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Wednesday, April 10, 2019

Boron nitride

From Wikipedia, the free encyclopedia

Boron nitride
Magnified sample of crystalline hexagonal boron nitride
Names
IUPAC name
Boron nitride
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.030.111
EC Number 233-136-6
216
MeSH Elbor
PubChem CID
RTECS number ED7800000
UNII
Properties
BN
Molar mass 24.82 g·mol−1
Appearance Colorless crystals
Density 2.1 (h-BN); 3.45 (c-BN) g/cm3
Melting point 2,973 °C (5,383 °F; 3,246 K) sublimates (cBN)
insoluble
Electron mobility 200 cm2/(V·s) (cBN)
1.8 (h-BN); 2.1 (c-BN)
Structure
hexagonal, sphalerite, wurtzite
Thermochemistry
19.7 J/(K·mol)
14.8 J/K mol
-254.4 kJ/mol
-228.4 kJ/mol
Hazards
Irritant Xi
R-phrases (outdated) R36/37
S-phrases (outdated) S26, S36
NFPA 704
Flammability code 0: Will not burn. E.g., waterHealth code 0: Exposure under fire conditions would offer no hazard beyond that of ordinary combustible material. E.g., sodium chlorideReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g., liquid nitrogenSpecial hazards (white): no codeNFPA 704 four-colored diamond
0
0
0
Related compounds
Related compounds
Boron arsenide Boron carbide Boron phosphide Boron trioxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Boron nitride is a heat and chemically resistant refractory compound of boron and nitrogen with the chemical formula BN. It exists in various crystalline forms that are isoelectronic to a similarly structured carbon lattice. The hexagonal form corresponding to graphite is the most stable and soft among BN polymorphs, and is therefore used as a lubricant and an additive to cosmetic products. The cubic (sphalerite structure) variety analogous to diamond is called c-BN; it is softer than diamond, but its thermal and chemical stability is superior. The rare wurtzite BN modification is similar to lonsdaleite and may even be harder than the cubic form.

Because of excellent thermal and chemical stability, boron nitride ceramics are traditionally used as parts of high-temperature equipment. Boron nitride has potential use in nanotechnology. Nanotubes of BN can be produced that have a structure similar to that of carbon nanotubes, i.e. graphene (or BN) sheets rolled on themselves, but the properties are very different.

Structure

Boron nitride exists in multiple forms that differ in the arrangement of the boron and nitrogen atoms, giving rise to varying bulk properties of the material.

Amorphous form (a-BN)

The amorphous form of boron nitride (a-BN) is non-crystalline, lacking any long-distance regularity in the arrangement of its atoms. It is analogous to amorphous carbon.

All other forms of boron nitride are crystalline.

Hexagonal form (h-BN)

The most stable crystalline form is the hexagonal one, also called h-BN, α-BN, g-BN, and graphitic boron nitride. Hexagonal boron nitride (point group = D6h; space group = P63/mmc) has a layered structure similar to graphite. Within each layer, boron and nitrogen atoms are bound by strong covalent bonds, whereas the layers are held together by weak van der Waals forces. The interlayer "registry" of these sheets differs, however, from the pattern seen for graphite, because the atoms are eclipsed, with boron atoms lying over and above nitrogen atoms. This registry reflects the polarity of the B–N bonds. Still, h-BN and graphite are very close neighbors and even the BC6N hybrids have been synthesized where carbon substitutes for some B and N atoms.

Cubic form (c-BN)

Cubic boron nitride has a crystal structure analogous to that of diamond. Consistent with diamond being less stable than graphite, the cubic form is less stable than the hexagonal form, but the conversion rate between the two is negligible at room temperature, as it is for diamond. The cubic form has the sphalerite crystal structure, the same as that of diamond, and is also called β-BN or c-BN.

Wurtzite form (w-BN)

The wurtzite form of boron nitride (w-BN; point group = C6v; space group = P63mc) has the same structure as lonsdaleite, a rare hexagonal polymorph of carbon. As in the cubic form, the boron and nitrogen atoms are grouped into tetrahedra, but in w-BN the angles between neighboring tetrahedra are different. As in the cubic form, the boron and nitrogen atoms are grouped into 6-membered rings; in the cubic form all rings are in the chair configuration, in w-BN the rings between 'layers' are in boat configuration. The Wurtzite form is thought to be very strong, and was estimated by a simulation as potentially having a strength 18% stronger than that of diamond, but because only small amounts of the mineral exist in nature, this has not yet been experimentally verified.

