Low-Temperature Deposition of Zirconium Oxide-Based Nanocrystalline Films by Alternate Supply of Zr[OC(CH3)3]4 and H2O

Articles you may be interested inStructural and dielectric properties of thin ZrO 2 films on silicon grown by atomic layer deposition from cyclopentadienyl precursor Characterization of atomic-layer-deposited silicon nitride / SiO 2 stacked gate dielectrics for highly reliable pmetal-oxide-semiconductor field-effect transistors Atomic-layer-deposited silicon-nitride/SiO 2 stacked gate dielectrics for highly reliable pmetal-oxide-semiconductor field-effect transistorsWe deposited ZrO 2 thin films by atomic-layer deposition ͑ALD͒ using zirconium tertiary-butoxide ͓Zr(t-OC 4 H 9 ) 4 , ͑ZTB͔͒ and H 2 O source gases on Si substrates at low temperatures. We grew ZrO 2 films layer by layer in a temperature range of 175-250°C to minimize surface roughness. The deposited ZrO 2 film thickness had self-limiting properties with the exposure time of ZTB and vapor pressures of ZTB and H 2 O. The deposition rate per cycle was independent of the vapor pressure of ZTB from 0.01 kPa to 0.04 kPa. Transmission electron microscopy revealed that the formation of an SiO x interfacial layer could be suppressed by using an ALD ZrO 2 /ALD Si-nitride ͑ϳ0.5 nm͒ stack structure. We found the fixed charge, interface trap density, and leakage current density in the ALD ZrO 2 /ALD Si-nitride stack dielectrics to be less than those in ALD ZrO 2 dielectrics. In spite of the same equivalent oxide thickness of 1.6 nm, the relative dielectric constant r ͑11.5͒ of the ALD ZrO 2 /ALD Si-nitride stack capacitor was higher than that ͑10.5͒ of the ALD ZrO 2 capacitor due to the suppression of formation of the interfacial SiO x layer ͑1.0-1.5 nm͒ by an ultrathin ALD Si nitride ͑ϳ0.5 nm͒. The current conduction mechanism is identified as direct tunneling of electron except at very low dielectric fields. Comparing structural and electrical properties, ALD ZrO 2 /ALD Si-nitride stack dielectrics are promising candidates for sub-0.1-m metal-oxide-semiconductor field-effect transistors.

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“…When the OH terminated surface is exposed to ZTB ambient, the following reaction occurs: 20,24 Zr͑OH͒*ϩZr͓OC͑CH 3 …”

Section: Resultsmentioning

confidence: 99%

“…However, only a few reports 20 have been published regarding the ALD of ZrO 2 using ZTB as a gas source. In particular, the growth in the ultrathin region has not yet been examined.…”

Section: Introductionmentioning

confidence: 99%

Growth and electrical properties of atomic-layer deposited ZrO2/Si-nitride stack gate dielectrics

Ishii

Nakajima

Yokoyama

2004

Journal of Applied Physics

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“…For example, a carbon content as high as 8 at.‐% was reported in the case of the Hf(O t Bu) 4 /O 3 process, 4 − 5 at.‐% of carbon and as much as 14 − 18 at.‐% of hydrogen as impurities when using Hf(mp) 4 and water . With the notable exception of Ti(OMe) 4 , which exists as a tetramer under standard conditions, and presented self‐limiting GPC at 350°C when used together with water, alkoxides generally exhibit poor thermal stability, and the self‐limiting growth has been limited to well below 300°C (Table ) …”

Section: Ald Of Groups 4 and 5 Oxide Thin Filmsmentioning

confidence: 99%

Atomic Layer Deposition of Groups 4 and 5 Transition Metal Oxide Thin Films: Focus on Heteroleptic Precursors

Blanquart

Niinistö

Ritala

et al. 2014

Chemical Vapor Deposition

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The atomic layer deposition (ALD) process, an alternative to CVD, is universally appreciated for its unique advantages such as excellent repeatability, conformity, and thickness control at the atomic level. ALD precursor chemistry has mainly been based on homoleptic compounds such as, but not limited to, metal halides, alkylamides, and alkoxides, however these precursors have drawbacks such as possible halide contamination and low thermal stabilities in the case of the alkylamides and alkoxides. Consequently, heteroleptic precursors have been investigated as alternatives to the existing homoleptic counterparts, leading to the development of several advantageous processes. Nevertheless, there is no thematic review dedicated to the heteroleptic precursors and their properties, and it seems that no coherent strategy has been adopted for the development of heteroleptic precursors. This review gives a brief description of ALD and presents studies on the deposition of thin films of groups 4 and 5 metal oxides using ALD. A description of the general ALD properties of homoleptic precursors, in addition to a review on the thermal ALD of groups 4 and 5 metal oxides from heteroleptic precursors, is provided. Trends in the properties of heteroleptic ALD precursors, based on the literature review and recent experimental data, are discussed.

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“…Zirconium tertiary-butoxide ͓Zr(t-OC 4 H 9 ) 4 ,(ZTB)͔ is one of the alternative Zr precursors with the highest vapor pressure, allowing evaporation at low temperatures. However, only a few reports 17 have been published regarding the ALD of ZrO 2 using ZTB as a gas source. In particular, the growth in the ultrathin region has not yet been examined.…”

mentioning

confidence: 99%

Atomic-layer deposition of ZrO2 with a Si nitride barrier layer

Nakajima

Kidera

Ishii

et al. 2002

Applied Physics Letters

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Growth and electrical properties of atomic-layer deposited ZrO 2 / Si -nitride stack gate dielectrics J. Appl. Phys. 95, 536 (2004); 10.1063/1.1629773Atomic layer deposition of metal and nitride thin films: Current research efforts and applications for semiconductor device processing ZrO 2 thin films for gate dielectrics have been formed at low temperatures ͑200°C͒ by an atomic-layer deposition ͑ALD͒ technique using Zr(t-OC 4 H 9 ) 4 and H 2 O source gases. An ultrathin ͑physical thickness T phy of ϳ0.5 nm͒ Si nitride layer was deposited on a Si substrate by ALD before the deposition of ZrO 2 . Transmission electron microscopy showed that the Si nitride barrier layer successfully suppressed the formation of a SiO 2 interfacial layer. Because of the extremely uniform thickness control capability in the ultrathin region and the low thermal budget of the ALD process, the ALD process for the ZrO 2 /Si nitride stack structure is a promising candidate for fabricating the ultrathin gate dielectrics for sub-0.1-m complementary metal-oxide-semiconductor transistors.

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Low-Temperature Deposition of Zirconium Oxide-Based Nanocrystalline Films by Alternate Supply of Zr[OC(CH3)3]4 and H2O

Cited by 96 publications

References 17 publications

Growth and electrical properties of atomic-layer deposited ZrO2/Si-nitride stack gate dielectrics

Growth and electrical properties of atomic-layer deposited ZrO2/Si-nitride stack gate dielectrics

Atomic Layer Deposition of Groups 4 and 5 Transition Metal Oxide Thin Films: Focus on Heteroleptic Precursors

Atomic-layer deposition of ZrO2 with a Si nitride barrier layer

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