Department of Physics Indian Institute of Science …smr2626/hands_on/week2/july8/Manish...Mimicking...
Transcript of Department of Physics Indian Institute of Science …smr2626/hands_on/week2/july8/Manish...Mimicking...
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Defects in materials
Manish Jain
Department of PhysicsIndian Institute of Science
Bangalore
July 8, 2014
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Outline
Motivation.
Computational methods.
Defects in oxides.
• Why are defects challenging?• Defects in high-κ dielectric � HfO2.• Defects in technologically important material � TiO2.• Defects for quantum computing.
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Outline
Motivation.
Computational methods.
Defects in oxides.
• Why are defects challenging?• Defects in high-κ dielectrics � HfO2.• Defects in technologically important material � TiO2.• Defects for quantum computing.
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Motivation � High-κ dielectric material HfO2
Moore's law about size of transistor.HfO2 has replaced SiO2 in todays MOSFET devices.
κSiO2 ≈ 3.9
κHfO2≈ 16− 17
1http://www.intel.com/technology/45nm/index.htm
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High-κ dielectric materials � Motivation
High defect density.
Charge trapping by defects in the interfacial layer or oxide �threshold voltage instability1.
Oxygen-related defects � vacancy2 (VO) or interstitials (IO)major cause.
Study the stability of point defects � VO.
1G. Ribes et. al., IEEE Trans. Device Mater. Reliab. 5, 5 (2005).2K. Shiraishi et. al., Jpn. J. Appl. Phys., Part 2 43 L1413 (2004); H. Park et. al., IEEEElectron Device Lett. 29, 54 (2008).
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Motivation � TiO2
Photovoltaic material in solar cells1.
Photocatalytic material � hydrolysis of water2.
Memresistive switches for non-volatile memory3.
Oxygen vacancies are believed to play a very important role inall these applications.
1B. O'Regan and M. G�ratzel, Nature (London) 353, 737 (1991).2A. Fujishima and K. Honda, Nature (London) 238, 37 (1972).3J. J. Yang, M. D. Pickett, X. Li, D. A. A. Ohlberg, D. R. Stewart, and R. S. Williams,Nature Nanotechnology 3, 429 (2008).
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Outline
Motivation.
Computational methods.
Defects in oxides.
• Why are defects challenging?• Defects in high-κ dielectrics � HfO2.• Defects in technologically important material � TiO2.• Defects for quantum computing.
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Methods � Ground-state properties
Properties that are intrinsic to a system with all its electrons inequilibrium.
Density functional theory is the �standard model�for understanding ground-state properties.
Total energy is a functional of the charge density.
Kohn-Sham formulation: Map the interactingmany-electron problem to non-interactingelectrons moving in a self-consistent �eld.
(− ∇
2
2+Vionic(r) +VHartree(r) + Vxc(r)
)ψ(r) = ε ψ(r)
Local density approximationGeneralized gradient approximation
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Methods � Excited-state properties
Spectroscopic properties that involve experiments creating anexcited particle above the ground state.
Concept and formalism of the interacting particle Green'sfunction (G).Many-body perturbation theory is the �standard model� forunderstanding excited-state properties.
G−1 = G−10 + Σ
GW approximation to the self-energy (Σ).
Σ= = iGW
W = ε−1 v
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Outline
Motivation.
Computational methods.
Defects in oxides.
• Why are defects challenging?• Defects in high-κ dielectric � HfO2.• Defects in technologically important material � TiO2.• Defects for quantum computing.
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Why are defects challenging?
Potentially strong electron-electron correlations.
− Can be open-shell systems.− Multiple localized, interacting electrons.
Lattice relaxation e�ects.
Screening from the host.
− Mimicking the system by isolated cluster may be incorrect.
Experiments often involve excited-state properties (deep leveltransient spectroscopy or optical absorption etc.)
Computational di�culty � isolated defect.
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Outline
Motivation.
Computational methods.
Defects in oxides.
• Why are defects challenging?• Defects in high-κ dielectric � HfO2.• Defects in technologically important material � TiO2.• Defects for quantum computing.
