Filling Narrow Trenches by Iodine-Catalyzed CVD of Copper and Manganese on Manganese Nitride Barrier/Adhesion Layers

Au, Yeung Billy; Lin, Yaojian; Gordon, Roy G.

doi:10.1149/1.3556699

Cited by 53 publications

(47 citation statements)

References 15 publications

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“…7 Here, a direct-liquid-injection (DLI) CVD method was adopted instead to provide consistently higher partial pressure of copper precursor vapor, thereby enhancing the growth rate and the conformality of the copper films. To prepare copper films using the DLI-CVD method, 25 g of copper precursor was first dissolved in 100 mL of dodecane (C 12 H 26 ), a solvent with vapor pressure close to that of the copper precursor, to make a solution with a concentration of 0.72 molal or 0.43 molar and a density of 0.79 g/mL, measured at 21…”

Section: Methodsmentioning

confidence: 99%

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Vapor Deposition of Highly Conformal Copper Seed Layers for Plating Through-Silicon Vias (TSVs)

Au¹,

Wang²,

Li³

et al. 2012

J. Electrochem. Soc.

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Through-silicon vias (TSV) will speed up interconnections between chips. Manufacturable and cost-effective TSVs will allow faster computer systems. In this paper, we report the successful formation of seed layers for plating copper TSVs with aspect ratios greater than 25:1. Following the rapid atomic layer deposition (ALD) of a conformal insulating layer of silica inside the silicon vias, manganese nitride (Mn 4 N) is deposited conformally on the silica surface by chemical vapor deposition (CVD). Mn 4 N forms an effective copper diffusion barrier and provides strong adhesion between the silica and the subsequently-deposited copper. Conformal copper or copper-manganese alloy films are then deposited by an iodine-catalyzed direct-liquid-injection (DLI) CVD process. Diffusion of manganese during post-deposition annealing further enhances the barrier and adhesion properties at the copper/dielectric interface.

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Section: Methodsmentioning

confidence: 99%

“…4,7,10,11 When vapors of ethyl iodide are exposed to manganese nitride films, iodine atoms are chemisorbed onto the surface. During subsequent CVD of copper, the iodine desorbs from the Mn 4 N surface and floats on the surface of the growing copper film.…”

mentioning

confidence: 99%

Vapor Deposition of Highly Conformal Copper Seed Layers for Plating Through-Silicon Vias (TSVs)

Au¹,

Wang²,

Li³

et al. 2012

J. Electrochem. Soc.

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“…The follo wing process steps are proposed to form very narrow, low resistance and robust copper interconnects at the lowest levels within chips [1]:…”

Section: Narrow Interconeections Within Chipsmentioning

confidence: 99%

Vapor deposition of copper-manganese interconnects

Gordon

Feng

et al. 2016

2016 IEEE International Interconnect Technology Conference / Advanced Metallization Conference (IITC/AMC)

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Abstract-Chemical vapor deposition (CVD) of copper and manganese can produce interconnects scaled down to below 10 nm, while enhancing their conductivity and lifetime. CVD using similar super-conformal processes can enable very narrow through-silicon-vias, as well as tiny and robust flexible wires between chips. Silica insulating layers can be made by a superconformal and rapid atomic layer deposition (ALD) process.

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“…Two Cu precursors were used: β-diketonato 5,6 and amidinato. 3,4,8,9 The remainder of the paper is organized as follows. First, it presents a strategy to achieve high-density nucleation leading to the formation of ultra-thin, continuous Cu films using classical nucleation theory coupled with existing experimental evidence.…”

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confidence: 99%

Comparative Study on Cu-CVD Nucleation Using β-diketonato and Amidinato Precursors for Sub-10-nm-Thick Continuous Film Growth

Shima

Shimizu

Momose

et al. 2015

ECS J. Solid State Sci. Technol.

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We demonstrate the growth of sub-10-nm-thick continuous Cu films using chemical vapor deposition (CVD) for next-generation Cu interconnects for ultra-large-scale integration (ULSI). The thickness of such films is equivalent to that of Cu during coalescence, and optimized operating conditions and substrate materials are required to form high-density nucleates. Ru was used as an underlayer, and the time evolution of nucleation and grain growth were studied with systematically varied conditions using two Cu precursors: conventional β-diketonato and newly developed amidinato precursor compounds. The revealed geometry of the initial nano-scale Cu grains prior to coalescence suggests the required nucleate density for 7-nm-thick continuous film growth, and which was 2.4 × 10 11 /cm 2 . The maximum nucleate density was achieved with the lowest deposition temperature and highest precursor concentration for both precursors; i.e., 6.9 × 10 11 /cm 2 for β-diketonato at 100 • C, and 4.6 × 10 11 /cm 2 for amidinato at 150 • C. A 10-nm-thick continuous Cu film was formed using amidinato under the optimized conditions. Furthermore, the framework used in this study to enable a high nucleate density suggests that it is possible to form thinner (4 nm∼) Cu films using amidinato. Because of the inherent good step coverage of CVD, this process is a promising candidate for next-generation ULSI Cu interconnects. Cu interconnects for ultra-large-scale integration (ULSI) are currently fabricated using the so-called 'damascene process,' which consists of: (i) the formation of three-dimensional features (i.e., trenches and via-holes) in the inter-layer dielectric using etching; (ii) sputtering of TaN x onto the inter-layer dielectric to form a Cu diffusion barrier; (iii) sputtering of Ta as an adhesion layer; (iv) sputtering of Cu as a seed layer for subsequent electro-plating; and (v) electro-plating of Cu to fill the remaining gaps. As the dimensions of complementary metal-oxide-semiconductor (CMOS) transistors in ULSI have reduced, the feature size of the Cu interconnects has also reduced. 1After 2016, the Cu line width will become smaller than 22 nm, so the Cu seed layer must be thinner than 7 nm.2 With such small dimensions, conventional physical vapor deposition (PVD) processes (including sputtering) face difficulties in forming conformal Cu films on narrow and high aspect-ratio (AR) features. Hence, it is essential to develop alternative deposition processes that are capable of highly conformal film growth. The current leading candidates are atomic layer deposition (ALD), 3,4 chemical vapor deposition (CVD), 5-9 and supercritical fluid deposition (SCFD).10 ALD-grown films exhibit the required properties for this purpose, but the growth rate of 0.1-1.9 Å/cycle 11 is too slow for mass production. SCFD is an emerging technology, but it requires a high-pressure environment, which is not compatible with current vacuum processes and now under investigation. 12,13 CVD is the most widely studied method, due to its fast growth rate of 2.0-14...

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Filling Narrow Trenches by Iodine-Catalyzed CVD of Copper and Manganese on Manganese Nitride Barrier/Adhesion Layers

Cited by 53 publications

References 15 publications

Vapor Deposition of Highly Conformal Copper Seed Layers for Plating Through-Silicon Vias (TSVs)

Vapor Deposition of Highly Conformal Copper Seed Layers for Plating Through-Silicon Vias (TSVs)

Vapor deposition of copper-manganese interconnects

Comparative Study on Cu-CVD Nucleation Using β-diketonato and Amidinato Precursors for Sub-10-nm-Thick Continuous Film Growth

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