![ARPES - Cu(111) surface state - 21](https://upload.wikimedia.org/wikipedia/commons/b/b4/ARPES_-_Cu%28111%29_surface_state_-_21.22eV_300K.svg)
Angle-resolved photoemission spectroscopy (ARPES) is an experimental technique used in
condensed matter physics
Condensed matter physics is the field of physics that deals with the macroscopic and microscopic physical properties of matter, especially the solid and liquid phases which arise from electromagnetic forces between atoms. More generally, the sub ...
to probe the allowed
energies
In physics, energy (from Ancient Greek: ἐνέργεια, ''enérgeia'', “activity”) is the quantitative property that is transferred to a body or to a physical system, recognizable in the performance of work and in the form of heat ...
and
momenta of the
electrons
The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family,
and are generally thought to be elementary particles because they have no ...
in a material, usually a
crystalline solid
A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macros ...
. It is based on the
photoelectric effect
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 st ...
, in which an incoming
photon
A photon () is an elementary particle that is a quantum of the electromagnetic field, including electromagnetic radiation such as light and radio waves, and the force carrier for the electromagnetic force. Photons are massless, so they always ...
of sufficient energy ejects an electron from the surface of a material. By directly measuring the
kinetic energy
In physics, the kinetic energy of an object is the energy that it possesses due to its motion.
It is defined as the work needed to accelerate a body of a given mass from rest to its stated velocity. Having gained this energy during its accele ...
and emission
angle
In Euclidean geometry, an angle is the figure formed by two Ray (geometry), rays, called the ''Side (plane geometry), sides'' of the angle, sharing a common endpoint, called the ''vertex (geometry), vertex'' of the angle.
Angles formed by two ...
distributions of the emitted photoelectrons, the technique can map the
electronic band structure
In solid-state physics, the electronic band structure (or simply band structure) of a solid describes the range of energy levels that electrons may have within it, as well as the ranges of energy that they may not have (called ''band gaps'' or ' ...
and
Fermi surface In condensed matter physics, the Fermi surface is the surface in reciprocal space which separates occupied from unoccupied electron states at zero temperature. The shape of the Fermi surface is derived from the periodicity and symmetry of the crys ...
s. ARPES is best suited for the study of one- or two-dimensional materials. It has been used by physicists to investigate
high-temperature superconductors
High-temperature superconductors (abbreviated high-c or HTS) are defined as materials that behave as superconductors at temperatures above , the boiling point of liquid nitrogen. The adjective "high temperature" is only in respect to previo ...
,
graphene
Graphene () is an allotrope of carbon consisting of a single layer of atoms arranged in a hexagonal lattice nanostructure. ,
Topological insulator, topological materials,
quantum well states, and materials exhibiting
charge density wave
A charge density wave (CDW) is an ordered quantum fluid of electrons in a linear chain compound or layered crystal. The electrons within a CDW form a standing wave pattern and sometimes collectively carry an electric current. The electrons in such ...
s.
ARPES systems consist of a monochromatic light source to deliver a narrow beam of photons, a sample holder connected to a
manipulator used to position the sample of a material, and an
electron spectrometer. The equipment is contained within an
ultra-high vacuum
Ultra-high vacuum (UHV) is the vacuum regime characterised by pressures lower than about . UHV conditions are created by pumping the gas out of a UHV chamber. At these low pressures the mean free path of a gas molecule is greater than approximately ...
(UHV) environment, which protects the sample and prevents
scattering of the emitted electrons. After being dispersed along two perpendicular directions with respect to kinetic energy and emission angle, the electrons are directed to a
detector
A sensor is a device that produces an output signal for the purpose of sensing a physical phenomenon.
In the broadest definition, a sensor is a device, module, machine, or subsystem that detects events or changes in its environment and sends ...
and counted to provide ARPES spectra—slices of the band structure along one momentum direction. Some ARPES instruments can extract a portion of the electrons alongside the detector to measure the
polarization of their spin.
Principle
Electrons in crystalline solids can only populate states of certain energies and momenta, others being forbidden by
quantum mechanics
Quantum mechanics is a fundamental theory in physics that provides a description of the physical properties of nature at the scale of atoms and subatomic particles. It is the foundation of all quantum physics including quantum chemistry, ...