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High-κ dielectric materials � De�nitions
Formation energy of an oxygen-vacancy:
Ef [~R] = E[~R]− Eref +1
2EO2
From slides by C. G. Van de Walle13/46
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High-κ dielectric materials � De�nitions
Formation energy of an oxygen-vacancy:
Efq [~Rq](EF) = Eq[~Rq]− Eref +1
2EO2 + q(EF + Ev)
From slides by C. G. Van de Walle13/46
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High-κ dielectric materials � De�nitions
Formation energy of an oxygen-related defect in hafnia :
Efq [~Rq](EF) = Eq[~Rq]− EHfO2 − nOµO + q(EF + Ev)
where µO is the oxygen chemical potential.
Charge transition level : εq/q-1 = Fermi energy where defect q→ q− 1.
= Efq-1[
~Rq-1](EF = 0)− Efq [~Rq](EF = 0)
EF
VBM CBM
Efq
ε+1/0
0+1
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High-κ dielectric materials � De�nitions
Formation energy of an oxygen-related defect in hafnia :
Efq [~Rq](EF) = Eq[~Rq]− EHfO2 − nOµO + q(EF + Ev)
where µO is the oxygen chemical potential.
Charge transition level : εq/q-1 = Fermi energy where defect q→ q− 1.
= Efq-1[
~Rq-1](EF = 0)− Efq [~Rq](EF = 0)
EF
VBM CBM
Efq
ε+1/0
0+1
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High-κ dielectric materials � De�nitions
Formation energy of an oxygen-related defect in hafnia :
Efq [~Rq](EF) = Eq[~Rq]− EHfO2 − nOµO + q(EF + Ev)
where µO is the oxygen chemical potential.
Charge transition level : εq/q-1 = Fermi energy where defect q→ q− 1.
= Efq-1[
~Rq-1](EF = 0)− Efq [~Rq](EF = 0)
EF
VBM CBM
Efq
ε+1/0
0+1
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High-κ dielectric materials � Methodology
DFT + GW methodology.
Generalized coordinate
Formationenergy
Efq
Efq−1
~Rq~Rq−1
Efq−1(
~Rq−1)
Efq(~Rq)
εq/q−1
M. Hedström, A. Schindlmayr, G. Schwarz, and M. Sche�er, Phys. Rev. Lett. 97,226401 (2006); P. Rinke, A. Janotti, M. Sche�er, and C. G. Van de Walle, Phys. Rev.Lett. 102, 026402 (2009); M. Jain, J. R. Chelikowsky and S. G. Louie, Phys. Rev. Lett.107, 216803 (2011). 15/46
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High-κ dielectric materials � Methodology
DFT + GW methodology.
Generalized coordinate
Formationenergy
Efq
Efq−1
~Rq~Rq−1
Efq−1(
~Rq−1)
Efq(~Rq)
εq/q−1
M. Hedström, A. Schindlmayr, G. Schwarz, and M. Sche�er, Phys. Rev. Lett. 97,226401 (2006); P. Rinke, A. Janotti, M. Sche�er, and C. G. Van de Walle, Phys. Rev.Lett. 102, 026402 (2009); M. Jain, J. R. Chelikowsky and S. G. Louie, Phys. Rev. Lett.107, 216803 (2011). 15/46
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High-κ dielectric materials � Computational details
Three fold coordinated (VO(3)) and four fold coordinated(VO(4)) vacancies in charge states {0, +1, +2}
96 atom super cells.
Norm conserving pseudopotentials - Hf 5s25p65d26s2 and O2s22p4.
250 Ry energy cuto� for wavefunctions.
PBE functional for structural energies.
`One shot' GW done within generalized plasmon pole modeldone with BerkeleyGW.
Bulk structural parameters and band gap (6.00 eV) in goodagreement with experiment.
SIESTA for large supercells to get electrostatic corrections.
