Reactive Vapor-Phase Inhibitors for Area-Selective Depositions at Tunable Critical Dimensions

Abstract

Area-selective depositions (ASD) take advantage of the chemical contrast between material surfaces in device fabrication, where a film can be selectively grown by chemical vapor deposition on metal versus a dielectric, for instance, and can provide a path to nontraditional device architectures as well as the potential to improve existing device fabrication schemes. While ASD can be accessed through a variety of methods, the incorporation of reactive moieties in inhibitors presents several advantages, such as increasing thermal stability and limiting precursor diffusion into the blocking layer. Alkyne-terminated small molecule inhibitors (SMIs)�propargyl, dipropargyl, and tripropargylamine�were evaluated as metal-selective inhibitors. Modeling these SMIs provided insight into the binding mechanism, influence of sterics, and complex polymer network formed from the reaction between inhibitors consisting of alkene, aromatic, and network branchpoints. While a significant contrast in the binding of the SMIs on copper versus a dielectric was observed, residual amounts were detected on the dielectric surfaces, leading to variable ALD growth rates dependent on pattern-critical dimensions. This behavior can be controlled and utilized to direct film growth on patterns only above a critical threshold dimension; below this threshold, both the dielectric and metal features are protected. This method provides another design parameter for ASD processes and may extend its application to broader-ranging device fabrication schemes.

Light-Mediated Contact Printing of Phosphorus Species onto Silicon Using Carbene-Based Molecular Layers

“…Strategies for the bottom-up manufacturing of semiconductor devices are increasingly relying on the selective functionalization of surfaces with small molecules or monatomic films that can act as deposition resists, , dopants, or active device components . In combination with parallel patterning techniques, these molecular and atomic-scale interfaces can play an integral role in self-aligned fabrication schemes for biotemplates , or doping of ultrashallow junctions , or act as effective resists in area-selective deposition (ASD) techniques. − However, traditional patterning methods, such as photolithography and shadow mask deposition, are not directly compatible with monomolecular or atomic layers, which are projected to play a bigger role in electronic device manufacturing as a result of the continuous downsizing of device components .…”

“…Strategies for the bottom-up manufacturing of semiconductor devices are increasingly relying on the selective functionalization of surfaces with small molecules or monatomic films that can act as deposition resists, 1 , 2 dopants, 3 or active device components. 4 In combination with parallel patterning techniques, these molecular and atomic-scale interfaces can play an integral role in self-aligned fabrication schemes for biotemplates 5 , 6 or doping of ultrashallow junctions 7 , 8 or act as effective resists in area-selective deposition (ASD) techniques.…”