The 2,2,6,6-Tetramethyl-2-Sila-3,5-Heptanedione Route to the Chemical Vapor Deposition of Copper for Gigascale Interconnect Applications

2000 ◽  
Vol 612 ◽  
Author(s):  
Rolf U. Claessen ◽  
John T. Welch ◽  
Paul J. Toscano ◽  
Kulbinder K. Banger ◽  
Andrei M. Kornilov ◽  
...  

AbstractA new class of copper(II) precursors containing silylated β-diketonate ligands has been developed for the chemical vapor deposition (CVD) growth of copper for applications in ultralarge scale integration interconnect schemes, including conformal seed layer for gigascale Cu integration and ultrathin Cu lines with enhanced conductivity characteristics. Cu(tmshd)2 (tmshdH = 2,2,6,6-tetramethyl-2-sila-3,5-heptanedione) has been studied as a representative compound and is appreciably more volatile than nonsilylated compounds such as Cu(tmhd)2 or Cu(tmod)2 (tmhdH = 2,2,6,6-tetramethyl-3,5-heptanedione; tmodH = 2,2,7-trimethyl- 3,5- octanedione). The CVD process employs Cu(tmshd)2 as the metalorganic precursor and hydrogen as the reducing and carrier gas. These films were deposited using a custom made, cold wall, stainless steel CVD. Copper films were produced at a substrate temperature of 250 – 320 °C, hydrogen flow rates of 20 - 100 sccm, deposition pressure of 0.2 - 1 Torr, and a source temperature of 120 – 135 °C. The films were analyzed by X-ray photoelectron spectroscopy, cross section scanning electron microscopy, transmission electron microscopy, four-point resistivity probe, Rutherford backscattering spectrometry and Auger electron spectroscopy.

2004 ◽  
Vol 19 (3) ◽  
pp. 697-706 ◽  
Author(s):  
Anna W. Topol ◽  
Kathleen A. Dunn ◽  
Karl W. Barth ◽  
Guillermo M. Nuesca ◽  
Brian K. Taylor ◽  
...  

Results are presented from a systematic investigation to design and optimize a low-pressure chemical vapor deposition (CVD) process for manganese-doped zinc sulfide (ZnS:Mn) thin films for electroluminescent (EL) device applications. The CVD process used diethylzinc (DEZ), di-π-cyclopentadienyl manganese (CPMn), and hydrogen sulfide (H2S) as co-reactants and hydrogen (H2) as carrier gas. A design of experiments approach was used to derive functionality curves for the dependence of ZnS:Mn film properties on substrate temperature and flow rates (partial pressures) of DEZ, CPMn, H2S, and H2. Film physical, chemical, structural, and optical properties were examined using Rutherford backscattering spectrometry, dynamic secondary ion mass spectroscopy, x-ray photoelectron spectroscopy, nuclear-reaction analysis, x-ray diffraction, transmission electron microscopy, atomic force microscopy, and scanning electron microscopy. EL measurements were carried out on ZnS:Mn-based dielectric–sulfur–dielectric stacks incorporated into alternating-current thin-film electroluminescent devices. An optimized process window was established for the formation of films with predominantly (0 0 2) orientation, grain size larger than 0.2 μm, and Mn dopant level approximately 0.5 at.%. A brightness of 407 cd/m2 (119 fL) and efficiency of 1.6 lm/W were obtained, as measured at 40 V above threshold voltage and 60 Hz frequency.


2002 ◽  
Vol 716 ◽  
Author(s):  
Filippos Papadatos ◽  
Spyridon Skordas ◽  
Zubin Patel ◽  
Steven Consiglio ◽  
Eric Eisenbraun

AbstractIn this work, Ru and RuO2 films have been investigated for potential applications in emerging CMOS gate electrode and memory capacitor bottom electrode applications. Films were deposited on SiO2 using chemical vapor deposition (CVD) and low power plasma assisted CVD (PACVD) in a 200-mm wafer deposition cluster tool using a metal beta-diketonate precursor [Bis (2,2,6,6-tetramethyl-3,5-heptanedionato) (1,5-cyclooctadiene) ruthenium (II)]. Hydrogen and oxygen were employed as the reactive gases to deposit, respectively, Ru and RuO2, over a wafer temperature range from 320°C to 480°C. The resulting film properties were analyzed using cross-sectional scanning electron microscopy (CS-SEM), four point resistance probe, x-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectrometry (RBS) and x-ray diffraction (XRD). Both Ru and RuO2 films could be deposited with minimal carbon concentration (∼5 at. %). The purity of the films was also reflected in the as-deposited resistivity of the films, which was as low as 47 μΩ-cm, and was strongly dependent on processing conditions. In order to assess thermal stability, the films were subsequently annealed in forming gas and oxygen ambients for 60 min at 650°C. It was observed that, generally speaking, CVD RuO2 films were stable, with respect to resistivity, in oxidizing ambients, while annealing in a reducing ambient resulted in significant film densification and reduction of the film resistivities to as low as 43 μΩ-cm. Ru films demonstrated good adhesion after anneals in oxidizing, but not in reducing ambients.


