APh 114b Lecture 17

Solid State Physics Optical Properties of Solids

Photoemission
Photoemission is one of the most important techniques for mapping
energy band structure in solids. The incident excitation is a photon
and the excited particle is an electron ejected into vacuum and then
measured with an electron spectrometer. This provides a
measurement of the dielectric function. Photoemission is also
capable of measuring chemical shifts due to charge transfer which
alters the binding energy of photoelectrons. The photoemission
current can be written in the form

I  IE,  e ,  e , , ,  p ,  p ,  p 

where E is the electron energy, e ,  e are the polar and azimuthal

electron scattering angles,  is the electron spin,  is the photon
energy, ρp is the photon polarization, and θp and φp are the polar and
azimuthal incident photon angles.

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© (2005) H.A. Atwater, Caltech
APh 114b Lecture 17
Solid State Physics Optical Properties of Solids
Photoemission
Different photoemission techniques
measure different variables:
1. Energy Distributions I=I(E) with
all other variables held constant
2. Constant Initial State
Spectroscopy where  − E
is kept constant, i.e.,I  IE,  ∣ E−cons tant
3. Constant Final State
Spectroscopy where
4. Angle Resolved I  I
Photoemission, where all the
angles are allowed to vary but
photon energy and electron
kinetic energy are fixed.
The photoelectric yield is the measurement of
the number of electrons emission per incident
photon, and energy distributions are measured
by spectroscopic resolution of the
photoemitted electrons in an electrostatic or 2
magnetic analyzer. © (2005) H.A. Atwater, Caltech
APh 114b Lecture 17
Solid State Physics Optical Properties of Solids

Photoemission
Historically, after ultraviolet
photon sources were developed,
ultraviolet photoemission
spectroscopy (UPS) was first
used to measure the work
function of solids and
development of X-ray sources
enabled study of core levels in
molecules and solids. In
photemission, light is absorbed
within a optical skin depth (~ few
microns) at ultraviolet or X-ray
energies, but electrons are
photoemitted into vacuum from a
much shallower electron escape
depth corresponding to the mean “Universal”electron escape depth
free path for electron scattering.

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© (2005) H.A. Atwater, Caltech
APh 114b Lecture 17
Solid State Physics Optical Properties of Solids

Photoemission
Angle-resolved photoemission can be used
to directly map out energy band structure by
Resolving photoelectron energy and momentum

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© (2005) H.A. Atwater, Caltech
APh 114b Lecture 17
Solid State Physics Optical Properties of Solids

Photoemission

Energy
Measurements of photoemission spectra
provide information about band structure
through analysis of the structure in the Eo
eφ
energy-dependent photoelectric yield. (Vacuum Level)
For a metal surface oriented in the x-y hω hωc
plane, with photoelectron momentum
normal to the surface pz,and electron can
escape and be photoemitted in vacuum if
z
p 2z
  ≥ E o metal surface
2m
where Eo is the vacuum level. The work function eφ represents the
minimum kinetic energy for electron escape from the solid into vacuum.
The photocurrent is proportional to the number of electrons escaping
from the solid surface

where D(pz) is the escape probability for

I  e p z np z Dp z dp z an electron of momentum pz and n(pz) is
the electron density.
o 5
© (2005) H.A. Atwater, Caltech
APh 114b Lecture 17
Solid State Physics Optical Properties of Solids

Photoemission
The electron density is then

npz   23
h
− dp x dpy p2
1
 2m −EF /kT
e 1
In a semiconductor, there is an energy gap,
and the Fermi energy lies in the energy gap.

Energy
The work function is also defined relative to
the Fermi energy but the threshold for
photoemission is now eφ + δ . The electron
affinity χ is a Fermi energy-independent Eo χ eφ
parameter equal to the energy difference EF Eg δ
from the bottom of the conduction band the
the vacuum level. The photoemission hω
threshold is:

p 2z z
  ≥ e      E g
2m semiconductor surface
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© (2005) H.A. Atwater, Caltech
APh 114b Lecture 17
Solid State Physics Optical Properties of Solids

Photoemission
In semiconductors, valence band photoemission will dominate until the
photoemitted electrons are themselves energetic enough to form
electron-hole pairs via collisions with other electrons. There is then a
secondary interband transition threshold
Yield
p 2z
  ≥   E g   E g    2E g
2m

χ+Eg χ+2Eg Energy

This illustrates that both primary photoelectrons and
inelastically scattered photoelectrons contribute to the
photoelectron yield.

