Photoelectric effect

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The emission of electrons from a metal plate caused by light quanta – photons.

The photoelectric effect is the emission of electrons when electromagnetic radiation,

such as light, hits a material. Electrons emitted in this manner are called photoelectrons.
The phenomenon is studied in condensed matter physics, and solid state and quantum
chemistry to draw inferences about the properties of atoms, molecules and solids. The
effect has found use in electronic devices specialized for light detection and precisely
timed electron emission.
The experimental results disagree with classical electromagnetism, which predicts that
continuous light waves transfer energy to electrons, which would then be emitted when
they accumulate enough energy. An alteration in the intensity of light would theoretically
change the kinetic energy of the emitted electrons, with sufficiently dim light resulting in
a delayed emission. The experimental results instead show that electrons are dislodged
only when the light exceeds a certain frequency—regardless of the light's intensity or
duration of exposure. Because a low-frequency beam at a high intensity could not build
up the energy required to produce photoelectrons like it would have if light's energy was
coming from a continuous wave, Albert Einstein proposed that a beam of light is not a
wave propagating through space, but a swarm of discrete energy packets, known
as photons.
Emission of conduction electrons from typical metals requires a few electron-volt (eV)
light quanta, corresponding to short-wavelength visible or ultraviolet light. In extreme
cases, emissions are induced with photons approaching zero energy, like in systems
with negative electron affinity and the emission from excited states, or a few hundred
keV photons for core electrons in elements with a high atomic number.[1] Study of the
photoelectric effect led to important steps in understanding the quantum nature of light
and electrons and influenced the formation of the concept of wave–particle duality.
  Other phenomena where light affects the movement of electric charges include
[2]

the photoconductive effect, the photovoltaic effect, and the photoelectrochemical effect.

Contents

 1Emission mechanism

o 1.1Experimental observation of photoelectric emission

o 1.2Theoretical explanation

o 1.3Photoemission from atoms, molecules and solids

 1.3.1Models of photoemission from solids

 2History

o 2.119th century

o 2.220th century

 3Uses and effects

o 3.1Photomultipliers

o 3.2Image sensors

o 3.3Photoelectron spectroscopy

o 3.4Night vision devices

o 3.5Spacecraft

o 3.6Moon dust

 4Competing processes and photoemission cross section

 5See also

 6References

 7External links

Emission mechanism[edit]
The photons of a light beam have a characteristic energy, called photon energy, which
is proportional to the frequency of the light. In the photoemission process, when an
electron within some material absorbs the energy of a photon and acquires more energy
than its binding energy, it is likely to be ejected. If the photon energy is too low, the
electron is unable to escape the material. Since an increase in the intensity of low-
frequency light will only increase the number of low-energy photons, this change in
intensity will not create any single photon with enough energy to dislodge an electron.
Moreover, the energy of the emitted electrons will not depend on the intensity of the
incoming light of a given frequency, but only on the energy of the individual photons.
While free electrons can absorb any energy when irradiated as long as this is followed
by an immediate re-emission, like in the Compton effect, in quantum systems all of the
energy from one photon is absorbed—if the process is allowed by quantum mechanics
—or none at all. Part of the acquired energy is used to liberate the electron from its
atomic binding, and the rest contributes to the electron's kinetic energy as a free
particle.[3][4][5] Because electrons in a material occupy many different quantum states with
different binding energies, and because they can sustain energy losses on their way out
of the material, the emitted electrons will have a range of kinetic energies. The electrons
from the highest occupied states will have the highest kinetic energy. In metals, those
electrons will be emitted from the Fermi level.
When the photoelectron is emitted into a solid rather than into a vacuum, the
term internal photoemission is often used, and emission into a vacuum is distinguished
as external photoemission.
Experimental observation of photoelectric emission[edit]
Even though photoemission can occur from any material, it is most readily observed
from metals and other conductors. This is because the process produces a charge
imbalance which, if not neutralized by current flow, results in the increasing potential
barrier until the emission completely ceases. The energy barrier to photoemission is
usually increased by nonconductive oxide layers on metal surfaces, so most practical
experiments and devices based on the photoelectric effect use clean metal surfaces in
evacuated tubes. Vacuum also helps observing the electrons since it prevents gases
from impeding their flow between the electrodes.
As sunlight, due to atmosphere's absorption, does not provide much ultraviolet light, the
light rich in ultraviolet rays used to be obtained by burning magnesium or from an arc
lamp. At the present time, mercury-vapor lamps, noble-gas discharge UV lamps
and radio-frequency plasma sources,[6][7][8] ultraviolet lasers,[9] and synchrotron insertion
device[10] light sources prevail.
Schematic of the experiment to demonstrate the photoelectric effect. Filtered, monochromatic light of certain
wavelength strikes the emitting electrode (E) inside a vacuum tube. The collector electrode (C) is biased to a
voltage VC that can be set to attract the emitted electrons, when positive, or prevent any of them from reaching
the collector when negative.

