Boron–oxygen complex yields n-type surface layer in semiconducting diamond

Xiaobing Liu; Xin Chen; David J. Singh; Richard A. Stern; Jinsong Wu; Sylvain Petitgirard; Craig R. Bina; Steven D. Jacobsen

doi:10.1073/pnas.1821612116

Boron–oxygen complex yields n-type surface layer in semiconducting diamond

Xiaobing Liu^*, Xin Chen, David J. Singh, Richard A. Stern, Jinsong Wu, Sylvain Petitgirard, Craig R. Bina, Steven D. Jacobsen

^*Corresponding author for this work

Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

76 Scopus citations

Abstract

Diamond is a wide-bandgap semiconductor possessing exceptional physical and chemical properties with the potential to miniaturize high-power electronics. Whereas boron-doped diamond (BDD) is a well-known p-type semiconductor, fabrication of practical diamond-based electronic devices awaits development of an effective n-type dopant with satisfactory electrical properties. Here we report the synthesis of n-type diamond, containing boron (B) and oxygen (O) complex defects. We obtain high carrier concentration (∼0.778 × 10²¹ cm⁻³) several orders of magnitude greater than previously obtained with sulfur or phosphorous, accompanied by high electrical conductivity. In high-pressure high-temperature (HPHT) boron-doped diamond single crystal we formed a boron-rich layer ∼1–1.5 μm thick in the {111} surface containing up to 1.4 atomic % B. We show that under certain HPHT conditions the boron dopants combine with oxygen defects to form B–O complexes that can be tuned by controlling the experimental parameters for diamond crystallization, thus giving rise to n-type conduction. First-principles calculations indicate that B₃O and B₄O complexes with low formation energies exhibit shallow donor levels, elucidating the mechanism of the n-type semiconducting behavior.

Original language	English (US)
Pages (from-to)	7703-7711
Number of pages	9
Journal	Proceedings of the National Academy of Sciences of the United States of America
Volume	116
Issue number	16
DOIs	https://doi.org/10.1073/pnas.1821612116
State	Published - Apr 16 2019

Funding

The authors acknowledge help of Dr. J. G. Guo for LT-resistance measurements at Rice University and Prof. X. P. Jia and H. A. Ma for sample preparation and Hall effect measurements at Jilin University. This work was supported by the National Science Foundation of China Grant 11804184 (to X.C.) and by awards from the US National Science Foundation (NSF) Grant DMR-1508577, the David and Lucile Packard Foundation, the Alexander von Humboldt Foundation, and the Department of Energy (DOE) through the Capital/DOE Alliance Center (S.D.J.). D.J.S. acknowledges support from the DOE, Basic Energy Sciences, Grant DE-SC0019114. This work made use of the TEM, SEM, and XPS facilities of Northwestern University Atomic and Nanoscale Characterization Experimental Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF Grant ECCS-1542205), the Materials Research Science and Engineering Centers program (NSF Grant DMR-1121262) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. The FIB at Bayerisches Geoinstitut, University of Bayreuth, Germany, was financed by DFG Grant INST 91/315-1 FUGG. IXS measurements were performed at HPCAT (Sector 16), APS, Argonne National Laboratory (ANL). HPCAT operations are supported by DOE–National Nuclear Security Administration under Award DE-NA0001974, with partial instrumentation funding by NSF. The APS is a DOE Office of Science User Facility operated by ANL under Contract DE-AC02-06CH11357. The calculations were performed in the High Performance Computing Center of Qufu Normal University and Quest high performance computing facility at Northwestern University. ACKNOWLEDGMENTS. The authors acknowledge help of Dr. J. G. Guo for LT-resistance measurements at Rice University and Prof. X. P. Jia and H. A. Ma for sample preparation and Hall effect measurements at Jilin University. This work was supported by the National Science Foundation of China Grant 11804184 (to X.C.) and by awards from the US National Science Foundation (NSF) Grant DMR-1508577, the David and Lucile Packard Foundation, the Alexander von Humboldt Foundation, and the Department of Energy (DOE) through the Capital/DOE Alliance Center (S.D.J.). D.J.S. acknowledges support from the DOE, Basic Energy Sciences, Grant DE-SC0019114. This work made use of the TEM, SEM, and XPS facilities of Northwestern University Atomic and Nanoscale Characterization Experimental Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF Grant ECCS-1542205), the Materials Research Science and Engineering Centers program (NSF Grant DMR-1121262) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. The FIB at Bayerisches Geoinstitut, University of Bayreuth, Germany, was financed by DFG Grant INST 91/315-1 FUGG. IXS measurements were performed at HPCAT (Sector 16), APS, Argonne National Laboratory (ANL). HPCAT operations are supported by DOE–National Nuclear Security Administration under Award DE-NA0001974, with partial instrumentation funding by NSF. The APS is a DOE Office of Science User Facility operated by ANL under Contract DE-AC02-06CH11357. The calculations were performed in the High Performance Computing Center of Qufu Normal University and Quest high performance computing facility at Northwestern University.

