Photoemission spectroscopy

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Principle of angle-resolved photoemission spectroscopy. ARPES analyzer cross section.svg
Principle of angle-resolved photoemission spectroscopy.

Photoemission spectroscopy (PES), also known as photoelectron spectroscopy, [1] refers to energy measurement of electrons emitted from solids, gases or liquids by the photoelectric effect, in order to determine the binding energies of electrons in the substance. The term refers to various techniques, depending on whether the ionization energy is provided by X-ray, XUV or UV photons. Regardless of the incident photon beam, however, all photoelectron spectroscopy revolves around the general theme of surface analysis by measuring the ejected electrons. [2]

Contents

Types

X-ray photoelectron spectroscopy (XPS) was developed by Kai Siegbahn starting in 1957 [3] [4] and is used to study the energy levels of atomic core electrons, primarily in solids. Siegbahn referred to the technique as "electron spectroscopy for chemical analysis" (ESCA), since the core levels have small chemical shifts depending on the chemical environment of the atom that is ionized, allowing chemical structure to be determined. Siegbahn was awarded the Nobel Prize in 1981 for this work. XPS is sometimes referred to as PESIS (photoelectron spectroscopy for inner shells), whereas the lower-energy radiation of UV light is referred to as PESOS (outer shells) because it cannot excite core electrons. [5]

Ultraviolet photoelectron spectroscopy (UPS) is used to study valence energy levels and chemical bonding, especially the bonding character of molecular orbitals. The method was developed originally for gas-phase molecules in 1961 by Feodor I. Vilesov [6] and in 1962 by David W. Turner, [7] and other early workers included David C. Frost, J. H. D. Eland and K. Kimura. Later, Richard Smalley modified the technique and used a UV laser to excite the sample, in order to measure the binding energy of electrons in gaseous molecular clusters.

Angle-resolved photoemission spectroscopy (ARPES) has become the most prevalent electron spectroscopy in condensed matter physics after recent advances in energy and momentum resolution, and widespread availability of synchrotron light sources. The technique is used to map the band structure of crystalline solids, to study quasiparticle dynamics in highly correlated materials, and to measure electron spin polarization.

Two-photon photoelectron spectroscopy (2PPE) extends the technique to optically excited electronic states through the introduction of a pump-and-probe scheme.

Extreme-ultraviolet photoelectron spectroscopy (EUPS) lies in between XPS and UPS. It is typically used to assess the valence band structure. [8] Compared to XPS, it gives better energy resolution, and compared to UPS, the ejected electrons are faster, resulting in less space charge and mitigated final state effects. [9] [10] [11]

Physical principle

The physics behind the PES technique is an application of the photoelectric effect. The sample is exposed to a beam of UV or XUV light inducing photoelectric ionization. The energies of the emitted photoelectrons are characteristic of their original electronic states, and depend also on vibrational state and rotational level. For solids, photoelectrons can escape only from a depth on the order of nanometers, so that it is the surface layer which is analyzed.

Because of the high frequency of the light, and the substantial charge and energy of emitted electrons, photoemission is one of the most sensitive and accurate techniques for measuring the energies and shapes of electronic states and molecular and atomic orbitals. Photoemission is also among the most sensitive methods of detecting substances in trace concentrations, provided the sample is compatible with ultra-high vacuum and the analyte can be distinguished from background.

Typical PES (UPS) instruments use helium gas sources of UV light, with photon energy up to 52 eV (corresponding to wavelength 23.7 nm). The photoelectrons that actually escaped into the vacuum are collected, slightly retarded, energy resolved, and counted. This results in a spectrum of electron intensity as a function of the measured kinetic energy. Because binding energy values are more readily applied and understood, the kinetic energy values, which are source dependent, are converted into binding energy values, which are source independent. This is achieved by applying Einstein's relation . The term of this equation is the energy of the UV light quanta that are used for photoexcitation. Photoemission spectra are also measured using tunable synchrotron radiation sources.

The binding energies of the measured electrons are characteristic of the chemical structure and molecular bonding of the material. By adding a source monochromator and increasing the energy resolution of the electron analyzer, peaks appear with full width at half maximum (FWHM) less than 5–8 meV.

