A new metalorganic chemical vapor deposition process for MoS<sub>2</sub> with a 1,4-diazabutadienyl stabilized molybdenum precursor and elemental sulfur

Wree, Jan‐Lucas; Çiftyürek, Engin; Zanders, David; Boysen, Nils; Kostka, Aleksander; Rogalla, Detlef; Kasischke, Maren; Ostendorf, Andreas; Schierbaum, K.D.; Devi, Anjana

doi:10.1039/d0dt02471f

Cited by 17 publications

(41 citation statements)

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“…The plots yield that the bandgap energies are in a range of ~1.28-1.41 eV for the 2D MoS2 layers with a thickness of ~3.5-21 nm 41 (obtained from Mo seeds of 1-6 nm, respectively). These values are in good agreement with the bandgap energies of multilayer 2D MoS2 of comparable thickness known in the literature, 2,47,48 confirming that the 2D MoS2 layers well retained their intrinsic opto-electrical Please do not adjust margins Please do not adjust margins characteristics even after the integration on TOCN substrates. The inset graph in Fig.…”

Section: Please Do Not Adjust Marginssupporting

confidence: 89%

“…Furthermore, the shapes of the UV-vis spectral profiles are consistent with previous observations with thickness-varying 2D MoS2 layers integrated on other optically transparent substrates. [43][44][45][46] Detailed optical characteristics of the integrated 2D MoS2 layers were further analysed by developing Tauc plots from the UV-vis spectra, 47,48 as shown in Fig. 2d.…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

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Mechanically rollable photodetectors enabled by centimetre-scale 2D MoS₂ layer/TOCN composites

Yoo

Han

et al. 2021

Nanoscale Adv.

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confidence: 89%

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

Mechanically rollable photodetectors enabled by centimetre-scale 2D MoS₂ layer/TOCN composites

Yoo

Han

et al. 2021

Nanoscale Adv.

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“…Compounds with DAD ligands are also redox active, and the doubly-reduced 1,4-di-tertbutyl-1,3-diazabutadienyl ligand had previously been used to prepare the volatile bis(tert-butylimido)-molybdenum(VI) compound (E). [24] Direct treatment of 1a with 1,4-di-tert-butyl-1,3diazabutadiene ( tBu DAD H ) in THF gave ( t BuN)2MoCl2•( tBu DAD H ) (5) in good yield.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

“…[21] N,N'-chelating ligands have also been used to prepare volatile bis(tert-butylimido)molybdenum(VI) compounds, such as amidinates (B), [22] pyrazolates (C), [10] guanidinates (D), [23] and diazabutadienyls (E). [24] However, only the amidinate B has been used for ALD to prepare MoO3 films with O3. [3] It has also been used by CVD for the deposition of MoS2 [25] and MoNx.…”

Section: Introductionmentioning

confidence: 99%

“…[22,26] The pyrazolate C and the guanidinates D have been used as single-source precursors for the CVD of Mo2N [27] and MoCxNy, [28] respectively, whereas MoS2 films have been prepared by CVD with the diazabutadienyl E and S8. [24] The thiolate compound (F) has been used for the ALD Chart 1. General bis(tert-butylimido)molybdenum(VI) frameworks, and known ALD and CVD precursors that incorporate them.…”

Section: Introductionmentioning

confidence: 99%

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Thermal Stability and Decomposition Pathways in Volatile Molybdenum(VI) Bis-Imides

Land

Bačić

Robertson³

et al. 2021

Preprint

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The vapor deposition of many molybdenum-containing films relies on the delivery of volatile compounds with the general bis(tert-butylimido)molybdenum(VI) framework, both in atomic layer deposition and chemical vapor deposition. We have prepared a series of (tBuN)2MoCl2 adducts using neutral N,N’-chelates and investigated their volatility, thermal stability, and decomposition pathways. Volatility has been determined by thermogravimetric analysis, with the 1,4-di-tert-butyl-1,3-diazabutadiene adduct (5) found to be the most volatile (1 Torr of vapor pressure at 135 ºC). Thermal stability was measured primarily using differential scanning calorimetry, and the 1,10-phenanthroline adduct (4) was found to be the most stable, with an onset of decomposition of 303 ºC. We have also investigated molybdenum compounds with other alkyl-substituted imido groups: these compounds all follow a similar decomposition pathway, γ-H activation, with varying reaction barriers. The tert-pentyl, 1-adamantyl, and a cyclic imido (from 2,5-dimethylhexane-2,5-diamine) were systematically studied to probe the kinetics of this pathway. All of these compounds have been fully characterized, including via single-crystal X-ray diffraction, and a total of 19 unique structures are reported.