Properties

Physical

Properties of amorphous and crystalline BN, graphite and diamond.
Some properties of h-BN and graphite differ within the basal planes (∥) and perpendicular to them (⟂)
Material a-BN h-BN c-BN w-BN graphite diamond
Density (g/cm3) 2.28 ~2.1 3.45 3.49 ~2.1 3.515
Knoop hardness (GPa) 10
45 34
100
Bulk modulus (GPa) 100 36.5 400 400 34 440
Thermal conductivity (W/(m·K)) 3 600 ∥, 30 ⟂ 740
200–2000 ∥, 2–800 ⟂ 600–2000
Thermal expansion (10−6/°C)
−2.7 ∥, 38 ⟂ 1.2 2.7 −1.5 ∥, 25 ⟂ 0.8
Bandgap (eV) 5.05 5.2 6.4 4.5–5.5 0 5.5
Refractive index 1.7 1.8 2.1 2.05
2.4
Magnetic susceptibility (µemu/g)
−0.48 ∥, −17.3 ⟂

−0.2...−2.7 ∥, −20...−28 ⟂ −1.6

The partly ionic structure of BN layers in h-BN reduces covalency and electrical conductivity, whereas the interlayer interaction increases resulting in higher hardness of h-BN relative to graphite. The reduced electron-delocalization in hexagonal-BN is also indicated by its absence of color and a large band gap. Very different bonding – strong covalent within the basal planes (planes where boron and nitrogen atoms are covalently bonded) and weak between them – causes high anisotropy of most properties of h-BN. 

For example, the hardness, electrical and thermal conductivity are much higher within the planes than perpendicular to them. On the contrary, the properties of c-BN and w-BN are more homogeneous and isotropic.
Those materials are extremely hard, with the hardness of bulk c-BN being slightly smaller and w-BN even higher than that of diamond. Polycrystalline c-BN with grain sizes on the order of 10 nm is also reported to have Vickers hardness comparable or higher than diamond. Because of much better stability to heat and transition metals, c-BN surpasses diamond in mechanical applications, such as machining steel. The thermal conductivity of BN is among the highest of all electric insulators.

Boron nitride can be doped p-type with beryllium and n-type with boron, sulfur, silicon or if co-doped with carbon and nitrogen. Both hexagonal and cubic BN are wide-gap semiconductors with a band-gap energy corresponding to the UV region. If voltage is applied to h-BN or c-BN, then it emits UV light in the range 215–250 nm and therefore can potentially be used as light-emitting diodes (LEDs) or lasers. 

Little is known on melting behavior of boron nitride. It sublimates at 2973 °C at normal pressure releasing nitrogen gas and boron, but melts at elevated pressure.

Thermal stability

Hexagonal and cubic (and probably w-BN) BN show remarkable chemical and thermal stabilities. For example, h-BN is stable to decomposition at temperatures up to 1000 °C in air, 1400 °C in vacuum, and 2800 °C in an inert atmosphere. The reactivity of h-BN and c-BN is relatively similar, and the data for c-BN are summarized in the table below. 

Reactivity of c-BN with solids
Solid Ambient Action Threshold T (°C)
Mo 10−2 Pa vacuum reaction 1360
Ni 10−2 Pa vacuum wetting 1360
Fe, Ni, Co argon react 1400–1500
Al 10−2 Pa vacuum wetting and reaction 1050
Si 10−3 Pa vacuum wetting 1500
Cu, Ag, Au, Ga, In, Ge, Sn 10−3 Pa vacuum no wetting 1100
B
no wetting 2200
Al2O3 + B2O3 10−2 Pa vacuum no reaction 1360

Thermal stability of c-BN can be summarized as follows:
  • In air or oxygen: B2O3 protective layer prevents further oxidation to ~1300 °C; no conversion to hexagonal form at 1400 °C.
  • In nitrogen: some conversion to h-BN at 1525 °C after 12 h.
  • In vacuum (10−5 Pa): conversion to h-BN at 1550–1600 °C.

Chemical stability

Boron nitride is insoluble in the usual acids, but is soluble in alkaline molten salts and nitrides, such as LiOH, KOH, NaOH-Na2CO3, NaNO3, Li3N, Mg3N2, Sr3N2, Ba3N2 or Li3BN2, which are therefore used to etch BN.

