Influence of process parameters on atomic layer deposition of ZrO2 thin films from CpZr(NMe2)3 and H2O

Aarik, Lauri; Alles, Harry; Aidla, Aleks; Kahro, Tauno; Kukli, Kaupo; Niinistö, Jaakko; Mändar, Hugo; Tamm, Aile; Rammula, Raul; Sammelselg, Väinö; Aarik, Jaan

doi:10.1016/j.tsf.2014.06.052

Cited by 19 publications

(11 citation statements)

References 39 publications

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“…The thick ZrO 2 films grown with CpZr(NMe 2 ) 3 and O 3 at 250 and 300 °C exhibited only the cubic phase, whereas that grown at 350 °C showed a mixture of the cubic and monoclinic phases [21]. The thick ZrO 2 films that were grown with CpZr(NMe 2 ) 3 and H 2 O at temperatures from 200 to 400 °C contained mixtures of the tetragonal, cubic, and monoclinic phases [22]. The maximum intensity of the dominant peak of the tetragonal phase at 30.5° was obtained for the film grown at 250 °C and the small intensity of the peak at 28.2° from the monoclinic phase remained constant for films grown at 200 to 300 °C.…”

Section: Resultsmentioning

confidence: 99%

Effect of Growth Temperature on the Structural and Electrical Properties of ZrO2 Films Fabricated by Atomic Layer Deposition Using a CpZr[N(CH3)2]3/C7H8 Cocktail Precursor

Chung

Kim

et al. 2018

Materials

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The effect of growth temperature on the atomic layer deposition of zirconium oxide (ZrO2) dielectric thin films that were fabricated using a CpZr[N(CH3)2]3/C7H8 cocktail precursor with ozone was investigated. The chemical, structural, and electrical properties of ZrO2 films grown at temperatures from 250 to 350 °C were characterized. Stoichiometric ZrO2 films formed at 250–350 °C with an atomic ratio of O to Zr of 1.8–1.9 and a low content of carbon impurities. The film formed at 300 °C was predominantly the tetragonal crystalline phase, whereas that formed at 350 °C was a mixture of tetragonal and monoclinic phases. Electrical properties, such as capacitance, leakage current, and voltage linearity of TiN/ZrO2/TiN capacitors fabricated using the thin ZrO2 films grown at different temperatures were compared capacitor applications. The ZrO2 film grown at 300 °C exhibited low impurity content, predominantly tetragonal crystalline structure, a high dielectric permittivity of 38.3, a low leakage current of below 10−7 A/cm2 at 2 V, and low-voltage linearity.

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Section: Resultsmentioning

confidence: 99%

Effect of Growth Temperature on the Structural and Electrical Properties of ZrO2 Films Fabricated by Atomic Layer Deposition Using a CpZr[N(CH3)2]3/C7H8 Cocktail Precursor

Chung

Kim

et al. 2018

Materials

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“…The situation with water is particularly interesting, because of the high reactivity of Cp-based precursor molecules with water in the gas phase. ALD processes using Cp-based precursors for oxide films generally have high growth rates and include those for the deposition of ZrO 2 , ,− HfO 2 , ,,,− and metal oxides of group 2 − and rare-earth − elements, among others. Surprisingly, the growth rate achieved with water has been found in some cases not only to exceed that of the analogous ozone process but also to be relatively high for typical ALD processes. , These intriguing results provide a strong motivation to investigate the interaction of a Cp-based molecule with water within an ALD situation, that is, when water is adsorbed on the surface.…”

Section: Introductionmentioning

confidence: 99%

Selective Atomic Layer Deposition Mechanism for Titanium Dioxide Films with (EtCp)Ti(NMe₂)₃: Ozone versus Water

et al. 2018

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The need for the conformal deposition of TiO 2 thin films in device fabrication has motivated a search for thermally robust titania precursors with noncorrosive byproducts. Alkylamido-cyclopentadienyl precursors are attractive because they are readily oxidized, yet stable, and afford environmentally mild byproducts. We have explored the deposition of TiO 2 films on OH-terminated SiO 2 surfaces by in situ Fourier transform infrared spectroscopy using a novel titanium precursor [(EtCp)-Ti(NMe 2 ) 3 (1), Et = CH 2 CH 3 ] with either ozone or water. This precursor initially reacts with surface hydroxyl groups at ≥150 °C through the loss of its NMe 2 groups. However, once the precursor is chemisorbed, its subsequent reactivities toward ozone and water are very different. There is a clear reaction with ozone, characterized by the formation of monodentate formate and/or chelate bidentate carbonate surface species; in contrast, there is no detectable reaction with water. For the ozone-based ALD process, the surface formate/carbonate species react with the NMe 2 groups during the subsequent pulse of 1, forming TiOTi bonds. Ligand exchange is observed within the 250−300 °C ALD window. X-ray photoelectron spectroscopy confirms the deposition of stoichiometric TiO 2 films with no detectable impurities. For the water-based process, ligand exchange is not observed. Once 1 is adsorbed, there is no spectroscopic evidence for further reaction. However, there is still TiO 2 deposition under typical ALD conditions. Co-adsorption experiments with controlled vapor pressures of water and 1 indicate that deposition arises solely from 1/water gas-phase reactions. This striking lack of reactivity between chemisorbed 1 and water is attributed to the electronic and steric effects of the EtCp group and facilitates the observation of gas-phase reactions.

