Electrical and materials properties of ZrO2 gate dielectrics grown by atomic layer chemical vapor deposition

Perkins, C.; Triplett, B. B.; McIntyre, Paul C.; Saraswat, Krishna C.; Haukka, Suvi; Tuominen, M.

doi:10.1063/1.1362331

Cited by 203 publications

(108 citation statements)

References 5 publications

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“…Both types of interfacial layers have been reported [10,15,[24][25][26][27]. The interface between interfacial SiO 2 and the high-k layer tends to be rough, and intermixing can be difficult to distinguish from roughness [28].…”

Section: B) Uncapped Anneals Under Conditions That Favor Reaction (1)mentioning

confidence: 99%

See 1 more Smart Citation

Thermodynamic considerations in the stability of binary oxides for alternative gate dielectrics in complementary metal–oxide–semiconductors

Stemmer¹

2004

Journal of Vacuum Science &Amp; Technology B: Microelectronics and Nanometer Structures Processing, Measurement, and Phenomena

110

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A number of binary oxides have been predicted to be thermodynamically stable in contact with Si and are candidates to replace SiO 2 in CMOS. However, reactions leading to the formation of interfacial silicide, silicate or SiO 2 layers have been reported when these oxides are exposed to high temperatures during device processing. Different pathways have been proposed in the literature to explain these reactions. In this paper, a thermodynamic analysis of the proposed reactions is performed. The analysis includes gaseous species, because typical gate dielectrics are ultra-thin layers and diffusivities for species from the surrounding atmosphere, such as oxygen, may be high. Furthermore, nonstoichiometry of the high-k oxide, as may be resulting from nonequilibrium deposition processes or reducing atmospheres during processing is also considered. Studies are proposed to distinguish between possible reaction mechanisms. Finally guidelines for stable interfaces are presented.3

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Section: B) Uncapped Anneals Under Conditions That Favor Reaction (1)mentioning

confidence: 99%

“…[19] and Table I [ 19,39] (6), two main reactions schemes have been proposed in literature [4][5][6][7]9,17,18,24]. The first approach is to include gaseous species, in particular SiO, as part of the thermodynamic analysis of interfacial reactions under reducing conditions [4][5][6][7]17,18].…”

Section: Silicide Formationmentioning

confidence: 99%

Thermodynamic considerations in the stability of binary oxides for alternative gate dielectrics in complementary metal–oxide–semiconductors

Stemmer¹

2004

Journal of Vacuum Science &Amp; Technology B: Microelectronics and Nanometer Structures Processing, Measurement, and Phenomena

110

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“…For instance, in the last 5-6 years, oxides with wide band-gap and high dielectric constant, known as high-k oxides [1][2][3][4][5], have attracted great attention in the electronic industry. High-k oxides, such as Al 2 O 3 , HfO 2 , ZrO 2 , and TiO 2 , are widely used in optical devices as well [6][7][8].…”

Section: Introductionmentioning

confidence: 99%

Structural study of TiO2 thin films by micro-Raman spectroscopy

et al. 2006

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Abstract:The Raman spectroscopy method was used for structural characterization of TiO 2 thin films prepared by atomic layer deposition (ALD) and pulsed laser deposition (PLD) on fused silica and single-crystal silicon and sapphire substrates. Using ALD, anatase thin films were grown on silica and silicon substrates at temperatures 125-425 • C. At higher deposition temperatures, mixed anatase and rutile phases grew on these substrates. Post-growth annealing resulted in anatase-to-rutile phase transitions at 750 • C in the case of pure anatase films. The films that contained chlorine residues and were amorphous in their as-grown stage transformed into anatase phase at 400 • C and retained this phase even after annealing at 900 • C. On single crystal sapphire substrates, phase-pure rutile films were obtained by ALD at 425 • C and higher temperatures without additional annealing. Thin films that predominantly contained brookite phase were grown by PLD on silica substrates using rutile as a starting material.

