<i>k</i>-Restoring Processes at Carbon Depleted Ultralow-<i>k</i> Surfaces

Böhm, Oliver; Leitsmann, R.; Plänitz, Philipp; Radehaus, C.; Schreiber, Michael; Schaller, Μ.

doi:10.1021/jp202851p

Cited by 7 publications

(5 citation statements)

References 28 publications

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“…Reaction of the DMADMS with surface hydroxyl groups leading to CH 3 -termination of the surface involves small free energy of activation values (Δ G ‡ ) of ca. 20 kcal/mol, and a negative free energy of reaction (Δ G ) . Therefore, it can be inferred that DMADMS would prefer a dually bound configuration with both amino ligands substituted by surface oxygens (*O 2 –Si(CH 3 ) 2 ).…”

Section: Resultsmentioning

confidence: 99%

“…20 kcal/mol, and a negative free energy of reaction (ΔG). 28 Therefore, it can be inferred that DMADMS would prefer a dually bound configuration with both amino ligands substituted by surface oxygens (*O 2 −Si(CH 3 ) 2 ). Monodentate, singly bound DMADMS (*O−Si[N(CH 3 ) 2 ](CH 3 ) 2 , marked "1 DMA ↑" on Figure 4a) can also be a product structure, if only one isolated hydroxyl is locally available for adsorption.…”

Section: ■ Introductionmentioning

confidence: 99%

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Area-Selective Atomic Layer Deposition Using Si Precursors as Inhibitors

Khan

Shong

et al. 2018

Chem. Mater.

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Short-chain aminosilanes, namely, bis(N,Ndimethylamino)dimethylsilane (DMADMS) and (N,Ndimethylamino)trimethylsilane (DMATMS), have been used as Si precursors for atomic layer deposition (ALD) of SiO 2 . In this work, the DMADMS and DMATMS Si precursors are utilized as inhibitors for area-selective ALD (AS-ALD). The inhibitors selectively adsorb on a SiO 2 surface but not on H− Si, so that SiO 2 becomes selectively deactivated toward subsequent ALD. The deactivation of the SiO 2 surface by the inhibitors was investigated using various experimental and theoretical methods, including surface potential measurements, spectroscopic ellipsometry, and X-ray photoelectron spectroscopy. Better inhibition was observed for ALD of Ru and Pt than for ALD of Al 2 O 3 and HfO 2 . Through quantum mechanical and stochastic simulations, the difference in the blocking ability for noble metal and metal oxide ALD by the aminosilane inhibitors could be attributed to the inherently partial surface coverage by the inhibitors at their saturation and the reactivity of the subsequent ALD precursors. As silane inhibitors can be easily integrated with vacuum-based processes to facilitate high volume manufacturing of upcoming electronic devices, the current study provides a potential approach for the utilization of AS-ALD in pattern fabrication inside 3D nanostructures.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Area-Selective Atomic Layer Deposition Using Si Precursors as Inhibitors

Khan

Shong

et al. 2018

Chem. Mater.

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“…To study the repair behavior of the fragments, we composed a small set of ULK-fragments (refer figure 2). The approach to use fragments to study surface reactions has been successfully employed with regard to atomic layer deposition (ALD) processes [21] and was also applied to ULK materials by Böhm et al [11,23] .…”

Section: Model Systemmentioning

confidence: 99%

“…The silylation process [9][10][11][12][13], on the other hand, works at much lower temperatures (T<300°C). However, due to the size of the silylation precursors they are not able to diffuse into deeper regions of the damaged material.…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigation of an in situ k-restore process for damaged ultra-low-k materials based on plasma enhanced fragmentation

Förster

Wagner

Gemming

et al. 2015

Journal of Vacuum Science &Amp; Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phen

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The authors present theoretical investigations of a k-restore process for damaged porous ultra-low-k (ULK) materials. The process is based on plasma enhanced fragmented silylation precursors to replace k-value damaging, polar Si-OH and Si-H bonds by k-value lowering Si-CH3 bonds. The authors employ density functional theory to determine the favored fragments of silylation precursors and show the successful repair of damaged bonds on our model system. This model system consists of a small set of ULK-fragments, which represent various damaged states of ULK materials. Our approach provides a fast scanning method for a wide variety of possible repair reactions. Further, the authors show that oxygen containing fragments are required to repair Si-H bonds and fragments with dangling Si-bonds are most effective to repair polar Si-OH bonds

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“…Given that plasma-induced damage is difficult to prevent in BEOL processing, one alternative is to chemically repair the process-induced damage [ 35 , 36 , 37 ]. In accordance with this viewpoint, several methods have been extensively proposed for damage restoration in the past, such as aqueous [ 38 ], vapor [ 39 , 40 ] or super-critical CO 2 enhanced [ 41 , 42 ] chemical silylation processes.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Thermo–Mechanical Reliability of Ultralow-K Dielectrics with Self-Organized Molecular Pores

Ma¹,

Bang

Son

et al. 2021

Materials

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This paper reported the enhancement in thermo-mechanical properties and chemical stability of porous SiCOH dielectric thin films fabricated with molecularly scaled pores of uniform size and distribution. The resulting porous dielectric thin films were found to exhibit far stronger resistance to thermo-mechanical instability mechanisms common to conventional SiCOH dielectric thin films without forgoing an ultralow dielectric constant (i.e., ultralow-k). Specifically, the elastic modulus measured by nano-indentation was 13 GPa, which was substantially higher than the value of 6 GPa for a porous low-k film deposited by a conventional method, while dielectric constant exhibited an identical value of 2.1. They also showed excellent resistance against viscoplastic deformation, as measured by the ball indentation method, which represented the degree of chemical degradation of the internal bonds. Indentation depth was measured at 5 nm after a 4-h indentation test at 400 °C, which indicated an ~89% decrease compared with conventional SiCOH film. Evolution of film shrinkage and dielectric constant after annealing and plasma exposure were reduced in the low-k film with a self-organized molecular film. Analysis of the film structure via Fourier-transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) indicated an increase in symmetric linear Si–O–Si molecular chains with terminal –CH3 bonds that were believed to be responsible for both the decrease in dipole moment/dielectric constant and the formation of molecular scaled pores. The observed enhanced mechanical and chemical properties were also attributed to this unique nano-porous structure.

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k-Restoring Processes at Carbon Depleted Ultralow-k Surfaces

Cited by 7 publications

References 28 publications

Area-Selective Atomic Layer Deposition Using Si Precursors as Inhibitors

Area-Selective Atomic Layer Deposition Using Si Precursors as Inhibitors

Theoretical investigation of an in situ k-restore process for damaged ultra-low-k materials based on plasma enhanced fragmentation

Enhanced Thermo–Mechanical Reliability of Ultralow-K Dielectrics with Self-Organized Molecular Pores

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