Single crystal

Crystallization
Concepts
Crystallization · Crystal growth
Recrystallization · Seed crystal
Protocrystalline · Single crystal
Methods and technology
Boules
Bridgman–Stockbarger technique
Czochralski process
Fractional crystallization
Fractional freezing
Hydrothermal synthesis
Laser-heated pedestal growth
Crystal bar process
Fundamentals
Nucleation · Crystal
Crystal structure · Solid

A single crystal 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. The absence of the defects associated with grain boundaries can give monocrystals unique properties, particularly mechanical, optical and electrical, which can also be anisotropic, depending on the type of crystallographic structure. These properties, in addition to making them precious in some gems, are industrially used in technological applications, especially in optics and electronics.

Because entropic effects favor the presence of some imperfections in the microstructure of solids, such as impurities, inhomogeneous strain and crystallographic defects such as dislocations, perfect single crystals of meaningful size are exceedingly rare in nature, and are also difficult to produce in the laboratory, though they can be made under controlled conditions. On the other hand, imperfect single crystals can reach enormous sizes in nature: several mineral species such as beryl, gypsum and feldspars are known to have produced crystals several metres across.

The opposite of a single crystal is an amorphous structure where the atomic position is limited to short range order only. In between the two extremes exist polycrystalline, which is made up of a number of smaller crystals known as crystallites, and paracrystalline phases.

Uses

A single-crystal quartz bar grown by the hydrothermal method
A huge KDP crystal grown from a seed crystal in a supersaturated aqueous solution at LLNL which is to be cut into slices and used on the National Ignition Facility for frequency doubling and tripling.

Semiconductor industry

Single crystal silicon is used in the fabrication of semiconductors. On the quantum scale that microprocessors operate on, the presence of grain boundaries would have a significant impact on the functionality of field effect transistors by altering local electrical properties. Therefore, microprocessor fabricators have invested heavily in facilities to produce large single crystals of silicon.

Optics

Materials engineering

Another application of single crystal solids is in materials science in the production of high strength materials with low thermal creep, such as turbine blades.[1][2] 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.

Electrical conductors

Single crystals provide a means to understand, and perhaps realize, the ultimate performance of metallic conductors.

Of all the metallic elements, silver and copper have the best conductivity at room temperature, so set 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, 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.[3]

Electrical Resistivity ρ for Silver (Ag) / Copper (Cu) Materials at Room Temperature (293 K) [4]
Material ρ (μΩ∙cm) IACS [5]
single-crystal Ag, doped with 3 mol% Cu 1.35 127%
single-crystal Cu, further processed[6] 1.472 117.1%
single-crystal Ag 1.49
single-crystal Cu 1.52 113.4%
high purity Ag wire (polycrystalline) 1.59 108%
high purity Cu wire (polycrystalline) ˃103%

But there were surprises in store (see table). 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. And although impurities are usually bad for conductivity, a silver single-crystal with a small amount of copper substitutions was a better conductor than them all.

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 metre of length.

In research

Single crystals are essential in research especially condensed-matter physics, materials science, surface science etc. The detailed study of the crystal structure of a material by techniques such as Bragg diffraction and helium atom scattering is much easier with monocrystals. Only in single crystals it is possible to study directional dependence of various properties. Furthermore, techniques such as scanning tunneling microscopy are only possible on surfaces of single crystals. In superconductivity 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 form.

Manufacture

In the case of silicon and metal single crystal fabrication the techniques used involve highly controlled and therefore relatively slow crystallization.

Specific techniques to produce large single crystals (aka boules) include the Czochralski process and the Bridgman technique. Other less exotic methods of crystallization may be used, depending on the physical properties of the substance, including hydrothermal synthesis, sublimation, or simply solvent-based crystallization.

A different technology to create single crystalline materials is called epitaxy. As of 2009, this process is used to deposit very thin (micrometre 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.

See also

References

  1. Spittle, Peter. "Gas turbine technology" Rolls-Royce plc, 2003. Retrieved: 21 July 2012.
  2. Crown jewels - These crystals are the gems of turbine efficiency Article on single crystal turbine blades memagazine.com
  3. Cho, Yong Chan; Seunghun Lee, Muhammad Ajmal, Won-Kyung Kim, Chae Ryong Cho, Se-Young Jeong, Jeung Hun Park, Sang Eon Park, Sungkyun Park, Hyuk-Kyu Pak, and Hyoung Chan Kim (March 22, 2010). "Copper Better than Silver: Electrical Resistivity of the Grain-Free Single-Crystal Copper Wire". Crystal Growth & Design. 10: 2780–2784. doi:10.1021/cg1003808. Retrieved 1 June 2011. Cite uses deprecated parameter |coauthors= (help)
  4. Ji Young Kim, Min-Wook Oh, Seunghun Lee, Yong Chan Cho, Jang-Hee Yoon, Geun Woo Lee, Chae-Ryong Cho, Chul Hong Park and Se-Young Jeong (June 26, 2014). "Abnormal drop in electrical resistivity with impurity doping of single-crystal Ag" (PDF). Scientific Reports. 4: 5450. doi:10.1038/srep05450. Retrieved November 14, 2016.
  5. "The International Annealed Copper Standard". Nondestructive Testing Resource Center. The Collaboration for NDT Education, Iowa State University. n.d. Retrieved November 14, 2016.
  6. Muhammad Ajmal, Seunghun Lee, Yong Chan Cho, Su Jae Kim, Sang Eon Park, Chae Ryong Choa and Se-Young Jeong (2012). "Fabrication of the best conductor from single-crystal copper and the contribution of grain boundaries to the Debye temperature". CrystEngComm. 14: 1463–1467. doi:10.1039/C1CE06026K. Retrieved November 14, 2016.

Further reading

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