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PBE and quasiparticle level diagram - VO(3)
3.58
V+2O(3)
2.40
3.59
V+1O(3)
2.70
V0O(3)
0
1
2
3
4
Energy
(eV)
PBE
5.10
V+2O(3)
2.67
4.84
V+1O(3)
2.89
V0O(3)
0
1
2
3
4
5
Energy
(eV)
GW
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Electrostatic corrections - VO(3)
0 0.1 0.2 0.3 0.4 0.51
2
3
V+2O(3) V+1
O(3)
V+1O(3) V0
O(3)
Number of atoms in supercell
∝ V−13
ε defect−
ε v(eV)
961500768 324
PBE defect levels.
GW charge transitionlevels (eV)
w/o withcor. cor.
ε+2/+1 4.50
2.66
ε+2/+1 3.42
2.45
ε+1/0 3.55
3.55
ε+1/0 4.33
3.36
Generalized coordinate
Formationenergy
Efq
Efq-1
~Rq~Rq-1
Efq-1(
~Rq-1)
Efq (~Rq)
ε
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Electrostatic corrections - VO(3)
S. Lany and A. Zunger, Phys. Rev. B 81 113201 (2010)
GW charge transitionlevels (eV)
w/o withcor. cor.
ε+2/+1 4.50
2.66
ε+2/+1 3.42
2.45
ε+1/0 3.55
3.55
ε+1/0 4.33
3.36
Generalized coordinate
Formationenergy
Efq
Efq-1
~Rq~Rq-1
Efq-1(
~Rq-1)
Efq (~Rq)
ε
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Electrostatic corrections - VO(3)
0 0.1 0.2 0.3 0.4 0.51
2
3
V+2O(3) V+1
O(3)
V+1O(3) V0
O(3)
Number of atoms in supercell
∝ V−13
ε defect−
ε v(eV)
961500768 324
PBE defect levels.
GW charge transitionlevels (eV)
w/o withcor. cor.
ε+2/+1 4.50
2.66
ε+2/+1 3.42
2.45
ε+1/0 3.55
3.55
ε+1/0 4.33
3.36
Generalized coordinate
Formationenergy
Efq
Efq-1
~Rq~Rq-1
Efq-1(
~Rq-1)
Efq (~Rq)
ε
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Electrostatic corrections - VO(3)
0 0.1 0.2 0.3 0.4 0.51
2
3
V+2O(3) V+1
O(3)
V+1O(3) V0
O(3)
Number of atoms in supercell
∝ V−13
ε defect−
ε v(eV)
961500768 324
PBE defect levels.
GW charge transitionlevels (eV)
w/o withcor. cor.
ε+2/+1 4.50 2.66
ε+2/+1 3.42 2.45
ε+1/0 3.55 3.55
ε+1/0 4.33 3.36
Generalized coordinate
Formationenergy
Efq
Efq-1
~Rq~Rq-1
Efq-1(
~Rq-1)
Efq (~Rq)
ε
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High-κ dielectric materials � Formation energy of VO
0 2 4 6−2
−1
0
1
2
1 3 50 2 4 6−2
−1
0
1
2
1 3 5
VO(3)
VBM CBM
V0O
V+1O
V+2O
Fermi energy (eV)
Relativeform
ation
energy
(eV)
VBM CBM
Si
1M. Jain, J. R. Chelikowsky and S. G. Louie, Phys. Rev. Lett. 107, 216803 (2011).19/46
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High-κ dielectric materials � Formation energy of VO
0 2 4 6−2
−1
0
1
2
1 3 50 2 4 6−2
−1
0
1
2
1 3 5
VO(3)
VO(4)
VBM CBM
V0O
V+1O
V+2O
Fermi energy (eV)
Relativeform
ation
energy
(eV)
VBM CBM
Si
1M. Jain, J. R. Chelikowsky and S. G. Louie, Phys. Rev. Lett. 107, 216803 (2011).19/46
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High-κ dielectric materials � Formation energy of VO
0 2 4 6−2
−1
0
1
2
1 3 50 2 4 6−2
−1
0
1
2
1 3 5
VO(3)
VO(4)
VBM CBM
V0O
V+1O
V+2O
Fermi energy (eV)
Relativeform
ation
energy
(eV)
VBM CBM
Si
1M. Jain, J. R. Chelikowsky and S. G. Louie, Phys. Rev. Lett. 107, 216803 (2011).19/46
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High-κ dielectric materials � Formation energy of vacancies
0 1 2 3 4 5 6Fermi Energy (eV)
�6
�4
�2
0
2
4
6
Form
ati
on E
nerg
y (
eV
)
Oxyge
n po
orV2+O(3)
V1+O(3)
V0O(4)
Oxyge
n ric
h
V2+O(3)
V1+O(3)
V0O(4)
1M. Jain, J. R. Chelikowsky and S. G. Louie, Phys. Rev. Lett. 107, 216803 (2011).20/46
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Defect charging energy � U
U, defect charging energy, is de�ned as the energy of the reaction:
2V+ → V2+ +V0
U = Ef+2(
~R+2) + Ef0(~R0)− 2Ef+1(
~R+1)
= −ε+2/+1 + ε+1/0
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Comparison with previous studies
All values are in eV.
