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The photoelectric effect is the emission of from a material caused by electromagnetic radiation such as ultraviolet light. Electrons emitted in this manner are called photoelectrons. The phenomenon is studied in condensed matter physics, solid state, and quantum chemistry to draw inferences about the properties of atoms, molecules and solids. The effect has found use in Electronics 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 does not build up the energy required to produce photoelectrons, as would be the case if light's energy accumulated over time from a continuous wave, Albert Einstein proposed that a beam of light is not a wave propagating through space, but discrete energy packets, which were later popularised as by Gilbert N. Lewis.
Emission of conduction electrons from typical requires a few Electronvolt (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 in Chemical element with a high atomic number. 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. (1990). 9780030302589, Saunders. ISBN 9780030302589 Other phenomena where light affects the movement of electric charges include the photoconductive effect, the photovoltaic effect, and the photoelectrochemical effect.
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. 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.
Sunlight is an inconsistent and variable source of ultraviolet light. Cloud cover, ozone concentration, altitude, and surface reflection all alter the amount of UV. Laboratory sources of UV are based on xenon arc lamps or, for more uniform but weaker light, fluorescent lamps. More specialized sources include Laser and synchrotron radiation.
The classical setup to observe the photoelectric effect includes a light source, a set of filters to Monochromator 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. 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), 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 to peak in the direction of polarization of linearly polarized light. The experimental technique that can measure these distributions to infer the material's properties is angle-resolved photoemission spectroscopy.
[[File:Photoelectric effect - stopping voltage diagram for zinc - English.svg|thumb|Diagram of the maximum kinetic energy as a function of the frequency of light on zinc|alt=]]
In 1905, Albert Einstein proposed a theory of the photoelectric effect using a concept 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. In the range of kinetic energies of the electrons that are removed from their varying atomic bindings by the absorption of a photon of energy , the highest kinetic energy is
Here, 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 . 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. 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.
There are cases where the three-step model fails to explain peculiarities of the photoelectron intensity distributions. The more elaborate one-step model 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.
Julius 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.Asimov, A. (1964) Asimov's Biographical Encyclopedia of Science and Technology, Doubleday, .
(1998). 9780815315612, Science Museum, London, and National Museum of American History, Smithsonian Institution. ISBN 9780815315612 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.
In 1887, Heinrich Hertz observed the photoelectric effect
The discoveries by Hertz led to a series of investigations by Wilhelm Hallwachs,Hallwachs, Wied. Ann. xxxiii. p. 301, 1888. Hoor,Hoor, Repertorium des Physik, xxv. p. 91, 1889. Augusto RighiBighi, C. R. cvi. p. 1349; cvii. p. 559, 1888 and Aleksander StoletovStoletov. C. R. cvi. pp. 1149, 1593; cvii. p. 91; cviii. p. 1241; Physikalische Revue, Bd. i., 1892.
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, 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. 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 .
Many substances besides metals discharge negative electricity under the action of ultraviolet light. G. C. SchmidtSchmidt, G. C. (1898) Wied. Ann. Uiv. p. 708. and O. Knoblauch compiled a list of these substances.
In 1897, J. J. Thomson investigated ultraviolet light in Geissler tube. The International Year Book. (1900). New York: Dodd, Mead & Company. p. 659. 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. (2025). 9780262269483, MIT Press. ISBN 9780262269483 It was thought that the oscillating electromagnetic fields caused the atoms' field to resonate and, after reaching a certain amplitude, caused 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.
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 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.
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. However, Lenard's results were qualitative rather than quantitative because of the difficulty in performing the experiments: the experiments needed to be done on freshly cut metal so that the pure metal was observed, but it oxidized in a matter of minutes even in the partial vacuums he used. The current emitted by the surface was determined by the light's intensity, or brightness: doubling the intensity of the light doubled the number of electrons emitted from the surface.
Initial investigation of the photoelectric effect in gasses by Lenard were followed up by J. J. Thomson and then more decisively by Frederic Palmer Jr. The gas photoemission was studied and showed very different characteristics than those at first attributed to it by Lenard.