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“…35 Atomic layer deposited hafnia has been made from HfCl 4 and H 2 O at 300 • C. 36,37 Film growth at 300 • C was analyzed for comparison, using different metal precursors HfCl 4 and HfI 4 , and the oxidizer was water. 38 HfCl 4 -H 2 O and HfI 4 -O 2 processes were compared in the temperature range of 300-600 • C. 39 HfO 2 and ZrO 2 have been fabricated, using Hf[N(CH 3 ) 2 ] 4 (TDMA-HF) and ZyALD ((tris(dimethylamino)cylcopentadienyl)-zirconium), as respective Hf and Zr precursors, and O 3 as oxidizer, at 260 • C and 285 • C. 20 ZrO 2 films have been atomic layer deposited using (CpMe) 2 ZrMe 2 and (CpMe) 2 Zr(OMe)Me as Zr precursors, and O 3 as the oxidant at 300 or 350 • C. 40 ZrO 2 films from tris(dimethylamino)cyclopentadienylzirconium CpZr(NMe 2 ) 3 and H 2 O, were investigated using real-time characterization of the growth process at substrate temperatures ranging from 120 to 350 • C. 41 ZrO 2 growth has been carried out in the case of ZrCl 4 and H 2 O as precursors 37 and this process has also been monitored in real time. 42 Zirconia has also been deposited from TEMAZ (tetrakis(ethylmethylamide) zirconium) and water.…”

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confidence: 99%

Electric and Magnetic Properties of Atomic Layer Deposited ZrO₂-HfO₂Thin Films

Kalam

Seemen

Mikkor

et al. 2018

ECS J. Solid State Sci. Technol.

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Atomic layer deposition method was employed to deposit thin films consisting of ZrO 2 and HfO 2. Zirconia films were doped with hafnia and vice versa, and also nanolaminates were formed. All depositions were carried out at 300 • C. Most films were crystalline in their as-deposited state. Zirconia exhibited the metastable cubic and tetragonal phases by a large majority, whereas hafnia was mostly in its stable monoclinic phase. Magnetic and electrical properties of the films were assessed. Un-doped zirconia was ferromagnetic and this property diminished with increasing the amount of hafnia in a film. All films exhibited ferroelectric-like behavior and the polarization curves also changed with respect to the film composition.

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Influence of process parameters on atomic layer deposition of ZrO2 thin films from CpZr(NMe2)3 and H2O

Cited by 19 publications

References 39 publications

Effect of Growth Temperature on the Structural and Electrical Properties of ZrO2 Films Fabricated by Atomic Layer Deposition Using a CpZr[N(CH3)2]3/C7H8 Cocktail Precursor

Effect of Growth Temperature on the Structural and Electrical Properties of ZrO2 Films Fabricated by Atomic Layer Deposition Using a CpZr[N(CH3)2]3/C7H8 Cocktail Precursor

Selective Atomic Layer Deposition Mechanism for Titanium Dioxide Films with (EtCp)Ti(NMe₂)₃: Ozone versus Water

Electric and Magnetic Properties of Atomic Layer Deposited ZrO₂-HfO₂Thin Films

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Influence of process parameters on atomic layer deposition of ZrO2 thin films from CpZr(NMe2)3 and H2O

Cited by 19 publications

References 39 publications

Effect of Growth Temperature on the Structural and Electrical Properties of ZrO2 Films Fabricated by Atomic Layer Deposition Using a CpZr[N(CH3)2]3/C7H8 Cocktail Precursor

Effect of Growth Temperature on the Structural and Electrical Properties of ZrO2 Films Fabricated by Atomic Layer Deposition Using a CpZr[N(CH3)2]3/C7H8 Cocktail Precursor

Selective Atomic Layer Deposition Mechanism for Titanium Dioxide Films with (EtCp)Ti(NMe2)3: Ozone versus Water

Electric and Magnetic Properties of Atomic Layer Deposited ZrO2-HfO2Thin Films

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Selective Atomic Layer Deposition Mechanism for Titanium Dioxide Films with (EtCp)Ti(NMe₂)₃: Ozone versus Water

Electric and Magnetic Properties of Atomic Layer Deposited ZrO₂-HfO₂Thin Films