Keywords

Boron
Defects
Diamond
High pressure
Semiconductor

ASJC Scopus subject areas

General

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10.1073/pnas.1821612116

Cite this

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title = "Boron–oxygen complex yields n-type surface layer in semiconducting diamond",

abstract = "Diamond is a wide-bandgap semiconductor possessing exceptional physical and chemical properties with the potential to miniaturize high-power electronics. Whereas boron-doped diamond (BDD) is a well-known p-type semiconductor, fabrication of practical diamond-based electronic devices awaits development of an effective n-type dopant with satisfactory electrical properties. Here we report the synthesis of n-type diamond, containing boron (B) and oxygen (O) complex defects. We obtain high carrier concentration (∼0.778 × 1021 cm−3) several orders of magnitude greater than previously obtained with sulfur or phosphorous, accompanied by high electrical conductivity. In high-pressure high-temperature (HPHT) boron-doped diamond single crystal we formed a boron-rich layer ∼1–1.5 μm thick in the {111} surface containing up to 1.4 atomic % B. We show that under certain HPHT conditions the boron dopants combine with oxygen defects to form B–O complexes that can be tuned by controlling the experimental parameters for diamond crystallization, thus giving rise to n-type conduction. First-principles calculations indicate that B3O and B4O complexes with low formation energies exhibit shallow donor levels, elucidating the mechanism of the n-type semiconducting behavior.",

keywords = "Boron, Defects, Diamond, High pressure, Semiconductor",

author = "Xiaobing Liu and Xin Chen and Singh, {David J.} and Stern, {Richard A.} and Jinsong Wu and Sylvain Petitgirard and Bina, {Craig R.} and Jacobsen, {Steven D.}",

note = "Funding Information: The authors acknowledge help of Dr. J. G. Guo for LT-resistance measurements at Rice University and Prof. X. P. Jia and H. A. Ma for sample preparation and Hall effect measurements at Jilin University. This work was supported by the National Science Foundation of China Grant 11804184 (to X.C.) and by awards from the US National Science Foundation (NSF) Grant DMR-1508577, the David and Lucile Packard Foundation, the Alexander von Humboldt Foundation, and the Department of Energy (DOE) through the Capital/DOE Alliance Center (S.D.J.). D.J.S. acknowledges support from the DOE, Basic Energy Sciences, Grant DE-SC0019114. This work made use of the TEM, SEM, and XPS facilities of Northwestern University Atomic and Nanoscale Characterization Experimental Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF Grant ECCS-1542205), the Materials Research Science and Engineering Centers program (NSF Grant DMR-1121262) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. The FIB at Bayerisches Geoinstitut, University of Bayreuth, Germany, was financed by DFG Grant INST 91/315-1 FUGG. IXS measurements were performed at HPCAT (Sector 16), APS, Argonne National Laboratory (ANL). HPCAT operations are supported by DOE–National Nuclear Security Administration under Award DE-NA0001974, with partial instrumentation funding by NSF. The APS is a DOE Office of Science User Facility operated by ANL under Contract DE-AC02-06CH11357. The calculations were performed in the High Performance Computing Center of Qufu Normal University and Quest high performance computing facility at Northwestern University. Funding Information: ACKNOWLEDGMENTS. The authors acknowledge help of Dr. J. G. Guo for LT-resistance measurements at Rice University and Prof. X. P. Jia and H. A. Ma for sample preparation and Hall effect measurements at Jilin University. This work was supported by the National Science Foundation of China Grant 11804184 (to X.C.) and by awards from the US National Science Foundation (NSF) Grant DMR-1508577, the David and Lucile Packard Foundation, the Alexander von Humboldt Foundation, and the Department of Energy (DOE) through the Capital/DOE Alliance Center (S.D.J.). D.J.S. acknowledges support from the DOE, Basic Energy Sciences, Grant DE-SC0019114. This work made use of the TEM, SEM, and XPS facilities of Northwestern University Atomic and Nanoscale Characterization Experimental Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF Grant ECCS-1542205), the Materials Research Science and Engineering Centers program (NSF Grant DMR-1121262) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. The FIB at Bayerisches Geoinstitut, University of Bayreuth, Germany, was financed by DFG Grant INST 91/315-1 FUGG. IXS measurements were performed at HPCAT (Sector 16), APS, Argonne National Laboratory (ANL). HPCAT operations are supported by DOE–National Nuclear Security Administration under Award DE-NA0001974, with partial instrumentation funding by NSF. The APS is a DOE Office of Science User Facility operated by ANL under Contract DE-AC02-06CH11357. The calculations were performed in the High Performance Computing Center of Qufu Normal University and Quest high performance computing facility at Northwestern University. Publisher Copyright: {\textcopyright} 2019 National Academy of Sciences. All rights reserved.",

year = "2019",

month = apr,

day = "16",

doi = "10.1073/pnas.1821612116",

language = "English (US)",

volume = "116",

pages = "7703--7711",

journal = "Proceedings of the National Academy of Sciences of the United States of America",

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publisher = "National Academy of Sciences",

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TY - JOUR

T1 - Boron–oxygen complex yields n-type surface layer in semiconducting diamond

AU - Liu, Xiaobing

AU - Chen, Xin

AU - Singh, David J.

