Surface characterization of a low dielectric constant polymer–SiLK* polymer, and investigation of its interface with Cu

Rajagopal, A.; Grégoire, Chantal; Lemaire, Juliette; Pireaux, Jean‐Jacques; Baklanov, Mikhaı̈l R.; Vanhaelemeersch, Serge; Maex, Karen; Waeterloos, J.

doi:10.1116/1.590914

Cited by 30 publications

(20 citation statements)

References 15 publications

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“…28 These XPS investigations also detected a small amount of oxygen in the SiLK substrate. 28 These XPS investigations also detected a small amount of oxygen in the SiLK substrate.…”

Section: A Tin Atomic Layer Deposition On Silkmentioning

confidence: 83%

Improved nucleation of TiN atomic layer deposition films on SiLK low-k polymer dielectric using an Al2O3 atomic layer deposition adhesion layer

Elam

Wilson

Schuisky

et al. 2003

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

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Diffusion barriers are required to prevent copper from diffusing into low-k polymer dielectrics in backend interconnects. The ability to deposit conformal diffusion barriers onto high aspect ratio, low-k polymer features requires atomic layer deposition ͑ALD͒ techniques. This study examined TiN ALD on SiLK ͑a trademark of the Dow Chemical Company͒ low-k polymer dielectric using tetrakis-dimethylamino titanium and NH 3 . X-ray fluorescence spectroscopy ͑XRFS͒, optical microscopy, and surface profiling of the TiN ALD films deposited on SiLK revealed discontinuous films displaying distinct patchy regions. The patches corresponded to a thinner TiN coating and were attributed to difficulties for TiN ALD nucleation on SiLK. To study TiN ALD nucleation, in situ quartz-crystal microbalance ͑QCM͒ measurements were performed by spincoating SiLK onto the QCM sensor. Subsequent QCM measurements during TiN ALD revealed very low initial TiN ALD growth rates indicating poor nucleation. Al 2 O 3 ALD was then performed on the SiLK film using trimethyl aluminum and H 2 O. Surface profiling, XRFS, QCM, and transmission electron microscopy measurements revealed that the Al 2 O 3 ALD film nucleates immediately on SiLK producing a continuous Al 2 O 3 film. In addition, QCM measurements showed that TiN ALD nucleates readily on the Al 2 O 3 surface. The Al 2 O 3 ALD adhesion layer facilitated the growth of a continuous TiN ALD film on SiLK. Examination of TiN ALD films prepared on SiLK with progressively thinner Al 2 O 3 ALD adhesion layers revealed that 10 Al 2 O 3 ALD cycles were sufficient to promote the nucleation of the TiN ALD film.

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“…28 These XPS investigations also detected a small amount of oxygen in the SiLK substrate. 28 These XPS investigations also detected a small amount of oxygen in the SiLK substrate.…”

Section: A Tin Atomic Layer Deposition On Silkmentioning

confidence: 83%

Improved nucleation of TiN atomic layer deposition films on SiLK low-k polymer dielectric using an Al2O3 atomic layer deposition adhesion layer

Elam

Wilson

Schuisky

et al. 2003

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

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“…This was confirmed from FTIR analysis, which is shown in Fig. As-deposited SiLK-D™ shows only a single peak at 285 eV 19,21,22 while plasma treated SiLK-D™ shows a slight shift in the C 1s peak and a broad shoulder indicative of the changed bonding state of carbon in Fig. There is no change in the FTIR peaks before and after plasma treatment, confirming that the plasma treatment does not alter the bulk chemical structure and it oxidizes only the surface layers of the dielectric.…”

Section: B Plasma Surface Modification Of Silk-d™mentioning

confidence: 56%

Role of reactive surface oxygen in causing enhanced copper ionization in a low-k polymer

Achanta

Gill

Plawsky

et al. 2006

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

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Copper oxidation, ionization, and penetration into a low-k polymer, SiLK-D™, are studied here. It is demonstrated by exposure to an oxidizing plasma and subsequent bias-temperature-stress experiments that an increase in the content of reactive or weakly bound oxygen at the SiLK-D™ surface in contact with the copper leads to the oxidation of the copper and injection of the copper into the polymer. The oxidation and injection are driven by the applied external electric field. X-ray photoelectron spectroscopy has been used to characterize the surface oxygen content on as-deposited ͑low oxygen content, the reference͒ and oxygen plasma treated films ͑high surface oxygen content͒. Capacitors were fabricated on both materials and bias temperature stress tests were done for several O 2 plasma exposure times and for external electric fields of 1, 0.5, and 0.1 MV/ cm to detect copper ionization and injection. With an electric field of only 0.1 MV/ cm, copper injection was not detectable even though oxygen at the SiLK-D™ surface had been increased by exposure to oxygen plasma.

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“…Plasma treatment reduces the amount of components containing C-C or C-H bonds and causes the aromatic components to disappear, while at the same time increasing the amount of components with binding energies in the range 286-288 eV, which are related to oxygen or nitrogen. 4 For N 2 plasma treatment, an N 1s peak was observed, indicating surface nitriding.…”

Section: (C) Silkmentioning

confidence: 99%

“…Ł shake-up transition caused by the aromatic rings in the resin. 4,7 After plasma treatment, the shape of the main spectrum does not change significantly, but no satellites will be observed.…”

Section: (C) Silkmentioning

confidence: 99%

X‐ray photoelectron spectroscopic study of surface modification of low‐k organic materials by plasma treatment

Uchida

Fukuda

Yanazawa

2004

Surface & Interface Analysis

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The surface modification of SiLK resin (trademark of the Dow Chemical Company) by means of N 2 or Ar plasma treatment was studied using XPS. This surface modification is supposed to improve the adhesion of tantalum. XPS spectra of the surface of plasma-treated resin exhibited an oxygen peak, and also a nitrogen peak after N 2 plasma treatment, in addition to a carbon peak. The plasma treatment was found to break some of the C-C bonds and to cause the disappearance of components related to aromatic rings. In consequence, carbon components with low amounts of oxygen are produced which are probably from the atmosphere. In addition, the N 2 plasma also nitrides the surface layer. The Ar plasma produces damage, such as unbonded carbon atoms, that can reach deeper into the resin films if the exposure time is long enough; while N 2 plasma prevents the penetration of damage, probably because of the nitride layer on the surface. The plasma treatment produces phenomena like the restructuring of carbon bonds. Furthermore, the XPS analysis indicates that oxidation of the resin at the surface suppresses the reaction between the resin and Ta, resulting in a more metal-like Ta layer. The reconstructed surface layer resulting from the bonding of unbonded carbon atoms with other atoms should provide better adhesion, thus allowing deposition of a Ta layer with a different chemical state.

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Surface characterization of a low dielectric constant polymer–SiLK* polymer, and investigation of its interface with Cu

Cited by 30 publications

References 15 publications

Improved nucleation of TiN atomic layer deposition films on SiLK low-k polymer dielectric using an Al2O3 atomic layer deposition adhesion layer

Improved nucleation of TiN atomic layer deposition films on SiLK low-k polymer dielectric using an Al2O3 atomic layer deposition adhesion layer

Role of reactive surface oxygen in causing enhanced copper ionization in a low-k polymer

X‐ray photoelectron spectroscopic study of surface modification of low‐k organic materials by plasma treatment

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