2000 ◽  
Vol 648 ◽  
Author(s):  
Y.-M. Sun ◽  
S.Y. Lee ◽  
E. R. Engbrecht ◽  
K. Pfeifer ◽  
S. Smith ◽  
...  

Abstract:Low temperature chemical vapor deposition of tungsten, tungsten carbide and tantalum carbide films on SiO2/Si(100) surfaces was studied by X-ray photoelectron spectroscopy (XPS) and electron microscopy. Tungsten carbide films were deposited using the W(CO)6precursor with and without ethylene over temperatures ranging from 250 to 500 °C. The films grown without ethylene contained approximately 13 % carbon and 6 % oxygen. Cross section scanning electron microscopy imaging of the films grown at various temperatures without ethylene shows a polycrystalline microstructure, and the grain size increases dramatically as the growth temperature increases. Introducing ethylene increased carbon incorporation and changed the microstructure to amorphous-like. The tungsten to carbon ratio was approximately 2 at growth below 500 °C, and reached ~ 1.2 above 500 °C. The tantalum carbide films were deposited in a plasma enhanced chemical vapor deposition (PECVD) process using methane. The PECVD tantalum carbide films were conductive with a resistivity of ~1000 µΩ cm, which is about one order of magnitude lower than thermally grown films from pentakisdimethylamino tantalum.


2021 ◽  
Vol 12 ◽  
pp. 1365-1371
Author(s):  
Vladislav Dřínek ◽  
Stanislav Tiagulskyi ◽  
Roman Yatskiv ◽  
Jan Grym ◽  
Radek Fajgar ◽  
...  

Chemical vapor deposition was applied to synthetize nanostructured deposits containing several sorts of nanoobjects (i.e., nanoballs, irregular particles, and nanowires). Analytical techniques, that is, high-resolution transmission electron microscopy, scanning electron microscopy, electron dispersive X-ray analysis, selected area electron diffraction, and X-ray photoelectron spectroscopy, showed that unlike nanoballs and particles composed of crystalline germanium, the layer was made of chromium germanide CrGex. The nanowires possessed a complex structure, namely a thin crystalline germanium core and amorphous CrGex coating. The composition of the nanowire coating was [Cr]/[Ge] = 1:(6–7). The resistance of the nanowire–deposit system was estimated to be 2.7 kΩ·cm using an unique vacuum contacting system.


2000 ◽  
Vol 15 (12) ◽  
pp. 2800-2810 ◽  
Author(s):  
Alain E. Kaloyeros ◽  
Xiomeng Chen ◽  
Sarah Lane ◽  
Harry L. Frisch ◽  
Barry Arkles

As-deposited and annealed tantalum films, grown by plasma-promoted chemical vapor deposition (PPCVD) using pentabromotantalum and hydrogen as coreactants, were evaluated as diffusion barriers in copper metallization. Stacks consisting of 500-nm-thick sputtered Cu/55-nm-thick untreated PPCVD Ta/Si were annealed in argon in the range 450 to 650 °C, in 50 °C intervals, along with sputtered Cu/preannealed PPCVD Ta/Si and sputtered Cu/sputtered Ta/Si stacks of identical thickness. Pre- and postannealed stacks were characterized by x-ray photoelectron spectroscopy, Auger electron spectroscopy, Rutherford backscattering spectrometry, hydrogen profiling, x-ray diffraction, atomic force microscopy, sheet resistance measurements, and Secco chemical treatment and etch-pit observation by scanning electron microscopy. The sputtered and preannealed PPCVD Ta films acted as viable diffusion barriers up to 550 °C, while the as-deposited PPCVD Ta films failed above 500 °C. In all cases, breakdown occurred through the migration of Cu into Si, rather than an interfacial reaction between Ta and Si, in agreement with previously reported results for sputtered Ta films. The accelerated barrier failure for as-deposited PPCVD Ta might have been caused by the presence of approximately 20 at.% hydrogen in the as-deposited PPCVD Ta, an observation which was supported by the enhanced performance of the same PPCVD Ta films after annealing-induced hydrogen removal.