. They form a continuum of states known as the band structure of the solid. The band structure determines if a material is an
insulator, a
semiconductor
A semiconductor is a material which has an electrical resistivity and conductivity, electrical conductivity value falling between that of a electrical conductor, conductor, such as copper, and an insulator (electricity), insulator, such as glas ...
, or a
metal
A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...
, how it conducts
electricity
Electricity is the set of physical phenomena associated with the presence and motion of matter that has a property of electric charge. Electricity is related to magnetism, both being part of the phenomenon of electromagnetism, as described ...
and in which directions it conducts best, or how it behaves in a
magnetic field
A magnetic field is a vector field that describes the magnetic influence on moving electric charges, electric currents, and magnetic materials. A moving charge in a magnetic field experiences a force perpendicular to its own velocity and to ...
.
Angle-resolved photoemission spectroscopy determines the band structure and helps understand the scattering processes and interactions of electrons with other constituents of a material. It does so by observing the electrons ejected by photons from their initial energy and momentum state into the state whose energy is by the energy of the photon higher than the initial energy, and higher than the binding energy of the electron in the solid. In the process, the electron's momentum remains virtually intact, except for its component perpendicular to the material's surface. The band structure is thus translated from energies at which the electrons are bound within the material, to energies that free them from the crystal binding and enable their detection outside of the material.
By measuring the freed electron's kinetic energy, its velocity and absolute momentum can be calculated. By measuring the emission angle with respect to the surface normal, ARPES can also determine the two in-plane components of momentum that are in the photoemission process preserved. In many cases, if needed, the third component can be reconstructed as well.
Instrumentation
![ARPES setup - ultraviolet source - sample holder - electron analyzer](https://upload.wikimedia.org/wikipedia/commons/2/24/ARPES_setup_-_ultraviolet_source_-_sample_holder_-_electron_analyzer.svg)
A typical instrument for angle-resolved photoemission consists of a light source, a sample holder attached to a manipulator, and an electron spectrometer. These are all part of an ultra-high vacuum system that provides the necessary protection from
adsorbate
Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the ''adsorbate'' on the surface of the ''adsorbent''. This process differs from absorption, in which a f ...
s for the sample surface and eliminates scattering of the electrons on their way to the analyzer.
[ ]
The light source delivers to the sample a
monochromatic, usually
polarized, focused, high-intensity beam of ~10
12 photons/s with a few
meV
In physics, an electronvolt (symbol eV, also written electron-volt and electron volt) is the measure of an amount of kinetic energy gained by a single electron accelerating from rest through an electric potential difference of one volt in vacu ...
energy spread.
Light sources range from compact
noble-gas discharge UV lamps and
radio-frequency plasma
Radio frequency (RF) is the oscillation rate of an alternating electric current or voltage or of a magnetic, electric or electromagnetic field or mechanical system in the frequency range from around to around . This is roughly between the u ...
sources (10–40 eV),
ultraviolet
laser
A laser is a device that emits light through a process of optical amplification based on the stimulated emission of electromagnetic radiation. The word "laser" is an acronym for "light amplification by stimulated emission of radiation". The fir ...
s (5–11 eV) to
synchrotron insertion device
An insertion device (ID) is a component in modern synchrotron light sources, so called because they are "inserted" into accelerator tracks. They are periodic magnetic structures that stimulate highly brilliant, forward-directed synchrotron radiati ...
s that are optimized for different parts of the
electromagnetic spectrum
The electromagnetic spectrum is the range of frequencies (the spectrum) of electromagnetic radiation and their respective wavelengths and photon energies.
The electromagnetic spectrum covers electromagnetic waves with frequencies ranging from ...
(from 10 eV in the ultraviolet to 1000 eV X-rays).