Thermal conductivity

The theoretical thermal conductivity of hexagonal Boron nitride nanoribbons (BNNRs) can approach 1700–2000 W/(m·K), which has the same order of magnitude as the experimental measured value for graphene, and can be comparable to the theoretical calculations for graphene nanoribbons. Moreover, the thermal transport in the BNNRs is anisotropic. The thermal conductivity of zigzag-edged BNNRs is about 20% larger than that of armchair-edged nanoribbons at room temperature.

Natural occurrence

In 2009, a naturally occurring boron nitride mineral in the cubic form (c-BN) was reported in Tibet, with a proposed name of qingsongite. The substance was found in dispersed micron-sized inclusions in chromium-rich rocks. In 2013, the International Mineralogical Association affirmed the mineral and the name.

Synthesis

Preparation and reactivity of hexagonal BN

Boron nitride is produced synthetically. Hexagonal boron nitride is obtained by the reacting boron trioxide (B2O3) or boric acid (H3BO3) with ammonia (NH3) or urea (CO(NH2)2) in a nitrogen atmosphere:
B2O3 + 2 NH3 → 2 BN + 3 H2O (T = 900 °C)
B(OH)3 + NH3 → BN + 3 H2O (T = 900 °C)
B2O3 + CO(NH2)2 → 2 BN + CO2 + 2 H2O (T > 1000 °C)
B2O3 + 3 CaB6 + 10 N2 → 20 BN + 3 CaO (T > 1500 °C)
The resulting disordered (amorphous) boron nitride contains 92–95% BN and 5–8% B2O3. The remaining B2O3 can be evaporated in a second step at temperatures > 1500 °C in order to achieve BN concentration >98%. Such annealing also crystallizes BN, the size of the crystallites increasing with the annealing temperature.

h-BN parts can be fabricated inexpensively by hot-pressing with subsequent machining. The parts are made from boron nitride powders adding boron oxide for better compressibility. Thin films of boron nitride can be obtained by chemical vapor deposition from boron trichloride and nitrogen precursors. Combustion of boron powder in nitrogen plasma at 5500 °C yields ultrafine boron nitride used for lubricants and toners.

Boron nitride reacts with iodine fluoride in trichlorofluoromethane at −30 °C to produce an extremely sensitive contact explosive, NI3, in low yield. Boron nitride reacts with nitrides of alkali metals and lanthanides to form nitridoborate compounds. For example:
Li3N + BN → Li3BN2

Intercalation of hexagonal BN

Structure of hexagonal boron nitride intercalated with potassium (B4N4K)
 
Similar to graphite, various molecules, such as NH3 or alkali metals, can be intercalated into hexagonal boron nitride, that is inserted between its layers. Both experiment and theory suggest the intercalation is much more difficult for BN than for graphite.

Preparation of cubic BN

Synthesis of c-BN uses same methods as that of diamond: Cubic boron nitride is produced by treating hexagonal boron nitride at high pressure and temperature, much as synthetic diamond is produced from graphite. Direct conversion of hexagonal boron nitride to the cubic form has been observed at pressures between 5 and 18 GPa and temperatures between 1730 and 3230 °C, that is similar parameters as for direct graphite-diamond conversion. The addition of a small amount of boron oxide can lower the required pressure to 4–7 GPa and temperature to 1500 °C. As in diamond synthesis, to further reduce the conversion pressures and temperatures, a catalyst is added, such as lithium, potassium, or magnesium, their nitrides, their fluoronitrides, water with ammonium compounds, or hydrazine. Other industrial synthesis methods, again borrowed from diamond growth, use crystal growth in a temperature gradient, or explosive shock wave. The shock wave method is used to produce material called heterodiamond, a superhard compound of boron, carbon, and nitrogen.

Low-pressure deposition of thin films of cubic boron nitride is possible. As in diamond growth, the major problem is to suppress the growth of hexagonal phases (h-BN or graphite, respectively). Whereas in diamond growth this is achieved by adding hydrogen gas, boron trifluoride is used for c-BN. Ion beam deposition, plasma-enhanced chemical vapor deposition, pulsed laser deposition, reactive sputtering, and other physical vapor deposition methods are used as well.

