Growth and Physical Properties of MOCVD-Deposited Hafnium Oxide Films and Their Properties on Silicon

Elshocht, Sven Van; Caymax, Matty; Gendt, Stefan De; Conard, Thierry; Pétry, J.; Claes, Martine; Witters, T.; Zhao, Chao; Brijs, Bert; Richard, Olivier; Bender, Hugo; Vandervorst, Wilfried; Carter, R.; Kluth, J.; Daté, L.; Pique, D.; Heyns, Marc

doi:10.1557/proc-745-n5.15

Cited by 6 publications

(5 citation statements)

References 2 publications

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“…Similar mixed phases at intermediate temperatures have also been reported for other precursors. 21,22 For films from the ͓Hf͑NEt 2 ͒ 2 ͑guanid͒ 2 ͔ precursor ͑Fig. 3b͒ this crystallization sequence is clearly visible.…”

Section: Resultsmentioning

confidence: 87%

Thin Films of HfO[sub 2] for High-k Gate Oxide Applications from Engineered Alkoxide- and Amide-Based MOCVD Precursors

Thomas¹,

Rije²,

Ehrhart³

et al. 2007

J. Electrochem. Soc.

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HfO2 thin films with thickness between 2 and 20nm were grown by liquid injection metallorganic chemical vapor deposition, LI-MOCVD, on SiOx∕Si(100) substrates. Different mononuclear precursors ([Hf(OPrnormali)2(tbaoac)2] , [Hf(NEt2)2(guanid)2] , and [Hf(OBunormalt)2(dmae)2] were tested in combination with different solvents. Growth rate, surface morphology, crystal structure, and crystal density of the as-deposited films were analyzed as a function of deposition temperature. The influence of postdeposition annealing on the densification and crystallization was studied. Correlation of the structural properties with the electrical properties of metal insulator semiconductor capacitors with Pt top electrodes is discussed. Fully silicided metal gate stacks are additionally discussed for selected samples.

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Section: Resultsmentioning

confidence: 87%

Thin Films of HfO[sub 2] for High-k Gate Oxide Applications from Engineered Alkoxide- and Amide-Based MOCVD Precursors

Thomas¹,

Rije²,

Ehrhart³

et al. 2007

J. Electrochem. Soc.

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“…It is not easy to calculate the atomic concentration from the thickness of the layer because the density of ultrathin film (< 5 nm) was not equal (50-60 %) to the bulk value. [1,28,29] It appears that the incubation time at the beginning of the deposition of each hafnia or alumina layer is not significant, and if we know the density of each layer, the atomic composition can be predicted from the number of cycles of each layer. No impurities (such as carbon and nitrogen) were detected by X-ray photoelectron spectroscopy (XPS).…”

Section: Film Depositionmentioning

confidence: 99%

Cyclic Atomic Layer Deposition of Hafnium Aluminate Thin Films Using Tetrakis(diethylamido)hafnium, Trimethyl Aluminum, and Water

Kim¹,

Rhee²

2006

Chemical Vapor Deposition

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Hafnium aluminate thin films were deposited at 225°C by cyclic atomic layer deposition (ALD) of hafnia and alumina with Hf(N(C 2 H 5 ) 2 ) 4 (tetrakis(diethylamido)hafnium: TDEAH), Al(CH 3 ) 3 (trimethyl aluminum: TMA), and H 2 O. The multi-component thin films were formed by switching between the alumina and hafnia deposition cycles, and the chemical composition of the film was controlled by adjusting the number of cycles of each oxide. The surface of the film was very smooth and the formation of an interfacial layer was suppressed. The crystallization temperature of the film became higher as the Al incorporation in the film was increased. The hafnium aluminate thin film with the composition Hf 0.68 Al 0.32 O x showed a dielectric constant of 13.94 and leakage current of 4.3 × 10 -7 A cm -2 at 1 MV cm -1 . At this composition, the formation of an interfacial layer was minimal after rapid thermal annealing (RTA).

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“…Indeed, the as-deposited layer still contains some impurities like C or Cl, depending on the CVD technique used. 17,18 Therefore, it is speculated that the layer is present as a HfO 2Ϫx Y x ͑with Y ϭ C, Cl or other ligands͒ layer. This oxygen-deficient HfO 2 layer is now subjected to further reactions and can be a source of defects.…”

Section: High-k Layer Quality/defect Screening By Wet Chemical Etching-mentioning

confidence: 99%

Effect of Postdeposition Anneal Conditions on Defect Density of HfO[sub 2] Layers Measured by Wet Etching

Claes¹,

Gendt²,

Witters³

et al. 2004

J. Electrochem. Soc.

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The quality of HfO 2 dielectric layers was systematically evaluated using wet etching monitored by open-circuit potential analysis. Scanning electron microscopy imaging was used to observe changes in the topography after etching. Our results showed that surface pretreatment prior to high-k deposition, as well as postdeposition treatments, have an effect on the quality of the high-k material as seen from the etch behavior of these materials. The wet etch defect monitoring was subsequently used to improve the quality of the high-k films. As-deposited films may have a high defect density of 1.10 9 wet-etch defects/cm 2 . However, after appropriate postdeposition annealing, high-k layers with reduced defect density can be obtained. A lower defect density can also be correlated to improved electrical properties of the high-k layer. The presence of defects is speculated as being due to crystallization phenomena and/or an oxygen-deficient HfO 2 film, evidenced by Si/SiO up-diffusion upon thermal treatment.

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Growth and Physical Properties of MOCVD-Deposited Hafnium Oxide Films and Their Properties on Silicon

Cited by 6 publications

References 2 publications

Thin Films of HfO[sub 2] for High-k Gate Oxide Applications from Engineered Alkoxide- and Amide-Based MOCVD Precursors

Thin Films of HfO[sub 2] for High-k Gate Oxide Applications from Engineered Alkoxide- and Amide-Based MOCVD Precursors

Cyclic Atomic Layer Deposition of Hafnium Aluminate Thin Films Using Tetrakis(diethylamido)hafnium, Trimethyl Aluminum, and Water

Effect of Postdeposition Anneal Conditions on Defect Density of HfO[sub 2] Layers Measured by Wet Etching

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