VO(3) VO(4)
ε+2/+1 ε+1/0 U ε+2/+1 ε+1/0 U
GGA 2.74 2.69 -0.05 2.38 2.41 -0.03HSE1 3.93 4.42 0.49 � � �PBE02 3.7 4.1 0.4 � � �GW3 (24 atoms) 4.00 3.10 -0.90 3.22 2.43 -0.79GW4 (96 atoms) 2.56 3.46 0.90 2.21 3.03 0.82
1J.L. Lyons, A. Janotti and C.G. Van de Walle, Microelectronic Engineering 88, 1452 (2011).2P. Broqvist and A. Pasquarello, Appl. Phys. Lett. 89, 262904 (2006).3E.-A. Choi, and K. J. Chang, Appl. Phys. Lett., 94, 122901 (2009).4M. Jain, J. R. Chelikowsky and S. G. Louie, Phys. Rev. Lett. 107, 216803 (2011).
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Defect charging energy � U
U, defect charging energy, is de�ned as the energy of the reaction:
2V+ → V2+ +V0
U = Ef+2(
~R+2) + Ef0(~R0)− 2Ef+1(
~R+1)
= −ε+2/+1 + ε+1/0
≡ Uelec +Urelax
= {Ef+2(~R+1) + E
f0(~R+1)− 2Ef+1(
~R+1)}+{[Ef+2(
~R+2)− Ef+2(~R+1)] + [Ef0(~R0)− Ef0(~R+1)]}
Uelec ≥ 0 and Urelax ≤ 0
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Defect charging energy � U
U, defect charging energy, is de�ned as the energy of the reaction:
2V+ → V2+ +V0
U = Ef+2(
~R+2) + Ef0(~R0)− 2Ef+1(
~R+1)
= −ε+2/+1 + ε+1/0
≡ Uelec +Urelax
= {Ef+2(~R+1) + E
f0(~R+1)− 2Ef+1(
~R+1)}+{[Ef+2(
~R+2)− Ef+2(~R+1)] + [Ef0(~R0)− Ef0(~R+1)]}
Uelec ≥ 0 and Urelax ≤ 0
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Defect charging energy � U
U, defect charging energy, is de�ned as the energy of the reaction:
2V+ → V2+ +V0
U = Ef+2(
~R+2) + Ef0(~R0)− 2Ef+1(
~R+1)
= −ε+2/+1 + ε+1/0
≡ Uelec +Urelax
= {Ef+2(~R+1) + E
f0(~R+1)− 2Ef+1(
~R+1)}+{[Ef+2(
~R+2)− Ef+2(~R+1)] + [Ef0(~R0)− Ef0(~R+1)]}
Uelec ≥ 0 and Urelax ≤ 0
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Defect charging energy � U
2V+ → V2+ +V0
Uelec Urelax U
VO(3) 2.24 -1.33 0.90
VO(4) 2.13 -1.35 0.81
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High-κ dielectric materials � Conclusions
DFT+GW method for calculating the stability of oxygenvacancies.
