The Kyropoulos method, KY method, or Kyropoulos technique, is a method of bulk

crystal growth A crystal is a solid material whose constituent atoms, molecules, or ions are arranged in an orderly repeating pattern extending in all three spatial dimensions. Crystal growth is a major stage of a crystallization process, and consists of the ...

used to obtain

single crystal In materials science, a single crystal (or single-crystal solid or monocrystalline solid) is a material in which the crystal lattice of the entire sample is continuous and unbroken to the edges of the sample, with no grain boundaries.RIWD. "Re ...

s. The largest application of the Kyropoulos method is to grow large

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, ...

of single crystal sapphire used to produce substrates for the manufacture

gallium nitride Gallium nitride () is a binary III/ V direct bandgap semiconductor commonly used in blue light-emitting diodes since the 1990s. The compound is a very hard material that has a Wurtzite crystal structure. Its wide band gap of 3.4 eV affords ...

-based

LEDs A light-emitting diode (LED) is a semiconductor device that emits light when current flows through it. Electrons in the semiconductor recombine with electron holes, releasing energy in the form of photons. The color of the light (cor ...

, and as a durable optical material.Dobrovinskaya, Elena R., Leonid A. Lytvynov, and Valerian Pishchik. Sapphire: material, manufacturing, applications. Springer Science & Business Media, 2009.

History

The method is named for , who proposed the technique in 1926 as a method to grow brittle alkali halide and

alkali earth metal The alkaline earth metals are six chemical elements in group 2 of the periodic table. They are beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).. The elements have very similar properties: they are all ...

crystals for precision optics. The method was a response to the limited boule sizes attainable by the Czochralski and Verneuil methods at the time. The Kyropoulos method was applied to sapphire crystal growth in the 1970s in the

Soviet Union The Soviet Union,. officially the Union of Soviet Socialist Republics. (USSR),. was a transcontinental country that spanned much of Eurasia from 1922 to 1991. A flagship communist state, it was nominally a federal union of fifteen nationa ...

The method

The feedstock is melted in a

crucible A crucible is a ceramic or metal container in which metals or other substances may be melted or subjected to very high temperatures. While crucibles were historically usually made from clay, they can be made from any material that withstands te ...

. (For sapphire crystal growth, the feedstock is high-purity aluminum oxide—only a few parts per million of impurities—which is then heated above 2100 °C in a

tungsten Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isol ...

molybdenum Molybdenum is a chemical element with the symbol Mo and atomic number 42 which is located in period 5 and group 6. The name is from Neo-Latin ''molybdaenum'', which is based on Ancient Greek ', meaning lead, since its ores were confused with lead ...

crucible.) A precisely oriented

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 ...

is dipped into the molten material. The seed crystal is slowly pulled upwards and may be rotated simultaneously. By precisely controlling the temperature gradients, rate of pulling and rate of temperature decrease, it is possible to produce a large, single-crystal, roughly cylindrical ingot from the melt. In contrast with the Czochralski method, the Kyropoulos technique crystallizes the entire feedstock volume into the boule. The size and aspect ratio of the crucible is close to that of the final crystal, and the crystal grows downward into the crucible, rather than being pulled up and out of the crucible as in the Czochralski method. The upward pulling of the seed is at a much slower rate than the downward growth of the crystal, and serves primarily to shape the meniscus of the solid-liquid

interface Interface or interfacing may refer to: Academic journals * ''Interface'' (journal), by the Electrochemical Society * '' Interface, Journal of Applied Linguistics'', now merged with ''ITL International Journal of Applied Linguistics'' * '' Int ...

via

surface tension Surface tension is the tendency of liquid surfaces at rest to shrink into the minimum surface area possible. Surface tension is what allows objects with a higher density than water such as razor blades and insects (e.g. water striders) t ...

. The growth rate is controlled by slowly decreasing the temperature of the furnace until the entire melt has solidified. Hanging the seed from a weight sensor can provide

feedback Feedback occurs when outputs of a system are routed back as inputs as part of a chain of cause-and-effect that forms a circuit or loop. The system can then be said to ''feed back'' into itself. The notion of cause-and-effect has to be handled ...

to determine the growth rate, although precise measurements are complicated by the changing and imperfect shape of the crystal diameter, the unknown convex shape of the solid-liquid interface, and these features' interaction with buoyant forces and

convection Convection is single or multiphase fluid flow that occurs spontaneously due to the combined effects of material property heterogeneity and body forces on a fluid, most commonly density and gravity (see buoyancy). When the cause of the c ...

within the melt. The Kyropoulos method is characterized by smaller temperature gradients at the crystallization front than the Czochralski method. Like the Czochralski method, the crystal grows free of any external mechanical shaping forces, and thus has few lattice defects and low

internal stress In continuum mechanics, stress is a physical quantity. It is a quantity that describes the magnitude of forces that cause deformation. Stress is defined as ''force per unit area''. When an object is pulled apart by a force it will cause elonga ...

. This process can be performed in an inert atmosphere, such as

argon Argon is a chemical element with the symbol Ar and atomic number 18. It is in group 18 of the periodic table and is a noble gas. Argon is the third-most abundant gas in Earth's atmosphere, at 0.934% (9340 ppmv). It is more than twice a ...

, or under high

vacuum A vacuum is a space devoid of matter. The word is derived from the Latin adjective ''vacuus'' for "vacant" or " void". An approximation to such vacuum is a region with a gaseous pressure much less than atmospheric pressure. Physicists often ...

Advantages

The major advantages include technical simplicity of the process and possibility to grow crystals with large sizes (≥30 cm). The method also shows low dislocation density.

Disadvantages

The most significant disadvantage of the method is an unstable speed of growth which happens due to heat exchange changes incurred by a growing boule size and which are difficult to predict. Due to this problem the crystals are typically grown at very slow speed in order to avoid unnecessary internal defects.

Application

Currently the method is used by several companies around the world to produce

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 ...

for the

electronics The field of electronics is a branch of physics and electrical engineering that deals with the emission, behaviour and effects of electrons using electronic devices. Electronics uses active devices to control electron flow by amplification ...

and optics industries.

Crystal sizes

The sizes of sapphire crystals grown by the Kyropoulos method have increased dramatically since the 1980s. In the mid-2000s sapphire crystals up to 30 kg were developed which could yield 150 mm diameter substrates. By 2017, the largest reported sapphire grown by the Kyropoulos method was 350 kg, and could produce 300 mm diameter substrates. Because of sapphire's

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 ...

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 ...

, the orientation of the cylindrical axis of the boules grown by the Kyropoulos method is perpendicular to the orientation required for deposition of GaN on the LED substrates. This means that cores must be drilled through the sides of the boule before being sliced into wafers. This means the as-grown boules have a significantly larger diameter than the resulting wafers. As of 2017 the leading manufacturers of blue and white LEDs used 150 mm diameter sapphire substrates, with some manufacturers still using 100 mm, and 2 inch substrates.

References

External links

Crystal growth technique summaries
{{DEFAULTSORT:Kyropoulos Process Semiconductor growth Industrial processes Crystals Methods of crystal growth