Chemical vapor deposition of ruthenium–phosphorus alloy thin films: Using phosphine as the phosphorus source

Bost, Daniel E.; Ekerdt, John G.

doi:10.1016/j.tsf.2014.03.018

Cited by 6 publications

(23 citation statements)

References 14 publications

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“…16 To date, only few approaches for the deposition of Ru(P) layers by chemical vapor deposition (CVD) or atomic layer deposition (ALD) have been described. 11,[16][17][18][19] Most commonly, Ru 3 (CO) 12 and a phosphine PR 3 (R = H, Me, Ph) are deposited simultaneously forming a Ru(P) layer. [15][16][17][18] In this dual-source approach, the films contain 10-50 mol% C with decreasing C contents in the order PPh 3 4 PMe 3 4 PH 3 .…”

Section: Introductionmentioning

confidence: 99%

“…11,[16][17][18][19] Most commonly, Ru 3 (CO) 12 and a phosphine PR 3 (R = H, Me, Ph) are deposited simultaneously forming a Ru(P) layer. [15][16][17][18] In this dual-source approach, the films contain 10-50 mol% C with decreasing C contents in the order PPh 3 4 PMe 3 4 PH 3 . 13,15,17,18 Furthermore, precise control and reproducibility of the film stoichiometry are difficult to achieve, because of the different vapor pressures and reactivities of both components.…”

Section: Introductionmentioning

confidence: 99%

“…[15][16][17][18] In this dual-source approach, the films contain 10-50 mol% C with decreasing C contents in the order PPh 3 4 PMe 3 4 PH 3 . 13,15,17,18 Furthermore, precise control and reproducibility of the film stoichiometry are difficult to achieve, because of the different vapor pressures and reactivities of both components. 18 Much better reproducibilities are obtained in the single-source approach that uses precursors containing both elements in the same molecule.…”

Section: Introductionmentioning

confidence: 99%

“…13,15,17,18 Furthermore, precise control and reproducibility of the film stoichiometry are difficult to achieve, because of the different vapor pressures and reactivities of both components. 18 Much better reproducibilities are obtained in the single-source approach that uses precursors containing both elements in the same molecule. Moreover, a better homogeneity is provided as the desired elements are premixed at the molecular level.…”

Section: Introductionmentioning

confidence: 99%

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Chemical vapor deposition of ruthenium-based layers by a single-source approach

et al. 2016

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A series of ruthenium complexes of the general type Ru(CO)2(P(n-Bu)3)2(O2CR)2 (4a, R = Me; 4b, R = Et; 4c, R = i-Pr; 4d, R = t-Bu; 4e, R = CH2OCH3; 4f, R = CF3; 4g, R = CF2CF3) was synthesized by a single-step reaction of Ru3(CO)12 with P(n-Bu)3 and the respective carboxylic acid. The molecular structures of 4b, 4c and 4e–g in the solid state are discussed. All ruthenium complexes are stable against air and moisture and possess low melting points. The physical properties including the vapor pressure can be adjusted by modification of the carboxylate ligands. The chemical vapor deposition of ruthenium precursors 4a–f was carried out in a vertical cold-wall CVD reactor at substrate temperatures between 350 and 400 °C in a nitrogen atmosphere. These experiments show that all precursors are well suited for the deposition of phosphorus-doped ruthenium layers without addition of any reactive gas or an additional phosphorus source. In the films, phosphorus contents between 11 and 16 mol% were determined by XPS analysis. The obtained layers possess thicknesses between 25 and 65 nm and are highly conformal and dense as proven by SEM and AFM studies

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Chemical vapor deposition of ruthenium-based layers by a single-source approach

et al. 2016

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“…Co-W alloys [5], Ru(P) [14], and VO x and self-forming V-Cu alloys [15] have also been examined for barrier properties at low thickness. Some three-element alloys and non-metallic components have also shown promising results, such as TaSiC [16] and WGeN [17], and graphene [2].…”

Section: Several Responses To This Have Been Proposed and Tested Atomentioning

confidence: 99%

First-principles predictions of ruthenium-phosphorus and ruthenium-boron glassy structures and chemical vapor deposition of thin amorphous ruthenium-boron alloy films

et al. 2017

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First-principles density-functional calculations are presented revealing that Ru(P) and Ru(B) alloys with moderate P or B content can result in a glassy structure exhibiting strong chemical short-to-medium range order. Amorphous phases are predicted to be energetically more favorable than the crystalline counterparts for the Ru(P) and Ru(B) alloys above ~20 at.% P and ~10 at.% B. The relative stability of amorphous and crystalline Ru(B) alloys is examined along with local atomic ordering in the amorphous alloys. The growth of ultrathin (3nm) amorphous Ru(B) alloy films of varying B concentration via chemical vapor deposition is explored using Ru 3 (CO) 12 and B 2 H 6 as the Ru and B sources, respectively. Experiments reveal the films grown at 250 C are amorphous at B contents in excess of 15 at.% and polycrystalline below 10 at.% B, consistent with first-principles predictions. Amorphous Ru(B) films remain amorphous following annealing at 450 °C and become polycrystalline at 500 °C. Film resistivity ranged from 40 to 120 μΩ-cm and was independent of B loading. Electric field stress tests to failure for Cu/3-nm Ru(B)/SiO 2 /Si stacks are used to indicate suitability of Ru(B) as a copper diffusion barrier layer.

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Ruthenium(II) MOCVD Precursors for Phosphorus‐Doped Ruthenium Layer Formation

et al. 2020

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The synthesis and solid‐state structure of Ru(CO)2(PEt3)2(O2CR)2 (4a–f, R = Me, Et, iPr, tBu, CH2OMe, CF3) is reported. The vapor pressure of 4a–f was measured, ranging from 6.3 mbar (4f) to 14.8 at 190 °C (4e). Complexes 4a–f decompose between 210–350 °C of which 4c shows the lowest (248 °C) and 4e (280 °C) the highest onset temperature. TG‐MS studies (4f) showed subsequent decarbonylation and decarboxylation processes. To determine the gas phase composition VT IR studies were performed. Based on TG‐MS, VT IR and DFT calculations decomposition mechanisms are discussed. Complexes 4a–f are suited as MOCVD precursors, producing dense layers of 25–50 nm thickness, consisting of 57 at‐% Ru, up to 18.2 at‐% P and as impurities C, N and O. A carbon‐free Ru(P) layer was obtained with 4a as CVD precursor.

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Chemical vapor deposition of ruthenium–phosphorus alloy thin films: Using phosphine as the phosphorus source

Cited by 6 publications

References 14 publications

Chemical vapor deposition of ruthenium-based layers by a single-source approach

Chemical vapor deposition of ruthenium-based layers by a single-source approach

First-principles predictions of ruthenium-phosphorus and ruthenium-boron glassy structures and chemical vapor deposition of thin amorphous ruthenium-boron alloy films

Ruthenium(II) MOCVD Precursors for Phosphorus‐Doped Ruthenium Layer Formation

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