A Selectively Colorful yet Chilly Perspective on the <sup>Highs</sup> and <sub>Lows</sub> of Dielectric Materials for CMOS Nanoelectronics

King, Sean W.; Plombon, John J.; Bielefeld, J.; Blackwell, James M.; Vyas, Sumit; Chebiam, Ramanan; Naylor, Carl H.; Michalak, David J.; Kobrinsky, Mauro J.; Gstrein, Florian; Metz, M.; Clarke, James Stanier; Thapa, Resham; Paquette, Michelle M.; Vemuri, Vamseedhara; Strandwitz, Nicholas C.; Ye, Fan; Orłowski, M.

doi:10.1109/iedm13553.2020.9371942

Cited by 4 publications

(2 citation statements)

References 24 publications

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“…We focus on carboranethiol SAMs on copper, based on the archetypal thiol–metal monolayer chemistry. , Carboranethiols have been previously shown to form ∼1 nm thick monolayers on a series of metals, , with demonstration of corrosion resistance on silver and the ability to modify the surface electronic properties of gold, , silver, − and germanium . The unique properties of boron-based materials, and carborane-based materials in particular, including mechanical, thermal, and chemical robustness, − unique etch chemistry, as well as tunable electronic, optical, and electrical properties, , make these of interest for a multitude of additional nanoelectronic applications including barrier layers, etch stops, and other patterning assist layers. − …”

Section: Introductionmentioning

confidence: 99%

Effect of Heat and Plasma Treatment on Carboranethiol Self-Assembled Monolayers on Copper

Thapa,

Dorsett,

Bale

et al. 2023

J. Phys. Chem. C

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Carborane (C2B10H12) molecules are unique precursors for self-assembled monolayer (SAM) applications. These 3D, icosahedral (12-vertex) molecules allow for the formation of well-ordered layers, potentially with fewer defects than traditional linear alkyl SAMs, and are amenable to cross-linking via labile H atoms with a variety of mechanisms including heat, plasma, and radiation (e.g., UV, e-beam). We have investigated the deposition of SAMs of 1,2-dithiol-ortho-carborane (O) and 9-thiol-meta-carborane (M) on copper from the vapor phase in ultrahigh-vacuum conditions, along with the effect of thermal (150–400 °C) and plasma (N2, H2, Ar, O2) postgrowth treatment. Both films show rapid deposition in the vapor phase with approximate monolayer or few layer coverage, as well as a mixture of physisorption (thiol adsorption) and chemisorption (thiolate binding). Both films additionally show notable stability to thermal treatment up to 400 °C, with only gradual (not abrupt) decrease in boron coverage and minor changes in chemical composition/makeup; however, with the monothiol derivative M showing greater loss of boron and greater oxidation. Nitrogen (N2) plasma treatment leads to partial nitrogenation of boron, while hydrogen (H2) and argon (Ar) plasma treatments lead to partial oxidation of boron, with some parasitic growth (increase in B coverage) especially for the dithiol derivative O. Oxygen (O2) plasma treatment shows an aggressive oxidation (of boron, carbon, sulfur, and copper), but appears to passivate the layers (i.e., the boron oxide based layer formed remains stable and does not change with further plasma exposure). Both heat and plasma treatments reduce copper oxide at the interface and increase thiolate binding (thus conceivably stabilizing the films). Indeed, exposure to N2 plasma appears to further stabilize the films toward heat treatment. These findings highlight that these carboranethiol SAMs represent a robust option for various functional and protective layer applications, and that heat and plasma may be used to further stabilize these films, to modify their properties, or as part of a more complex fabrication scheme.

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Section: Introductionmentioning

confidence: 99%

Effect of Heat and Plasma Treatment on Carboranethiol Self-Assembled Monolayers on Copper

Thapa,

Dorsett,

Bale

et al. 2023

J. Phys. Chem. C

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“…The PMO materials are deposited by using spin-on-glass technology and have an excellent gap filling capability [11]. The gap filling capability is presently becoming important because of possible replacement of Cu by plasma patternable metals (Ru, Mo, W …) and transition from damascene to subtractive integration (metal patterning first) [11,12].…”

Section: Introductionmentioning

confidence: 99%

Effect of H atoms and UV wideband radiation on cured low-k OSG films

Lopaev¹,

Zotovich²,

Zyryanov³

et al. 2022

J. Phys. D: Appl. Phys.

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Effects of hydrogen atoms and UV radiation (λ > 210 nm) on nanoporous organosilicate glass (OSG) low-k films are studied in the temperature range from 20°C to 300°C. The purpose of the study is to understand the mechanisms of low-k films modification that can happen during the cleaning from carbon containing residues formed from sacrificial porogen and accumulated during the air storage. It is shown that exposure of low-k films to hydrogen atoms at low temperature leads to slight modification of hydrocarbon bonds in hydrocarbon residues not bonded to Si. At high temperature (T≥300°C), the relative concentration of -CHx bonds changes in a complex way and depends on the amount and structure of the carbon-containing compounds. The general trend is relatively rapid decrease of –CH2 bonds concentration, while the terminal –CH3 groups are more stable. Temperature also initiates the reaction of hydrogen atoms with low-k with partial modification of low-k matrix breaking Si-O bonds. The destruction of Si-O and Si-CH2 groups leads to the formation of oxygen-deficient centers, followed by the formation of Si-(CH3)2 groups due to their interaction with methyl groups. At 300°C, the total number of Si-CH3 + Si-(CH3)2 groups starts to decrease indicating on partial removal of the methyl groups bonded to silicon. Besides with increasing temperature a slight modification of the structure of matrix under exposure to H atoms is also observed. UV radiation has almost no effect on these processes in the studied conditions. Thus, there exist the “optimal” conditions for H atom impact on OSG low-k films which allows improving film performance by removing porogen residue without damage.

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Dielectric Material Technologies for 2-D Semiconductor Transistor Scaling

Lin

Chen

et al. 2023

IEEE Trans. Electron Devices

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A Selectively Colorful yet Chilly Perspective on the ^Highs and _Lows of Dielectric Materials for CMOS Nanoelectronics

Cited by 4 publications

References 24 publications

Effect of Heat and Plasma Treatment on Carboranethiol Self-Assembled Monolayers on Copper

Effect of Heat and Plasma Treatment on Carboranethiol Self-Assembled Monolayers on Copper

Effect of H atoms and UV wideband radiation on cured low-k OSG films

Dielectric Material Technologies for 2-D Semiconductor Transistor Scaling

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A Selectively Colorful yet Chilly Perspective on the Highs and Lows of Dielectric Materials for CMOS Nanoelectronics

Cited by 4 publications

References 24 publications

Effect of Heat and Plasma Treatment on Carboranethiol Self-Assembled Monolayers on Copper

Effect of Heat and Plasma Treatment on Carboranethiol Self-Assembled Monolayers on Copper

Effect of H atoms and UV wideband radiation on cured low-k OSG films

Dielectric Material Technologies for 2-D Semiconductor Transistor Scaling

Contact Info

Product

Resources

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A Selectively Colorful yet Chilly Perspective on the ^Highs and _Lows of Dielectric Materials for CMOS Nanoelectronics