Atomic Layer Deposition of Noble Metals and Their Oxides

Hämäläinen, Jani; Ritala, Mikko; Leskelä, Markku

doi:10.1021/cm402221y

Cited by 332 publications

(200 citation statements)

References 143 publications

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“…The tetramer is predicted to contain a cubic Zn 4 Cl 4 core. The Xray crystal structure of [Zn(Si(tBu) 3 )Br] 4 has been reported, 16 and exists with a cubic Zn 4 Br 4 core, thus supporting the DFT calculations of [Zn(Si(SiMe 3 ) 3 )Cl] 4 . However, it is not clear if the tetramer is accessible after THF loss in the current experiments.…”

supporting

confidence: 71%

“…Recently, the ALD growth of Sb thin films was demonstrated using SbCl 3 and Sb(SiEt 3 ) 3 . 9 This process proceeds by elimination of SiEt 3 Cl, and is a totally new approach for the ALD of element films, in this case a nonmetal.…”

mentioning

confidence: 99%

“…9 Related reactions could represent powerful methodologies for the ALD growth of metallic first row transition and electropositive metal films, and could avoid potential problems associated with H 2 and highly reactive hydride reagents. 1,5 Within this context, we describe a series of reactions that occur upon treatment of bis(hypersilyl)zinc, Zn(Si(SiMe 3 ) 3 ) 2 , 11 with ZnX 2 (X = Cl, Br, I) ultimately to afford Zn metal and Si(SiMe 3 ) 3 X. These results demonstrate that reductive eliminations of silyl halides from Zn(II) centers are facile, thus suggesting new, potentially general chemistry for the growth of metal films.…”

mentioning

confidence: 99%

“…12 The gas phase compounds [Zn(Si(SiMe 3 ) 3 )Cl] n increase in stability upon oligomerization, with n = 4 predicted to be the most stable (E = -49.1 kJ/mol-Zn relative to ZnCl 2 and Zn(Si(SiMe 3 ) 3 ) 2 ). The tetramer is predicted to contain a cubic Zn 4 Cl 4 core.…”

mentioning

confidence: 99%

“…However, it is not clear if the tetramer is accessible after THF loss in the current experiments. Thermolysis of solid 2 at 111 °C/0.05 Torr for 24 hours in a drying tube afforded a THF-free complex of the apparent formula [Zn(Si(SiMe 3 ) 3 )Br] x , 12 however, X-ray quality crystals could not be obtained despite multiple attempts and the compound was not pursued further. The DFT calculations revealed that formation of THF adducts from [Zn(Si(SiMe 3 ) 3 )Cl] n is thermodynamically favorable for n = 1-3.…”

mentioning

confidence: 99%

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Reductive Elimination of Hypersilyl Halides from Zinc(II) Complexes. Implications for Electropositive Metal Thin Film Growth

et al. 2014

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Treatment of Zn(Si(SiMe 3 ) 3 ) 2 with ZnX 2 (X = Cl, Br, I) in tetrahydrofuran (THF) at 23 °C afforded [Zn(Si(SiMe 3 ) 3 )X(THF)] 2 in 83−99% yield. X-ray crystal structures revealed dimeric structures with Zn 2 X 2 cores. Thermogravimetric analyses of [Zn(Si(SiMe 3 ) 3 )X(THF)] 2 demonstrated a loss of coordinated THF between 50 and 155 °C and then single-step weight losses between 200 and 275 °C. The nonvolatile residue was zinc metal in all cases. Bulk thermolyses of [Zn(Si(SiMe 3 ) 3 )X(THF)] 2 between 210 and 250 °C afforded zinc metal in 97−99% yield, Si(SiMe 3 ) 3 X in 91−94% yield, and THF in 81−98% yield. Density functional theory calculations confirmed that zinc formation becomes energetically favorable upon THF loss. Similar reactions are likely to be general for M(SiR 3 ) n /MX n pairs and may lead to new metal-filmgrowth processes for chemical vapor deposition and atomic layer deposition.

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confidence: 71%

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confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Reductive Elimination of Hypersilyl Halides from Zinc(II) Complexes. Implications for Electropositive Metal Thin Film Growth

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Atomic Layer Deposition

Ommen

Goulas

Puurunen

2021

Kirk-Othmer Encyclopedia of Chemical Technology

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Atomic layer deposition (ALD) is a gas‐phase method to grow layers of solid materials with subnanometer precision. It has been invented independently in the Soviet Union in the 1960s under the name molecular layering, and in the 1970s in Finland under the name atomic layer epitaxy. ALD relies on alternatingly exposing a surface to gaseous reactants—separated by a purge step—that react in a self‐terminating manner. This article introduces the fundamentals of the surface chemistry of ideal ALD, including saturating and irreversible reactions, growth per cycle, monolayer concepts relevant to ALD, typical surface reaction mechanisms, saturation‐limiting factors, growth modes, area‐selective ALD, growth kinetics, and conformality. It also discusses typical deviations from ideal ALD. Over the years, many different ALD process chemistries have been developed. A range of reactor systems is available, depending on the type of substrate and required productivity. ALD is broadly applicable in practice since it couples nanoscale precision with a good scalability and can be used to deposit a large variety of materials. In recent years, the interest in ALD has been growing strongly. The most important sector regarding commercial applications of ALD is currently the semiconductor industry.

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Atomic Layer Deposition

Ghazaryan

Pfeiffer

Schmitt

et al. 2020

Digital Encyclopedia of Applied Physics

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Atomic layer deposition (ALD) is a key coating technology which enables conformal coatings on high aspect ratio substrates. In addition, it allows for a precise thickness control of thin films, multilayers, and nanolaminates. It is a chemical coating technology where the precursors are introduced sequentially in the reactor or are spatially separated. Herein, basic principles of ALD are introduced, reactor geometries are overviewed, and typical ALD materials and applications are summarized. ALD thin films are one pillar of modern computer technologies where ultra‐thin, conformal coatings with exceptional physical, electrical, and chemical properties are essential. Numerous emerging applications have been demonstrated and some are already in mass‐production. Precursor and process development, tool design and engineering, extensive thin‐film optimization, the search for better materials and composites combined with expert knowledge in the application fields have led to this success.

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Atomic Layer Deposition of Noble Metals and Their Oxides

Cited by 332 publications

References 143 publications

Reductive Elimination of Hypersilyl Halides from Zinc(II) Complexes. Implications for Electropositive Metal Thin Film Growth

Reductive Elimination of Hypersilyl Halides from Zinc(II) Complexes. Implications for Electropositive Metal Thin Film Growth

Atomic Layer Deposition

Atomic Layer Deposition

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