Manganese Precursor Selection and the Thermal Atomic Layer Deposition of Copper/Manganese Alloy Films

Kalutarage, Lakmal C.; Clendenning, Scott B.; Winter, Charles H.

doi:10.1149/06409.0147ecst

Cited by 8 publications

(6 citation statements)

References 30 publications

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“…Intermetallic phases in Pt–In, Pt–Sn, and Ni–Fe systems have been obtained by the postdeposition reduction of the corresponding ALD oxides. There are also some ALD studies on metal alloys, such as Pt–Ir, Pd–Pt, Ru–Pt, Ru–Co, Co–W, Co–Pt, Ru–Mn, and Cu–Mn, but no reports exist on materials exhibiting a specific intermetallic structure. Co–Sn and Ni–Sn with varying stoichiometry, including the intermetallic Co 3 Sn 2 and Ni 3 Sn 2 phases, have generally been prepared by, for example, ball milling, melting, different solution‐based techniques, solvo‐ and hydrothermal routes, electrodeposition, sputtering, and electron beam evaporation .…”

Section: Introductionmentioning

confidence: 99%

Atomic Layer Deposition of Intermetallic Co₃Sn₂ and Ni₃Sn₂ Thin Films

Väyrynen

Hatanpää

Mattinen

et al. 2018

Adv Materials Inter

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crystal structures of the participating metal components. An intermetallic compound is formed when the bonds between the dissimilar atoms are stronger than the bonds between the atoms of the same element.Because of their specific structure, intermetallic compounds usually exhibit unique physical and chemical properties that are potentially superior to their disordered alloy analogues and the pure metals. Such properties include, for example, magnetoresistance, [3,4] superconductivity, [5][6][7] enhanced catalytic activity, [8,9] and hydrogen storage capability. [10] Intermetallics and alloys containing Co or Ni and Sn with varying stoichiometry have mostly been studied as anode materials for Li-and Na-ion batteries. [11][12][13][14][15][16][17][18][19] As ferromagnetic materials, they also show potential for magnetic devices. [20][21][22] Furthermore, intermetallic Co-Sn and Ni-Sn compounds have also been studied for catalytic purposes. [23][24][25][26] For future applications like nanoelectronic devices, it is pivotal to be able to control the thickness and composition of thin films with sub-nanometer accuracy. Atomic layer deposition (ALD) is a thin film preparation method based on repeated, saturative, and irreversible surface reactions between alternately supplied gaseous precursors ensuring self-limiting growth of the desired material. [27,28] Owing to the self-limiting growth mechanism, ALD can be used to deposit uniform thin films over complex structures in a controlled and reproducible manner. No previous reports on the ALD of intermetallic Co 3 Sn 2 or Ni 3 Sn 2 thin films are found in the literature, and the ALD of other intermetallic compounds has also been scarce if existent at all. Intermetallic phases in Pt-In, [29] Pt-Sn, [30] and Ni-Fe [31] systems have been obtained by the postdeposition reduction of the corresponding ALD oxides. There are also some ALD studies on metal alloys, such as Pt-Ir, [32] Pd-Pt, [33][34][35] Ru-Pt, [36] Ru-Co, [37] Co-W, [38,39] Co-Pt, [40] Ru-Mn, [41] and Cu-Mn, [42] but no reports exist on materials exhibiting a specific intermetallic structure. Co-Sn and Ni-Sn with varying stoichiometry, including the intermetallic Co 3 Sn 2 and Ni 3 Sn 2 phases, have generally been prepared by, for example, ball Intermetallics form a versatile group of materials that possess unique properties ranging from superconductivity to giant magnetoresistance. The intermetallic Co-Sn and Ni-Sn compounds are promising materials for magnetic applications as well as for anodes in lithium-and sodium-ion batteries. Herein, a method is presented for the preparation of Co 3 Sn 2 and Ni 3 Sn 2 thin films using diamine adducts of cobalt(II) and nickel(II) chlorides, CoCl 2 (TMEDA) and NiCl 2 (TMPDA) (TMEDA = N,N,N′,N′tetramethylethylenediamine, TMPDA = N,N,N′,N′-tetramethyl-1,3propanediamine) combined with tributyltin hydride. The films are grown by atomic layer deposition (ALD), a technique that enables conformal film deposition with sub-nanometer thickness control. The Co 3 Sn 2 process fulfills the ...

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Section: Introductionmentioning

confidence: 99%

Atomic Layer Deposition of Intermetallic Co₃Sn₂ and Ni₃Sn₂ Thin Films

Väyrynen

Hatanpää

Mattinen

et al. 2018

Adv Materials Inter

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“…[18][19][20] This chemistry does not extend to Ta metal and TaSix films are produced instead. 21,22 Subsequently, BH3(NHMe2) has been used to deposit Cu and other first row transition metal films [23][24][25] and has also been evaluated for Ag 26 and Au 27 metal ALD, but film growth in all cases is highly substrate dependent. Thus, there is a great need to develop new volatile reducing agents for ALD of these challenging elements and materials.…”

Section: Introductionmentioning

confidence: 99%

Aluminum dihydride complexes and their unexpected application in atomic layer deposition of titanium carbonitride films

