Surface roughness reducing effect of iodine sources (CH3I, C2H5I) on Ru and RuO2 composite films grown by MOCVD

Kim, Jae Jeong; Jung, Doo‐Hwan; Kim, Moon Soo; Kim, Sang Hyun; Yoon, Do Young

doi:10.1016/s0040-6090(02)00098-6

Cited by 27 publications

(25 citation statements)

References 27 publications

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“…at 2092 and 2036 cm 21 . This observation is in good agreement with the electron withdrawing property of the hfac ligand, making it a poor s-donor.…”

Section: Synthesis and Characterization Of Ru Complexesmentioning

confidence: 97%

Deposition of Ru and RuO2 thin films employing dicarbonyl bis-diketonate ruthenium complexes as CVD source reagents

et al. 2003

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Reaction of Ru 3 (CO) 12 with 6 eq. of b-diketone ligands (hfac)H, (tmhd)H, (acac)H and (tfac)H at 160-170 uC in a hydrocarbon solvent (pentane or hexane) affords the diketonate complexes [Ru(CO) 2 (hfac) 2 ] (1), [Ru(CO) 2 (tmhd) 2 ] (2), [Ru(CO) 2 (acac) 2 ] (3) and [Ru(CO) 2 (tfac) 2 ] (4) in high yields. These ruthenium complexes were characterized by spectroscopic methods; a single crystal X-ray diffraction study was carried out on one isomer of the tfac complex (4a), revealing an octahedral coordination geometry with two CO ligands located at cis-positions and with the CF 3 groups of the b-diketonate ligands trans to the CO ligands. Thermogravimetric analysis of complex (1) showed an enhanced volatility compared to the parent acac complex (3), attributed to the CF 3 group reducing intermolecular attraction. Employing complexes (1) and (2) as CVD source reagents, ruthenium thin films can be deposited at temperatures of 350 uC-450 uC under an H 2 atmosphere or at temperatures of 275 uC-400 uC using a 2% mixture of O 2 in argon as carrier gas. For deposition carried out using complex (1) and under 100% O 2 atmosphere, RuO 2 thin films with a preferred (200) orientation were obtained. The as-deposited thin films were characterized by surface and physical analytical techniques, such as scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction analysis (XRD) and four-point probe measurement.Ruthenium-containing thin films show great promise for fabricating bottom electrodes or non-corrosive diffusion barriers for next generation, tantalum oxide (Ta 2 O 5 ), barium strontium titanate (BST) and lead zirconate titanate (PZT) based nonvolatile random access memory (RAM) devices.1 The advantages of ruthenium over other conducting materials include: lower resistivity, good etching ability, good barrier properties against oxygen diffusion, high resistance against capacitor shorting due to the formation of hillocks, severe polarization fatigue and aging.2 Moreover, its oxide phase, RuO 2 , which crystallizes in the rutile structure, belongs to a class of conductive oxide materials that exhibit excellent chemical stability at higher temperatures in O 2 ambient. These combined characteristics make RuO 2 an idea candidate for the fabrication of diffusion barriers for contact metallizations in very large scale integration (VLSI) applications, buffer layers of high T c superconducting films on silicon, and electrodes of ferroelectric thin films.Chemical vapor deposition (CVD) has received more attention in recent years, particularly in depositing these ruthenium-containing thin films, for its obvious capability of alleviating problems associated with the physical vapor deposition or sputtering process, such as low conformal coverage, poor crystallinity, and high stress level. As a result, several Ru metal-containing complexes have been examined as potential CVD precursors, including (a) ruthenocene 3 and its alkyl substituted derivatives such as Ru (C 5 hfb~hexafluoro-2-butyne, and Ru 3 ...

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“…at 2092 and 2036 cm 21 . This observation is in good agreement with the electron withdrawing property of the hfac ligand, making it a poor s-donor.…”

Section: Synthesis and Characterization Of Ru Complexesmentioning

confidence: 97%

Deposition of Ru and RuO2 thin films employing dicarbonyl bis-diketonate ruthenium complexes as CVD source reagents

et al. 2003

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“…The sticking probabilities can be largely increased when surfaces were modified via adsorptions of CH 3 I or C 2 H 5 I, and smoother films were obtained. [7,8] Importantly, the characterization of different surface O states on a seed layer of Ru suggests that, in the film growth, the reaction rates are not just dependent on the substrate temperature, but on the population of the different surface oxygen states. In our experiments, the substrate was exposed to 5 10 ±4 torr of O 2 for 1 h prior to the reaction, and was presumably saturated with surface oxygen.…”

Section: Relevance To Practical Cvd Processesmentioning

confidence: 99%

UHV Surface Chemistry of bis(ethylcyclopentadienyl)ruthenium, (C₂H₅C₅H₄)₂Ru on an Oxide Substrate

Luo¹,

Wang²,

White³

2004

Chemical Vapor Deposition

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The interactions of an organometallic precursor to Ru thin films, bis(ethylcyclopentadienyl)ruthenium, (C 2 H 5 C 5 H 4 ) 2 Ru, with an amorphous Al 2 O 3 substrate were probed using tools of ultra-high vacuum surface science. The precursor adsorbs and desorbs with no decomposition on Al 2 O 3 that is bare, or covered with patches of O-saturated Ru. In the absence of pre-existing Ru sites, there was no reaction up to 950 K with or without co-dosed O 2 at pressures up to 10 ±6 torr. Film-forming reactions do occur under UHV dosing conditions when Ru sites and chemisorbed oxygen are both present. The distribution of chemical states of surface oxygen changes with temperature and influences reaction kinetics and film growth.

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“…This dioxide offers: (i) good thermal and chemical stabilities [7,8], (ii) strong resistance against chemical corrosion [9], and (iii) excellent chemical diffusion barrier [10]. In the area of microelectronics, RuO 2 was proposed as complementary metal-oxide-semiconductor (CMOS) component, and as electrode for DRAM (random access memory) capacitor [11,12].…”

Section: Introductionmentioning

confidence: 99%

Structure, microstructure, and size dependent catalytic properties of nanostructured ruthenium dioxide

Nowakowski

Dallas

Villain

et al. 2008

Journal of Solid State Chemistry

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Surface roughness reducing effect of iodine sources (CH3I, C2H5I) on Ru and RuO2 composite films grown by MOCVD

Cited by 27 publications

References 27 publications

Deposition of Ru and RuO2 thin films employing dicarbonyl bis-diketonate ruthenium complexes as CVD source reagents

Deposition of Ru and RuO2 thin films employing dicarbonyl bis-diketonate ruthenium complexes as CVD source reagents

UHV Surface Chemistry of bis(ethylcyclopentadienyl)ruthenium, (C₂H₅C₅H₄)₂Ru on an Oxide Substrate

Structure, microstructure, and size dependent catalytic properties of nanostructured ruthenium dioxide

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Surface roughness reducing effect of iodine sources (CH3I, C2H5I) on Ru and RuO2 composite films grown by MOCVD

Cited by 27 publications

References 27 publications

Deposition of Ru and RuO2 thin films employing dicarbonyl bis-diketonate ruthenium complexes as CVD source reagents

Deposition of Ru and RuO2 thin films employing dicarbonyl bis-diketonate ruthenium complexes as CVD source reagents

UHV Surface Chemistry of bis(ethylcyclopentadienyl)ruthenium, (C2H5C5H4)2Ru on an Oxide Substrate

Structure, microstructure, and size dependent catalytic properties of nanostructured ruthenium dioxide

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UHV Surface Chemistry of bis(ethylcyclopentadienyl)ruthenium, (C₂H₅C₅H₄)₂Ru on an Oxide Substrate