See also

Related Research Articles

<span class="mw-page-title-main">Photoelectric effect</span> Emission of electrons when light hits a material

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, 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.

<span class="mw-page-title-main">Auger electron spectroscopy</span> Analytical technique used specifically in the study of surfaces

Auger electron spectroscopy is a common analytical technique used specifically in the study of surfaces and, more generally, in the area of materials science. It is a form of electron spectroscopy that relies on the Auger effect, based on the analysis of energetic electrons emitted from an excited atom after a series of internal relaxation events. The Auger effect was discovered independently by both Lise Meitner and Pierre Auger in the 1920s. Though the discovery was made by Meitner and initially reported in the journal Zeitschrift für Physik in 1922, Auger is credited with the discovery in most of the scientific community. Until the early 1950s Auger transitions were considered nuisance effects by spectroscopists, not containing much relevant material information, but studied so as to explain anomalies in X-ray spectroscopy data. Since 1953 however, AES has become a practical and straightforward characterization technique for probing chemical and compositional surface environments and has found applications in metallurgy, gas-phase chemistry, and throughout the microelectronics industry.

<span class="mw-page-title-main">X-ray photoelectron spectroscopy</span> Spectroscopic technique

X-ray photoelectron spectroscopy (XPS) is a surface-sensitive quantitative spectroscopic technique based on the photoelectric effect that can identify the elements that exist within a material or are covering its surface, as well as their chemical state, and the overall electronic structure and density of the electronic states in the material. XPS is a powerful measurement technique because it not only shows what elements are present, but also what other elements they are bonded to. The technique can be used in line profiling of the elemental composition across the surface, or in depth profiling when paired with ion-beam etching. It is often applied to study chemical processes in the materials in their as-received state or after cleavage, scraping, exposure to heat, reactive gasses or solutions, ultraviolet light, or during ion implantation.

<span class="mw-page-title-main">Synchrotron light source</span> Particle accelerator designed to produce intense x-ray beams

A synchrotron light source is a source of electromagnetic radiation (EM) usually produced by a storage ring, for scientific and technical purposes. First observed in synchrotrons, synchrotron light is now produced by storage rings and other specialized particle accelerators, typically accelerating electrons. Once the high-energy electron beam has been generated, it is directed into auxiliary components such as bending magnets and insertion devices in storage rings and free electron lasers. These supply the strong magnetic fields perpendicular to the beam that are needed to stimulate the high energy electrons to emit photons.

Photoemission electron microscopy is a type of electron microscopy that utilizes local variations in electron emission to generate image contrast. The excitation is usually produced by ultraviolet light, synchrotron radiation or X-ray sources. PEEM measures the coefficient indirectly by collecting the emitted secondary electrons generated in the electron cascade that follows the creation of the primary core hole in the absorption process. PEEM is a surface sensitive technique because the emitted electrons originate from a shallow layer. In physics, this technique is referred to as PEEM, which goes together naturally with low-energy electron diffraction (LEED), and low-energy electron microscopy (LEEM). In biology, it is called photoelectron microscopy (PEM), which fits with photoelectron spectroscopy (PES), transmission electron microscopy (TEM), and scanning electron microscopy (SEM).

<span class="mw-page-title-main">Photoionization</span> Ion formation via a photon interacting with a molecule or atom

Photoionization is the physical process in which an ion is formed from the interaction of a photon with an atom or molecule.

Inverse photoemission spectroscopy (IPES) is a surface science technique used to study the unoccupied electronic structure of surfaces, thin films, and adsorbates. A well-collimated beam of electrons of a well defined energy is directed at the sample. These electrons couple to high-lying unoccupied electronic states and decay to low-lying unoccupied states, with a subset of these transitions being radiative. The photons emitted in the decay process are detected and an energy spectrum, photon counts vs. incident electron energy, is generated. Due to the low energy of the incident electrons, their penetration depth is only a few atomic layers, making inverse photoemission a particularly surface sensitive technique. As inverse photoemission probes the electronic states above the Fermi level of the system, it is a complementary technique to photoemission spectroscopy.