![Sample holder in ultrahigh vacuum chamber for angle-resolved photoemission spectroscopy](https://upload.wikimedia.org/wikipedia/commons/e/e7/Sample_holder_in_ultrahigh_vacuum_chamber_for_angle-resolved_photoemission_spectroscopy.jpg)
The sample holder accommodates samples of crystalline materials, the electronic properties of which are to be investigated. It facilitates their insertion into the vacuum, cleavage to expose clean surfaces, and precise positioning. The holder works as the extension of a manipulator that makes translations along three axes, and rotations to adjust the sample's polar, azimuth and tilt angles possible. The holder has sensors or
thermocouple
A thermocouple, also known as a "thermoelectrical thermometer", is an electrical device consisting of two dissimilar electrical conductors forming an electrical junction. A thermocouple produces a temperature-dependent voltage as a result of the ...
s for precise temperature measurement and control. Cooling to temperatures as low as 1
kelvin
The kelvin, symbol K, is the primary unit of temperature in the International System of Units (SI), used alongside its prefixed forms and the degree Celsius. It is named after the Belfast-born and University of Glasgow-based engineer and phys ...
is provided by
cryogenic liquefied gases,
cryocooler
A refrigerator designed to reach cryogenic temperatures (below ) is often called a cryocooler. The term is most often used for smaller systems, typically table-top size, with input powers less than about 20 kW. Some can have input powers as l ...
s, and
dilution refrigerator
A 3He/4He dilution refrigerator is a cryogenic device that provides continuous cooling to temperatures as low as 2 mK, with no moving parts in the low-temperature region. The cooling power is provided by the heat of mixing of the Hel ...
s.
Resistive heaters attached to the holder provide heating up to a few hundred °C, whereas miniature backside electron-beam bombardment devices can yield sample temperatures as high as 2000 °C. Some holders can also have attachments for light beam focusing and
calibration
In measurement technology and metrology, calibration is the comparison of measurement values delivered by a device under test with those of a calibration standard of known accuracy. Such a standard could be another measurement device of know ...
.
The electron spectrometer disperses the electrons along two spatial directions in accordance with their kinetic energy and their emission angle when exiting the sample; in other words, it provides mapping of different energies and emission angles to different positions on the detector. In the type most commonly used, the
hemispherical electron energy analyzer
A hemispherical electron energy analyzer or hemispherical deflection analyzer is a type of electron energy spectrometer generally used for applications where high energy resolution is needed—different varieties of electron spectroscopy such as an ...
, the electrons first pass through an
electrostatic lens An electrostatic lens is a device that assists in the transport of charged particles. For instance, it can guide electrons emitted from a sample to an electron analyzer, analogous to the way an optical lens assists in the transport of light in an o ...
. The lens has a narrow
focal spot that is located some 40 mm from the entrance to the lens. It further enhances the angular spread of the electron plume, and serves it with adjusted energy to the narrow entrance slit of the energy dispersing part.
![Electron spectrometer for ARPES, working principle](https://upload.wikimedia.org/wikipedia/commons/7/70/Electron_spectrometer_for_ARPES%2C_working_principle.svg)
The energy dispersion is carried out for a narrow range of energies around the so-called pass energy in the direction perpendicular to the direction of angular dispersion, that is perpendicular to the cut of a ~25 mm long and ⪆0.1 mm wide slit. The angular dispersion previously achieved around the axis of the cylindrical lens is only preserved along the slit, and depending on the ''lens mode'' and the desired
angular resolution is usually set to amount to ±3°, ±7° or ±15°.
The hemispheres of the energy analyzer are kept at constant
voltage
Voltage, also known as electric pressure, electric tension, or (electric) potential difference, is the difference in electric potential between two points. In a static electric field, it corresponds to the work needed per unit of charge to m ...
s so that the central trajectory is followed by electrons that have the kinetic energy equal to the set pass energy; those with higher or lower energies end up closer to the outer or the inner hemisphere at the other end of the analyzer. This is where an electron
detector
A sensor is a device that produces an output signal for the purpose of sensing a physical phenomenon.
In the broadest definition, a sensor is a device, module, machine, or subsystem that detects events or changes in its environment and sends ...
is mounted, usually in the form of a 40 mm
microchannel plate paired with a
fluorescent
Fluorescence is the emission of light by a substance that has absorbed light or other electromagnetic radiation. It is a form of luminescence. In most cases, the emitted light has a longer wavelength, and therefore a lower photon energy, tha ...
screen. Electron detection events are recorded using an outside camera and are counted in hundreds of thousands of separate angle vs. kinetic energy channels. Some instruments are additionally equipped with an electron extraction tube at one side of the detector to enable the measurement of the electrons'
spin polarization
Spin polarization is the degree to which the spin, i.e., the intrinsic angular momentum of elementary particles, is aligned with a given direction. This property may pertain to the spin, hence to the magnetic moment, of conduction electrons in fe ...