The classical setup to observe the photoelectric effect includes a light source, a set of
filters to monochromatize the light, a vacuum tube transparent to ultraviolet light, an
emitting electrode (E) exposed to the light, and a collector (C) whose voltage VC can be
externally controlled.
A positive external voltage is used to direct the photoemitted electrons onto the
collector. If the frequency and the intensity of the incident radiation are fixed, the
photoelectric current I increases with an increase in the positive voltage, as more and
more electrons are directed onto the electrode. When no additional photoelectrons can
be collected, the photoelectric current attains a saturation value. This current can only
increase with the increase of the intensity of light.
An increasing negative voltage prevents all but the highest-energy electrons from
reaching the collector. When no current is observed through the tube, the negative
voltage has reached the value that is high enough to slow down and stop the most
energetic photoelectrons of kinetic energy Kmax. This value of the retarding voltage is
called the stopping potential or cut off potential Vo.[11] Since the work done by the
retarding potential in stopping the electron of charge e is eVo, the following must
hold eVo = Kmax.
The current–voltage curve is sigmoidal, but its exact shape depends on the
experimental geometry and the electrode material properties.
For a given metal surface, there exists a certain minimum frequency of
incident radiation below which no photoelectrons are emitted. This frequency is called
the threshold frequency. Increasing the frequency of the incident beam increases the
maximum kinetic energy of the emitted photoelectrons, and the stopping voltage has to
increase. The number of emitted electrons may also change because
the probability that each photon results in an emitted electron is a function of photon
energy.
An increase in the intensity of the same monochromatic light (so long as the intensity is
not too high[12]), which is proportional to the number of photons impinging on the surface
in a given time, increases the rate at which electrons are ejected—the photoelectric
current I—but the kinetic energy of the photoelectrons and the stopping voltage remain
the same. For a given metal and frequency of incident radiation, the rate at which
photoelectrons are ejected is directly proportional to the intensity of the incident light.
The time lag between the incidence of radiation and the emission of a photoelectron is
very small, less than 10−9 second. Angular distribution of the photoelectrons is highly
dependent on polarization (the direction of the electric field) of the incident light, as well
as the emitting material's quantum properties such as atomic and molecular orbital
symmetries and the electronic band structure of crystalline solids. In materials without
macroscopic order, the distribution of electrons tends peak in the direction of
polarization of linearly polarized light.[13] The experimental technique that can measure
these distributions to infer the material's properties is angle-resolved photoemission
spectroscopy.
Theoretical explanation[edit]

Diagram of the maximum kinetic energy as a function of the frequency of light on zinc.

In 1905, Einstein proposed a theory of the photoelectric effect using a concept first put

forward by Max Planck that light consists of tiny packets of energy known as photons or
light quanta. Each packet carries energy  that is proportional to the frequency  of the
corresponding electromagnetic wave. The proportionality constant  has become known
as the Planck constant. The maximum kinetic energy  of the electrons that were
delivered this much energy before being removed from their atomic binding is
where  is the minimum energy required to remove an electron from the surface of
the material. It is called the work function of the surface and is sometimes
denoted  or .[14] If the work function is written as
the formula for the maximum kinetic energy of the ejected electrons becomes
Kinetic energy is positive, and  is required for the photoelectric effect to
occur.[15] The frequency  is the threshold frequency for the given material.
Above that frequency, the maximum kinetic energy of the photoelectrons as
well as the stopping voltage in the experiment  rise linearly with the
frequency, and have no dependence on the number of photons and the
intensity of the impinging monochromatic light. Einstein's formula, however
simple, explained all the phenomenology of the photoelectric effect, and had
far-reaching consequences in the development of quantum mechanics.
Photoemission from atoms, molecules and solids[edit]
Electrons that are bound in atoms, molecules and solids each occupy distinct
states of well-defined binding energies. When light quanta deliver more than
this amount of energy to an individual electron, the electron may be emitted
into free space with excess (kinetic) energy that is  higher than the electron's
binding energy. The distribution of kinetic energies thus reflects the
distribution of the binding energies of the electrons in the atomic, molecular
or crystalline system: an electron emitted from the state at binding energy  is
found at kinetic energy . This distribution is one of the main characteristics of
the quantum system, and can be used for further studies in quantum
chemistry and quantum physics.
Models of photoemission from solids[edit]
The electronic properties of ordered, crystalline solids are determined by the
distribution of the electronic states with respect to energy and momentum—
the electronic band structure of the solid. Theoretical models of
photoemission from solids show that this distribution is, for the most part,
preserved in the photoelectric effect. The phenomenological three-step
model[16] for ultraviolet and soft X-ray excitation decomposes the effect into
these steps:[17][18][19]

