynamically favorable as demonstrated by their negative changes in Gibbs free energy (ΔG). These experimental and theoretical results provide guidelines for designing precursors for thermal ALE processes.
登录
查看更多内容
四甲基锆 Zr(CH3)4 的制备
影响因子：
--
作者：
H. J. Berthold;G. Groh
通讯作者：
G. Groh
通过电子碰撞分解 SF6、CF4 和 SiF4
影响因子：
--
作者：
V. H. Dibeler;F. L. Mohler
通讯作者：
F. L. Mohler
通过电子轰击质谱法直接分析金属卤化物
影响因子：
7.4
作者：
Kozo Matsumoto;N. Kiba;T. Takeuchi
通讯作者：
T. Takeuchi
716. 配位化学研究。
DOI：
10.1039/jr9510003245
发表时间：
1951
期刊：
Journal of The Chemical Society (resumed)
影响因子：
--
作者：
A. Kabesh;R. Nyholm
通讯作者：
R. Nyholm
使用 HF 和各种金属前体的顺序暴露对氧化镓进行热原子层蚀刻
影响因子：
8.6
作者：
Younghee Lee;Nicholas R. Johnson;S. George
通讯作者：
S. George