Precursors and chemistry for the atomic layer deposition of metallic first row transition metal films

Knisley, Thomas J.; Kalutarage, Lakmal C.; Winter, Charles H.

doi:10.1016/j.ccr.2013.03.019

Cited by 131 publications

(138 citation statements)

References 107 publications

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“…Knisley et al present chemical strategies for the deposition of the first row transition metals. 4 It can be seen that mainly the less electropositive transition metals have been successfully deposited so far.…”

Section: Introductionmentioning

confidence: 99%

“…5 Figure 1 illustrates the two distinct self-limiting processes that are thought to occur during each precursor pulse in steady-state ALD. In terms of adsorption, Al(CH 3 ) 3 behaves as a strong Lewis acid 6 and therefore, in pulse 1, it adsorbs onto the Lewis basic O sites of the OH-terminated surface, with elimination of ligands as a CH 4 by-product, until protons from the surface OH are exhausted (step 1a). This reaction thus self-limits as a result of the fixed coverage of Brønsted acidic H + in surface OH groups from step 2b.…”

Section: Introductionmentioning

confidence: 99%

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Classification of processes for the atomic layer deposition of metals based on mechanistic information from density functional theory calculations

Elliott

Dey

Maimaiti

2017

The Journal of Chemical Physics

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Original citationElliott Reaction cycles for the atomic layer deposition (ALD) of metals are presented, based on the incomplete data that exist about their chemical mechanisms, particularly from density functional theory (DFT) calculations. ALD requires self-limiting adsorption of each precursor, which results from exhaustion of adsorbates from previous ALD pulses and possibly from inactivation of the substrate through adsorption itself. Where the latter reaction does not take place, an "abbreviated cycle" still gives self-limiting ALD, but at a much reduced rate of deposition. Here, for example, ALD growth rates are estimated for abbreviated cycles in H 2 -based ALD of metals. A wide variety of other processes for the ALD of metals are also outlined and then classified according to which a reagent supplies electrons for reduction of the metal. Detailed results on computing the mechanism of copper ALD by transmetallation are summarized and shown to be consistent with experimental growth rates. Potential routes to the ALD of other transition metals by using complexes of non-innocent diazadienyl ligands as metal sources are also evaluated using DFT. Published by AIP Publishing.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Classification of processes for the atomic layer deposition of metals based on mechanistic information from density functional theory calculations

Elliott

Dey

Maimaiti

2017

The Journal of Chemical Physics

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“…8 As discussed by this review, copper (in its +2 state) has a standard reduction potential of 0.3419 V, making it the most easily reduced metal in the first row of the transition metals. In contrast, Ti 2+ has a standard reduction potential of -1.630 V. Although this means that copper films are easily produced, it also means that copper precursors need to be designed with stability in mind so that the compounds only undergo self-reduction in desired conditions.…”

Section: Copper Reductionmentioning

confidence: 99%

Trends in Copper Precursor Development for CVD and ALD Applications

Gordon

Kurek

Barry

2014

ECS J. Solid State Sci. Technol.

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The continued dominance of copper in microelectronic manufacturing is due in part to the techniques that have kept pace with the relentless trend towards smaller feature sizes. Pure and defect-free copper features can be created at these and smaller scales using gas phase deposition methods such as chemical vapor deposition (CVD) and atomic layer deposition (ALD). Here we review the deposition processes and in particular surface chemistry for depositing copper metal by CVD and ALD. A summary of known processes is given, and new trends in copper film deposition research are discussed. As well, process parameters and properties of copper films deposited from precursors using key ligand systems such as aminoalkoxides, amidinates, guanidinates, betadiketonates and betaketoiminates are presented. Surface chemistry is examined from the point of view of the similarities of CVD and ALD, considering precursors that can be used in both types of processes. This serves to highlight trends in decomposition mechanisms and illuminates some interesting similarities in process temperature and other parameters.

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“…In the classic ALD model, the precursors, once chemisorbed on the substrate, must also be thermally stable on the substrate, 11 meaning that the process must form a thermodynamically stable monolayer. In other words, ALD should have a surfacesaturating chemistry with chemisorption followed by stabilization.…”

Section: Time-resolved Precursor Supply In Cvdmentioning

confidence: 99%

Time as the Fourth Dimension: Opening up New Possibilities in Chemical Vapor Deposition

Pedersen

2016

Chem. Mater.

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Thin films of inorganic materials are essential to several technologies we take for granted in our everyday lives. They form the basis of touch screens in smart phones and the electronic components in computers. Dating back more than a century, chemical vapor deposition (CVD) is one of the most common methods to form these films. In CVD, the atoms needed for the thin film are typically supplied by a continuous flow of gaseous precursor molecules and incorporated into the film by gas phase and surface chemical reactions. The continuous demand for more precise thin film fabrication on more complex shapes at lower temperatures sets a demand for more advanced CVD methods. The development of better designed precursor molecules is one important path to evolve CVD, the other path is to evolve the way in which we do CVD. In this perspective I will describe how using time as a fourth dimension in CVD can enable fabrication of new thin film materials and material structures at lower temperatures and on more complex substrate geometries by accessing new types of CVD chemistries available in time-resolved CVD.

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Precursors and chemistry for the atomic layer deposition of metallic first row transition metal films

Cited by 131 publications

References 107 publications

Classification of processes for the atomic layer deposition of metals based on mechanistic information from density functional theory calculations

Classification of processes for the atomic layer deposition of metals based on mechanistic information from density functional theory calculations

Trends in Copper Precursor Development for CVD and ALD Applications

Time as the Fourth Dimension: Opening up New Possibilities in Chemical Vapor Deposition

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