Influence of oxygen plasma treatment on boron carbon nitride film composition

Aoki, Hidemitsu; Masuzumi, Takuro; Watanabe, Daisuke; Mazumder, M.K.; Sota, Hiroshi; Kimura, Chiharu; Sugino, Takashi

doi:10.1016/j.apsusc.2008.10.045

Cited by 12 publications

(5 citation statements)

References 11 publications

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“…Absolute oxygen concentration increases only slightly from 12.2% after initial growth to 14.7% after 65 s plasma treatment. Evidence for nitrogenation of the surface can be seen in the appearance of a peak in the high-resolution N 1s spectrum (Figure e) at a BE of ∼399 eV, consistent with N–B and/or N–C bonds. − Further, we observe from the high-resolution B 1s spectra (Figure a), in addition to the B–B/B–C carborane peak centered at a BE of ∼189.5 eV, a new peak grow in at a BE of 191.6 eV (which is slightly lower than the B–O peak observed at 192.5–193 eV) that we assign to B–N bonding. − The peak area ratio of the B–B/B–C peak to B–N peak decreases from 7.6 after a 5 s N 2 plasma treatment to 0.6 after a 65 s plasma treatment. This roughly follows the trend observed for the B:N ratio described earlier; however some deviation may suggest that some of the nitrogen is being incorporated into other types of bonds (e.g., C–N) and/or that there is an additional unresolvable B–O peak (with longer plasma exposure).…”

Section: Resultsmentioning

confidence: 63%

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: Resultsmentioning

confidence: 63%

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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“…36 Moreover formation of B-O ͑809 kJ/mol͒ bonding upon oxidation would be a stable arrangement based on these bond strengths. Indeed, Aoki et al 37 reported that the O 2 plasma etching rate of BCN films increases as the amount of B in the film increases, although these films were deposited from BCl 3 , CH 4 , and N 2 in a plasma-assisted process. The fact that the BCN films deposited in our laboratory are more susceptible to O uptake when the percentage of B is lower suggests that an alternative mechanism is responsible for the observed increase in percentage of O.…”

Section: Discussionmentioning

confidence: 98%

Electrical characteristics of thin boron carbonitride films on Ge(100) and Si(100)

Fitzpatrick

Ekerdt

2009

Journal of Vacuum Science &Amp; Technology B: Microelectronics and Nanometer Structures Processing, Measurement, and Phenomena

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Metal insulator semiconductor structures were fabricated from n-Si(100) and n-Ge(100) wafers passivated with thin (4.5–5 nm) films of N-rich BCxNy (0.09≤x≤0.15, 0.38≤y≤0.52) and with atomic layer deposition HfO2 (10 nm) as the gate dielectric. C-V and I-V characteristics of devices with BCxNy films grown at 275–400 °C by chemical vapor deposition showed that lower deposition temperatures resulted in improved electrical characteristics, including decreased hysteresis, lower VFB shift, lower leakage current, and less C-V stretch out. The electrical improvement is attributed to decreased bulk and interfacial defects in lower temperature deposited BCxNy films, which also had a higher optical bandgap [Eg=3.55 eV at 275 °C on Ge(100)], lower subbandgap absorption, lower index of refraction [n(633 nm)=1.84 at 275 °C on Ge(100)], reduced O uptake during ambient exposure, and increased percentage of B. Even for the lowest growth temperature studied (275 °C), BCxNy-passivated Ge(100) devices had considerable hysteresis (1.05 V), and electrical characteristics worsened after a postmetallization anneal. BCxNy-passivated Si(100) devices outperformed similar Ge(100) devices likely due to the higher interface state densities at the BCxNy–Ge(100) interface associated with the higher relative inertness of Ge(100) to thermal nitridation. C-rich BC0.61N0.08 films were also investigated but large amounts of hysteresis and fixed negative charge motivated the abandonment of these films.

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“…This phenomenon indicates the films have excellent thermalstability in vacuum. However, for films annealing in air, the spectra show a strong absorption peak at 1450 cm −1 which contributed to B-O bonds 37 and two weaker absorption peaks at 1052 and 1190 cm −1 associated with the antisymmetric C-O-C and C-O bonds. 38 The stronger B-O bonds may be led by the relatively weaker bond energies of B-N (389 kJ/mol) and B-C (448 kJ/mol) than that of C-N (754 kJ/mol), 37 which caused the bonding of B and O in air.…”

Section: Resultsmentioning

confidence: 99%

Stoichiometric controlling of boroncarbonitride thin films with using BN-C dual-targets

Zhang

Yang

et al. 2015

AIP Advances

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High carbon-rich boroncarbonitride thin films have been grown by pulsed laser deposition (PLD) technique with using BN-C dual-targets. Fourier-transform infrared (FTIR) spectroscopy results presented B-N, B-C and C-N bonds, indicating the as-deposited thin films were new ternary compounds. B-N, B-C and C-N bonding structures were also detected by X-ray photoelectron spectroscopy (XPS), and carbon content fell into a large range of 45.8 to 85.9%. The films exhibited good thermalstability in vacuum, whereas were oxidized at 600 oC in air.

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Influence of oxygen plasma treatment on boron carbon nitride film composition

Cited by 12 publications

References 11 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

Electrical characteristics of thin boron carbonitride films on Ge(100) and Si(100)

Stoichiometric controlling of boroncarbonitride thin films with using BN-C dual-targets

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