Tungsten Nitrido Complexes as Precursors for Low Temperature Chemical Vapor Deposition of WNxCy Films as Diffusion Barriers for Cu Metallization

McClain, K. Randall; O’Donohue, Christopher; Koley, Arijit; Bonsu, Richard O.; Abboud, Khalil A.; Revelli, Joseph C.; Anderson, Timothy J.; McElwee‐White, Lisa

doi:10.1021/ja4117582

Cited by 27 publications

(43 citation statements)

References 87 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Depositions were carried out according to details briefly described in the last section and as previously reported. 25 Films were grown using pyridine as solvent at growth temperature ranging from 100 to 650…”

Section: Resultsmentioning

confidence: 99%

“…25 The simplest of these complexes, WN(NMe 2 ) 3 , has been used to deposit both WN x nanospheres (at temperatures as low as 75…”

mentioning

confidence: 99%

“…25,26 We now report the deposition of WN x C y thin films from the related complex, WN(NEt 2 ) 3 , for low temperature diffusion barrier and contact applications. z E-mail: tim@ufl.eduExperimental WN x C y film growth.-WN(NEt 2 ) 3 was synthesized as previously reported (Scheme 1) 25 and film growth was studied on Si substrates. Si(100) and Si (111) substrates (Cemat Silicon and Crysteco, respectively) were cut to a size of 1 cm x 1 cm, treated for 3 min each in boiling trichloroethylene, boiling acetone and boiling methanol to remove organic contamination from the surface, and subsequently rinsed for 30 sec in boiling deionized water.…”

mentioning

confidence: 99%

“…25,26 We now report the deposition of WN x C y thin films from the related complex, WN(NEt 2 ) 3 , for low temperature diffusion barrier and contact applications. z E-mail: tim@ufl.edu…”

mentioning

confidence: 99%

“…We have previously reported the synthesis and characterization of tungsten nitrido complexes of the general formula WN(NR 2 ) 3 . 25 The simplest of these complexes, WN(NMe 2 ) 3 , has been used to deposit both WN x nanospheres (at temperatures as low as 75…”

mentioning

confidence: 99%

See 4 more Smart Citations

Low Temperature Deposition of WN_xC_yDiffusion Barriers Using WN(NEt₂)₃as a Single-Source Precursor

O’Donohue

McClain

Koley

et al. 2014

ECS J. Solid State Sci. Technol.

View full text Add to dashboard Cite

Deposition of high quality WN x C y barrier films at very low temperature using aerosol-assisted chemical vapor deposition (AACVD) is reported. The single-source tungsten nitrido complex, WN(NEt 2 ) 3 , was designed to reduce the temperature required for WN x C y film deposition in an effort to minimize thermal stresses on neighboring layers in device structures. Using either pyridine or heptane as a solvent, WN x C y films were successfully deposited at temperatures from 100 to 650 • C. Film growth in pyridine and heptane at low temperature (100-350 • C and 125-550 • C, respectively) showed weak temperature dependence consistent with mass-transfer limited growth. At higher temperature the growth rate decreased rapidly with apparent activation energy of 0.375 ± 0.057 eV. The effects of solvent choice on film properties including composition, crystallinity, density, and surface roughness are discussed. Films deposited at low temperature (<350 • C) were highly smooth, amorphous and with a stoichiometry approaching W 2 NC; characteristics desirable for diffusion barrier applications. In Cu diffusion barrier tests, Cu (∼ 100 nm)/WN x C y (∼ 5.5 nm)/Si stacks subjected to a 500 Thin interlayer materials are increasingly being used in electronic devices to modify interfacial characteristics, including the film work function, chemical, thermal and charge transport rates, surface tension, and adhesion. Due to their low resistivity, appropriate work function, and thermal stability, refractory metal nitrides have been proposed for a number of applications, ranging from wafer level hermetic sealing 1 to field effect transistor (FET) gate electrodes. 2 In particular, the tungsten-based materials WN x and WN x C y have been considered as an alternative for both diffusion barriers 3,4 and gate electrodes 5 due to their low resistivity, appropriate and tunable work function (4.39-5.01 eV 6 ), thermal and mechanical stability, good barrier performance, and processing simplicity. 7,8 Depositions of WN x and WN x C y typically use ammonia and WCl 6 , WF 6 or W(CO) 6 as co-reactants. 4,[9][10][11][12] Despite being volatile, simple, and cost-effective, these chemistries generally require high deposition temperature, can introduce impurities, and can yield corrosive byproducts. To overcome these drawbacks, organometallic precursors have drawn considerable interest for metal-organic CVD (MOCVD). Typically, these complexes include nitrogen-bound moieties such as amido, imido, hydrazido, amidinate or guanidinate ligands, 13,14 and have been used in single-source or NH 3 /H 2 co-reacting conditions to deposit WN x . Unfortunately, many of these precursors still require relatively high deposition temperature (>350• C) 15-22 that can compromise contact level structures 2,23 and neighboring dielectrics. 24In addition, the development of ultra-low temperature CVD WN x C y has potential application to flexible and organic devices. Therefore, there is interest in developing organometallic precursors for ultra-low deposition temperature. We h...