<span class="mw-page-title-main">Extreme ultraviolet</span> Ultraviolet light with a wavelength of 10–121nm

Extreme ultraviolet radiation or high-energy ultraviolet radiation is electromagnetic radiation in the part of the electromagnetic spectrum spanning wavelengths shorter that the hydrogen Lyman-alpha line from 121 nm down to the X-ray band of 10 nm, and therefore having photons with energies from 10.26 eV up to 124.24 eV. EUV is naturally generated by the solar corona and artificially by plasma, high harmonic generation sources and synchrotron light sources. Since UVC extends to 100 nm, there is some overlap in the terms.

Electron spectroscopy refers to a group formed by techniques based on the analysis of the energies of emitted electrons such as photoelectrons and Auger electrons. This group includes X-ray photoelectron spectroscopy (XPS), which also known as Electron Spectroscopy for Chemical Analysis (ESCA), Electron energy loss spectroscopy (EELS), Ultraviolet photoelectron spectroscopy (UPS), and Auger electron spectroscopy (AES). These analytical techniques are used to identify and determine the elements and their electronic structures from the surface of a test sample. Samples can be solids, gases or liquids.

X-ray absorption near edge structure (XANES), also known as near edge X-ray absorption fine structure (NEXAFS), is a type of absorption spectroscopy that indicates the features in the X-ray absorption spectra (XAS) of condensed matter due to the photoabsorption cross section for electronic transitions from an atomic core level to final states in the energy region of 50–100 eV above the selected atomic core level ionization energy, where the wavelength of the photoelectron is larger than the interatomic distance between the absorbing atom and its first neighbour atoms.

<span class="mw-page-title-main">Characterization (materials science)</span> Study of material structure and properties

Characterization, when used in materials science, refers to the broad and general process by which a material's structure and properties are probed and measured. It is a fundamental process in the field of materials science, without which no scientific understanding of engineering materials could be ascertained. The scope of the term often differs; some definitions limit the term's use to techniques which study the microscopic structure and properties of materials, while others use the term to refer to any materials analysis process including macroscopic techniques such as mechanical testing, thermal analysis and density calculation. The scale of the structures observed in materials characterization ranges from angstroms, such as in the imaging of individual atoms and chemical bonds, up to centimeters, such as in the imaging of coarse grain structures in metals.

<span class="mw-page-title-main">Angle-resolved photoemission spectroscopy</span> Experimental technique to determine the distribution of electrons in solids

Angle-resolved photoemission spectroscopy (ARPES) is an experimental technique used in condensed matter physics to probe the allowed energies and momenta of the electrons in a material, usually a crystalline solid. It is based on the photoelectric effect, in which an incoming photon of sufficient energy ejects an electron from the surface of a material. By directly measuring the kinetic energy and emission angle distributions of the emitted photoelectrons, the technique can map the electronic band structure and Fermi surfaces. ARPES is best suited for the study of one- or two-dimensional materials. It has been used by physicists to investigate high-temperature superconductors, graphene, topological materials, quantum well states, and materials exhibiting charge density waves.

Ultraviolet photoelectron spectroscopy (UPS) refers to the measurement of kinetic energy spectra of photoelectrons emitted by molecules which have absorbed ultraviolet photons, in order to determine molecular orbital energies in the valence region.

Laser-based angle-resolved photoemission spectroscopy is a form of angle-resolved photoemission spectroscopy that uses a laser as the light source. Photoemission spectroscopy is a powerful and sensitive experimental technique to study surface physics. It is based on the photoelectric effect originally observed by Heinrich Hertz in 1887 and later explained by Albert Einstein in 1905 that when a material is shone by light, the electrons can absorb photons and escape from the material with the kinetic energy: , where is the incident photon energy, the work function of the material. Since the kinetic energy of ejected electrons are highly associated with the internal electronic structure, by analyzing the photoelectron spectroscopy one can realize the fundamental physical and chemical properties of the material, such as the type and arrangement of local bonding, electronic structure and chemical composition.

Photoelectrochemical processes are processes in photoelectrochemistry; they usually involve transforming light into other forms of energy. These processes apply to photochemistry, optically pumped lasers, sensitized solar cells, luminescence, and photochromism.

