Optical Properties of Solids: Lecture 12 Stefan Zollner › sites › default › files ›...
Transcript of Optical Properties of Solids: Lecture 12 Stefan Zollner › sites › default › files ›...
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Optical Properties of Solids: Lecture 12
Stefan ZollnerNew Mexico State University, Las Cruces, NM, USA
and Institute of Physics, CAS, Prague, CZR (Room 335)[email protected] or [email protected]
NSF: DMR-1505172http://ellipsometry.nmsu.edu
These lectures were supported by • European Union, European Structural and Investment Funds (ESIF) • Czech Ministry of Education, Youth, and Sports (MEYS), Project IOP
Researchers Mobility – CZ.02.2.69/0.0/0.0/0008215
Thanks to Dr. Dejneka and his department at FZU.
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Optical Properties of Solids: Lecture 12Quantum structures: wells, wires, dotsAbsorption and emission of quantum wellsIntersubband absorptionQuantum cascade lasers
Defects (deep, shallow)
Stress and strain
Strained Si
Relaxed SiGeRelaxed SiGe
Relaxed Si
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New Mexico State University
References: Band Structure and Optical Properties
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 3
Solid-State Theory and Semiconductor Band Structures:• Mark Fox, Optical Properties of Solids (6,8,9)• Ashcroft and Mermin, Solid-State Physics • Yu and Cardona, Fundamentals of Semiconductors• Dresselhaus/Dresselhaus/Cronin/Gomes, Solid State Properties• Cohen and Chelikowsky, Electronic Structure and Optical Properties• Klingshirn, Semiconductor Optics• Grundmann, Physics of Semiconductors• Ioffe Institute web site: NSM Archive
http://www.ioffe.ru/SVA/NSM/Semicond/index.html
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Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 4
Outline
Quantum confinement and Heisenberg uncertainty principleGrowth of quantum structuresCarbon nanostructures, two-dimensional materialsElectronic states, quantum well absorption and emissionIntersubband transitionsMetamaterials and metasurfaces
Defects Transition metal and rare earth impurities in insulatorsShallow defects in semiconductors
Stress and strain, deformation potentials
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Quantum structures and density of states
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 5 Fox, Chapter 6
E1/2
E0
E−1/2
δ(E)
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Two-dimensional semiconductors
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 6
dichalcogenides
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Dirac point in graphene
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 7
Graphite: Strong bond in the graphene plane, weak bond between planes. Remove single graphene plane.
Fox, Chapter 8
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Carbon nanotubes and fullerenes
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 8
Graphene sheets are rolled up to form tubes.Many Raman studies, doping with defects.
Jorio, Dresselhaus, DresselhausCarbon Nanotubes
Zig-zag
armchair
(n,m)
C-60
Fox, Chapter 8
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Carbon nanotubes: electrical properties
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 9
(n,m)
Fox, Chapter 8
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Two-dimensional semiconductors
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 10
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Two-dimensional semiconductors: WSe2, MoSe2
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 11
N. Briggs, 2D Materials 6, 022001 (2019)
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Growth of vertical quantum wires
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 12
Mäntynen, Nanophotonics 8, 747 (2019)
Vapor-liquid-solid
Selective area epitaxy
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Glancing angle deposition (GLAD) of quantum wires
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 13
Initial imperfections on the substrateShadow effect leads to tilted column growth.
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Colloidal quantum dots
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 14
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Colloidal quantum dots
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 15
Fox, Chapter 6C.R. Kagan, C.B. Murray, M.G. Bawendi, PRB 54, 8633 (1996)
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Epitaxial quantum dots
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 16
Fox, Chapter 6
Stranski-Krastanov growth of semiconductor islands by MBE
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Metamaterials
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 17
Metamaterials are artificially structured three-dimensional materials with feature size less than a wavelength. They have unusual properties: Photonic band gaps, left-handed materials, negative index.
Sajeev JohnShelby, APL 78, 489 (2001)
Faraday: 𝑘𝑘 × 𝐸𝐸0 = 𝜔𝜔𝜔𝜔𝜔𝜔0𝐻𝐻0
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Metasurfaces
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 18
Metasurfaces can be designed to have reflection, absorption, and emission properties not possible in homogeneous materials. Especially useful for sensors and antennas.