1. Inner photoelectric effect in the bulk of the material that is a direct

optical transition between an occupied and an unoccupied electronic
state. This effect is subject to quantum-mechanical selection
rules for dipole transitions. The hole left behind the electron can give
rise to secondary electron emission, or the so-called Auger effect,
which may be visible even when the primary photoelectron does not
leave the material. In molecular solids phonons are excited in this
step and may be visible as satellite lines in the final electron energy.
2. Electron propagation to the surface in which some electrons may be
scattered because of interactions with other constituents of the solid.
Electrons that originate deeper in the solid are much more likely to
suffer collisions and emerge with altered energy and momentum.
 Their mean-free path is a universal curve dependent on electron's
energy.
3. Electron escape through the surface barrier into free-electron-like
states of the vacuum. In this step the electron loses energy in the
amount of the work function of the surface, and suffers from the
momentum loss in the direction perpendicular to the surface.
Because the binding energy of electrons in solids is conveniently
expressed with respect to the highest occupied state at the Fermi
energy , and the difference to the free-space (vacuum) energy is the
work function of the surface, the kinetic energy of the electrons
emitted from solids is usually written as .
There are cases where the three-step model fails to explain peculiarities of
the photoelectron intensity distributions. The more elaborate one-step
model[20] treats the effect as a coherent process of photoexcitation into the
final state of a finite crystal for which the wave function is free-electron-like
outside of the crystal, but has a decaying envelope inside. [19]

History[edit]
19th century[edit]
In 1839, Alexandre Edmond Becquerel discovered the photovoltaic
effect while studying the effect of light on electrolytic cells.[21] Though not
equivalent to the photoelectric effect, his work on photovoltaics was
instrumental in showing a strong relationship between light and electronic
properties of materials. In 1873, Willoughby
Smith discovered photoconductivity in selenium while testing the metal for its
high resistance properties in conjunction with his work involving submarine
telegraph cables.[22]
Johann Elster (1854–1920) and Hans Geitel (1855–1923), students
in Heidelberg, investigated the effects produced by light on electrified bodies
and developed the first practical photoelectric cells that could be used to
measure the intensity of light.[23][24]:458 They arranged metals with respect to their
power of discharging negative electricity: rubidium, potassium, alloy of
potassium and sodium, sodium, lithium, magnesium, thallium and zinc;
for copper, platinum, lead, iron, cadmium, carbon, and mercury the effects
with ordinary light were too small to be measurable. The order of the metals
for this effect was the same as in Volta's series for contact-electricity, the
most electropositive metals giving the largest photo-electric effect.
The gold leaf electroscope to demonstrate the photoelectric effect. When the electroscope is
negatively charged, there is an excess of electrons and the leaves are separated. If low-
wavelength, high-frequency light (such as ultraviolet light obtained from an arc lamp, or by
burning magnesium, or by using an induction coil between zinc or cadmium terminals to produce
sparking) shines on the cap, the electroscope discharges, and the leaves fall limp. If, however,
the frequency of the light waves is below the threshold value for the cap, the leaves will not
discharge, no matter how long one shines the light at the cap.

