Formation and Ripening of Self-Assembled Multilayers from the Vapor-Phase Deposition of Dodecanethiol on Copper Oxide

Bergsman, David S.; Liu, Tzu‐Ling; Closser, Richard G.; Nardi, Katie Lynn; Draeger, Nerissa; Hausmann, Dennis M.; Bent, Stacey F.

doi:10.1021/acs.chemmater.8b02150

Cited by 33 publications

(51 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…While the bare Cu and Al substrates were hydrophilic, after the deposition of ODPA on Cu and Al, or DDT deposition on Cu, all samples exhibited hydrophobic surfaces because of the SAM formation. The water contact angle (WCA) was measured to evaluate the quality of the SAM because it has been reported to increase, approaching a value near 110°, when highly ordered SAMs form on metal substrates. , The WCAs for ODPA-Cu, DDT-Cu, and ODPA-Al were 110, 108, and 112°, respectively, suggesting the formation of well-packed SAMs. Following SAM formation, 10–100 cycles of SiOC were deposited on bare and SAM-modified substrates.…”

Section: Resultsmentioning

confidence: 99%

“…The degradation of the ODPA SAM is attributed to the presence of HCl, a byproduct for the SiOC MLD process (Figure ), which can readily attack the surface CuO x and destroy the ODPA binding to the CuO x . Alternatively, we tested DDT SAMs on Cu pretreated with acetic acid, which may be more suitable because in this system, DDT molecules bind directly to metallic Cu atoms. ,,, Therefore, the degradation of the DDT SAM can be avoided because no etchable oxidized Cu layer exists. After SiOC deposition on both Cu and DDT-Cu, XPS spectra were collected.…”

Section: Resultsmentioning

confidence: 99%

“…Alternatively, we tested DDT SAMs on Cu pretreated with acetic acid, which may be more suitable because in this system, DDT molecules bind directly to metallic Cu atoms. 7,17,31,32 Therefore, the degradation of the DDT SAM can be avoided because no etchable oxidized Cu layer exists. After SiOC deposition on both Cu and DDT-Cu, XPS spectra were collected.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…In recent years, AS-ALD has been demonstrated on dielectric versus metal patterns for several high- k dielectrics, such as ZnO, Al 2 O 3 , HfO 2 , and ZrO 2 . − For reactions having no inherent selectivity on different surfaces, inhibitors are required to selectively block deposition on the nongrowth area . A group of inhibitors that have been successfully used are self-assembled monolayers (SAMs).…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Area-Selective Molecular Layer Deposition of a Silicon Oxycarbide Low-k Dielectric

Bobb-Semple

et al. 2021

Chem. Mater.

Self Cite

View full text Add to dashboard Cite

Area-selective deposition (ASD) of low-k materials is desired in back-end-of-line processes for fabricating nanopatterns such as fully self-aligned vias. However, the high temperature and/or aggressive coreactants used in conventional low-k material deposition have limited the application of the organic inhibitors used in ASD. Here, we report a strategy to selectively deposit low-k methylene-bridged silicon oxycarbide (SiOC) thin films on metal/dielectric patterns by combining growth using molecular layer deposition (MLD) and inhibition using self-assembled monolayers (SAMs). By using bis (trichlorosilyl)-methane and water as a precursor and coreactant, respectively, SiOC thin films with a dielectric constant of 3.6–3.8 are deposited at 40 °C and at a growth rate of 1.5 Å/cycle. We demonstrate area-selective MLD of this SiOC material for up to 30 cycles (equiv. 4.5 nm) on SiO2 vs Cu using a dodecanethiol SAM to block growth on Cu, and up to 70 cycles (equiv. 10 nm) on SiO2 vs Al using an octadecylphosphonic acid SAM to block growth on native oxide-covered Al. Positive and negative pattern transfer of SiOC films on a Cu/Al2O3 pattern is exhibited as a proof of concept. Moreover, because the Cu substrates are contaminated by HCl which is generated as a byproduct in the MLD process, we develop a mild post-treatment method using ethanol to remove chlorine residues.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Area-Selective Molecular Layer Deposition of a Silicon Oxycarbide Low-k Dielectric