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Modeling Metamaterials and Metasurfaces
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 19
Bruggeman effective medium approximation (BEMA)
�𝑖𝑖=1
𝑛𝑛
𝑓𝑓𝑖𝑖𝜀𝜀𝑖𝑖 − 𝜀𝜀𝜀𝜀𝑖𝑖 + 2𝜀𝜀
= 0
Schmidt, JAP 114083519 (2013)Diebold, APL Mater. 6, 058201 (2018)
Rigorous coupled wave approximation:• Fourier method for periodic structures• Numerical solution of Maxwell’s equations
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Quantum well with infinite barriers
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 20
Ψ 𝑥𝑥,𝑦𝑦, 𝑧𝑧 = 𝜓𝜓 𝑥𝑥,𝑦𝑦 𝜑𝜑 𝑧𝑧
𝐸𝐸 𝑘𝑘,𝑛𝑛 =ℏ2𝑘𝑘2
2𝑚𝑚+ℏ2
2𝑚𝑚𝑛𝑛𝜋𝜋𝑑𝑑
2
Use carrier effective mass.(Electrons more affected than holes).
Finite barrier:Confinement energies are lower.Wave function leaks into barrier.Finite number of bound states.Solve numerically.
Fox, Chapter 6
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Quantum wells and superlattices (or MQW)
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 21
Quantum well: wave function entirely contained in one well.Superlattice: wave function leaks through the barrier into
the next well (barrier thin or low).
Fox, Chapter 6
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Superlattice minibands
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 22
VB
CB
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Enhanced absorption/emission in quantum structures
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 23 Fox, Chapter 6
1𝜏𝜏
=2𝜋𝜋ℏ
𝑓𝑓 𝐻𝐻𝑒𝑒𝑒𝑒 𝑖𝑖 2𝑔𝑔𝑓𝑓𝑖𝑖 ℏ𝜔𝜔
Modified density of states
Confinement enhances overlap matrix element
∆n=0
(l=0)
(l=1)
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Quantum well absorption
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 24 Fox, Chapter 6
Electron and hole subbands
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Quantum well absorption in GaAs/AlAs MQW
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 25 Fox, Chapter 6
Steps: 2-D absorptionPeaks: Discrete excitons (arrows show forbidden transitions)
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Excitonic effects are enhanced in quantum wells
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 26 Fox, Chapter 6
Bulk GaAs:RX=4.2 meV
Here (d=10 nm):RX=10 meVIncreased overlap integral
hh/lh splitting:Confinement or strain ???
𝐸𝐸 𝑘𝑘,𝑛𝑛 =ℏ2𝑘𝑘2
2𝑚𝑚+ℏ2
2𝑚𝑚𝑛𝑛𝜋𝜋𝑑𝑑
2
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Confinement shifts in quantum wells
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 27
W.T. Tsang & E.F. Schubert, Appl. Phys. Lett. 49, 220 (1986)
ℏ𝜔𝜔 = 𝐸𝐸𝑔𝑔 + 𝐸𝐸ℎℎ1 + 𝐸𝐸𝑒𝑒1
Δ𝐸𝐸 =ℏ2
2𝑚𝑚𝑛𝑛𝜋𝜋𝑑𝑑
2
thickthin
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Intersubband transitions, quantum cascade lasers
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 28 Fox, Chapter 6
Infrared detectors and lasersLight polarized along z (beam in quantum well plane)
∆n odd
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Defects
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 29 Yu & Cardona
Vacancy VA missing atomInterstitial IA extra atom between lattice sitesSubstitutional CA defect atom replaces host atomAntisite atoms are switchedFrenkel defect pair VA-IA atom moved to interstitial siteMore complex defects (combinations)
Donor: Substitutional defect, adds an electronAcceptor: Substitutional defect, adds a holeIsoelectronic: Impurity has same number of electrons as host
Shallow and deep defects.
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Defects: Frank-Condon principle
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 30 Fox, Chapter 8
Born-Oppenheimer approximation
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Defects: Color centers (F-centers)
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 31 Fox, Chapter 9
Alkali halide: large-gap insulatorVacancy: positively charged hole
F-center: electron trapped at anion vacancy.
