Role of hydrogen in Sb film deposition and characterization of Sb and Ge xSb y films deposited by cyclic plasma enhanced chemical vapor deposition using metal-organic precursors

Hyung Keun Kim, Jin Hwan Jung, Doo Jin Choi

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Abstract

To meet increasing demands for chemical vapor deposition methods for high performance phase-change memory, cyclic plasma enhanced chemical vapor deposition of Sb and Ge xSb y phase-change films and characterization of their properties were performed. Two cycle sequences were designed to investigate the role of hydrogen gas as a reduction gas during Sb film deposition. Hydrogen gas was not introduced into the reaction chamber during the purge step in cycle sequence A and was introduced during the purge step for cycle sequence B. The role of hydrogen gas was investigated by comparing the results obtained from these two cycle sequences and was concluded to exert an effect by a combination of precursor decomposition, surface maintenance as a hydrogen termination agent, and surface etching. These roles of hydrogen gas are discussed through consideration of changes in deposition rates, the oxygen concentration on the surface of the Sb film, and observations of film surface morphology. Based on these results, Ge xSb y phase-change films were deposited with an adequate flow rate of hydrogen gas. The Ge and Sb composition of the film was controlled with the designed cycle sequences. A strong oxygen affinity for Ge was observed during the X-ray photoelectron spectroscopy analysis of Sb 3d, Sb 4d, and Ge 3d orbitals. Based on the XPS results, the ratios of Ge to Sb were calculated to be Ge 0.32Sb 0.68, Ge 0.38Sb 0.62, Ge 0.44Sb 0.56, Ge 0.51Sb 0.49 and Ge 0.67Sb 0.33 for the G1S7, G1S3, G1S2, G1S1, and G2S1 cycles, respectively. Crystal structures of Sb, Ge, and the GeSb metastable phase were observed with various Ge xSb y film compositions. Sb crystallinity decreased with respect to Ge crystallinity by increasing the Ge fraction. A current-voltage curve was introduced, and an electro-switching phenomenon was clearly generated at a typical voltage, V th. V th values increased in conjunction with an increased proportion of Ge. The Sb crystallinity decrease and V th increase were explained via the bonding characteristics of each element.

Original languageEnglish
Pages (from-to)6947-6953
Number of pages7
JournalThin Solid Films
Volume520
Issue number23
DOIs
Publication statusPublished - 2012 Sep 30

Fingerprint

Plasma enhanced chemical vapor deposition
metalorganic chemical vapor deposition
Hydrogen
Metals
Gases
hydrogen
cycles
gases
crystallinity
X ray photoelectron spectroscopy
vapor deposition
Oxygen
Phase change memory
Metastable phases
Electric potential
electric potential
oxygen
Deposition rates
Chemical analysis
maintenance

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Surfaces and Interfaces
  • Surfaces, Coatings and Films
  • Metals and Alloys
  • Materials Chemistry

Cite this

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title = "Role of hydrogen in Sb film deposition and characterization of Sb and Ge xSb y films deposited by cyclic plasma enhanced chemical vapor deposition using metal-organic precursors",
abstract = "To meet increasing demands for chemical vapor deposition methods for high performance phase-change memory, cyclic plasma enhanced chemical vapor deposition of Sb and Ge xSb y phase-change films and characterization of their properties were performed. Two cycle sequences were designed to investigate the role of hydrogen gas as a reduction gas during Sb film deposition. Hydrogen gas was not introduced into the reaction chamber during the purge step in cycle sequence A and was introduced during the purge step for cycle sequence B. The role of hydrogen gas was investigated by comparing the results obtained from these two cycle sequences and was concluded to exert an effect by a combination of precursor decomposition, surface maintenance as a hydrogen termination agent, and surface etching. These roles of hydrogen gas are discussed through consideration of changes in deposition rates, the oxygen concentration on the surface of the Sb film, and observations of film surface morphology. Based on these results, Ge xSb y phase-change films were deposited with an adequate flow rate of hydrogen gas. The Ge and Sb composition of the film was controlled with the designed cycle sequences. A strong oxygen affinity for Ge was observed during the X-ray photoelectron spectroscopy analysis of Sb 3d, Sb 4d, and Ge 3d orbitals. Based on the XPS results, the ratios of Ge to Sb were calculated to be Ge 0.32Sb 0.68, Ge 0.38Sb 0.62, Ge 0.44Sb 0.56, Ge 0.51Sb 0.49 and Ge 0.67Sb 0.33 for the G1S7, G1S3, G1S2, G1S1, and G2S1 cycles, respectively. Crystal structures of Sb, Ge, and the GeSb metastable phase were observed with various Ge xSb y film compositions. Sb crystallinity decreased with respect to Ge crystallinity by increasing the Ge fraction. A current-voltage curve was introduced, and an electro-switching phenomenon was clearly generated at a typical voltage, V th. V th values increased in conjunction with an increased proportion of Ge. The Sb crystallinity decrease and V th increase were explained via the bonding characteristics of each element.",
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T1 - Role of hydrogen in Sb film deposition and characterization of Sb and Ge xSb y films deposited by cyclic plasma enhanced chemical vapor deposition using metal-organic precursors

