Growth and properties of W–Si–N diffusion barriers deposited by chemical vapor deposition

Fleming, J. G.; Roherty-Osmun, E.; Smith, Paul Martin; Custer, Jonathan S.; Kim, Y.-D; Kacsich, T.; Nicolet, M.‐A.; Galewski, C.

doi:10.1016/s0040-6090(97)01058-4

Cited by 26 publications

(15 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Even with the sensitive grazing-angle XRD analysis, the result does not show any specific peaks related to tungsten silicides or tungsten nitrides at all. This indicates that the ALD-grown W–Si–N film might form an amorphous phase, as similar in other deposition systems such as sputtering and chemical vapor deposition. − ,, The plan-view TEM image of the W–Si–N film (∼20 nm thick) (Figure b) shows the microstructure of the film more obviously. It seems to be featureless, which is typical in the amorphous structure.…”

Section: Resultssupporting

confidence: 58%

“…This indicates that the ALD-grown W−Si−N film might form an amorphous phase, as similar in other deposition systems such as sputtering and chemical vapor deposition. [31][32][33]39,40 The plan-view TEM image of the W−Si−N film (∼20 nm thick) (Figure 7b) shows the microstructure of the film more obviously. It seems to be featureless, which is typical in the amorphous structure.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Highly Conformal Amorphous W–Si–N Thin Films by Plasma-Enhanced Atomic Layer Deposition as a Diffusion Barrier for Cu Metallization

Hong¹,

Jung

Yeo

et al. 2015

J. Phys. Chem. C

View full text Add to dashboard Cite

Ternary and amorphous tungsten silicon nitride (W–Si–N) thin films were grown by atomic layer deposition (ALD) using a sequential supply of a new fluorine-free, silylamide-based W metallorganic precursor, bis(tert-butylimido)bis(bis(trimethylsilylamido))tungsten(VI) [W(N t Bu)2{N(SiMe3)2}2], and H2 plasma at a substrate temperature of 300 °C. Here, W(N t Bu)2{N(SiMe3)2}2 was prepared through a metathesis reaction of W(N t Bu)2Cl2(py)2 (py = pyridine) with 2 equiv of LiN(SiMe3)2 [Li(btsa)]. The newly proposed ALD system exhibited typical ALD characteristics, such as self-limited film growth and linear dependency of the film growth on the number of ALD cycles, and showed a high growth rate of 0.072 nm/cycle on a thermally grown SiO2 substrate with a nearly zero incubation cycle. Such ideal ALD growth characteristics enabled excellent step coverage of ALD-grown W–Si–N film, ∼100%, onto nanotrenches with a width of 25 nm and an aspect ratio ∼4.5. Rutherford backscattering spectrometry and X-ray photoelectron spectroscopy analysis confirmed that the incorporated Si and W were mostly bonded to N, as in Si–N and W–N chemical bonds. The film kept its amorphous nature until annealing at 800 °C, and crystallization happened at local areas after annealing at a very high temperature of 900 °C. An ultrathin (only ∼4 nm thick) ALD-grown W–Si–N film effectively prevented diffusion of Cu into Si after annealing at a temperature up to 600 °C.

show abstract

Section: Resultssupporting

confidence: 58%

Section: Resultsmentioning

confidence: 99%

Highly Conformal Amorphous W–Si–N Thin Films by Plasma-Enhanced Atomic Layer Deposition as a Diffusion Barrier for Cu Metallization

Hong¹,

Jung

Yeo

et al. 2015

J. Phys. Chem. C

View full text Add to dashboard Cite

show abstract

“…10,11 It has been shown that amorphous refractory ternary phase materials such as TiSi x N y , TaSi x N y , WSi x N y , and WB x N y have better performance as Cu diffusion barriers than binary phase metal nitrides due to higher recrystallization temperature and thus lack of grain boundaries, which can serve as Cu diffusion pathways. [12][13][14][15] Aerosol-assisted CVD ͑AACVD͒ is a useful technique for growing films of refractory metal nitrides because this technique has less stringent volatility restrictions in selecting precursors. 16 Recently, we reported the synthesis of the diorganohydrazido͑2-͒ tungsten complexes Cl 4 ͑CH 3 CN͒W͑NNR 2 ͒ ͓͑1-3, R 2 = -͑CH 2 ͒ 5 -, Ph 2 , Me 2 ͒ and Cl 4 ͑pyridine͒W͑NNR 2 ͔͒ ͑4, R 2 =Ph 2 ͒ by reacting 1,1diorganohydrazines with tungsten hexachloride ͑WCl 6 ͒, followed by treatment with acetonitrile ͑CH 3 CN͒ or pyridine ͑C 5 H 5 N͒.…”

