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Liberation of electron using a photon
photoelectric effect/photoemission
Science By The Slice
Xiaoshan Xu
July 22, 2016
PHOTOELECTRIC EFFECT
The complete absorption of a photon by a solid with the emission of an
electron. (Handbook of chemistry and physics, David Lide, 87th edition,
Boca Raton, FL : CRC Press, 2006)
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Light (𝐼, 𝜈 ) Electron (𝐸𝑘 , 𝐼𝐸)
Metal: Li, Na, K
Photoelectric effect
https://phet.colorado.edu/en/simulation/photoelectric
𝐼: light intensity
𝜈: light frequency
𝐸𝑘: kinetic energy of
emitted electron
𝐼𝐸: photoelectric
current
Light (𝐼, 𝜈 )
Electron (𝐸𝑘 , 𝐼𝐸)
Properties of the photoelectric effect
𝐼𝐸 ∝ 𝐼 (The intensity of light is
proportional to the induced photo
electric current.)
There is an threshold for the light
frequency to generate photocurrent.
The maximum kinetic energy
increases with the light frequencyhttp://hyperphysics.phy-astr.gsu.edu/hbase/mod2.html
Na
Quantization of light: photon
• The energy of the light propagates in discrete wave packets (photons):
𝐸𝑝 = ℎ𝜈, ℎ is the Plank constant
• Conservation of energy:
𝐸𝑘𝑚𝑎𝑥 = 𝐸𝑝 − 𝜙 = ℎ𝜈 − 𝜙
Vacuum level
Metal
𝜙:𝑤𝑜𝑟𝑘 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛
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Light (𝐼, 𝜈 )
Measurement of Plank constant
Robert Millikan
ℎ = 6.6 × 10−34 Js
http://hyperphysics.phy-astr.gsu.edu/hbase/mod2.html
𝐸𝑘𝑚𝑎𝑥 = 𝐸𝑝 − 𝜙 = ℎ𝜈 − 𝜙
Work functions of metals (eV)Ag 4.26 – 4.74 Al 4.06 – 4.26 As 3.75
Au 5.1 – 5.47 B ~4.45 Ba 2.52 – 2.7
Be 4.98 Bi 4.31 C ~5
Ca 2.87 Cd 4.08 Ce 2.9
Co 5 Cr 4.5 Cs 2.1
Cu 4.53 – 5.10 Eu 2.5 Fe: 4.67 – 4.81
Ga 4.32 Gd 2.90 Hf 3.9
Hg 4.475 In 4.09 Ir 5.00 – 5.67
K 2.29 La 3.5 Li 2.9
Lu ~3.3 Mg 3.66 Mn 4.1
Mo 4.36 – 4.95 Na 2.36 Nb 3.95 – 4.87
Nd 3.2 Ni 5.04 – 5.35 Os 5.93
Pb 4.25 Pd 5.22 – 5.6 Pt 5.12 – 5.93
Rb 2.261 Re 4.72 Rh 4.98
Ru 4.71 Sb 4.55 – 4.7 Sc 3.5
Se 5.9 Si 4.60 – 4.85 Sm 2.7
Sn 4.42 Sr ~2.59 Ta 4.00 – 4.80
Tb 3.00 Te 4.95 Th 3.4
Ti 4.33 Tl ~3.84 U 3.63 – 3.90
V 4.3 W 4.32 – 5.22 Y 3.1
Yb 2.60 [13] Zn 3.63 – 4.9 Zr 4.05
Visible light:
1.6-3.1 eV
Light: Wave and particle
• Klein–Gordon equation (Relativistic)
−ℏ2𝜕2
𝜕𝑡2𝜓 = −ℏ2𝑐2𝛻2 +𝑚2𝑐4 𝜓 = 𝐸2
m=0 for photon:
−ℏ2𝜕2
𝜕𝑡2𝜓 = −ℏ2𝑐2𝛻2𝜓 = 𝐸2
𝜓 = Ae𝑖(2𝜋𝜆𝑥−𝜔𝑡)
, 𝐸 = ℏ𝜔 = ℎ𝜈
𝜔 ≡ 2𝜋𝜈, ℏ ≡ℎ
2𝜋
Light Induced Quantum Transitions
• Transition matrix
𝐻12 = 𝜓1 𝐸0𝑒−𝑖𝜔𝑡 𝜓2
= 𝜓10 𝐸0 𝜓2
0 𝑒−𝑖(𝐸2−𝐸1
ℏ−𝜔)𝑡
Transition probability
𝑃 𝑡 ∝ න0
𝑡
𝐻12𝑑𝑡
2
∝ න0
𝑡
𝑒−𝑖
𝐸2−𝐸1ℏ
−𝜔 𝑡𝑑𝑡
2
∝ 𝜓10 𝐸0 𝜓2
0 2𝛿(𝐸2 − 𝐸1
ℏ− 𝜔)
Light e−𝑖𝜔𝑡
𝜓1 = 𝜓10𝑒−𝑖
𝐸1ℏ𝑡
𝜓2 = 𝜓20𝑒−𝑖
𝐸2ℏ𝑡
Application of photoelectric effect
• Photoelectric cell for light sensing
• Photomultiplier tube for single-photon
detection
Excitation in an insulator (semiconductor)
Vacuum level
Metal
𝜙:𝑤𝑜𝑟𝑘 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛
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Light (𝐼, 𝜈 )
Vacuum level
Insulator
𝐸𝑔: 𝑏𝑎𝑛𝑑 𝑔𝑎𝑝