Qualitative agreement with previous hybrid functionalcalculations on the vacancies.
Quantitative disagreement with previous hybrid functionalcalculations - vacancies near a Si/HfO2 interface.
DFT+GW HSE
VO +1,0 +2,+1
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Outline
Motivation.
Computational methods.
Defects in oxides.
• Why are defects challenging?• Defects in high-κ dielectric � HfO2.• Defects in technologically important material � TiO2.• Defects for quantum computing.
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Vacancies in TiO2 � Computational details
Oxygen vacancies (VO) in rutile in charge states {0, +1, +2}
72 atom super cells.
200 Ry energy cuto� for wavefunctions.
HSE functional for structural energies.
`One shot' GW done within generalized plasmon pole modeldone with BerkeleyGW.
Bulk structural parameters and band gap (3.13 eV) in goodagreement with experiment.
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Schematic quasiparticle level diagram - VO
V+2O V+1
OV0O
0
1
2
3Energy
(eV)
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Polaron formation � V+1O
Relaxation of the atoms : Two minima
A state in the gap � polaron.
V+1O → V+2
O + polaron.
Lower in energy by 1.2 eV.
Not relevant for chargetransition level
A state in the gap � defect state.
Charge density on the defect site.
Local minima.
Relevant for charge transitionlevel
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Polaron formation � V+1O
Relaxation of the atoms : Two minima
A state in the gap � polaron.
V+1O → V+2
O + polaron.
Lower in energy by 1.2 eV.
Not relevant for chargetransition level
A state in the gap � defect state.
Charge density on the defect site.
Local minima.
Relevant for charge transitionlevel
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TiO2 � Formation energy of vacancies
Oxygen rich Titanium rich
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Comparison with previous studies
All values are in eV.
VO
ε+2/+1 ε+1/0 U
GGA1 2.0 2.0 0HSE2 3.8 3.1 �0.7GW3 3.01 2.56 �0.45
Negative U defect.
1H. Iddir, S. Ogut, P. Zapol, and N. D. Browning, Phys. Rev. B 75, 073203 (2007). (valuefrom plot)2A. Janotti, J. B. Varley, P. Rinke, N. Umezawa, G. Kresse, and C. G. Van de Walle, Phys.Rev. B 81 085212 (2010). (value from plot)3A. Malashevich, M. Jain and S. G. Louie, Phys. Rev. B 89, 075205, (2014).
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TiO2 � Conclusions
DFT+GW method for calculating the stability of oxygenvacancies.
Negative U defect.
Qualitative agreement with previous hybrid functionalcalculations.
Quantitative disagreement with previous hybrid functionalcalculations.
DFT+GW HSE
VO +2,0 +2
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Outline
Motivation.
Computational methods.
Defects in oxides.
• Why are defects challenging?• Defects in high-κ dielectric � HfO2.• Defects in technologically important material � TiO2.• Defects for quantum computing.
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Defects for spin-qubit applications
Room temperature individually addressable spin systems in thesolid-state for quantum computing.
NV− center in diamond is the leading candidate.
Possible room-temperature qubit with long coherence time(∼1ms) for quantum computing.
High sensitivity, high-spatial resolution magnetometry.
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Defects for spin-qubit applications
Room temperature individually addressable spin systems in thesolid-state for quantum computing.
NV− center in diamond is the leading candidate.
Possible room-temperature qubit with long coherence time(∼1ms) for quantum computing.
High sensitivity, high-spatial resolution magnetometry.
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Defects for spin-qubit applications
Room temperature individually addressable spin systems in thesolid-state for quantum computing.
NV− center in diamond is the leading candidate.
Possible room-temperature qubit with long coherence time(∼1ms) for quantum computing.
High sensitivity, high-spatial resolution magnetometry.
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NV− center in diamond � Motivation
Optical initialization at room-temperature provides initial spin purestate for spin-qubit operation.