AU - Stern, Richard A.

AU - Wu, Jinsong

AU - Petitgirard, Sylvain

AU - Bina, Craig R.

AU - Jacobsen, Steven D.

N1 - Funding Information: The authors acknowledge help of Dr. J. G. Guo for LT-resistance measurements at Rice University and Prof. X. P. Jia and H. A. Ma for sample preparation and Hall effect measurements at Jilin University. This work was supported by the National Science Foundation of China Grant 11804184 (to X.C.) and by awards from the US National Science Foundation (NSF) Grant DMR-1508577, the David and Lucile Packard Foundation, the Alexander von Humboldt Foundation, and the Department of Energy (DOE) through the Capital/DOE Alliance Center (S.D.J.). D.J.S. acknowledges support from the DOE, Basic Energy Sciences, Grant DE-SC0019114. This work made use of the TEM, SEM, and XPS facilities of Northwestern University Atomic and Nanoscale Characterization Experimental Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF Grant ECCS-1542205), the Materials Research Science and Engineering Centers program (NSF Grant DMR-1121262) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. The FIB at Bayerisches Geoinstitut, University of Bayreuth, Germany, was financed by DFG Grant INST 91/315-1 FUGG. IXS measurements were performed at HPCAT (Sector 16), APS, Argonne National Laboratory (ANL). HPCAT operations are supported by DOE–National Nuclear Security Administration under Award DE-NA0001974, with partial instrumentation funding by NSF. The APS is a DOE Office of Science User Facility operated by ANL under Contract DE-AC02-06CH11357. The calculations were performed in the High Performance Computing Center of Qufu Normal University and Quest high performance computing facility at Northwestern University. Funding Information: ACKNOWLEDGMENTS. The authors acknowledge help of Dr. J. G. Guo for LT-resistance measurements at Rice University and Prof. X. P. Jia and H. A. Ma for sample preparation and Hall effect measurements at Jilin University. This work was supported by the National Science Foundation of China Grant 11804184 (to X.C.) and by awards from the US National Science Foundation (NSF) Grant DMR-1508577, the David and Lucile Packard Foundation, the Alexander von Humboldt Foundation, and the Department of Energy (DOE) through the Capital/DOE Alliance Center (S.D.J.). D.J.S. acknowledges support from the DOE, Basic Energy Sciences, Grant DE-SC0019114. This work made use of the TEM, SEM, and XPS facilities of Northwestern University Atomic and Nanoscale Characterization Experimental Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF Grant ECCS-1542205), the Materials Research Science and Engineering Centers program (NSF Grant DMR-1121262) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois through the IIN. The FIB at Bayerisches Geoinstitut, University of Bayreuth, Germany, was financed by DFG Grant INST 91/315-1 FUGG. IXS measurements were performed at HPCAT (Sector 16), APS, Argonne National Laboratory (ANL). HPCAT operations are supported by DOE–National Nuclear Security Administration under Award DE-NA0001974, with partial instrumentation funding by NSF. The APS is a DOE Office of Science User Facility operated by ANL under Contract DE-AC02-06CH11357. The calculations were performed in the High Performance Computing Center of Qufu Normal University and Quest high performance computing facility at Northwestern University. Publisher Copyright: © 2019 National Academy of Sciences. All rights reserved.

PY - 2019/4/16

Y1 - 2019/4/16

N2 - Diamond is a wide-bandgap semiconductor possessing exceptional physical and chemical properties with the potential to miniaturize high-power electronics. Whereas boron-doped diamond (BDD) is a well-known p-type semiconductor, fabrication of practical diamond-based electronic devices awaits development of an effective n-type dopant with satisfactory electrical properties. Here we report the synthesis of n-type diamond, containing boron (B) and oxygen (O) complex defects. We obtain high carrier concentration (∼0.778 × 1021 cm−3) several orders of magnitude greater than previously obtained with sulfur or phosphorous, accompanied by high electrical conductivity. In high-pressure high-temperature (HPHT) boron-doped diamond single crystal we formed a boron-rich layer ∼1–1.5 μm thick in the {111} surface containing up to 1.4 atomic % B. We show that under certain HPHT conditions the boron dopants combine with oxygen defects to form B–O complexes that can be tuned by controlling the experimental parameters for diamond crystallization, thus giving rise to n-type conduction. First-principles calculations indicate that B3O and B4O complexes with low formation energies exhibit shallow donor levels, elucidating the mechanism of the n-type semiconducting behavior.

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KW - Boron

KW - Defects

KW - Diamond

KW - High pressure

KW - Semiconductor

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Boron–oxygen complex yields n-type surface layer in semiconducting diamond

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