.
Modern analyzers are capable of resolving the electron emission angles as low as 0.1°. Energy resolution is pass-energy and slit-width dependent so the operator chooses between measurements with ultrahigh resolution and low intensity (<1 meV at 1 eV pass energy) or poorer energy resolutions of 10 or more meV at higher pass energies and with wider slits resulting in higher signal intensity. The instrument's resolution shows up as artificial broadening of the spectral features: a
Fermi energy
The Fermi energy is a concept in quantum mechanics usually referring to the energy difference between the highest and lowest occupied single-particle states in a quantum system of non-interacting fermions at absolute zero temperature.
In a Fermi ga ...
cutoff wider than expected from the sample's temperature alone, and the theoretical electron's spectral function
convolved
In mathematics (in particular, functional analysis), convolution is a mathematical operation on two functions ( and ) that produces a third function (f*g) that expresses how the shape of one is modified by the other. The term ''convolution'' ...
with the instrument's resolution function in both energy and momentum/angle.
Sometimes, instead of hemispherical analyzers,
time-of-flight
Time of flight (ToF) is the measurement of the time taken by an object, particle or wave (be it acoustic, electromagnetic, etc.) to travel a distance through a medium. This information can then be used to measure velocity or path length, or as a w ...
analyzers are used. These, however, require pulsed photon sources and are most common in
laser-based ARPES labs.
Basic relations
Angle-resolved photoemission spectroscopy is a potent refinement of ordinary
photoemission spectroscopy
Photoemission spectroscopy (PES), also known as photoelectron spectroscopy, 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 th ...
. Light of frequency
made up of
photons
A photon () is an elementary particle that is a quantum of the electromagnetic field, including electromagnetic radiation such as light and radio waves, and the force carrier for the electromagnetic force. Photons are massless, so they alway ...
of energy
, where
is
Planck's constant, is used to stimulate the transitions of electrons from occupied to unoccupied
electronic state
A quantum mechanical system or particle that is bound—that is, confined spatially—can only take on certain discrete values of energy, called energy levels. This contrasts with classical particles, which can have any amount of energy. The t ...
of the solid. If a photon's energy is greater than the
binding energy
In physics and chemistry, binding energy is the smallest amount of energy required to remove a particle from a system of particles or to disassemble a system of particles into individual parts. In the former meaning the term is predominantly use ...
of an electron
, the electron will eventually leave the solid without being
scattered, and be observed with
kinetic energy
In physics, the kinetic energy of an object is the energy that it possesses due to its motion.
It is defined as the work needed to accelerate a body of a given mass from rest to its stated velocity. Having gained this energy during its accele ...
:
at angle
relative to the
surface normal
In geometry, a normal is an object such as a line, ray, or vector that is perpendicular to a given object. For example, the normal line to a plane curve at a given point is the (infinite) line perpendicular to the tangent line to the curve at ...
, both characteristic of the studied material.
Electron emission intensity maps measured by ARPES as a function of
and
are representative of the intrinsic distribution of electrons in the solid expressed in terms of their binding energy
and the
Bloch wave vector , which is related to the electrons'
crystal momentum and
group velocity
The group velocity of a wave is the velocity with which the overall envelope shape of the wave's amplitudes—known as the ''modulation'' or ''envelope'' of the wave—propagates through space.
For example, if a stone is thrown into the middl ...
. In the photoemission process, the Bloch wave vector is linked to the measured electron's momentum
, where the magnitude of the momentum
is given by the equation
:
.
As the electron crosses the surface barrier, losing part of its energy due to the
surface work function,
[For simplicity reasons, the work function has been included in the expression for as part of (true meaning of the binding energy). In practice, however, the binding energy is expressed relative to a material's Fermi level, which can be read off of an ARPES spectrum. The work function is the difference between the Fermi level and the ''vacuum level'' where electrons are free.] only the component of
that is parallel to the surface,
, is preserved. From ARPES, therefore, only
is known for certain and its magnitude is given by
:
.
