Guanidinato-based precursors for MOCVD of metal nitrides (MxN: M = Ta,W)

Rische, Daniel; Parala, Harish; Baunemann, Arne; Thiede, Tobias; Fischer, Roland A.

doi:10.1016/j.surfcoat.2007.04.072

Cited by 21 publications

(32 citation statements)

References 15 publications

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“…Novel chemistry for ALD and CVD precursors has recently been introduced using guanidinate ligands. [116,137] The flexibility of the guanidinate structure with respect to the modification of its steric and electronic properties makes it an interesting ligand. Additionally, its well-known decomposition pathways allow the control of its thermal chemistry.…”

Section: Alkylamide-guanidinatesmentioning

confidence: 99%

Atomic Layer Deposition of Groups 4 and 5 Transition Metal Oxide Thin Films: Focus on Heteroleptic Precursors

Blanquart

Niinistö

Ritala

et al. 2014

Chemical Vapor Deposition

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The atomic layer deposition (ALD) process, an alternative to CVD, is universally appreciated for its unique advantages such as excellent repeatability, conformity, and thickness control at the atomic level. ALD precursor chemistry has mainly been based on homoleptic compounds such as, but not limited to, metal halides, alkylamides, and alkoxides, however these precursors have drawbacks such as possible halide contamination and low thermal stabilities in the case of the alkylamides and alkoxides. Consequently, heteroleptic precursors have been investigated as alternatives to the existing homoleptic counterparts, leading to the development of several advantageous processes. Nevertheless, there is no thematic review dedicated to the heteroleptic precursors and their properties, and it seems that no coherent strategy has been adopted for the development of heteroleptic precursors. This review gives a brief description of ALD and presents studies on the deposition of thin films of groups 4 and 5 metal oxides using ALD. A description of the general ALD properties of homoleptic precursors, in addition to a review on the thermal ALD of groups 4 and 5 metal oxides from heteroleptic precursors, is provided. Trends in the properties of heteroleptic ALD precursors, based on the literature review and recent experimental data, are discussed.

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Section: Alkylamide-guanidinatesmentioning

confidence: 99%

Atomic Layer Deposition of Groups 4 and 5 Transition Metal Oxide Thin Films: Focus on Heteroleptic Precursors

Blanquart

Niinistö

Ritala

et al. 2014

Chemical Vapor Deposition

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“…• C) [15][16][17][18][19][20][21][22] that can compromise contact level structures 2,23 and neighboring dielectrics. 24 In addition, the development of ultra-low temperature CVD WN x C y has potential application to flexible and organic devices.…”

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confidence: 99%

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.

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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...

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“…So far, guanidinate compounds have been introduced as either homo‐ or heteroleptic ALD precursors in the deposition of high‐ k oxides (TiO 2 , ZrO 2 , HfO 2 , Gd 2 O 3 , Dy 2 O 3 ). In addition, they have been used in the metal‐organic (MO)CVD of rare‐earth oxides (Gd, Dy) as well as Gd, Ta, and W nitrides.…”

Section: Introductionmentioning

confidence: 99%

Atomic Layer Deposition of TiO₂ and ZrO₂ Thin Films Using Heteroleptic Guanidinate Precursors

Kaipio

Blanquart

Banerjee

et al. 2014

Chemical Vapor Deposition

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Review: This review provides a brief description of ALD and presents studies on the deposition of thin films of groups 4 and 5 metal oxides using ALD. A description of the general ALD properties of homoleptic precursors, in addition to a review of the thermal ALD of groups 4 and 5 metal oxides from heteroleptic precursors, is presented. Trends in the properties of heteroleptic ALD precursors based on the literature review and recent experimental data are discussed. Full Paper: Atomic layer deposition of TiO 2 and ZrO 2 is performed using heteroleptic amido/guanidinate metal precursors, and ozone and water as oxygen sources. The results are compared to previous studies and the effect of the ligands on the precursor properties are discussed.

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Guanidinato-based precursors for MOCVD of metal nitrides (MxN: M = Ta,W)

Cited by 21 publications

References 15 publications

Atomic Layer Deposition of Groups 4 and 5 Transition Metal Oxide Thin Films: Focus on Heteroleptic Precursors

Atomic Layer Deposition of Groups 4 and 5 Transition Metal Oxide Thin Films: Focus on Heteroleptic Precursors

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

Atomic Layer Deposition of TiO₂ and ZrO₂ Thin Films Using Heteroleptic Guanidinate Precursors

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Guanidinato-based precursors for MOCVD of metal nitrides (MxN: M = Ta,W)

Cited by 21 publications

References 15 publications

Atomic Layer Deposition of Groups 4 and 5 Transition Metal Oxide Thin Films: Focus on Heteroleptic Precursors

Atomic Layer Deposition of Groups 4 and 5 Transition Metal Oxide Thin Films: Focus on Heteroleptic Precursors

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

Atomic Layer Deposition of TiO2 and ZrO2 Thin Films Using Heteroleptic Guanidinate Precursors

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

Atomic Layer Deposition of TiO₂ and ZrO₂ Thin Films Using Heteroleptic Guanidinate Precursors