AU - Kim, Hyung Keun

AU - Jung, Jin Hwan

AU - Choi, Doo Jin

PY - 2012/9/30

Y1 - 2012/9/30

N2 - To meet increasing demands for chemical vapor deposition methods for high performance phase-change memory, cyclic plasma enhanced chemical vapor deposition of Sb and Ge xSb y phase-change films and characterization of their properties were performed. Two cycle sequences were designed to investigate the role of hydrogen gas as a reduction gas during Sb film deposition. Hydrogen gas was not introduced into the reaction chamber during the purge step in cycle sequence A and was introduced during the purge step for cycle sequence B. The role of hydrogen gas was investigated by comparing the results obtained from these two cycle sequences and was concluded to exert an effect by a combination of precursor decomposition, surface maintenance as a hydrogen termination agent, and surface etching. These roles of hydrogen gas are discussed through consideration of changes in deposition rates, the oxygen concentration on the surface of the Sb film, and observations of film surface morphology. Based on these results, Ge xSb y phase-change films were deposited with an adequate flow rate of hydrogen gas. The Ge and Sb composition of the film was controlled with the designed cycle sequences. A strong oxygen affinity for Ge was observed during the X-ray photoelectron spectroscopy analysis of Sb 3d, Sb 4d, and Ge 3d orbitals. Based on the XPS results, the ratios of Ge to Sb were calculated to be Ge 0.32Sb 0.68, Ge 0.38Sb 0.62, Ge 0.44Sb 0.56, Ge 0.51Sb 0.49 and Ge 0.67Sb 0.33 for the G1S7, G1S3, G1S2, G1S1, and G2S1 cycles, respectively. Crystal structures of Sb, Ge, and the GeSb metastable phase were observed with various Ge xSb y film compositions. Sb crystallinity decreased with respect to Ge crystallinity by increasing the Ge fraction. A current-voltage curve was introduced, and an electro-switching phenomenon was clearly generated at a typical voltage, V th. V th values increased in conjunction with an increased proportion of Ge. The Sb crystallinity decrease and V th increase were explained via the bonding characteristics of each element.

AB - To meet increasing demands for chemical vapor deposition methods for high performance phase-change memory, cyclic plasma enhanced chemical vapor deposition of Sb and Ge xSb y phase-change films and characterization of their properties were performed. Two cycle sequences were designed to investigate the role of hydrogen gas as a reduction gas during Sb film deposition. Hydrogen gas was not introduced into the reaction chamber during the purge step in cycle sequence A and was introduced during the purge step for cycle sequence B. The role of hydrogen gas was investigated by comparing the results obtained from these two cycle sequences and was concluded to exert an effect by a combination of precursor decomposition, surface maintenance as a hydrogen termination agent, and surface etching. These roles of hydrogen gas are discussed through consideration of changes in deposition rates, the oxygen concentration on the surface of the Sb film, and observations of film surface morphology. Based on these results, Ge xSb y phase-change films were deposited with an adequate flow rate of hydrogen gas. The Ge and Sb composition of the film was controlled with the designed cycle sequences. A strong oxygen affinity for Ge was observed during the X-ray photoelectron spectroscopy analysis of Sb 3d, Sb 4d, and Ge 3d orbitals. Based on the XPS results, the ratios of Ge to Sb were calculated to be Ge 0.32Sb 0.68, Ge 0.38Sb 0.62, Ge 0.44Sb 0.56, Ge 0.51Sb 0.49 and Ge 0.67Sb 0.33 for the G1S7, G1S3, G1S2, G1S1, and G2S1 cycles, respectively. Crystal structures of Sb, Ge, and the GeSb metastable phase were observed with various Ge xSb y film compositions. Sb crystallinity decreased with respect to Ge crystallinity by increasing the Ge fraction. A current-voltage curve was introduced, and an electro-switching phenomenon was clearly generated at a typical voltage, V th. V th values increased in conjunction with an increased proportion of Ge. The Sb crystallinity decrease and V th increase were explained via the bonding characteristics of each element.

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