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Unveiling Ruthenium(II) Diazadienyls for Gas Phase Deposition Processes: Low Resistivity Ru Thin Films and Their Performance in the Acidic Oxygen Evolution Reaction

Zanders

Obenlüneschloß

Wree

et al. 2022

Adv Materials Inter

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devices has driven academic and industrial research on alternatives such as cobalt (Co) and ruthenium (Ru) to a new dimension. [1,2] These endeavors are based on the inherent limitations of Cu thin films as interconnect in the back end of line (BEOL) and middle of line (MOL) facing scale-down toward 2 nm. At these dimensions, Cu layers are exhibiting lower resistance toward electromigration as well as the tendency toward diffusion under thermal or current-induced stress. [3,4] Both, Co and Ru provide more suited physical, mechanical, and electrical properties. Especially shorter electron mean free paths and higher chemical stability are to be named in this regard. [1,[5][6][7] Recent studies have shown that the chosen metallization approach may decide which of the two is favored: Murdoch and co-workers demonstrated superior performance of Ru thin films in semidamascene structures outperforming those of Cu and Co layers. [8] Beyond great promise for IC applications, Ru catalysts are garnering significant interest, foremost in the context of electrocatalysis for hydrogen production through water splitting. Specifically, their outstanding performance in the oxygen Two novel ruthenium complexes belonging to the Ru(II)(DAD)(Cym) (DAD = diazadienyl) (Cym = cymene) compound family are introduced as promising precursors. Their chemical nature, potential for chemical vapor deposition (CVD), and possibly atomic layer deposition (ALD) are demonstrated. The development of nonoxidative CVD processes yielding high-quality Ru thin films is realized. Chemical analyses are exercised that vitiate the deceptive assumption of Ru(DAD)(Aryl) complexes being zero-valent through clear evidence for the redox noninnocence of the DAD ligand. Two different CVD routes for the growth of Ru films are developed using Ru( tBu2 DAD)(Cym). Ru thin films from both processes are subjected to thorough and comparative analyses that allowed to deduce similarities and differences in film growth. Ru thin films with a thickness of 30-35 nm grown on SiO 2 yielded close-to-bulk resistivity values ranging from 12 to 16 µΩ cm. Catalysis evaluation of the films in the acidic oxygen evolution reaction (OER) results in promising performances based on overpotentials as low as 240 mV with Tafel slopes of 45-50 mV dec −1 . Based on the degradation observed during electrochemical measurements, the impact of OER conditions on the layers is critically assessed by complementary methods.

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A new metalorganic chemical vapor deposition process for MoS₂ with a 1,4-diazabutadienyl stabilized molybdenum precursor and elemental sulfur

Abstract: Molybdenum disulfide (MoS2) is known for its versatile properties and hence promising for a wide range of applications. The fabrication of high-quality MoS2 either as homogeneous films or as two-dimensional...

Cited by 17 publications

References 74 publications

Mechanically rollable photodetectors enabled by centimetre-scale 2D MoS₂ layer/TOCN composites

Mechanically rollable photodetectors enabled by centimetre-scale 2D MoS₂ layer/TOCN composites

Thermal Stability and Decomposition Pathways in Volatile Molybdenum(VI) Bis-Imides

Unveiling Ruthenium(II) Diazadienyls for Gas Phase Deposition Processes: Low Resistivity Ru Thin Films and Their Performance in the Acidic Oxygen Evolution Reaction

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A new metalorganic chemical vapor deposition process for MoS2 with a 1,4-diazabutadienyl stabilized molybdenum precursor and elemental sulfur

Abstract: Molybdenum disulfide (MoS2) is known for its versatile properties and hence promising for a wide range of applications. The fabrication of high-quality MoS2 either as homogeneous films or as two-dimensional...

Cited by 17 publications

References 74 publications

Mechanically rollable photodetectors enabled by centimetre-scale 2D MoS2 layer/TOCN composites

Mechanically rollable photodetectors enabled by centimetre-scale 2D MoS2 layer/TOCN composites

Thermal Stability and Decomposition Pathways in Volatile Molybdenum(VI) Bis-Imides

Unveiling Ruthenium(II) Diazadienyls for Gas Phase Deposition Processes: Low Resistivity Ru Thin Films and Their Performance in the Acidic Oxygen Evolution Reaction

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A new metalorganic chemical vapor deposition process for MoS₂ with a 1,4-diazabutadienyl stabilized molybdenum precursor and elemental sulfur

Mechanically rollable photodetectors enabled by centimetre-scale 2D MoS₂ layer/TOCN composites

Mechanically rollable photodetectors enabled by centimetre-scale 2D MoS₂ layer/TOCN composites