Notation :2S+1 Λ
Λ : Irreducible representation of the orbital symmetry
S : Total Spin
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NV− center in diamond � Motivation
Optical initialization at room-temperature provides initial spin purestate for spin-qubit operation.
Notation :2S+1 Λ
Λ : Irreducible representation of the orbital symmetry
S : Total Spin
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NV− center in diamond � Unsolved problem
Identi�cation of singlet-level structure.
E�ective optical initialization path between the two tripletlevels.
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NV− center in diamond � Single particle levels
NV− is a deep level center in a band gap of diamondwith multiple localized, interacting electrons.
VBM
CBM
Open-shell problem1.
Correlation due todegenerate ground-states.
1J. Lischner, J. Deslippe, M. Jain and S. G. Louie, Phys. Rev. Lett. 109, 036406 (2012)37/46
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NV− center in diamond � Dangling orbitals
8 dangling spin-orbitalsin and near band-gap ofdiamond
Good basis for low energyexcitations.
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NV− center in diamond � Extended Hubbard model
H =∑i,σ
Einiσ +∑i 6=j,σ
ti,jc†i,σcj,σ
+∑i
Uni,↑nj,↓ +∑
i 6=j,σ,σ′Vni,σnj,σ′
i, j :Atomic sites (C or N)
σ, σ′ :Spin direction
Ei :On-site energy
ti,j :Hopping integral
U :On-site Coulomb repulsion
V :Nearest neighbor
Coulomb repulsion
E�ective Coulombinteraction parameters
Geometry dependentparameter sets
Strong electron-electroncorrelation
Screening from diamond
Large structural relaxation
Hindered by the di�culty in getting physically grounded modelparameters. 39/46
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NV− center in diamond � Model parameters from GW
Use ab initio GW to get model parameters, incorporating realisticelectron-electron interactions.
Ab initio GW
Defect state quasiparticle energy Defect state quasiparticle energy
Extended Hubbard model GW
Initial sets of parameters
Eabqp = EHqp? Tune model parameters
Done
No
Yes
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NV− center in diamond � Model parameters from GW
U/t > 3→ strongly correlated system.
Reasonable values of parameters.
Geometry dependent parameters.
All parameters are in eV.
EC-EN tNC tCC U V
Ground-state 2.56 �0.68 �1.03 3.43 0.83
Excited-state 2.86 �0.75 �0.90 3.45 0.67
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NV− center in diamond � Level diagram
Level diagram1 from exact diagonalization of model Hamiltonian� all many-electron correlation e�ects within our Hilbert space.
All energies in eV.
1S. Choi, M. Jain and S. G. Louie, Phys. Rev. B 86, 041202 (2012)42/46
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NV− center in diamond � Proposed optical pathway1
Spin triplet
3A2
3E
Spin singlet
1E
1A1
1E′
SO
coupling
ms = ±1
SO
coupling
ms = 0
Qualitatively and quantitatively consistent with availableexperimental data.
1S. Choi, M. Jain and S. G. Louie, Phys. Rev. B 86, 041202 (2012)
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NV− center in diamond � Conclusion
Constructed extended Hubbard Hamiltonian from ab initio GWcalculations.
Through exact diagonalization, many-electron e�ects stronglya�ect the energy level diagram qualitatively and quantitatively.
Computed ground- and excited-state energy surfaces andtransition rates between them provided a consistent picturewith experiments.
Proposed an optical initialization pathway in whichinter-sytstem crossing plays a crucial role.
S. Choi, M. Jain and S. G. Louie, Phys. Rev. B 86, 041202 (2012)
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Conclusion
Ab initio methods to understand and predict properties ofdefects in materials.
Oxygen vacancies in high-κ material � HfO2 andphotocatalytic material � TiO2.
NV− center in diamond for quantum computing application.
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Acknowledgements
Prof. Steven LouieProf. James Chelikowsky Dr. Andrei Malashevich
Dr. Johannes Lischner Dr. Sang-Kook Choi
Dr. Jack Deslippe Dr. Georgy Samsonidze Prof. Marvin Cohen
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