Preparation of wurtzite BN

Wurtzite BN can be obtained via static high-pressure or dynamic shock methods. The limits of its stability are not well defined. Both c-BN and w-BN are formed by compressing h-BN, but formation of w-BN occurs at much lower temperatures close to 1700 °C.

Production statistics

Whereas the production and consumption figures for the raw materials used for BN synthesis, namely boric acid and boron trioxide, are well known, the corresponding numbers for the boron nitride are not listed in statistical reports. An estimate for the 1999 world production is 300 to 350 metric tons. The major producers and consumers of BN are located in the United States, Japan, China and Germany. In 2000, prices varied from about $75/kg to $120/kg for standard industrial-quality h-BN and were about up to $200–$400/kg for high purity BN grades.

Applications

Hexagonal BN

Ceramic BN crucible
 
Hexagonal BN (h-BN) is the most widely used polymorph. It is a good lubricant at both low and high temperatures (up to 900 °C, even in an oxidizing atmosphere). h-BN lubricant is particularly useful when the electrical conductivity or chemical reactivity of graphite (alternative lubricant) would be problematic. Another advantage of h-BN over graphite is that its lubricity does not require water or gas molecules trapped between the layers. Therefore, h-BN lubricants can be used even in vacuum, e.g. in space applications. The lubricating properties of fine-grained h-BN are used in cosmetics, paints, dental cements, and pencil leads.

Hexagonal BN was first used in cosmetics around 1940 in Japan. However, because of its high price, h-BN was soon abandoned for this application. Its use was revitalized in the late 1990s with the optimization h-BN production processes, and currently h-BN is used by nearly all leading producers of cosmetic products for foundations, make-up, eye shadows, blushers, kohl pencils, lipsticks and other skincare products.

Because of its excellent thermal and chemical stability, boron nitride ceramics are traditionally used as parts of high-temperature equipment. h-BN can be included in ceramics, alloys, resins, plastics, rubbers, and other materials, giving them self-lubricating properties. Such materials are suitable for construction of e.g. bearings and in steelmaking. Plastics filled with BN have less thermal expansion as well as higher thermal conductivity and electrical resistivity. Due to its excellent dielectric and thermal properties, BN is used in electronics e.g. as a substrate for semiconductors, microwave-transparent windows and as a structural material for seals. It can also be used as dielectric in resistive random access memories.

Hexagonal BN is used in xerographic process and laser printers as a charge leakage barrier layer of the photo drum. In the automotive industry, h-BN mixed with a binder (boron oxide) is used for sealing oxygen sensors, which provide feedback for adjusting fuel flow. The binder utilizes the unique temperature stability and insulating properties of h-BN.

Parts can be made by hot pressing from four commercial grades of h-BN. Grade HBN contains a boron oxide binder; it is usable up to 550–850 °C in oxidizing atmosphere and up to 1600 °C in vacuum, but due to the boron oxide content is sensitive to water. Grade HBR uses a calcium borate binder and is usable at 1600 °C. Grades HBC and HBT contain no binder and can be used up to 3000 °C.

Boron nitride nanosheets (h-BN) can be deposited by catalytic decomposition of borazine at a temperature ~1100 °C in a chemical vapor deposition setup, over areas up to about 10 cm2. Owing to their hexagonal atomic structure, small lattice mismatch with graphene (~2%), and high uniformity they are used as substrates for graphene-based devices. BN nanosheets are also excellent proton conductors. Their high proton transport rate, combined with the high electrical resistance, may lead to applications in fuel cells and water electrolysis.

h-BN has been used since the mid-2000s as a bullet and bore lubricant in precision target rifle applications as an alternative to molybdenum disulfide coating, commonly referred to as "moly". It is claimed to increase effective barrel life, increase intervals between bore cleaning, and decrease the deviation in point of impact between clean bore first shots and subsequent shots.

Cubic boron nitride

Cubic boron nitride (CBN or c-BN) is widely used as an abrasive. Its usefulness arises from its insolubility in iron, nickel, and related alloys at high temperatures, whereas diamond is soluble in these metals. Polycrystalline c-BN (PCBN) abrasives are therefore used for machining steel, whereas diamond abrasives are preferred for aluminum alloys, ceramics, and stone. When in contact with oxygen at high temperatures, BN forms a passivation layer of boron oxide. Boron nitride binds well with metals, due to formation of interlayers of metal borides or nitrides. Materials with cubic boron nitride crystals are often used in the tool bits of cutting tools. For grinding applications, softer binders, e.g. resin, porous ceramics, and soft metals, are used. Ceramic binders can be used as well. Commercial products are known under names "Borazon" (by Diamond Innovations), and "Elbor" or "Cubonite" (by Russian vendors).