In 1900, while studying black-body radiation, the German physicist Max Planck suggested in his "On the Law of Distribution of Energy in the Normal Spectrum" paper that the energy carried by electromagnetic waves could only be released in packets of energy. In 1905, Albert Einstein published a paper advancing the hypothesis that light energy is carried in discrete quantized packets to explain experimental data from the photoelectric effect. Einstein theorized that the energy in each quantum of light was equal to the frequency of light multiplied by a constant, later called the Planck constant. A photon above a threshold frequency has the required energy to eject a single electron, creating the observed effect. This was a step in the development of quantum mechanics. In 1914, Robert A. Millikan's highly accurate measurements of the Planck constant from the photoelectric effect supported Einstein's model, even though a corpuscular theory of light was for Millikan, at the time, "quite unthinkable". Einstein was awarded the 1921 Nobel Prize in Physics for "his discovery of the law of the photoelectric effect", and Millikan was awarded the Nobel Prize in 1923 for "his work on the elementary charge of electricity and on the photoelectric effect". In quantum perturbation theory of atoms and solids acted upon by electromagnetic radiation, the photoelectric effect is still commonly analyzed in terms of waves; the two approaches are equivalent because photon or wave absorption can only happen between quantized energy levels whose energy difference is that of the energy of photon.
Albert Einstein's mathematical description of how the photoelectric effect was caused by absorption of quantum of light was in one of his Annus Mirabilis papers, named "On a Heuristic Viewpoint Concerning the Production and Transformation of Light".Einstein, A. " On a Heuristic Viewpoint Concerning the Emission and Transformation of Light." Annalen der Physik 17 (1905) The paper proposed a simple description of energy quanta, and showed how they explained the blackbody radiation spectrum. His explanation in terms of absorption of discrete quanta of light agreed with experimental results. It explained why the energy of photoelectrons was not dependent on incident light intensity. This was a theoretical leap, but the concept was strongly resisted at first because it contradicted the wave theory of light that followed naturally from James Clerk Maxwell's equations of electromagnetism, and more generally, the assumption of infinite divisibility of energy in physical systems.
Einstein's work predicted that the energy of individual ejected electrons increases linearly with the frequency of the light. The precise relationship had not at that time been tested. By 1905 it was known that the energy of photoelectrons increases with increasing frequency of incident light and is independent of the intensity of the light. However, the manner of the increase was not experimentally determined until 1914 when Millikan showed that Einstein's prediction was correct.
The photoelectric effect helped to propel the then-emerging concept of wave–particle duality in the nature of light. Light simultaneously possesses the characteristics of both waves and particles, each being manifested according to the circumstances. The effect was impossible to understand in terms of the classical wave description of light,Resnick, Robert (1972) Basic Concepts in Relativity and Early Quantum Theory, Wiley, p. 137, .Knight, Randall D. (2004) Physics for Scientists and Engineers With Modern Physics: A Strategic Approach, Pearson-Addison-Wesley, p. 1224, .Penrose, Roger (2005) The Road to Reality: A Complete Guide to the Laws of the Universe, Knopf, p. 502, as the energy of the emitted electrons did not depend on the intensity of the incident radiation. Classical theory predicted that the electrons would 'gather up' energy over a period of time, and then be emitted.Resnick, Robert (1972) Basic Concepts in Relativity and Early Quantum Theory, Wiley, p. 138, .
The quantum of light was given its modern name by Gilbert N. Lewis when he coined the term 'photon' in his letter "The Conservation of Photons" to Nature published in 18 December 1926.
The role of electric field in photoelectric effect has also been empirically studied and it was found that electromagnetic radiation with a specific orientation of electric field can excite electrons leading to enhanced emission in the Terahertz range.
Photoelectron spectroscopy measurements are usually performed in a high-vacuum environment, because the electrons would be scattered by gas molecules if they were present. However, some companies are now selling products that allow photoemission in air. The light source can be a laser, a discharge tube, or a synchrotron radiation source.
The concentric hemispherical analyzer is a typical electron energy analyzer. It uses an electric field between two hemispheres to change (disperse) the trajectories of incident electrons depending on their kinetic energies.
Here Z is the atomic number and n is a number which varies between 4 and 5. The photoelectric effect rapidly decreases in significance in the gamma-ray region of the spectrum, with increasing photon energy. It is also more likely from elements with high atomic number. Consequently, high- Z materials make good Gamma ray shields, which is the principal reason why lead ( Z = 82) is preferred and most widely used.
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