Atomic layer deposition of titanium dioxide films using a metal organic precursor (C12H23N3Ti) and H2O (DI water)

Kim, Byunguk; Lee, Namgue; Park, Suhyeon; Park, Taehun; Song, Jaiwon; Han, Seungwook; Park, Hyun-Woo; Lee, Dahyun; Kim, Hohoon; Jeon, Hyeongtag

doi:10.1016/j.jallcom.2020.157931

Cited by 12 publications

(19 citation statements)

References 33 publications

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“…In the case of precursor injection time, the thin film growth rate is saturated when it exceeds a certain level. According to previous published paper, the growth rate of TiO 2 thin films was saturated when Ti precursor was injected for 4 s, and the growth rate of Al 2 O 3 thin film was saturated when TMA precursor was injected 1 s. Therefore, in this study, we injected Ti precursor for 4 s and TMA precursor for 1 s. 15,27 The Al 2 O 3 thin film ALD process consisted of precursor injection (1 s), purging (30 s), reactant supply (1 s), and purging (40 s). In this study, TiO 2 : Al 2 O 3 thin films were deposited in three proportions (120: 1, 90: 1, 60: 1) and the characteristics of as-deposited TiO 2 z E-mail: hjeon@hanyang.ac.kr ECS Journal of Solid State Science and Technology, 2021 10 083006 thin films and Al doped TiO 2 thin films were analyzed.…”

Section: Methodsmentioning

confidence: 85%

“…11,12 In the ALD process, thin film can be deposited at a lower temperature compared to the CVD (chemical vapor deposition) process, and is excellent in many aspects such as uniformity of thin film and step coverage. [13][14][15] Therefore ALD is being studied as a next-generation deposition process. TiO 2 thin films have two crystalline structures, anatase and rutile crystal structures, which have a relatively high k value greater than 20.…”

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confidence: 99%

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Leakage Current Characteristics of Atomic Layer Deposited Al-Doped TiO₂Thin Film for Dielectric in DRAM Capacitor

Kim

Choi

Lee³

et al. 2021

ECS J. Solid State Sci. Technol.

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We researched the reduction of leakage current by Al doping in TiO 2 thin film. During the TiO 2 thin film deposition process, Al 2 O 3 thin film deposition was used for Al doping. XPS analysis showed that the greater the amount of Al doping in TiO 2 thin film, the fewer oxygen vacancies were found. The n-type characteristic of TiO 2 thin films is reduced as oxygen vacancies are reduced. An anatase (211) peak was detected by GIXRD analysis, and crystallinity was reduced with greater Al doping; the full width half maximum showed the crystalline size was reduced. UV-visible analysis showed the energy bandgap increased as the crystalline size became smaller, and I-V measurements showed the current density decreased to 3 × 10 −4 A cm −2 (As-dep TiO 2 : 10 −1 A cm −2 ) with Al doping. The dielectric constant remained above 20 even when doped with Al, confirming the superior properties of Al-doping TiO 2 thin film over conventional TiO 2 thin films.

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Section: Methodsmentioning

confidence: 85%

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confidence: 99%

Leakage Current Characteristics of Atomic Layer Deposited Al-Doped TiO₂Thin Film for Dielectric in DRAM Capacitor

Kim

Choi

Lee³

et al. 2021

ECS J. Solid State Sci. Technol.

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“…It offers some advantages as a precursor, including the noncorrosive nature of by-products of ligand elimination, higher reactivity due to the weak Me-N bonds and good thermal stability. [54] We perform DFT calculations to study the feasibility of the growth of titanicone films using Ti(DMA)4 and EG or GL as MLD precursors and to investigate the molecular mechanism behind the possible growth. The hydroxylated anatase TiO2 surface, hydroxylated rutile TiO2 surface and hydroxylated Al2O3 surface were selected as surface models.…”

Section: Resultsmentioning

confidence: 99%

Role of Titanium and Organic Precursors in Molecular Layer Deposition of “Titanicone” Hybrid Materials

Muriqi

Nolan

2022

Preprint

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The development of hybrid inorganic-organic films with well-controlled properties is important for many applications. Molecular layer deposition (MLD) allows the deposition of these hybrid films using sequential, self-limiting reactions, similar to atomic layer deposition (ALD). In this paper, we use first principles density functional theory (DFT) to investigate the growth mechanism of titanium-containing hybrid organic-inorganic MLD films, known as “titanicones”. We investigate in detail the chemistry between the most common Ti precursors, namely titanium tetrachloride (TiCl4) and tetrakis(dimethylamido)titanium (Ti(DMA)4,) and ethylene glycol (EG) and glycerol (GL) as the organic precursors. We analyse the impact of the substrate on the initial MLD reactions in titanicone film growth using three different surface models: anatase TiO2, rutile TiO2 and Al2O3. Calculated energetics show that while TiCl4 is reactive towards the anatase and rutile TiO2 surfaces, it is not reactive towards the Al2O3 surface. Ti(DMA)4 is reactive towards all surfaces. This is attributed to the stronger Ti-Cl bonds in TiCl4 compared to Ti-N bonds in Ti(DMA)4. Ti(DMA)4 also shows high reactivity to the organics compared to TiCl4. Double reactions of EG and GL with the TiCl3 species from TiCl4 and TiDMA species from Ti(DMA)4 are also explored to better understand the origin of the different thicknesses of EG-titanicone and GL-titanicone films observed in experimental work. We find that EG and GL coupled with TiCl4 can orient in a flat lying configuration on anatase while on rutile, the preferred orientation is upright. When combined with Ti(DMA)4, EG and GL prefer the flat lying configuration on all surfaces. This work shows that the choice of the surface and the metallic precursor has a major impact on the behaviour of organic species. DFT findings provide motivation to develop a low temperature rutile TiO2/titanicone film suggesting that the desired film growth could be achieved.

