Highly-conformal nanocrystalline molybdenum nitride thin films by atomic layer deposition as a diffusion barrier against Cu

Jang, Yujin; Kim, Jun Beom; Hong, Tae Eun; Yeo, So Jeong; Lee, Sun-Ju; Jung, Eun‐Hee; Park, Bo Keun; Chung, Taek‐Mo; Kim, Chang Gyoun; Lee, Do-Joong; Lee, Han‐Bo‐Ram; Kim, Soohyun

doi:10.1016/j.jallcom.2015.12.148

Cited by 37 publications

(35 citation statements)

References 29 publications

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“…28 An ALD-grown MoN x thin film was also successfully demonstrated as a potential Cu diffusion barrier. 29,30 Similar to other TMNs, MoN x has relatively low resistivity, high thermal stability (the melting points of MoN and Mo 2 N are approximately 1750 and 2000 °C, respectively), and extremely low Mo reactivity with Si. 30 In addition to the ALD, several studies have been carried out using chemical vapor deposition (CVD) involving MoF 6 , MoCl 5 , Mo(CO) 6 , and metalorganic (MO) precursor and physical vapor deposition-like sputtering to deposit MoN x .…”

Section: ■ Introductionmentioning

confidence: 94%

“…An ALD-grown MoN x thin film was also successfully demonstrated as a potential Cu diffusion barrier. , Similar to other TMNs, MoN x has relatively low resistivity, high thermal stability (the melting points of MoN and Mo 2 N are approximately 1750 and 2000 °C, respectively), and extremely low Mo reactivity with Si . In addition to the ALD, several studies have been carried out using chemical vapor deposition (CVD) involving MoF 6 , MoCl 5 , Mo(CO) 6 , and metalorganic (MO) precursor and physical vapor deposition-like sputtering to deposit MoN x . − Some of these compounds suffer from high resistivity (the MO precursor yielded a resistivity of 10 000 μΩ cm) of the deposited MoN x film, whereas others require a very high deposition temperature (MoF 6 requires a temperature of 500–700 °C for MoN x deposition).…”

Section: Introductionmentioning

confidence: 99%

“…To address these issues, the MO precursor was later introduced . For example, Mo(N t Bu) 2 (S t Bu) 2 was introduced with an H 2 plasma reactant to deposit Mo 2 N for the Cu diffusion barrier . However, the deposition temperature is still well above 300 °C, and the complex structures of these precursors make them expensive.…”

Section: Introductionmentioning

confidence: 99%

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Some Insights into Atomic Layer Deposition of MoN_x Using Mo(CO)₆ and NH₃ and Its Diffusion Barrier Application

et al. 2019

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Deposition providing precise control of the film thickness, low deposition temperature, and noncorrosive byproducts is essential for the efficient fabrication of barrier layers in semiconductor devices. Here, molybdenum nitride (MoN x ) is deposited for Cu diffusion barrier application at a relatively low temperature (180−300 °C) by atomic layer deposition (ALD) using molybdenum hexacarbonyl [Mo-(CO) 6 ] and ammonia gas (NH 3 ). The density functional theory calculations indicate favorable thermodynamics during the chemisorption of Mo(CO) 6 on −NH 2 -terminated Si clusters at 200 °C, confirming the suitability of Mo(CO) 6 for ALD. However, the films deposited beyond the ALD temperature window are of similar importance though decomposition-induced growth of the film is evident; nevertheless, other advantages exist (e.g., higher growth rate and improved film characteristics). Furthermore, a few experiments using NH 3 plasma as a reactant show further scope for this process. The as-grown MoN x film using thermal ALD is mostly amorphous with significant O impurity. Poorly structured nanocrystalline h-MoN and cubic Mo 2 N phase are formed in the film above 225 °C. These phases are converted into the crystalline cubic Mo 2 N phase upon annealing at higher temperature (500−700 °C) in a hydrogen atmosphere. The resistivity of the MoN x films decreases sharply with deposition temperature and is significantly reduced further upon post-annealing. The properties of the as-deposited and annealed films are characterized in detail by secondary-ion mass spectroscopy and X-ray photoelectron spectroscopy. The barrier properties against Cu diffusion for the asdeposited thin films (less than 10 nm) grown at 225 and 275 °C are analyzed using ex situ X-ray diffraction (XRD) and electrical impedance spectroscopy (EIS). EIS helps to determine the failure of the MoN x barrier layer qualitatively by comparing different EIS spectra obtained after annealing at different temperatures. Both XRD and EIS analyses show that the ALD-MoN x film deposited at the higher ALD temperature makes a better Cu diffusion barrier layer. This could be attributed to the higher density of the ALD MoN x film grown at 275 °C compared with that deposited at 225 °C.