2018

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Aluminum dihydride complexes containing amido-amine ligands were synthesized and evaluated as potential reducing precursors for thermal atomic layer deposition (ALD). Highly volatile monomeric complexes AlH2(tBuNCH2CH2NMe2) and AlH2(tBuNCH2CH2NC4H8) are more thermally stable than common Al hydride thin film precursors such as AlH3(NMe3). ALD film growth experiments using TiCl4 and AlH2(tBuNCH2CH2NMe2) produced titanium carbonitride films with a high growth rate of 1.6-2.0 Å per cycle and resistivities around 600 μΩ cm within a very wide ALD window of 220-400 °C. Importantly, film growth proceeded via self-limited surface reactions, which is the hallmark of an ALD process. Root mean square surface roughness was only 1.3% of the film thickness at 300 °C by atomic force microscopy. The films were polycrystalline with low intensity, broad reflections corresponding to the cubic TiN/TiC phase according to grazing incidence X-ray diffraction. Film composition by X-ray photoelectron spectroscopy was approximately TiC0.8N0.5 at 300 °C with small amounts of Al (6 at%), Cl (4 at%) and O (4 at%) impurities. Remarkably, self-limited growth and low Al content was observed in films deposited well above the solid-state thermal decomposition point of AlH2(tBuNCH2CH2NMe2), which is ca. 185 °C. Similar growth rates, resistivities, and film compositions were observed in ALD film growth trials using AlH2(tBuNCH2CH2NC4H8).

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“…4,13 In the past few years, it has been well demonstrated that the atomic layer deposition (ALD) technique can guarantee depositions of various ultrathin films with excellent step coverage and accurate thickness controllability due to the self-limiting surface reaction mechanism. 1,15,16 Therefore, it is inferred that the ALD technology also might provide a great opportunity to prepare ultrathin Mn-based barrier films for interconnects of nanoscale integrated circuits. In this article, manganese oxynitride (i.e., MON for short) thin films are deposited by plasma-enhanced ALD (PE-ALD) using bis(ethylcyclopentadienyl)manganese (Mn(EtCp) 2 ) and NH 3 plasma as precursors.…”

Section: Introductionmentioning

confidence: 99%

Plasma-Enhanced Atomic Layer Deposition of Low Resistivity and Ultrathin Manganese Oxynitride Films with Excellent Resistance to Copper Diffusion

Wang

Liu

et al. 2020

ACS Appl. Electron. Mater.

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Low resistivity, high conformability, and ultrathin barriers against Cu diffusion have always been a critical challenge for fabrications of extremely large-scale integrated circuits. In this article, manganese oxynitride (MON) barriers against Cu diffusion are explored by plasma-enhanced atomic layer deposition (PE-ALD) with Mn(EtCp)2 and NH3 precursors, demonstrating a growth rate of ∼0.39 Å/cycle and a root-mean-square (RMS) roughness down to 0.38 nm in the temperature range of 225–300 °C. As the deposition temperature increases from 225 to 300 °C, the atomic ratio of Mn/N in the as-deposited film increases from 1.96 to 2.7; however, the percentage of oxygen always stabilizes at 19 ± 1%, which results from the residual oxygen in the chamber. The film resistivity reduces from 3.4 × 10–2 to 5.5 × 10–3 Ω·cm and the film density increases from 5.35 to 5.61 g/cm3 with the increase of deposition temperature. Only a 2.4 nm MON film can effectively prevent Cu atoms from diffusing through it even after annealing at 550 °C for 30 min, and the failure temperature can be elevated to 650 °C for the 3.7 nm MON barrier. Further, the failure mechanism of the MON diffusion barrier is also addressed. Owing to combined advantages of ultrathin and uniform thickness, good conductivity, and excellent barrier effect, the PE-ALD MON ultrathin film is thus very promising for nanoscale copper interconnection technologies.

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Manganese Precursor Selection and the Thermal Atomic Layer Deposition of Copper/Manganese Alloy Films

Cited by 8 publications

References 30 publications

Atomic Layer Deposition of Intermetallic Co₃Sn₂ and Ni₃Sn₂ Thin Films

Atomic Layer Deposition of Intermetallic Co₃Sn₂ and Ni₃Sn₂ Thin Films

Aluminum dihydride complexes and their unexpected application in atomic layer deposition of titanium carbonitride films

Plasma-Enhanced Atomic Layer Deposition of Low Resistivity and Ultrathin Manganese Oxynitride Films with Excellent Resistance to Copper Diffusion

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Manganese Precursor Selection and the Thermal Atomic Layer Deposition of Copper/Manganese Alloy Films

Cited by 8 publications

References 30 publications

Atomic Layer Deposition of Intermetallic Co3Sn2 and Ni3Sn2 Thin Films

Atomic Layer Deposition of Intermetallic Co3Sn2 and Ni3Sn2 Thin Films

Aluminum dihydride complexes and their unexpected application in atomic layer deposition of titanium carbonitride films

Plasma-Enhanced Atomic Layer Deposition of Low Resistivity and Ultrathin Manganese Oxynitride Films with Excellent Resistance to Copper Diffusion

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Atomic Layer Deposition of Intermetallic Co₃Sn₂ and Ni₃Sn₂ Thin Films

Atomic Layer Deposition of Intermetallic Co₃Sn₂ and Ni₃Sn₂ Thin Films