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“…Ti(DMA) 4 is a metalorganic precursor containing Ti–N bonds to the organic ligands, dimethylamino (DMA, N(CH 3 ) 2 ), and with a much larger molecular size when compared to TiCl 4 . It offers some advantages as a precursor, including the noncorrosive nature of by-products of ligand elimination, higher reactivity due to the weak Me–N bonds and good thermal stability [ 38 ]. We performed DFT calculations to study the feasibility of the growth of titanicone films using Ti(DMA) 4 and EG or GL as MLD precursors and to investigate the molecular mechanism behind the possible growth.…”

Section: Resultsmentioning

confidence: 99%

“…In contrast this is non-corrosive compared to HCl by-products released during the TiCl 4 process. For TiCl 4 this is considered a significant drawback [ 38 ].…”

Section: Introductionmentioning

confidence: 99%

Role of titanium and organic precursors in molecular layer deposition of “titanicone” hybrid materials

Muriqi¹,

Nolan²

2022

Beilstein J. Nanotechnol.

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The development of hybrid inorganic–organic films with well-controlled properties is important for many applications. Molecular layer deposition (MLD) allows the deposition of these hybrid films using sequential, self-limiting reactions, similar to atomic layer deposition (ALD). In this paper, we use first principles density functional theory (DFT) to investigate the growth mechanism of titanium-containing hybrid organic–inorganic MLD films, known as “titanicones”. We investigate in detail the chemistry between the most common Ti precursors, namely titanium tetrachloride (TiCl4) and tetrakis(dimethylamido)titanium (Ti(DMA)4), and ethylene glycol (EG) and glycerol (GL) as the organic precursors. We analyse the impact of the substrate on the initial MLD reactions in titanicone film growth using three different surface models: anatase TiO2, rutile TiO2 and Al2O3. Calculated energetics show that while TiCl4 is reactive towards the anatase and rutile TiO2 surfaces, it is not reactive towards the Al2O3 surface. Ti(DMA)4 is reactive towards all surfaces. This is attributed to the stronger Ti–Cl bonds in TiCl4 compared to Ti–N bonds in Ti(DMA)4. Ti(DMA)4 also shows high reactivity to the organics compared to TiCl4. Double reactions of EG and GL with the TiCl3 species from TiCl4 and TiDMA species from Ti(DMA)4 are also explored to better understand the origin of the different thicknesses of EG–titanicone and GL–titanicone films observed in experimental work. We find that EG and GL coupled with TiCl4 can orient in a flat lying configuration on anatase while on rutile, the preferred orientation is upright. When combined with Ti(DMA)4, EG and GL prefer the flat lying configuration on all surfaces. This work shows that the choice of the surface and the metallic precursor has a major impact on the behaviour of organic species. DFT findings provide motivation to develop a low temperature rutile TiO2/titanicone film suggesting that the desired film growth could be achieved.

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Atomic layer deposition of titanium dioxide films using a metal organic precursor (C12H23N3Ti) and H2O (DI water)

Cited by 12 publications

References 33 publications

Leakage Current Characteristics of Atomic Layer Deposited Al-Doped TiO₂Thin Film for Dielectric in DRAM Capacitor

Leakage Current Characteristics of Atomic Layer Deposited Al-Doped TiO₂Thin Film for Dielectric in DRAM Capacitor

Role of Titanium and Organic Precursors in Molecular Layer Deposition of “Titanicone” Hybrid Materials

Role of titanium and organic precursors in molecular layer deposition of “titanicone” hybrid materials

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Atomic layer deposition of titanium dioxide films using a metal organic precursor (C12H23N3Ti) and H2O (DI water)

Cited by 12 publications

References 33 publications

Leakage Current Characteristics of Atomic Layer Deposited Al-Doped TiO2Thin Film for Dielectric in DRAM Capacitor

Leakage Current Characteristics of Atomic Layer Deposited Al-Doped TiO2Thin Film for Dielectric in DRAM Capacitor

Role of Titanium and Organic Precursors in Molecular Layer Deposition of “Titanicone” Hybrid Materials

Role of titanium and organic precursors in molecular layer deposition of “titanicone” hybrid materials

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Product

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Leakage Current Characteristics of Atomic Layer Deposited Al-Doped TiO₂Thin Film for Dielectric in DRAM Capacitor

Leakage Current Characteristics of Atomic Layer Deposited Al-Doped TiO₂Thin Film for Dielectric in DRAM Capacitor