Section: Introductionmentioning

confidence: 99%

Chemical vapor deposition of WNxCy using the tungsten piperidylhydrazido complex Cl4(CH3CN)W(N-pip): Deposition, characterization, and diffusion barrier evaluation

Kim

Anderson

et al. 2009

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

View full text Add to dashboard Cite

The tungsten piperidylhydrazido complex Cl 4 ͑CH 3 CN͒W͑N-pip͒ ͑1͒ was used for film growth of tungsten carbonitride ͑WN x C y ͒ by metal-organic chemical vapor deposition ͑CVD͒ in the absence and presence of ammonia ͑NH 3 ͒ in H 2 carrier. The microstructure of films deposited with NH 3 was x-ray amorphous between 300 and 450°C. The chemical composition of films deposited with NH 3 exhibited increased N levels and decreased C levels over the entire deposition temperature range ͑300-700°C͒ as compared to films deposited without NH 3. As determined by x-ray photoelectron spectroscopy, W is primarily bonded to N and C for films deposited at 400°C, but at lower deposition temperature the binding energy of the W-O bond becomes more evident. The growth rates of films deposited with NH 3 varied from 0.6 Å / min at 300°C to 4.2 Å / min at 600°C. Over 600°C, the growth rate decreased when using NH 3 presumably due to parasitic gas phase reactions that deplete the precursor. Diffusion barrier properties were investigated using Cu/ WN x C y / Si stacks consisting of 100 nm Cu deposited at room temperature by reactive sputtering on a 20 nm WN x C y film deposited at 400°C by CVD. X-ray diffraction and cross-sectional transmission electron microscopy were used to determine the performance of the diffusion barrier. Cu/ WN x C y / Si stacks annealed under N 2 at 500°C for 30 min maintained the integrity of both Cu/ WN x C y and WN x C y / Si interfaces.

show abstract

“…En general, los materiales elegidos para este fin son metales refractarios u sus nitruros, tales como TiN, TaN y TiZrN (Yeh et al, 2008;Lee y Kuo, 2007), dado que poseen estabilidad térmica y buenas propiedades eléctricas. De igual manera se ha encontrado que sistemas ternarios como el de TiSiN (Ee et al, 2006a;Watanabe et al, 2003), WSiN (Fleming et al, 1998;Nakajima et al, 1997), TaSiN (Letendu et al, 2006;Lee et al, 1999) ó ZrSiN (Zhang et al, 2007) son capaces de sustituir al TiN (Bonitz et al, 2005y Cheng et al, 2005 en la fabricación de dispositivos dieléctricos como barreras de difusión, debido al mezclado de su microestructura, el cual se ha encontrado una notable mejora en sus propiedades, debido principalmente a la formación de una fase nanocristalina embebida en una matriz amorfa, generalmente de nitruro de silicio (Gao et al, 2004;Procházka et al, 2004).…”

Section: Introductionunclassified

Influencia del Flujo de Nitrógeno en la Estructura, Dureza y Resistividad de Recubrimientos de TiSiNO

et al. 2009

View full text Add to dashboard Cite

Recubrimientos de TiSiNO fueron fabricados por la técnica de erosión catódica reactiva por corriente directa sobre sustratos de acero y silicio, utilizando un blanco de Ti y una pequeña placa de Si sobre una atmósfera reactiva de nitrógeno, oxigeno y argón. Usando el método de Warren-Averbach se analizaron los cambios estructurales de las muestras en función de la variación del flujo de nitrógeno. Cálculos estequiométricos, obtenidos de la técnica de espectroscopia de energía dispersada y corroborados por espectroscopia de descarga luminiscente, muestran que los recubrimientos se encuentran en la región de solución sólida de TiSi x N(O y) y SiN x O y , dominando la fase del oxinitruro de titanio. La muestra fabricada sobre sustratos de acero y silicio a un flujo de nitrógeno de 3 sscm, presentó el valor de dureza más alto y el valor de resistividad más bajo, respectivamente, debido a su estructura, orientación cristalina preferencial y fases cristalinas presentes en ella.

show abstract

Growth and properties of W–Si–N diffusion barriers deposited by chemical vapor deposition

Cited by 26 publications

References 9 publications

Highly Conformal Amorphous W–Si–N Thin Films by Plasma-Enhanced Atomic Layer Deposition as a Diffusion Barrier for Cu Metallization

Highly Conformal Amorphous W–Si–N Thin Films by Plasma-Enhanced Atomic Layer Deposition as a Diffusion Barrier for Cu Metallization

Chemical vapor deposition of WNxCy using the tungsten piperidylhydrazido complex Cl4(CH3CN)W(N-pip): Deposition, characterization, and diffusion barrier evaluation

Influencia del Flujo de Nitrógeno en la Estructura, Dureza y Resistividad de Recubrimientos de TiSiNO

Contact Info

Product

Resources

About