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“…Moreover, in recent years, zirconia-based materials, including ZrO 2 -SiO 2 , have been proposed as a promising high-gate dielectric material for metal-oxide-semiconductor ͑MOS͒ transistors. [1][2][3] Thin films of ZrO 2 can be prepared by a range of methods, including physical vapor deposition, 4 chemical vapor deposition, 5 atomic layer deposition, 6 chemical solution deposition, 3,7 and anodizing. 8,9 Anodizing is the most simple and easiest method to form dielectric oxides, and this has been extensively used to form dielectric oxide films on aluminum and tantalum for electrolytic capacitor applications.…”

mentioning

confidence: 99%

Phase Transformation and Capacitance Enhancement of Anodic ZrO[sub 2]–SiO[sub 2]

Koyama¹,

Aoki²,

Sakaguchi

et al. 2010

J. Electrochem. Soc.

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Capacitance enhancement of anodic oxide films on zirconium by adding silicon is reported here with correlation to the phase transformation of the oxide. The anodic oxide film formed on zirconium consists mainly of monoclinic ZrO 2 , which changes to tetragonal ZrO 2 phase on the Zr-5.5 atom % Si. Further increase in the silicon contents to 10 and 16 atom % results in the formation of amorphous oxide up to 30 V, above which two-layered films, comprising an outer crystalline tetragonal-phase oxide layer and an inner amorphous layer, are developed. The relative thickness of the outer crystalline layer to the total film thickness increases with formation voltage. The highest capacitance of the anodic oxide films is obtained on the Zr-10 atom % Si. The changes in capacitance, permittivity and formation ratio of anodic oxide films with alloy composition are discussed with phase transformation and growth process of anodic oxides. © 2010 The Electrochemical Society. ͓DOI: 10.1149/1.3503592͔ All rights reserved.Manuscript submitted August 9, 2010; revised manuscript received September 23, 2010. Published October 22, 2010 ZrO 2 is an important inorganic material for high-temperature applications, due to many useful properties such as high strength and stability at high temperatures, oxide ion conductivity at elevated temperatures and radiation-resistant properties. These features make ZrO 2 attractive for oxygen sensors, solid oxide fuel cells, and nuclear materials. Moreover, in recent years, zirconia-based materials, including ZrO 2 -SiO 2 , have been proposed as a promising high-gate dielectric material for metal-oxide-semiconductor ͑MOS͒ transistors. 8,9 Anodizing is the most simple and easiest method to form dielectric oxides, and this has been extensively used to form dielectric oxide films on aluminum and tantalum for electrolytic capacitor applications. Tantalum electrolytic capacitors are widely used in electronics industry, but due to limitation of natural resources of tantalum and for high demand of increasing capacitance, alternative abundant materials that form oxides with higher permittivity, such as niobium and titanium, have been studied. [10][11][12][13][14][15][16] Zirconium forms usually crystalline anodic oxide films, in contrast to the formation of amorphous anodic oxides on a range of valve metals, including aluminum, bismuth, niobium, tantalum and tungsten. 17 The crystalline structure of anodic zirconium oxide films is influenced by surface treatments prior to anodizing and electrolyte for anodizing. When magnetron-sputtered zirconium is anodized in ammonium pentaborate electrolyte without pretreatment of the deposited surface, crystalline oxide films, consisting mainly of monoclinic ZrO 2 , are developed. 9 The monoclinic phase of ZrO 2 is thermodynamically the most stable at ambient temperature, but amorphous and high-temperature stable phases of cubic or tetragonal ZrO 2 are also often found in the anodic oxide films formed on chemically polished zirconium, particularly at low formation voltage...

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Electrical and materials properties of ZrO2 gate dielectrics grown by atomic layer chemical vapor deposition

Cited by 203 publications

References 5 publications

Thermodynamic considerations in the stability of binary oxides for alternative gate dielectrics in complementary metal–oxide–semiconductors

Thermodynamic considerations in the stability of binary oxides for alternative gate dielectrics in complementary metal–oxide–semiconductors

Structural study of TiO2 thin films by micro-Raman spectroscopy

Phase Transformation and Capacitance Enhancement of Anodic ZrO[sub 2]–SiO[sub 2]

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