IE,   I p E,   I s E, 

The primary photoemission yield depends on three
factors
I p E,   PE, TEDE
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© (2005) H.A. Atwater, Caltech
APh 114b Lecture 17
Solid State Physics Optical Properties of Solids

Photoemission
again, on this page,

I p E,   PE, TEDE

where P(E,ω) is the energy distribution of photoelectrons and T(E) is
the transmission function of excited electrons in terms of the optical
skin depth λphoton(ω) and the electron mean free path (escape depth)
λelectron(E):
 electron E
 photon 
TE   E
1  electron
photon

The escape function D(E) is

1 EF 
2
1− ; E  E F
DE  E

0; otherwise
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© (2005) H.A. Atwater, Caltech
APh 114b Lecture 17
Solid State Physics Optical Properties of Solids

Density of States Function in Wells, Wires and Dots

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© (2005) H.A. Atwater, Caltech
APh 114b Lecture 17
Solid State Physics Optical Properties of Solids

GaAs/AlGaAs Quantum Well Heterostructure

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© (2005) H.A. Atwater, Caltech
APh 114b Lecture 17
Solid State Physics Optical Properties of Solids

Energy Picture of Optical Pumping:

Quantum Well
Bulk Semiconductor
Heterostructure

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© (2005) H.A. Atwater, Caltech
APh 114b Lecture 17
Solid State Physics Optical Properties of Solids

Quantum Well Active Region in GRINSCH Laser

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© (2005) H.A. Atwater, Caltech
APh 114b Lecture 17 Excitons in Quantum Dots
Solid State Physics Optical Properties of Solids
ae(bulk) Quantum confinement occurs when
Quantum
Dot Re(confined) R → ae, ah (electron/hole Bohr radius)
Rh(confined)

ah(bulk)

Analytic approx. for lowest 1s excited state:

η2 π 2 ⎡ 1 1 ⎤ 1.8e 2
E(R) = E g + ⎢ * + * ⎥− + ...
2R 2 ⎣ me mh ⎦ ε 2R
Weak confinement (R>>ae, ah):

Coulomb term (~1/R) important

→exciton confinement regime.
Strong confinement (R<<ae, ah):

Confinement term (~1/R2) dominates and e- and

h+ quantized
→molecular-type regime. Exciton Bohr
radius 13
© (2005) H.A. Atwater, Caltech
Si: < 4.3 nm; Ge: < 11.5 nm; GaAs: < 12.4
 APh 114b Lecture 17 Electronic States in
Solid State Physics Optical Properties of Solids
Quantum Dots
•Energy levels become discrete.
Si

•Density of states become delta-functions. (M.S. Hybertsen, PRL 72, 1514 (1994))
Envelope wave functions sample larger k-space:

Optical selection rules relax.

Optical absorption coeff. α increases
due to wave function overlap
2 1
α ∝ U p ( 0) ∝
Volume 14
© (2005) H.A. Atwater, Caltech
 Quantum Confinement Effects on Si and Ge

APh 114b Lecture 17

5 Optical Properties of Solids
Si
Solid StateCalculations:
Physics
Phonon-assisted
TD Tight-binding: Hill et al., PRL 75, 1130 (1995))
4 Pseudopotential: Wang et al.,
J. Phys. Chem. 98, 2158 (1994)
3rd NN T-B: Delerue et al., PRB 48, 11024 (1993)
Si
Calculated Band Gap (eV)

3 EMA: Takagahara et al., PRB 46, 15578 (1992)

1
Ge TD Tight-binding:
2.5 Hill, private comm.
Bulk E
EMA: Takagahara et al.,
g
PRB 46, 15578 (1992)
2.0
Zero phonon
(M.S. Hybertsen, PRL 72, 1514 (1994))
1.5

1.0 Radiative transition rate (1/τ) ↑ with ↑ confinement.

Si predicted to be “quasidirect” for d<~1.5 nm.

0.5 (ex. J.P. Proot et al., APL 61, 1948 (1992))
2 4 6 8 10
Nanocrystal Diameter (nm)
“Band gap” ↑ with ↑confinement
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(i.e., with ↓ nanocrystal diameter). © (2005) H.A. Atwater, Caltech
 APh 114b Lecture 17
Solid State Physics
Si Quantum
OpticalDots:
Properties of Solids
XPS and HRTEM
•Si 2p core level X-ray photoemission spectra :
106 104 102 100 98

5x1016 Si/cm2
Intensity (Arb. Units)

1100oC

1000oC
800oC
600oC
400oC Avg size 1~3 nm

As-Implanted As-implanted oxide is suboxide with

various Six+(x=1~4) species.
Thermal SiO
2
Onset of precipitation ~600oC.
Bulk Si (100)
SiO2 stoichiometric after annealing at
106 104 102 100 98 high T (T>1000oC). 16
© (2005) H.A. Atwater, Caltech
Binding Energy (eV)
APh 114b Lecture 17
Solid State Physics Emission Energy Tuning
Optical Properties by Oxidation:
of Solids
•PL vs. oxidation times:
Energy (eV)
2.2 2 1.8 1.6 1.4 1.2

Normalized PL Intensity (Arb. Units)

Ann. in O at 1000oC
1.0 2
0 min
3 min
0.8 10 min
15 min
20 min
0.6 25 min
30 min

0.4

0.2

0.0
600 700 800 900 1000 1100

Wavelength (nm) Bulk Si E

g

PL emission energy continuously tunable from 1.4 eV to 2.2 eV

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© (2005) H.A. Atwater, Caltech
APh 114b Lecture 17
Solid State Physics Colloidally Synthesized
Optical Properties Quantum Dots
of Solids

•PL emission energy continuously tunable from

0.5 eV to 3.2 eV

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© (2005) H.A. Atwater, Caltech
APh 114b Lecture 17
Solid State Physics Epitaxial InGaAs Quantum
Optical Properties of SolidsDots

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© (2005) H.A. Atwater, Caltech