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Defects: Shift between absorption and emission
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 32 Fox, Chapter 8,9
Two vacancies, one electronColor-center lasers
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Hund’s Rules (applied to Neodymium, Z=60)
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 33 Fox, Chapter 9
1. Maximize S2. Maximize L3. If shell is less than half full, J=L−S
If shell is more than half full, J=L+S.
Nd: 4f4 6s2 S=2, L=6, J=4
4f 6s
ml+3 +2 +1 0 −3−1 −2 0
Nd3+: 4f3 6s0 S=3/2, L=6, J=9/2
Nd3+: 4f3 6s0 S=3/2, L=3, J=3/2
atom: 4I4
3+ ion ground state: 4I9/2
3+ ion excited state: 4F3/2
2S+1LJ
Russell-Saunders (LS) coupling
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Defects: Rare earth metal ions in insulator (Nd:YAG)
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 34 Fox, Chapter 9
Atomic configuration
Weak crystal-field splitting
∆J=4 or 5forbidden
Transition weakly allowed with crystal-
field splitting
YAG: Y3Al5O12
Nd:YAG lasersYAG: 1064 nmYLiF4: 1053 nmBroad (120 GHz)
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Defects: Transition metal ions (Ti:sapphire)
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 35 Fox, Chapter 9
3d 4s
Ti: 3d2 4s2 S=1, L=3, J=2atom: 3F2
+2 +1 0 −1 −2
Ti3+: 3d1 4s0 S=1/2, L=2, J=3/2ion: 2D3/2
Strong vibronic couplingBroad lines (gain spectrum)Good for ultrafast lasers
Strong crystal-field splittingDepends on crystal environment
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Solid-State Lasers: Ti:sapphire and Nd:YAG
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 36
Fox, Chapter 9
Pumping with• Flash lamp (pulsed)• Xe lamp (CW)• GaAs diode (efficient)
SHG532 nm
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Erbium fiber laser
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 37Fox, Chapter 9
Pumped with 980 nm diode laser.Important for telecommunications.
ml+3 +2 +1 0 −3−1 −2 0
Er3+: 4f11 6s0 S=3/2, L=6, J=15/23+ ion ground state: 4I15/2
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Phosphors
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 38Fox, Chapter 9
Obsolete: Cathode ray tubes (TV, oscilloscope)Fluorescent tubes.Convert discrete LED (or Hg) emission into white light.
BaMgAl10O17:Eu2+ (4f7)450 nm (blue)
CeMgAl11O19:Tb3+ (4f8)550 nm (green)
Y2O3:Eu3+ (4f6)610 nm (red)
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White light emitting diodes (white LEDs)
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 39Fox, Chapter 9
Blue InGaN LED with green and red phosphorsI: SrSi2O2N2:Eu2+
II: Sr2Si5N8:Eu2+
Color temperature: 3200 K
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Shallow (hydrogenic) defect: Si donor in GaAs
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 40 Yu & Cardona
Extra valence electronP nucleus positively charged (but screened in crystal)Hydrogen-like energy spectrum (screened, heavy)
Extra potential:
Rydberg series:
Binding energy:
Bohr radius.Similar to exciton problem.
𝑉𝑉𝑆𝑆 = +𝑒𝑒
4𝜋𝜋𝜀𝜀0𝑟𝑟
𝐸𝐸 = 𝐸𝐸𝐶𝐶𝐶𝐶𝐶𝐶 −𝑅𝑅𝑛𝑛2
𝑅𝑅 =𝑚𝑚∗
𝑚𝑚0
1𝜀𝜀𝑠𝑠2
𝑒𝑒4𝑚𝑚0
2ℏ2 4𝜋𝜋𝜀𝜀0 2
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Shallow (hydrogenic) defect: Si donor in GaAs
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 41 Yu & Cardona
Works quite well for s-like conduction bands.Complications due to p-like VB, anisotropic bands (Ge, Si, GaP)
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Shallow (hydrogenic) defect: Donors in Si and Ge
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 42 Yu & Cardona
Poor agreement with theory (valley-orbit coupling)
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Shallow (hydrogenic) defect: Acceptors in Si and Ge
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 43 Yu & Cardona
Need to include valence band warping (Luttinger theory) and other corrections.
