Effects of Cl-Based Ligand Structures on Atomic Layer Deposited HfO2

Bo Eun Park, Il Kwon Oh, Chang Wan Lee, Gyeongho Lee, Young Han Shin, Clement Lansalot-Matras, Wontae Noh, Hyungjun Kim, Han Bo Ram Lee

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Atomic layer deposition (ALD) of HfO2 is a key technology for the application of high dielectric constant gate dielectrics ranging from conventional Si devices to novel nanodevices. The effects of the precursor on the growth characteristics and film properties of ALD HfO2 were investigated by using hafnium tetrachloride (HfCl4) and bis(ethylcyclopentadienyl)hafnium dichloride (Hf(EtCp)2Cl2, Hf(C2H5C5H4)2Cl2) with O2 plasma reactant. The growth characteristics were significantly affected even by simply changing the precursor. Theoretical calculations utilizing geometrical information on the precursor and density functional theory revealed that the steric demands of the precursor ligands have a dominant effect on the different growth characteristics rather than the reaction probability of the precursor on the surface. The chemical compositional analysis results showed that the Cl residue in the HfO2 films was reduced by using Hf(EtCp)2Cl2 due to the lower number of Cl atoms in each Hf precursor molecule and the relieved bridge formation of Hf-Cl-Hf bridge on the surface compared to HfCl4. The electrical property measurement results showed significantly improved insulating properties in HfO2 using Hf(EtCp)2Cl2 compared to HfCl4 due to the low concentration of Cl residue in the film. These results provide broad insights to researchers who are interested in the fabrication of high quality dielectric layers to achieve better device performance and overcome physical limitations in the nanoscale regime.

Original languageEnglish
Pages (from-to)5958-5967
Number of pages10
JournalJournal of Physical Chemistry C
Volume120
Issue number11
DOIs
Publication statusPublished - 2016 Mar 24

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Hafnium
Atomic layer deposition
hafnium
Ligands
atomic layer epitaxy
ligands
tetrachlorides
dichlorides
Gate dielectrics
chemical analysis
Density functional theory
low concentrations
Electric properties
Permittivity
electrical properties
permittivity
density functional theory
Plasmas
Fabrication
Atoms

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Park, B. E., Oh, I. K., Lee, C. W., Lee, G., Shin, Y. H., Lansalot-Matras, C., ... Lee, H. B. R. (2016). Effects of Cl-Based Ligand Structures on Atomic Layer Deposited HfO2 Journal of Physical Chemistry C, 120(11), 5958-5967. https://doi.org/10.1021/acs.jpcc.5b05286
Park, Bo Eun ; Oh, Il Kwon ; Lee, Chang Wan ; Lee, Gyeongho ; Shin, Young Han ; Lansalot-Matras, Clement ; Noh, Wontae ; Kim, Hyungjun ; Lee, Han Bo Ram. / Effects of Cl-Based Ligand Structures on Atomic Layer Deposited HfO2 In: Journal of Physical Chemistry C. 2016 ; Vol. 120, No. 11. pp. 5958-5967.
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abstract = "Atomic layer deposition (ALD) of HfO2 is a key technology for the application of high dielectric constant gate dielectrics ranging from conventional Si devices to novel nanodevices. The effects of the precursor on the growth characteristics and film properties of ALD HfO2 were investigated by using hafnium tetrachloride (HfCl4) and bis(ethylcyclopentadienyl)hafnium dichloride (Hf(EtCp)2Cl2, Hf(C2H5C5H4)2Cl2) with O2 plasma reactant. The growth characteristics were significantly affected even by simply changing the precursor. Theoretical calculations utilizing geometrical information on the precursor and density functional theory revealed that the steric demands of the precursor ligands have a dominant effect on the different growth characteristics rather than the reaction probability of the precursor on the surface. The chemical compositional analysis results showed that the Cl residue in the HfO2 films was reduced by using Hf(EtCp)2Cl2 due to the lower number of Cl atoms in each Hf precursor molecule and the relieved bridge formation of Hf-Cl-Hf bridge on the surface compared to HfCl4. The electrical property measurement results showed significantly improved insulating properties in HfO2 using Hf(EtCp)2Cl2 compared to HfCl4 due to the low concentration of Cl residue in the film. These results provide broad insights to researchers who are interested in the fabrication of high quality dielectric layers to achieve better device performance and overcome physical limitations in the nanoscale regime.",
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Park, BE, Oh, IK, Lee, CW, Lee, G, Shin, YH, Lansalot-Matras, C, Noh, W, Kim, H & Lee, HBR 2016, 'Effects of Cl-Based Ligand Structures on Atomic Layer Deposited HfO2 ', Journal of Physical Chemistry C, vol. 120, no. 11, pp. 5958-5967. https://doi.org/10.1021/acs.jpcc.5b05286