show abstract

Section: Resultsmentioning

confidence: 99%

“…25 The simplest of these complexes, WN(NMe 2 ) 3 , has been used to deposit both WN x nanospheres (at temperatures as low as 75…”

mentioning

confidence: 99%

mentioning

confidence: 99%

“…25,26 We now report the deposition of WN x C y thin films from the related complex, WN(NEt 2 ) 3 , for low temperature diffusion barrier and contact applications. z E-mail: tim@ufl.edu…”

mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Low Temperature Deposition of WN_xC_yDiffusion Barriers Using WN(NEt₂)₃as a Single-Source Precursor

O’Donohue

McClain

Koley

et al. 2014

ECS J. Solid State Sci. Technol.

View full text Add to dashboard Cite

show abstract

Synthesis and Characterization of Tungsten Nitrido Amido Guanidinato Complexes as Precursors for Chemical Vapor Deposition of WN_xC_y Thin Films

et al. 2018

Self Cite

View full text Add to dashboard Cite

Tungsten nitrido amido guanidinato complexes of the type WN(NR 2 )[(NR′) 2 C(NR 2 )] 2 (R = Me, Et ; R′ = iPr, Cy) were synthesized as precursors for aerosol-assisted chemical vapor deposition (AACVD) of WN x C y thin films. The reaction of tungsten nitrido amido complexes of the type WN(NR 2 ) 3 (R = Me, Et) with two equivalents of a carbodiimide R′N=C=NR′ (R′ = iPr, Cy) resulted in two insertions of a carbodiimide into W-N(amido) bonds, affording bis(guanidinato) amido nitrido

show abstract

In Situ Investigation of the Thermal Decomposition of Cl₄(CH₃CN)W(NⁱPr) During Simulated Chemical Vapor Deposition

et al. 2019

Self Cite

View full text Add to dashboard Cite

Design of precursors for thin film growth by chemical vapor deposition (CVD) can be informed by knowledge of the precursor decomposition mechanism. However, the vast majority of decomposition characterization is done by techniques that do not capture CVD conditions. This work used a custom CVD reactor with in situ Raman spectroscopy capabilities to investigate the gas phase thermal decomposition of the tungsten imido complex Cl4(CH3CN)WNiPr, a known precursor for the aerosol‐assisted (AA)CVD of tungsten carbonitride thin films. In combination with previous computational and ex situ data, we propose a decomposition mechanism for this precursor under CVD conditions, based on observation of gas phase products of N(imido)‐C bond homolysis and σ‐bond metathesis between the precursor W–Cl bond and H2.

show abstract

Tungsten Nitrido Complexes as Precursors for Low Temperature Chemical Vapor Deposition of WN_xC_y Films as Diffusion Barriers for Cu Metallization

Cited by 27 publications

References 87 publications

Low Temperature Deposition of WN_xC_yDiffusion Barriers Using WN(NEt₂)₃as a Single-Source Precursor

Low Temperature Deposition of WN_xC_yDiffusion Barriers Using WN(NEt₂)₃as a Single-Source Precursor

Synthesis and Characterization of Tungsten Nitrido Amido Guanidinato Complexes as Precursors for Chemical Vapor Deposition of WN_xC_y Thin Films

In Situ Investigation of the Thermal Decomposition of Cl₄(CH₃CN)W(NⁱPr) During Simulated Chemical Vapor Deposition

Contact Info

Product

Resources

About

Tungsten Nitrido Complexes as Precursors for Low Temperature Chemical Vapor Deposition of WNxCy Films as Diffusion Barriers for Cu Metallization

Cited by 27 publications

References 87 publications

Low Temperature Deposition of WNxCyDiffusion Barriers Using WN(NEt2)3as a Single-Source Precursor

Low Temperature Deposition of WNxCyDiffusion Barriers Using WN(NEt2)3as a Single-Source Precursor

Synthesis and Characterization of Tungsten Nitrido Amido Guanidinato Complexes as Precursors for Chemical Vapor Deposition of WNxCy Thin Films

In Situ Investigation of the Thermal Decomposition of Cl4(CH3CN)W(NiPr) During Simulated Chemical Vapor Deposition

Contact Info

Product

Resources

About

Tungsten Nitrido Complexes as Precursors for Low Temperature Chemical Vapor Deposition of WN_xC_y Films as Diffusion Barriers for Cu Metallization

Low Temperature Deposition of WN_xC_yDiffusion Barriers Using WN(NEt₂)₃as a Single-Source Precursor

Low Temperature Deposition of WN_xC_yDiffusion Barriers Using WN(NEt₂)₃as a Single-Source Precursor

Synthesis and Characterization of Tungsten Nitrido Amido Guanidinato Complexes as Precursors for Chemical Vapor Deposition of WN_xC_y Thin Films

In Situ Investigation of the Thermal Decomposition of Cl₄(CH₃CN)W(NⁱPr) During Simulated Chemical Vapor Deposition