Photoelectron photoion coincidence spectroscopy (PEPICO) is a combination of photoionization mass spectrometry and photoelectron spectroscopy. It is largely based on the photoelectric effect. Free molecules from a gas-phase sample are ionized by incident vacuum ultraviolet (VUV) radiation. In the ensuing photoionization, a cation and a photoelectron are formed for each sample molecule. The mass of the photoion is determined by time-of-flight mass spectrometry, whereas, in current setups, photoelectrons are typically detected by velocity map imaging. Electron times-of-flight are three orders of magnitude smaller than those of ions, which allows electron detection to be used as a time stamp for the ionization event, starting the clock for the ion time-of-flight analysis. In contrast with pulsed experiments, such as REMPI, in which the light pulse must act as the time stamp, this allows to use continuous light sources, e.g. a discharge lamp or a synchrotron light source. No more than several ion–electron pairs are present simultaneously in the instrument, and the electron–ion pairs belonging to a single photoionization event can be identified and detected in delayed coincidence.

<span class="mw-page-title-main">Two-photon photoelectron spectroscopy</span>

Time-resolved two-photon photoelectron (2PPE) spectroscopy is a time-resolved spectroscopy technique which is used to study electronic structure and electronic excitations at surfaces. The technique utilizes femtosecond to picosecond laser pulses in order to first photoexcite an electron. After a time delay, the excited electron is photoemitted into a free electron state by a second pulse. The kinetic energy and the emission angle of the photoelectron are measured in an electron energy analyzer. To facilitate investigations on the population and relaxation pathways of the excitation, this measurement is performed at different time delays.

<span class="mw-page-title-main">Solaris (synchrotron)</span>

SOLARIS is the only synchrotron in Central-Eastern Europe. Built in Poland in 2015, under the auspices of the Jagiellonian University, it is located on the Campus of the 600th Anniversary of the Jagiellonian University Revival, in the southern part of Krakow. It is the central facility of the National Synchrotron Radiation Centre SOLARIS.

Nano Angle-Resolved Photoemission Spectroscopy (Nano-ARPES), is a variant of the experimental technique ARPES. It has the ability to precisely determine the electronic band structure of materials in momentum space with submicron lateral resolution. Due to its demanding experimental setup, this technique is much less extended than ARPES, widely used in condensed matter physics to experimentally determine the electronic properties of a broad range of crystalline materials. Nano-ARPES can access the electronic structure of well-ordered monocrystalline solids with high energy, momentum, and lateral resolution, even if they are nanometric or heterogeneous mesoscopic samples. Nano-ARPES technique is also based on Einstein’s photoelectric effect, being photon-in electron-out spectroscopy, which has converted into an essential tool in studying the electronic structure of nanomaterials, like quantum and low dimensional materials.

References

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  9. Corder, Christopher; Zhao, Peng; Bakalis, Jin; Li, Xinlong; Kershis, Matthew D.; Muraca, Amanda R.; White, Michael G.; Allison, Thomas K. (2018-01-24). "Ultrafast extreme ultraviolet photoemission without space charge". Structural Dynamics. 5 (5): 054301. arXiv: 1801.08124 . doi:10.1063/1.5045578. PMC   6127013 . PMID   30246049.
  10. He, Yu; Vishik, Inna M.; Yi, Ming; Yang, Shuolong; Liu, Zhongkai; Lee, James J.; Chen, Sudi; Rebec, Slavko N.; Leuenberger, Dominik (January 2016). "Invited Article: High resolution angle resolved photoemission with tabletop 11 eV laser". Review of Scientific Instruments. 87 (1): 011301. arXiv: 1509.01311 . Bibcode:2016RScI...87a1301H. doi:10.1063/1.4939759. ISSN   0034-6748. PMID   26827301. S2CID   205211154.
  11. Roberts, F. Sloan; Anderson, Scott L.; Reber, Arthur C.; Khanna, Shiv N. (2015-03-05). "Initial and Final State Effects in the Ultraviolet and X-ray Photoelectron Spectroscopy (UPS and XPS) of Size-Selected Pdn Clusters Supported on TiO2(110)". The Journal of Physical Chemistry C. 119 (11): 6033–6046. doi:10.1021/jp512263w. ISSN   1932-7447.

Further reading