TY - JOUR
T1 - Thermodynamics of amorphous SiN(O)H dielectric films synthesized by plasma-enhanced chemical vapor deposition
AU - Chen, Jiewei
AU - Niu, Min
AU - Calvin, Jason
AU - Asplund, Megan
AU - King, Sean W.
AU - Woodfield, Brian F.
AU - Navrotsky, Alexandra
N1 - Funding Information:
Synthesis and partial characterization of the samples was performed at the Logic Technology Development facility of the Intel Corporation in Hillsboro, Oregon, USA. Some characterization and all calorimetric measurements were performed in the Peter A. Rock Thermochemistry Laboratory at the University of California, Davis, USA, supported by Intel Corporation. Salary support for JC came from Intel Corporation and from the A. P. Sloan Foundation’s Deep Carbon Observatory project. Heat capacity measurements were performed at the Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT, USA, supported by a grant from the U.S. Department of Energy under grant DE-SC0016446.
Publisher Copyright:
© 2017 The American Ceramic Society
PY - 2018/5
Y1 - 2018/5
N2 - Thin films of amorphous SiNH (a-SiNH) and amorphous SiNOH (a-SiNOH) synthesized by plasma-enhanced chemical vapor deposition (PECVD) are used extensively in the semiconductor industry, but little is known regarding their thermodynamic stability, and there are several long-term reliability issues for these materials. To address the stability issues, a detailed thermodynamic investigation has been conducted on a series of a-SiNH, and a-SiNOH dielectric films. High-temperature oxidative drop-solution calorimetry in molten sodium molybdate solvent at 1075 K was utilized to determine the formation enthalpies from the elements and from crystalline counterparts/gaseous products. Together with entropy data derived from cryogenic heat capacity measurements, we confirmed that the incorporation of more hydrogen and oxygen leads to more negative enthalpies and Gibbs free energies of formation from elements. Coupled with FTIR structural analysis, the thermochemical data suggest that the Si–H2 chain structure and Si–O–Si bonding configurations provide the system with extra thermodynamic stability. However, the Gibbs free energies of formation from crystalline constituents and gaseous products are either positive or nearly zero, indicating that these amorphous films are not stable against decomposition, which may cause problems in high-temperature applications.
AB - Thin films of amorphous SiNH (a-SiNH) and amorphous SiNOH (a-SiNOH) synthesized by plasma-enhanced chemical vapor deposition (PECVD) are used extensively in the semiconductor industry, but little is known regarding their thermodynamic stability, and there are several long-term reliability issues for these materials. To address the stability issues, a detailed thermodynamic investigation has been conducted on a series of a-SiNH, and a-SiNOH dielectric films. High-temperature oxidative drop-solution calorimetry in molten sodium molybdate solvent at 1075 K was utilized to determine the formation enthalpies from the elements and from crystalline counterparts/gaseous products. Together with entropy data derived from cryogenic heat capacity measurements, we confirmed that the incorporation of more hydrogen and oxygen leads to more negative enthalpies and Gibbs free energies of formation from elements. Coupled with FTIR structural analysis, the thermochemical data suggest that the Si–H2 chain structure and Si–O–Si bonding configurations provide the system with extra thermodynamic stability. However, the Gibbs free energies of formation from crystalline constituents and gaseous products are either positive or nearly zero, indicating that these amorphous films are not stable against decomposition, which may cause problems in high-temperature applications.
KW - amorphous low-k SiN(O)H films
KW - formation enthalpy
KW - thermodynamic stability
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U2 - 10.1111/jace.15350
DO - 10.1111/jace.15350
M3 - Article
AN - SCOPUS:85036583407
SN - 0002-7820
VL - 101
SP - 2017
EP - 2027
JO - Journal of the American Ceramic Society
JF - Journal of the American Ceramic Society
IS - 5
ER -