Novel cyclopentadienyl based precursors for CVD of W containing films

Anacleto, Antony Correia; Blasco, Nicolas; Pinchart, Audrey; Marot, Y.; Lachaud, Christophe

doi:10.1016/j.surfcoat.2007.04.112

Cited by 7 publications

(5 citation statements)

References 11 publications

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“…The GPC value was almost independent of the T dep value between 200 and 300 °C, suggesting that the ALD temperature window was 200–300 °C. The significant GPC increases upward from 0.9 Å occurring at 325 °C could have been caused by thermal decomposition of the W precursor, , whereas the GPC decrease at 175 °C could be due to the reduced chemical reactivity. Figure b shows the film thickness as a function of the ALD cycle number when T dep = 300 °C.…”

Section: Resultsmentioning

confidence: 99%

Radical-Enhanced Atomic Layer Deposition of a Tungsten Oxide Film with the Tunable Oxygen Vacancy Concentration

et al. 2020

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This work reports a radical-enhanced atomic layer deposition (REALD) process using WH 2 (Cp) 2 −O*−H* reaction cycles (Cp = cyclopentadienyl group) to grow WO 3−x films with a wide range of tunable oxygen vacancy (V O ) concentrations where O* and H* represent oxygen and hydrogen radicals, respectively. The fundamental WH 2 (Cp) 2 −O* ALD process was characterized by saturation behavior for the W-precursor/O* dose, high deposition uniformity, and a short incubation period. The V O concentration could be limitedly controlled up to ∼0.7 at. % when the O* dose was appropriately decreased within the ALD saturation range. However, a further increase in the V O concentration could hardly be achieved by simply decreasing the O* dose, which accompanied the carbon-related impurities due to incomplete ligand release from the growing film. The addition of the H* pulse step in each ALD cycle rendered it possible to achieve a much higher V O concentration up to ∼5 at. % without disturbing the ALD saturation conditions and involving any carboncontaining impurities. Ab initio calculations of the valence band (VB) spectra, assuming oxygen-deficient WO 3−x , showed good agreement with the experimental VB X-ray photoelectron spectroscopy (XPS) data, which corroborated the estimated V O concentrations based on the core-level XPS data. The increase in the V O concentration obtained in the new reaction cycle process was accompanied by a significant film resistivity decrease and a noticeable change in the crystalline structure. The V O concentrationcontrolled WO 3−x films could be a viable material for diverse electronic applications, including resistive random-access memory devices.

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Section: Resultsmentioning

confidence: 99%

Radical-Enhanced Atomic Layer Deposition of a Tungsten Oxide Film with the Tunable Oxygen Vacancy Concentration

et al. 2020

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“…As can be observed in Figure 5 the C1s region can be deconvolved into four peaks at ~282.2, 284.6, 286.3 and 288.0 eV (Mg-Kα source). The peak at around 282.2 eV is usually associated to metallic carbides [43][44][45]. However, there is no sound explanation for the presence of carbides on the ZnO surface.…”

Section: Xpsmentioning

confidence: 99%

Room temperature sintering of polar ZnO nanosheets: II-mechanism

Fernández-Pérez

Rodríguez-Casado

Valdés-Solı́s

et al. 2017

Phys. Chem. Chem. Phys.

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In a previous work by the authors (A. Fernández-Pérez el al., Room temperature sintering of polar ZnO nanosheets: I-evidence, 2017, DOI: 10.1039/C7CP02306E), polar ZnO nanosheets were stored at room temperature under different atmospheres and the evolution of their textural and crystal properties during storage was followed. It was found that the specific surface area of the nanosheets drastically decreased during storage, with a loss of up to 75%. The ZnO crystals increased in size mainly through the partial merging of their polar surfaces at the expense of narrow mesoporosity, in a process triggered by the action of moisture, oxygen and, in their absence, by light. In the present work, a set of spectroscopic techniques (FTIR, Raman and XPS) has been used in an attempt to unravel the mechanism behind this spontaneous sintering process. The mechanism starts with the molecular adsorption of water, which takes place on Zn atoms close to oxygen vacancies on the (100) surface, where HO dissociates to form two hydroxyl groups and to heal one oxygen vacancy. This process triggers the room temperature migration of Zn interstitials towards the outer surface of the polar region. What were previously interstitial Zn atoms now gradually occupy the mesopores, with interstitial oxygen being used to build up the O sublattice until total occupancy of the narrow mesoporosity is achieved.

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“…While several ALD chemistries are reactive enough to allow deposition of WN x /WN x C y at lower temperatures (180–350 °C), ,− higher temperatures (>350 °C) are generally still required for dissociation of critical bonds during film growth under single source CVD conditions (Table ). Temperatures above 350 °C can compromise some low-κ materials due to their low thermal stability and can encourage crystallization of barrier materials resulting in low-energy diffusion pathways for Cu migration by grain boundary formation .…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2014

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Tungsten nitrido complexes of the form WN(NR2)3 [R = combinations of Me, Et, (i)Pr, (n)Pr] have been synthesized as precursors for the chemical vapor deposition of WN(x)C(y), a material of interest for diffusion barriers in Cu-metallized integrated circuits. These precursors bear a fully nitrogen coordinated ligand environment and a nitrido moiety (W≡N) designed to minimize the temperature required for film deposition. Mass spectrometry and solid state thermolysis of the precursors generated common fragments by loss of free dialkylamines from monomeric and dimeric tungsten species. DFT calculations on WN(NMe2)3 indicated the lowest gas phase energy pathway for loss of HNMe2 to be β-H transfer following formation of a nitrido bridged dimer. Amorphous films of WN(x)C(y) were grown from WN(NMe2)3 as a single source precursor at temperatures ranging from 125 to 650 °C using aerosol-assisted chemical vapor deposition (AACVD) with pyridine as the solvent. Films with stoichiometry approaching W2NC were grown between 150 and 450 °C, and films grown at 150 °C were highly smooth, with a RMS roughness of 0.5 nm. In diffusion barrier tests, 30 nm of film withstood Cu penetration when annealed at 500 °C for 30 min.

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Novel cyclopentadienyl based precursors for CVD of W containing films

Cited by 7 publications

References 11 publications

Radical-Enhanced Atomic Layer Deposition of a Tungsten Oxide Film with the Tunable Oxygen Vacancy Concentration

Radical-Enhanced Atomic Layer Deposition of a Tungsten Oxide Film with the Tunable Oxygen Vacancy Concentration

Room temperature sintering of polar ZnO nanosheets: II-mechanism

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

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Novel cyclopentadienyl based precursors for CVD of W containing films

Cited by 7 publications

References 11 publications

Radical-Enhanced Atomic Layer Deposition of a Tungsten Oxide Film with the Tunable Oxygen Vacancy Concentration

Radical-Enhanced Atomic Layer Deposition of a Tungsten Oxide Film with the Tunable Oxygen Vacancy Concentration

Room temperature sintering of polar ZnO nanosheets: II-mechanism

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

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