Bobb-Semple

et al. 2021

Chem. Mater.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Furthermore, the direct or indirect real-time study of the formation of 2D layers of these structures has remained almost unexplored and has been based on bulk lamellar samples 27,50. However, during the revision process of our work, the formation and growth of multilayer motifs on copper with dodecanethiol has been just reported 51. In this article, we have presented the nucleation and evolution of 2D coordination polymer structures based on LMAs directly imaged by different microscopies.…”

Section: Discussionmentioning

confidence: 95%

Spontaneous growth of 2D coordination polymers on functionalized ferromagnetic surfaces

et al. 2018

View full text Add to dashboard Cite

show abstract

Copper Oxidation Improves Dodecanethiol Blocking Ability in Area‐Selective Atomic Layer Deposition

Liu

Bent

2022

Adv Materials Inter

Self Cite

View full text Add to dashboard Cite

allows precise control of material deposition only on desired areas. To enable areaselective deposition, the process usually involves two steps, surface modification followed by thin film deposition. [3][4][5][6][7][8][9] For the surface modification step, self-assembled monolayers (SAMs) are often used as the inhibitors to protect surfaces from the subsequent deposition step. [10][11][12][13][14][15][16][17] As for the deposition step, atomic layer deposition (ALD) is considered an excellent vehicle because ALD strongly depends on the surface properties of the substrates due to the self-limiting reactions between precursors and growth surfaces. In addition, the advantages provided by ALD, including atomic-level thickness control, excellent conformality, and uniformity, have made ALD a key tool for advanced semiconductor fabrication processing.One targeted application for area-selective atomic layer deposition (AS-ALD) is to selectively deposit dielectrics as an etch hard mask on the dielectric regions of metal/dielectric patterns for the fabrication of fully aligned vias in back-end semiconductor processes. [18][19][20] To enable selective deposition of "dielectric on dielectric," alkanethiols have attracted attention as the inhibitors for metal surfaces because of their ability to be deposited by vapor-phase approaches, which are more compatible with current semiconductor processing. Although alkanethiols have been shown to inhibit ALD of TiO 2 , ZnO, and Hf 3 N 4 on Cu surfaces, [12,[21][22][23][24] selective ALD of Al 2 O 3 is of particular interest because of the high etch selectivity between Al 2 O 3 and SiO 2 , [25] and the relatively low dielectric constant of ALD Al 2 O 3 (k = 6-7.6) [26] compared to other ALD metal oxides such as HfO 2 (k = 14) [27] and TiO 2 (k = 30-55). [28] However, previous results have shown that it is challenging to obtain good selectivity in AS-ALD of Al 2 O 3 . [23,29,30] Therefore, developing a more robust alkanethiol SAM inhibitor that is more effective for Al 2 O 3 ALD is essential.In this work, we demonstrate an approach to improve the packing of dodecanethiol (DDT) SAMs by applying an additional oxidation process on acid-etched Cu surfaces prior to DDT deposition. We follow the oxidation process, observing that Cu 2 O forms first followed by CuO, and show that the different oxide compositions at the Cu substrates influence the subsequent DDT formation. We demonstrate that performing DDT deposition on Cu 2 O surfaces improves the packing of the DDT SAM. However, when CuO is formed, multilayers of DDT start to emerge upon exposure to DDT. The blocking ability of

show abstract

Formation and Ripening of Self-Assembled Multilayers from the Vapor-Phase Deposition of Dodecanethiol on Copper Oxide

Cited by 33 publications

References 50 publications

Area-Selective Molecular Layer Deposition of a Silicon Oxycarbide Low-k Dielectric

Area-Selective Molecular Layer Deposition of a Silicon Oxycarbide Low-k Dielectric

Spontaneous growth of 2D coordination polymers on functionalized ferromagnetic surfaces

Copper Oxidation Improves Dodecanethiol Blocking Ability in Area‐Selective Atomic Layer Deposition

Contact Info

Product

Resources

About