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Light (𝐼, 𝜈 )
𝑉𝑎𝑙𝑒𝑛𝑐𝑒 𝑏𝑎𝑛𝑑
𝐶𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑏𝑎𝑛𝑑 Si
Si
Si
Si
Si
Si
Si
Si
Si
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Light induced electron-hole pair
Photovotaic effect
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h+++
---
𝑥
𝑉𝑑𝑟𝑜𝑝
Electric potential
Depletion zone
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h
+-
Photodetector: charge coupled device (CCD)
Gate
SiO2
p-Si
𝑉𝐺
e
h
PHOTOEMISSION
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Light (𝐼, 𝜈 ) Electron (𝐸𝑘 , 𝐼𝐸)
Metal and insulators
Photoemission
Binding energy: 𝐸𝐵 = ℎ𝜈 − 𝐸𝑘Binding energy of valence electron
< 100 eV ultraviolet light
Binding energy of core electron:
> keV x-ray
K, n=1
L, n=2M, n=3N, n=4Valence
Vacuum
https://en.wikipedia.org/wiki/X-ray_photoelectron_spectroscopy
Ultraviolet photoelectron spectroscopy (UPS)
http://en.wikipedia.org/wiki/File:ARPESgeneral.png
Fix photon energy
Measure kinetic energy
• Surface sensitive due to small kinetic energy
• Must be in UHV (typically <10-9 Torr)
X-ray photoelectron spectroscopy (XPS)
J. Phys.: Condens. Matter 27 (2015) 175004 .
h-LuFeO3
Auger effect (Secondary photoemission)
• 1st , x-ray excites electron to
conduction band and
generate a core hole
• 2nd , electron recombine
with the hole; the emitted
energy expels another
electronK, n=1
L, n=2M, n=3N, n=4Valence
Vacuum
K, n=1
L, n=2M, n=3N, n=4Valence
Vacuum
X-ray absorption Electron-hole recombination and
emission of another electron
ABSORPTION SPECTROSCOPY
𝜓1 = 𝜓10𝑒−𝑖
𝐸1ℏ𝑡
𝜓2 = 𝜓20𝑒−𝑖
𝐸2ℏ𝑡 𝑃 𝑡 ∝ 𝜓1
0 𝐸0 𝜓20
2𝛿(𝐸2 − 𝐸1
ℏ− 𝜔)
Optical absorption spectroscopy
1.2 1.4 1.6 1.8 2.0 2.20
100
200
300
400
500
600
700
(
cm-1
)
Energy (eV)
300 K
4 K
6A
1g
4T
1g
6A
1g
4T
2g
PHYSICAL REVIEW B 79, 134425 2009
BiFeO3
t2g
eg
Fe3+ 3d5
Spin Parity
Initial 5/2 Even
Final 3/2 Even6A1g
4T1g
Color of BiFeO3 comes from the absorption
X-ray absorption spectroscopy (XAS)
Transmission
Incident x-ray
Secondary
photoemission
(surface sensitive,
a few nm)Fluorescence
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• Transmission is normally
difficult to measure,
especially for thin films
• Fluorescence spectra is
often distorted by self
absorption
• Photoemission is often
used for its surface
sensitivity, especially for
thin films.
XAS using synchrotron x-ray
• Unlike XPS, UPS, the x-ray
energy is canned, which
requires synchrotron source
• UHV is also necessary
X-ray
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XAS at Canadian Light Source
Electronic structures by XAS
LuFeO3
hexagonal
orthorhombic
hexagonal
orthorhombic
X-ray magnetic circular dichroism (XMCD)
Stohr, Siegmann, Magnetism From Fundamentals to Nanoscale Dynamics, Springer, 2006.
Photoemission electron microscopy (PEEM)
Fe magnetic domains
Magnetic domains
hexagonal
orthorhombic
hexagonal
orthorhombic
Structural
domains
Thank you for your attention !