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Section: ■ Introductionmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

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Some Insights into Atomic Layer Deposition of MoN_x Using Mo(CO)₆ and NH₃ and Its Diffusion Barrier Application

et al. 2019

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“…34 Finally, the thiolate G has also been used for the ALD of Mo2N films with H2 plasma. 15 Chart 1. Known CVD and ALD precursors (A-H) that incorporate the bis(tertbutylimido)molybdenum(VI) framework and the general (RN)2MoCl2•L (L = neutral N,N'chelating ligand) compounds (1)(2)(3)(4)(5)(6)(7).…”

Section: Introductionmentioning

confidence: 99%

Thermal Decomposition Mechanisms of Volatile Molybdenum(VI) Bis-Imides

Land

Bačić

Robertson³

et al. 2022

Preprint

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The bis(tert-butylimido)-molybdenum(VI) framework has been used successfully in the design of vapor-phase precursors for molybdenum-containing thin films, so understanding its thermal behavior is important for such applications. Here we report the thermal decomposition mechanism for a series of volatile bis(alkylimido)-dichloromolybdenum(VI) adducts with neutral N,N’-chelating ligands, to probe the stability and decomposition pathways for these industrially relevant molecules. The alkyl groups explored were tert-butyl, tert-pentyl, 1-adamantyl, and a cyclic imido (from 2,5-dimethylhexane-2,5-diamine). We also report the synthesis of the new tert-octyl imido adducts, (tOctN)2MoCl2·L (L = N,N,N’,N’ tetramethylethylenediamine or 2,2'-bipyridine), which have been fully characterized by spectroscopic techniques as well as single-crystal X-ray diffraction and thermal analysis. We found that the decomposition of all compounds follows the same general pathway, proceeding first by the dissociation of the chelating ligand to give the coordinatively unsaturated species (RN)2MoCl2. Subsequent dimerization results in either an imido bridged adduct, [(RN)Mo(μ-NR)Cl2]2, or a chloride bridged adduct, [(RN)2Mo(μ-Cl)Cl]2, depending on the size of the R group. The dimeric species then undergoes an intramolecular γ-hydrogen transfer to yield a nitrido-amido adduct (RHN)MoNCl2, and an alkene. Ultimately, the resulting molybdenum species decomposes into free tert-alkylamine and β-Mo2N. The thermolysis reactions have been monitored using 1H NMR spectroscopy, and the volatile decomposition products were analyzed using gas chromatography–mass spectrometry. A key intermediate has also been detected using electron ionization high-resolution mass spectrometry. Finally, a detailed computational investigation supports the mechanism outlined above and helps explain the relative stabilities of different N,N’-chelated bis(alkylimido)-dichloromolybdenum(VI) adducts.

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“…1,2 Prior work has been demonstrated for depositing molybdenum nitride films using either atomic layer deposition (ALD) or plasma enhanced atomic layer deposition (PE-ALD) techniques at process temperatures >260 C, with a wide range of reported q values (100-1500 lX). [3][4][5][6] Molybdenum carbide films have been deposited with techniques including magnetron cosputtering 7 and chemical vapor deposition (CVD) at temperatures >500 C. [8][9][10] Molybdenum carbide is a transition metal carbide with superconducting properties, and demonstrated critical temperatures (T c ) extending from 5.1 to 12 K. [11][12][13][14] Twodimensional (2D) molybdenum carbide or nitride in a synthesized state with a surface termination group, called MXenes, exhibit either conducting or semiconducting properties and have been identified as potential thermoelectric materials. Synthesis and delimitation techniques have been demonstrated for 2D Mo 2 C. 15 The ( t BuN) 2 (NMe 2 ) 2 Mo molecule has been shown to be a viable avenue for depositing MoO 3 using either ozone or O 2 plasma as coreactants, 16,17 and for depositing nitrides using NH 3 as an ALD coreactant.…”

Section: Introductionmentioning

confidence: 99%

Plasma enhanced atomic layer deposition of molybdenum carbide and nitride with bis(tert-butylimido)bis(dimethylamido) molybdenum

Bertuch¹,

Keller²,

Ferralis³

et al. 2016

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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Highly-conformal nanocrystalline molybdenum nitride thin films by atomic layer deposition as a diffusion barrier against Cu

Cited by 37 publications

References 29 publications

Some Insights into Atomic Layer Deposition of MoN_x Using Mo(CO)₆ and NH₃ and Its Diffusion Barrier Application

Some Insights into Atomic Layer Deposition of MoN_x Using Mo(CO)₆ and NH₃ and Its Diffusion Barrier Application

Thermal Decomposition Mechanisms of Volatile Molybdenum(VI) Bis-Imides

Plasma enhanced atomic layer deposition of molybdenum carbide and nitride with bis(tert-butylimido)bis(dimethylamido) molybdenum

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Highly-conformal nanocrystalline molybdenum nitride thin films by atomic layer deposition as a diffusion barrier against Cu

Cited by 37 publications

References 29 publications

Some Insights into Atomic Layer Deposition of MoNx Using Mo(CO)6 and NH3 and Its Diffusion Barrier Application

Some Insights into Atomic Layer Deposition of MoNx Using Mo(CO)6 and NH3 and Its Diffusion Barrier Application

Thermal Decomposition Mechanisms of Volatile Molybdenum(VI) Bis-Imides

Plasma enhanced atomic layer deposition of molybdenum carbide and nitride with bis(tert-butylimido)bis(dimethylamido) molybdenum

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Some Insights into Atomic Layer Deposition of MoN_x Using Mo(CO)₆ and NH₃ and Its Diffusion Barrier Application

Some Insights into Atomic Layer Deposition of MoN_x Using Mo(CO)₆ and NH₃ and Its Diffusion Barrier Application