Here,
is the
reduced Planck constant
The Planck constant, or Planck's constant, is a fundamental physical constant of foundational importance in quantum mechanics. The constant gives the relationship between the energy of a photon and its frequency, and by the mass-energy equivale ...
.
Because of incomplete determination of the three-dimensional wave vector, and the pronounced
surface sensitivity of the elastic photoemission process, ARPES is best suited to the complete characterization of the band structure in ordered
low-dimensional systems such as
two-dimensional materials
In materials science, the term single-layer materials or 2D materials refers to crystalline solids consisting of a single layer of atoms. These materials are promising for some applications but remain the focus of research. Single-layer materials ...
,
ultrathin films, and
nanowire
A nanowire is a nanostructure in the form of a wire with the diameter of the order of a nanometre (10−9 metres). More generally, nanowires can be defined as structures that have a thickness or diameter constrained to tens of nanometers or less ...
s. When it is used for three-dimensional materials, the perpendicular component of the wave vector
is usually approximated, with the assumption of a
parabolic, free-electron-like final state with the bottom at energy
. This gives:
:
.
The inner potential
is an unknown parameter a priori. For d-electron systems, experiment suggest that
~15 eV. In general, the inner potential is estimated through a series of photon energy-dependent experiments, especially in photoemission band mapping experiments.
Fermi surface mapping
Electron analyzers that use a slit to prevent the mixing of momentum and energy channels are only capable of taking angular maps along one direction. To take maps over energy and two-dimensional momentum space, either the sample is rotated in the proper direction so that the slit receives electrons from adjacent emission angles, or the electron plume is steered inside the electrostatic lens with the sample fixed. The slit width will determine the step size of the angular scans. For example, when a ±15° plume dispersed around the axis of the lens is served to a 30 mm long and 1 mm wide slit, each millimeter of the slit receives a 1° portion—in both directions; but at the detector the other direction is interpreted as the electron's kinetic energy and the emission angle information is lost. This averaging determines the maximal angular resolution of the scan in the direction perpendicular to the slit: with a 1 mm slit, steps coarser than 1° lead to missing data, and finer steps to overlaps. Modern analyzers have slits as narrow as 0.05 mm. The energy-angle-angle maps are usually further processed to give ''energy''-''k''
x-''k''
y maps, and sliced in such a way to display constant energy surfaces in the band structure and, most importantly, the
Fermi surface In condensed matter physics, the Fermi surface is the surface in reciprocal space which separates occupied from unoccupied electron states at zero temperature. The shape of the Fermi surface is derived from the periodicity and symmetry of the crys ...
map when they are cut near the Fermi level.
Emission angle to momentum conversion
ARPES spectrometer measures angular dispersion in a slice α along its slit. Modern analyzers record these angles simultaneously, in their reference frame, typically in the range of ±15°. To map the band structure over a two-dimensional momentum space, the sample is rotated while keeping the light spot on the surface fixed. The most common choice is to change the
polar angle θ around the axis that is parallel to the slit and adjust the
tilt
Tilt may refer to:
Music
* Tilt (American band), a punk rock group, formed in 1992
* Tilt (British band), an electronic music group, formed in 1993
* Tilt (Polish band), a rock band, formed in 1979
Albums
* ''Tilt'' (Cozy Powell album), 1981
* ...
τ or
azimuth
An azimuth (; from ar, اَلسُّمُوت, as-sumūt, the directions) is an angular measurement in a spherical coordinate system. More specifically, it is the horizontal angle from a cardinal direction, most commonly north.
Mathematicall ...
φ so emission from a particular region of the
Brillouin zone
In mathematics and solid state physics, the first Brillouin zone is a uniquely defined primitive cell in reciprocal space. In the same way the Bravais lattice is divided up into Wigner–Seitz cells in the real lattice, the reciprocal lattice ...
can be reached.
The momentum components of the electrons can be expressed in terms of the quantities measured in the reference frame of the analyzer as
: