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In materials science, a single crystal (or single-crystal
solid Solid is one of the four fundamental states of matter (the others being liquid, gas, and plasma). The molecules in a solid are closely packed together and contain the least amount of kinetic energy. A solid is characterized by structur ...
or monocrystalline solid) is a material in which the
crystal lattice In geometry and crystallography, a Bravais lattice, named after , is an infinite array of discrete points generated by a set of discrete translation operations described in three dimensional space by : \mathbf = n_1 \mathbf_1 + n_2 \mathbf_2 + n ...
of the entire sample is continuous and unbroken to the edges of the sample, with no
grain boundaries In materials science, a grain boundary is the interface between two grains, or crystallites, in a polycrystalline material. Grain boundaries are two-dimensional defects in the crystal structure, and tend to decrease the electrical and therma ...
.RIWD. "Reade Advanced Materials – Single Crystals". ''www.reade.com''. Retrieved 2021-02-28. The absence of the defects associated with grain boundaries can give monocrystals unique properties, particularly mechanical, optical and electrical, which can also be
anisotropic Anisotropy () is the property of a material which allows it to change or assume different properties in different directions, as opposed to isotropy. It can be defined as a difference, when measured along different axes, in a material's physic ...
, depending on the type of
crystallographic Crystallography is the experimental science of determining the arrangement of atoms in crystalline solids. Crystallography is a fundamental subject in the fields of materials science and solid-state physics (condensed matter physics). The wor ...
structure. These properties, in addition to making some gems precious, are industrially used in technological applications, especially in optics and electronics. Because
entropic Entropy is a scientific concept, as well as a measurable physical property, that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynam ...
effects favor the presence of some imperfections in the microstructure of solids, such as
impurities In chemistry and materials science, impurities are chemical substances inside a confined amount of liquid, gas, or solid, which differ from the chemical composition of the material or compound. Firstly, a pure chemical should appear thermodynami ...
, inhomogeneous strain and crystallographic defects such as
dislocation In materials science, a dislocation or Taylor's dislocation is a linear crystallographic defect or irregularity within a crystal structure that contains an abrupt change in the arrangement of atoms. The movement of dislocations allow atoms to s ...
s, perfect single crystals of meaningful size are exceedingly rare in nature. The necessary laboratory conditions often add to the cost of production. On the other hand, imperfect single crystals can reach enormous sizes in nature: several
mineral In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid chemical compound with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. (2 ...
species such as
beryl Beryl ( ) is a mineral composed of beryllium aluminium silicate with the chemical formula Be3Al2Si6O18. Well-known varieties of beryl include emerald and aquamarine. Naturally occurring, hexagonal crystals of beryl can be up to several ...
,
gypsum Gypsum is a soft sulfate mineral composed of calcium sulfate dihydrate, with the chemical formula . It is widely mined and is used as a fertilizer and as the main constituent in many forms of plaster, blackboard or sidewalk chalk, and drywa ...
and
feldspar Feldspars are a group of rock-forming aluminium tectosilicate minerals, also containing other cations such as sodium, calcium, potassium, or barium. The most common members of the feldspar group are the ''plagioclase'' (sodium-calcium) felds ...
s are known to have produced crystals several meters across."Pure Element Single Crystals – Alfa Chemistry". ''www.alfa-chemistry.com''. Retrieved 2021-02-28. The opposite of a single crystal is an amorphous structure where the atomic position is limited to short-range order only."4.1: Introduction". ''Engineering LibreTexts''. 2019-02-08. Retrieved 2021-02-28. In between the two extremes exist ''
polycrystalline A crystallite is a small or even microscopic crystal which forms, for example, during the cooling of many materials. Crystallites are also referred to as grains. Bacillite is a type of crystallite. It is rodlike with parallel longulites. Stru ...
'', which is made up of a number of smaller crystals known as ''
crystallite A crystallite is a small or even microscopic crystal which forms, for example, during the cooling of many materials. Crystallites are also referred to as grains. Bacillite is a type of crystallite. It is rodlike with parallel longulites. Stru ...
s'', and ''
paracrystalline In materials science, paracrystalline materials are defined as having short- and medium-range ordering in their lattice (similar to the liquid crystal phases) but lacking crystal-like long-range ordering at least in one direction. Origin and ...
'' phases."DoITPoMS – TLP Library Atomic Scale Structure of Materials". ''www.doitpoms.ac.uk''. Retrieved 2021-02-28. Single crystals will usually have distinctive plane faces and some symmetry, where the angles between the faces will dictate its ideal shape. Gemstones are often single crystals artificially cut along crystallographic planes to take advantage of refractive and reflective properties.


Production methods

Although current methods are extremely sophisticated with modern technology, the origins of crystal growth can be traced back to salt purification by crystallization in 2500 BCE. A more advanced method using an aqueous solution was started in 1600 CE while the melt and vapor methods began around 1850 CE. Basic crystal growth methods can be separated into four categories based on what they are artificially grown from: melt, solid, vapor, and solution. Specific techniques to produce large single crystals (aka
boules ''Boules'' () is a collective name for a wide range of games similar to bowls and bocce (In French: jeu or jeux, in Croatian: boćanje and in Italian: gioco or giochi) in which the objective is to throw or roll heavy balls (called in France, ...
) include the Czochralski process (CZ), Floating zone (or Zone Movement), and the
Bridgman technique Bridgman is a surname, and may refer to: * David Bridgman, Australian architect * Elijah Coleman Bridgman (1801–1861), American missionary in China * Frederick Arthur Bridgman (1847-1928), American artist * George Bridgman (1865-1943), anatomis ...
. Dr. Teal and Dr. Little of Bell Telephone Laboratories were the first to use the Czochralski method to create Ge and Si single crystals. Other methods of crystallization may be used, depending on the physical properties of the substance, including
hydrothermal synthesis Hydrothermal synthesis includes the various techniques of crystallizing substances from high-temperature aqueous solutions at high vapor pressures; also termed "hydrothermal method". The term " hydrothermal" is of geologic origin. Geochemists and ...
, sublimation, or simply solvent-based crystallization. For example, a modified
Kyropoulos method The Kyropoulos method, KY method, or Kyropoulos technique, is a method of bulk crystal growth used to obtain single crystals. The largest application of the Kyropoulos method is to grow large boules of single crystal sapphire used to produce s ...
can be used to grow high quality 300 kg sapphire single crystals.Zalozhny, Eugene (Jul 13th, 2015). "Monocrystal enables high-volume LED and optical applications with 300-kg KY sapphire crystals". ''LED's Magazine''. Retrieved February 27, 2021. The
Verneuil method The Verneuil method (or Verneuil process or Verneuil technique), also called flame fusion, was the first commercially successful method of manufacturing synthetic gemstones, developed in the late 1883 by the French chemist Auguste Verneuil. It i ...
, also called the flame-fusion method, was used in the early 1900s to make rubies before CZ. The diagram on the right illustrates most of the conventional methods. There have been new breakthroughs such as chemical vapor depositions (CVD) along with different variations and tweaks to the existing methods. These are not shown in the diagram. In the case of metal single crystals, fabrication techniques also include
epitaxy Epitaxy refers to a type of crystal growth or material deposition in which new crystalline layers are formed with one or more well-defined orientations with respect to the crystalline seed layer. The deposited crystalline film is called an epit ...
and abnormal grain growth in solids. Epitaxy is used to deposit very thin (micrometer to nanometer scale) layers of the same or different materials on the surface of an existing single crystal. Applications of this technique lie in the areas of semiconductor production, with potential uses in other nanotechnological fields and catalysis.


Applications


Semiconductor industry

One of the most used single crystals is that of Silicon in the semiconductor industry. The four main production methods for semiconductor single crystals are from metallic solutions:
liquid phase epitaxy Epitaxy refers to a type of crystal growth or material deposition in which new crystalline layers are formed with one or more well-defined orientations with respect to the crystalline seed layer. The deposited crystalline film is called an epi ...
(LPE), liquid phase electroepitaxy (LPEE), the traveling heater method (THM), and liquid phase diffusion (LPD). However, there are many other single crystals besides inorganic single crystals capable semiconducting, including single-crystal organic semiconductors.
Monocrystalline silicon Monocrystalline silicon, more often called single-crystal silicon, in short mono c-Si or mono-Si, is the base material for silicon-based discrete components and integrated circuits used in virtually all modern electronic equipment. Mono-Si also s ...
used in the fabrication of semiconductors and
photovoltaics Photovoltaics (PV) is the conversion of light into electricity using semiconducting materials that exhibit the photovoltaic effect, a phenomenon studied in physics, photochemistry, and electrochemistry. The photovoltaic effect is commercially ...
is the greatest use of single-crystal technology today. In photovoltaics, the most efficient crystal structure will yield the highest light-to-electricity conversion. On the
quantum In physics, a quantum (plural quanta) is the minimum amount of any physical entity ( physical property) involved in an interaction. The fundamental notion that a physical property can be "quantized" is referred to as "the hypothesis of quantizat ...
scale that
microprocessor A microprocessor is a computer processor where the data processing logic and control is included on a single integrated circuit, or a small number of integrated circuits. The microprocessor contains the arithmetic, logic, and control circ ...
s operate on, the presence of grain boundaries would have a significant impact on the functionality of
field effect transistor The field-effect transistor (FET) is a type of transistor that uses an electric field to control the flow of current in a semiconductor. FETs (JFETs or MOSFETs) are devices with three terminals: ''source'', ''gate'', and ''drain''. FETs contro ...
s by altering local electrical properties. Therefore, microprocessor fabricators have invested heavily in facilities to produce large single crystals of silicon. The Czochralski method and floating zone are popular methods for the growth of Silicon crystals. Other
inorganic In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as ''inorganic chemist ...
semiconducting single crystals include GaAs, GaP, GaSb, Ge, InAs, InP, InSb, CdS, CdSe, CdTe, ZnS, ZnSe, and ZnTe. Most of these can also be tuned with various doping for desired properties. Single-crystal
graphene Graphene () is an allotrope of carbon consisting of a Single-layer materials, single layer of atoms arranged in a hexagonal lattice nanostructure.
is also highly desired for applications in electronics and optoelectronics with its large carrier mobility and high thermal conductivity, and remains a topic of fervent research. One of the main challenges has been growing uniform single crystals of bilayer or multilayer graphene over large areas; epitaxial growth and the new CVD (mentioned above) are among the new promising methods under investigation. Organic semiconducting single crystals are different from the inorganic crystals. The weak intermolecular bonds mean lower melting temperatures, and higher vapor pressures and greater solubility. For single crystals to grow, the purity of the material is crucial and the production of organic materials usually require many steps to reach the necessary purity. Extensive research is being done to look for materials that are thermally stable with high charge-carrier mobility. Past discoveries include naphthalene, tetracene, and 9,10-diphenylanthacene (DPA). Triphenylamine derivatives have shown promise, and recently in 2021, the single-crystal structure of α-phenyl-4′-(diphenylamino)stilbene (TPA) grown using the solution method exhibited even greater potential for semiconductor use with its anistropic hole transport property.


Optical application

Single crystals have unique physical properties due to being a single grain with molecules in a strict order and no grain boundaries. This includes optical properties, and single crystals of silicon is also used as optical windows because of its transparency at specific Infrared, infrared (IR) wavelengths, making it very useful for some instruments.
Sapphire Sapphire is a precious gemstone, a variety of the mineral corundum, consisting of aluminium oxide () with trace amounts of elements such as iron, titanium, chromium, vanadium, or magnesium. The name sapphire is derived via the Latin "sa ...
s: Better known as the alpha phase of aluminum oxide (Al2O3) by scientists, sapphire single crystals are widely used in hi-tech engineering. It can be grown from gaseous, solid, or solution phases. The diameter of the crystals resulting from the growth method are important when considering electronic uses after. They are used for
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 ...
s and
nonlinear optics Nonlinear optics (NLO) is the branch of optics that describes the behaviour of light in ''nonlinear media'', that is, media in which the polarization density P responds non-linearly to the electric field E of the light. The non-linearity is typic ...
. Some notable uses are as in the window of a biometric fingerprint reader, optical disks for long-term data storage, and X-ray interferometer.
Indium Phosphide Indium phosphide (InP) is a binary semiconductor composed of indium and phosphorus. It has a face-centered cubic (" zincblende") crystal structure, identical to that of GaAs and most of the III-V semiconductors. Manufacturing Indium phosphide ...
: These single crystals are particularly appropriate for combining optoelectronics with high-speed electronics in the form of optical fiber with its large-diameter substrates. Other photonic devices include lasers, photodetectors, avalanche photo diodes, optical modulators and amplifiers, signal processing, and both optoelectronic and photonic integrated circuits.
Germanium Germanium is a chemical element with the symbol Ge and atomic number 32. It is lustrous, hard-brittle, grayish-white and similar in appearance to silicon. It is a metalloid in the carbon group that is chemically similar to its group neighbors ...
: This was the material in the first transistor invented by Bardeen, Brattain, and Shockley in 1947. It is used in some gamma-ray detectors and infrared optics. Now it has become the focus of ultrafast electronic devices for its intrinsic carrier mobility.
Arsenide In chemistry, an arsenide is a compound of arsenic with a less electronegative element or elements. Many metals form binary compounds containing arsenic, and these are called arsenides. They exist with many stoichiometries, and in this respect a ...
: Arsenide III can be combined with various elements such as B, Al, Ga, and In, with the GaAs compound being in high demand for wafers.
Cadmium Telluride Cadmium telluride (CdTe) is a stable crystalline compound formed from cadmium and tellurium. It is mainly used as the semiconducting material in cadmium telluride photovoltaics and an infrared optical window. It is usually sandwiched with ca ...
: CdTe crystals have several applications as substrates for IR imaging, electrooptic devices, and
solar cells A solar cell, or photovoltaic cell, is an electronic device that converts the energy of light directly into electricity by the photovoltaic effect, which is a physical and chemical phenomenon.
. By alloying CdTe and ZnTe together room-temperature X-ray and gamma-ray detectors can be made.


Electrical conductors

Metals can surprisingly be produced in single-crystal form and provide a means to understand the ultimate performance of metallic conductors. It is vital for understanding the basic science such as catalytic chemistry, surface physics, electrons, and
monochromator A monochromator is an optical device that transmits a mechanically selectable narrow band of wavelengths of light or other radiation chosen from a wider range of wavelengths available at the input. The name is from the Greek roots ''mono-'', ...
s. Production of metallic single crystals have the highest quality requirements and are grown, or pulled, in the form of rods. Certain companies can produce specific geometries, grooves, holes, and reference faces along with varying diameters. Of all the metallic elements, silver and copper have the best
conductivity Conductivity may refer to: *Electrical conductivity, a measure of a material's ability to conduct an electric current **Conductivity (electrolytic), the electrical conductivity of an electrolyte in solution ** Ionic conductivity (solid state), ele ...
at room temperature, setting the bar for performance. The size of the market, and vagaries in supply and cost, have provided strong incentives to seek alternatives or find ways to use less of them by improving performance. The conductivity of commercial conductors is often expressed relative to the
International Annealed Copper Standard The International Annealed Copper Standard (IACS) is a standard established in 1914 by the United States Department of Commerce. It is an empirically derived standard value for the electrical conductivity of commercially available copper. Sometime ...
, according to which the purest copper wire available in 1914 measured around 100%. The purest modern copper wire is a better conductor, measuring over 103% on this scale. The gains are from two sources. First, modern copper is more pure. However, this avenue for improvement seems at an end. Making the copper purer still makes no significant improvement. Second, annealing and other processes have been improved. Annealing reduces the dislocations and other crystal defects which are sources of resistance. But the resulting wires are still polycrystalline. The grain boundaries and remaining crystal defects are responsible for some residual resistance. This can be quantified and better understood by examining single crystals. As anticipated, single-crystal copper did prove to have better conductivity than polycrystalline copper. However, the single-crystal copper not only became a better conductor than high purity polycrystalline silver, but with prescribed heat and pressure treatment could surpass even single-crystal silver. Although impurities are usually bad for conductivity, a silver single crystal with a small amount of copper substitutions proved to be the best. As of 2009, no single-crystal copper is manufactured on a large scale industrially, but methods of producing very large individual crystal sizes for copper conductors are exploited for high performance electrical applications. These can be considered meta-single crystals with only a few crystals per meter of length.


Single-crystal turbine blades

Another application of single-crystal solids is in materials science in the production of high strength materials with low thermal
creep Creep, Creeps or CREEP may refer to: People * Creep, a creepy person Politics * Committee for the Re-Election of the President (CRP), mockingly abbreviated as CREEP, an fundraising organization for Richard Nixon's 1972 re-election campaign Art ...
, such as .Spittle, Peter
"Gas turbine technology"
''
Rolls-Royce plc Rolls-Royce Holdings plc is a British multinational aerospace and defence company incorporated in February 2011. The company owns Rolls-Royce, a business established in 1904 which today designs, manufactures and distributes power systems for ...
'', 2003. Retrieved: 21 July 2012.
Here, the absence of grain boundaries actually gives a decrease in yield strength, but more importantly decreases the amount of creep which is critical for high temperature, close tolerance part applications.Crown jewels – These crystals are the gems of turbine efficiency
Article on single-crystal turbine blades ''memagazine.com''
Researcher Barry Piearcey found that a right-angle bend at the casting mold would decrease the number of columnar crystals and later, scientist Giamei used this to start the single-crystal structure of the turbine blade.


In research

Single crystals are essential in research especially
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 su ...
and all aspects of materials science such as
surface science Surface science is the study of physical and chemical phenomena that occur at the interface of two phases, including solid– liquid interfaces, solid– gas interfaces, solid–vacuum interfaces, and liquid– gas interfaces. It includes th ...
. The detailed study of the
crystal structure In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions or molecules in a crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric pattern ...
of a material by techniques such as Bragg diffraction and
helium atom scattering Helium atom scattering (HAS) is a surface analysis technique used in materials science. HAS provides information about the surface structure and lattice dynamics of a material by measuring the diffracted atoms from a monochromatic helium beam incid ...
is easier with single crystals because it is possible to study directional dependence of various properties and compare with theoretical predictions. Furthermore, macroscopically averaging techniques such as
angle-resolved photoemission spectroscopy 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 photoele ...
or low-energy electron diffraction are only possible or meaningful on surfaces of single crystals. In
superconductivity Superconductivity is a set of physical properties observed in certain materials where electrical resistance vanishes and magnetic flux fields are expelled from the material. Any material exhibiting these properties is a superconductor. Unlike ...
there have been cases of materials where superconductivity is only seen in single-crystalline specimen. They may be grown for this purpose, even when the material is otherwise only needed in
polycrystalline A crystallite is a small or even microscopic crystal which forms, for example, during the cooling of many materials. Crystallites are also referred to as grains. Bacillite is a type of crystallite. It is rodlike with parallel longulites. Stru ...
form. As such, numerous new materials are being studied in their single-crystal form. The young field of metal-organic-frameworks (MOF's) is one of many which qualify to have single crystals. In January 2021 Dr. Dong and Dr. Feng demonstrated how polycyclic aromatic ligands can be optimized to produce large 2D MOF single crystals of sizes up to 200 μm. This could mean scientists can fabricate single-crystal devices and determine intrinsic electrical conductivity and charge transport mechanism. The field of photodriven transformation can also be involved with single crystals with something called single-crystal-to-single-crystal (SCSC) transformations. These provide direct observation of molecular movement and understanding of mechanistic details. This photoswitching behavior has also been observed in cutting-edge research on intrinsically non-photo-responsive mononuclear lanthanide single-molecule-magnets (SMM).


See also

* Engineering aspects of crystallisation * Fractional crystallization * Laser-heated pedestal growth * Micro-pulling-down * Recrystallization *
Seed crystal A seed crystal is a small piece of single crystal or polycrystal material from which a large crystal of typically the same material is grown in a laboratory. Used to replicate material, the use of seed crystal to promote growth avoids the other ...


References


Further reading


"Small Molecule Crystallization"
(
PDF Portable Document Format (PDF), standardized as ISO 32000, is a file format developed by Adobe in 1992 to present documents, including text formatting and images, in a manner independent of application software, hardware, and operating systems. ...
) at
Illinois Institute of Technology Illinois Institute of Technology (IIT) is a private research university in Chicago, Illinois. Tracing its history to 1890, the present name was adopted upon the merger of the Armour Institute and Lewis Institute in 1940. The university has prog ...
website {{DEFAULTSORT:Single Crystal Crystals