Effects of Cl-Based Ligand Structures on Atomic Layer Deposited HfO2 . / Park, Bo Eun; Oh, Il Kwon; Lee, Chang Wan; Lee, Gyeongho; Shin, Young Han; Lansalot-Matras, Clement; Noh, Wontae; Kim, Hyungjun; Lee, Han Bo Ram.

In: Journal of Physical Chemistry C, Vol. 120, No. 11, 24.03.2016, p. 5958-5967.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Effects of Cl-Based Ligand Structures on Atomic Layer Deposited HfO2

AU - Park, Bo Eun

AU - Oh, Il Kwon

AU - Lee, Chang Wan

AU - Lee, Gyeongho

AU - Shin, Young Han

AU - Lansalot-Matras, Clement

AU - Noh, Wontae

AU - Kim, Hyungjun

AU - Lee, Han Bo Ram

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N2 - Atomic layer deposition (ALD) of HfO2 is a key technology for the application of high dielectric constant gate dielectrics ranging from conventional Si devices to novel nanodevices. The effects of the precursor on the growth characteristics and film properties of ALD HfO2 were investigated by using hafnium tetrachloride (HfCl4) and bis(ethylcyclopentadienyl)hafnium dichloride (Hf(EtCp)2Cl2, Hf(C2H5C5H4)2Cl2) with O2 plasma reactant. The growth characteristics were significantly affected even by simply changing the precursor. Theoretical calculations utilizing geometrical information on the precursor and density functional theory revealed that the steric demands of the precursor ligands have a dominant effect on the different growth characteristics rather than the reaction probability of the precursor on the surface. The chemical compositional analysis results showed that the Cl residue in the HfO2 films was reduced by using Hf(EtCp)2Cl2 due to the lower number of Cl atoms in each Hf precursor molecule and the relieved bridge formation of Hf-Cl-Hf bridge on the surface compared to HfCl4. The electrical property measurement results showed significantly improved insulating properties in HfO2 using Hf(EtCp)2Cl2 compared to HfCl4 due to the low concentration of Cl residue in the film. These results provide broad insights to researchers who are interested in the fabrication of high quality dielectric layers to achieve better device performance and overcome physical limitations in the nanoscale regime.

AB - Atomic layer deposition (ALD) of HfO2 is a key technology for the application of high dielectric constant gate dielectrics ranging from conventional Si devices to novel nanodevices. The effects of the precursor on the growth characteristics and film properties of ALD HfO2 were investigated by using hafnium tetrachloride (HfCl4) and bis(ethylcyclopentadienyl)hafnium dichloride (Hf(EtCp)2Cl2, Hf(C2H5C5H4)2Cl2) with O2 plasma reactant. The growth characteristics were significantly affected even by simply changing the precursor. Theoretical calculations utilizing geometrical information on the precursor and density functional theory revealed that the steric demands of the precursor ligands have a dominant effect on the different growth characteristics rather than the reaction probability of the precursor on the surface. The chemical compositional analysis results showed that the Cl residue in the HfO2 films was reduced by using Hf(EtCp)2Cl2 due to the lower number of Cl atoms in each Hf precursor molecule and the relieved bridge formation of Hf-Cl-Hf bridge on the surface compared to HfCl4. The electrical property measurement results showed significantly improved insulating properties in HfO2 using Hf(EtCp)2Cl2 compared to HfCl4 due to the low concentration of Cl residue in the film. These results provide broad insights to researchers who are interested in the fabrication of high quality dielectric layers to achieve better device performance and overcome physical limitations in the nanoscale regime.

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Park BE, Oh IK, Lee CW, Lee G, Shin YH, Lansalot-Matras C et al. Effects of Cl-Based Ligand Structures on Atomic Layer Deposited HfO2 Journal of Physical Chemistry C. 2016 Mar 24;120(11):5958-5967. https://doi.org/10.1021/acs.jpcc.5b05286