In 1887, Heinrich Hertz observed the photoelectric effect[25] and reported on

the production and reception[26] of electromagnetic waves.[27] The receiver in
his apparatus consisted of a coil with a spark gap, where a spark would be
seen upon detection of electromagnetic waves. He placed the apparatus in a
darkened box to see the spark better. However, he noticed that the maximum
spark length was reduced when inside the box. A glass panel placed
between the source of electromagnetic waves and the receiver absorbed
ultraviolet radiation that assisted the electrons in jumping across the gap.
When removed, the spark length would increase. He observed no decrease
in spark length when he replaced the glass with quartz, as quartz does not
absorb UV radiation.
The discoveries by Hertz led to a series of investigations by Hallwachs,[28]
[29]
 Hoor,[30] Righi[31] and Stoletov[32][33] on the effect of light, and especially of
ultraviolet light, on charged bodies. Hallwachs connected a zinc plate to
an electroscope. He allowed ultraviolet light to fall on a freshly cleaned zinc
plate and observed that the zinc plate became uncharged if initially
negatively charged, positively charged if initially uncharged, and more
positively charged if initially positively charged. From these observations he
concluded that some negatively charged particles were emitted by the zinc
plate when exposed to ultraviolet light.
With regard to the Hertz effect, the researchers from the start showed the
complexity of the phenomenon of photoelectric fatigue—the progressive
diminution of the effect observed upon fresh metallic surfaces. According to
Hallwachs, ozone played an important part in the phenomenon, [34] and the
emission was influenced by oxidation, humidity, and the degree of polishing
of the surface. It was at the time unclear whether fatigue is absent in a
vacuum.
In the period from 1888 until 1891, a detailed analysis of the photoeffect was
performed by Aleksandr Stoletov with results reported in six publications.
[33]
 Stoletov invented a new experimental setup which was more suitable for a
quantitative analysis of the photoeffect. He discovered a direct proportionality
between the intensity of light and the induced photoelectric current (the first
law of photoeffect or Stoletov's law). He measured the dependence of the
intensity of the photo electric current on the gas pressure, where he found
the existence of an optimal gas pressure corresponding to a
maximum photocurrent; this property was used for the creation of solar cells.
[citation needed]

Many substances besides metals discharge negative electricity under the

action of ultraviolet light. G. C. Schmidt[35] and O. Knoblauch[36] compiled a list
of these substances.
In 1899, J. J. Thomson investigated ultraviolet light in Crookes tubes.
[37]
 Thomson deduced that the ejected particles, which he called corpuscles,
were of the same nature as cathode rays. These particles later became
known as the electrons. Thomson enclosed a metal plate (a cathode) in a
vacuum tube, and exposed it to high-frequency radiation. [38] It was thought
that the oscillating electromagnetic fields caused the atoms' field to resonate
and, after reaching a certain amplitude, caused a subatomic corpuscles to be
emitted, and current to be detected. The amount of this current varied with
the intensity and color of the radiation. Larger radiation intensity or frequency
would produce more current.[citation needed]
During the years 1886–1902, Wilhelm Hallwachs and Philipp
Lenard investigated the phenomenon of photoelectric emission in detail.
Lenard observed that a current flows through an evacuated glass tube
enclosing two electrodes when ultraviolet radiation falls on one of them. As
soon as ultraviolet radiation is stopped, the current also stops. This initiated
the concept of photoelectric emission. The discovery of the ionization of
gases by ultraviolet light was made by Philipp Lenard in 1900. As the effect
was produced across several centimeters of air and yielded a greater
number of positive ions than negative, it was natural to interpret the
phenomenon, as J. J. Thomson did, as a Hertz effect upon the particles
present in the gas.[27]
20th century[edit]
In 1902, Lenard observed that the energy of individual emitted electrons
increased with the frequency (which is related to the color) of the light.[3] This
appeared to be at odds with Maxwell's wave theory of light, which predicted
that the electron energy would be proportional to the intensity of the
radiation.
Lenard observed the variation in electron energy with light frequency using a
powerful electric arc lamp which enabled him to investigate large changes in
intensity, and that had sufficient power to enable him to investigate the
variation of the electrode's potential with light frequency. He found the
electron energy by relating it to the maximum stopping potential (voltage) in a
phototube. He found that the maximum electron kinetic energy is determined
by the frequency of the light. For example, an increase in frequency results in
an increase in the maximum kinetic energy calculated for an electron upon
liberation – ultraviolet radiation would require a higher applied stopping
potential to stop current in a phototube than blue light. However, Lenard's
results were qualitative rathe