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Free and bound excitons (photoluminescence)
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 44
McClusky & Haller, Dopants and Defects
Band to defect recombination shifted from free exciton energy.
donor acceptor
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Infrared defect spectroscopy: P donor in Si
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 45
McClusky & Haller, Dopants and DefectsA.K. Ramdas, PRB 23, 2082 (1981)Pajot, Solid State Commun. 31, 759 (1979)
4 K
Energy (cm-1)
Water lines
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Stress and Strain: Hooke’s Law• Stress: Force per unit area (GPa),
(1st rank tensor)
• Strain: Describes the response to the stress, (1st rank tensor)
• Constituent relation (Hooke’s law) between stress and strain:compliance tensor , stiffness tensor (6x6 2nd rank tensors)
=
333231
232221
131211
XXXXXXXXX
X
εε
cXSX==
S c
Spring: Strain is ε=s/l,Relative change in length.
ε=s/l
Landau & Lifshiftz, Elasticity TheoryYu & Cardona, Fundamentals of Semiconductors.
( )unstrainedstrained
333231
232221
131211
aa −⊗∇=
=
εεεεεεεεε
ε
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 46
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Biaxial Stress in Epitaxial Film on (001) substrate• Stress:
Forces act along the wafer, but not along the growth direction.– SiGe on Si: Compressive stress (X<0)– Si on SiGe: Tensile stress (X>0)
• Resulting Strain:
• Hydrostatic strain component: tensile (>0), softens phonons, gap decreases
• (100) Shear strain component: compressive (<0), Splits phonons and bands into singlet/doublet. Selection rules!
S. Zollner, Properties of Silicon-Germanium-Carbon Alloys: Growth, Properties, Applications
=
0000000
biaxial XX
X
𝜀𝜀H = 2𝜀𝜀⊥ + 𝜀𝜀|| /3
𝜀𝜀S = 𝜀𝜀|| − 𝜀𝜀⊥ /3
ε||=0.553 X/1011 Pa tensile in-plane strain
ε⊥ =−0.979 X/1011 Pacompressive vertical strain
𝛆𝛆biaxial =𝑆𝑆11 + 𝑆𝑆12 𝑋𝑋 0 0
0 𝑆𝑆11 + 𝑆𝑆12 𝑋𝑋 00 0 2𝑆𝑆12𝑋𝑋
=𝜀𝜀∥ 0 00 𝜀𝜀∥ 00 0 𝜀𝜀⊥
X
XX
X
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 47
Strained Si
Relaxed SiGeRelaxed SiGe
Relaxed Si
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Thin Strained Silicon Layers for CMOS
• Biaxial tension lowers band gaps, reduces effective masses, and splits bands/valleys (reduced intervalley and inter-valence band scattering).
• Silicon under biaxial tension has higher electron and hole mobilities and therefore offers better transport properties than bulk silicon.
Graded SiGe buffer
Enhancement low for Ge <20%
p-channel (hole) devices
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 48
2/3 ∆Ε
1/3 ∆Ε
kx kykz
Si
CBΞu,Ξd
HHLH
SO
Energy
k
Energy
k
HH
LH
SO
VBa,b,d
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New Mexico State University
Deformation potentials
𝑎𝑎 =1𝑉𝑉𝜕𝜕𝐸𝐸𝑔𝑔𝜕𝜕𝑉𝑉
Δ𝐸𝐸𝑔𝑔 = 𝑎𝑎 Tr 𝜀𝜀
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Summary
Stefan Zollner, February 2019, Optical Properties of Solids Lecture 12 50
• Quantum confinement and Heisenberg uncertainty principle• Growth of quantum structures• Carbon nanostructures, two-dimensional materials• Electronic states, quantum well absorption and emission• Intersubband transitions• Metamaterials and metasurfaces
• Defects • Transition metal and rare earth impurities in insulators• Shallow defects in semiconductors
• Stress and strain, deformation potentials