1990 ◽  
Vol 204 ◽  
Author(s):  
Roy G. Gordon ◽  
David M. Hoffman ◽  
Umar Riaz

ABSTRACTThe atmospheric-pressure chemical vapor deposition of gallium nitride films from hexakis(dimethylamido)digallium, Ga2(NMe2)6, and ammonia precursors at 200 °C with growth rates up to 1000 Å/min is described. The films were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and Rutherford backscattering spectrometry. Rutherford backscattering analysis showed that the N/Ga ratio was 1.12–1.17. The films were crystalline with ≃ 5–15 nm crystallites.


MRS Advances ◽  
2018 ◽  
Vol 3 (4) ◽  
pp. 191-197
Author(s):  
José E. Nocua ◽  
Gerardo Morell

ABSTRACTBoron nitride (BN) has a very high thermal conductivity and excellent thermal shock resistance. These properties make BN an important material for industrial applications involving surfaces in contact with molten metals. These applications require straightforward deposition methods that produce uniform BN coatings. Using borazine (B3N3H6) as a precursor, we deposited BN coatings on silicon substrates by cold-wall chemical vapor deposition (CVD). The microstructure, composition, and morphology of the coatings were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and electron energy loss spectroscopy (EELS). These characterizations show that the BN coatings deposited are uniform, predominantly of hexagonal structure, and N-rich.


2001 ◽  
Vol 16 (6) ◽  
pp. 1838-1849 ◽  
Author(s):  
Kanchana Vydianathan ◽  
Guillermo Nuesca ◽  
Gregory Peterson ◽  
Eric T. Eisenbraun ◽  
Alain E. Kaloyeros ◽  
...  

A chemical vapor deposition process has been developed for titanium dioxide (TiOx) for applications as capacitor dielectric in sub-quarter-micron dynamic random-access memory devices, and as gate insulators in emerging generations of etal-oxide-semiconductor transistors. Studies using the β-diketonate source precursor (2,2,6,6-tetramethyl-3,5-heptanedionato) titanium were carried out to examine the underlying mechanisms that control film nucleation and growth kinetics and to establish the effects of key process parameters on film purity, composition, texture, morphology, and electrical properties. Resulting film properties were thoroughly analyzed by x-ray diffraction, x-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, scanning electron microscopy (SEM), focused-ion-beam SEM, and capacitance–voltage (C–V) measurements. The study resulted in the identification of an optimized process for the deposition of an anatase–rutile TiOx film with a dielectric constant approximately 85 at 1 MHz for a 330-nm thickness, and a leakage current below 2 × 10−8 A/cm2 for bias voltage values up to 3.5 V.


2002 ◽  
Vol 16 (06n07) ◽  
pp. 1091-1095 ◽  
Author(s):  
W. T. ZHENG ◽  
X. WANG ◽  
T. DING ◽  
X. T. LI ◽  
W. D. FEI ◽  
...  

The carbon nitride films were deposited on single crystalline Si(001) and polycrystalline diamond substrates using microwave plasma chemical vapor deposition (MPCVD) with CH4+N2 as well as CH4+NH3 mixtures as the reactive gas source, respectively. Different CH4/N2 and CH4/NH3 gas ratios were tested. The results showed that carbon nitride films with different nitrogen content could more readily be obtained using a mixture of CH4/N2 rather than CH4/NH3. The films grown by different CH4/N2 ratios showed different morphology, which was revealed by scanning electron microscopy (SEM). The crystalline carbon nitride films containing silicon were realized using a CH4:N2 = 1:100 ratio. X-ray photoelectron spectroscopy (XPS), Auger electron microscopy (AES), Raman spectroscopy, and X-ray diffraction were used to characterize the composition and chemical bonding of the deposited films.


2008 ◽  
Vol 23 (5) ◽  
pp. 1320-1326 ◽  
Author(s):  
Seongho Jeon ◽  
Kijung Yong

A simple thermal annealing was performed to prepare tungsten oxide nanorods directly from tungsten (W) film. The W film was deposited on Si(100) substrate by chemical vapor deposition (CVD) at 450 °C using W(CO)6. A high density of tungsten oxide nanorods was produced by heating of the W film at 600–700 °C. The morphology, structure, composition, and chemical binding states of the prepared nanorods were characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) analysis. XRD and TEM results showed that the grown nanorods were single-crystalline W18O49. According to XPS analysis, the W18O49 nanorods contained ∼55.69% W6+, ∼32.28% W5+, and ∼12.03% W4+. The growth mechanism based on thermodynamics is discussed for the growth of tungsten oxide nanorods from W film.


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