Contrary to diamond, large c-BN pellets can be produced in a simple process (called sintering) of annealing c-BN powders in nitrogen flow at temperatures slightly below the BN decomposition temperature. This ability of c-BN and h-BN powders to fuse allows cheap production of large BN parts.

Similar to diamond, the combination in c-BN of highest thermal conductivity and electrical resistivity is ideal for heat spreaders

As cubic boron nitride consists of light atoms and is very robust chemically and mechanically, it is one of the popular materials for X-ray membranes: low mass results in small X-ray absorption, and good mechanical properties allow usage of thin membranes, thus further reducing the absorption.

Amorphous boron nitride

Layers of amorphous boron nitride (a-BN) are used in some semiconductor devices, e.g. MOSFETs. They can be prepared by chemical decomposition of trichloroborazine with caesium, or by thermal chemical vapor deposition methods. Thermal CVD can be also used for deposition of h-BN layers, or at high temperatures, c-BN.

Other forms of boron nitride

Atomically thin boron nitride

Hexagonal boron nitride can be exfoliated to mono or few atomic layer sheets. Due to its analogous structure to that of graphene but white appearance, atomically thin boron nitride is sometimes call “white graphene”.

Mechanical properties. Atomically thin boron nitride is one of the strongest electrically insulating materials. Monolayer boron nitride has an average Young's modulus of 0.865TPa and fracture strength of 70.5GPa, and in contrast to graphene, whose strength decreases dramatically with increased thickness, few-layer boron nitride sheets have a strength similar to that of monolayer boron nitride.

Thermal conductivity. Atomically thin boron nitride has one of the highest thermal conductivity coefficients among semiconductors and electrical insulators, and its thermal conductivity increases with reduced thickness due to less intra-layer coupling.

Thermal stability. The air stability of graphene shows a clear thickness dependence: monolayer graphene is reactive to oxygen at 250 °C, strongly doped at 300 °C, and etched at 450 °C; in contrast, bulk graphite is not oxidized until 800 °C. Atomically thin boron nitride has much better oxidation resistance than graphene. Monolayer boron nitride is not oxidized till 700 °C and can sustain up to 850 °C in air; bilayer and trilayer boron nitride nanosheets have slightly higher oxidation starting temperatures. The excellent thermal stability, high impermeability to gas and liquid, and electrical insulation make atomically thin boron nitride potential coating materials for preventing surface oxidation and corrosion of metals and other two-dimensional (2D) materials, such as black phosphorus.

Better surface adsorption. Atomically thin boron nitride has been found to have better surface adsorption capabilities than bulk hexagonal boron nitride. According to theoretical and experimental studies, atomically thin boron nitride as an adsorbent experiences conformational changes upon surface adsorption of molecules, increasing adsorption energy and efficiency. The synergic effect of the atomic thickness, high flexibility, stronger surface adsorption capability, electrical insulation, impermeability, high thermal and chemical stability of BN nanosheets can increase the Raman sensitivity by up to two orders, and in the meantime attain long-term stability and extraordinary reusability not achievable by other materials.

Dielectric properties. Atomically thin hexagonal boron nitride is an excellent dielectric substrate for graphene, molybdenum disulphide (MoS2), and many other 2D material-based electronic and photonic devices. As shown by electric force microscopy (EFM) studies, the electric field screening in atomically thin boron nitride shows a weak dependence on thickness, which is in line with the smooth decay of electric field inside few-layer boron nitride revealed by the first-principles calculations.

Raman characteristics. Raman spectroscopy has been a useful tool to study a variety of 2D materials, and the Raman signature of high-quality atomically thin boron nitride was first reported by Gorbachev et al. and Li et al. However, the two reported Raman results of monolayer boron nitride did not agree with each other. Cai et al., therefore, conducted systematic experimental and theoretical studies to reveal the intrinsic Raman spectrum of atomically thin boron nitride. It reveals that atomically thin boron nitride without interaction with a substrate has a G band frequency similar to that of bulk hexagonal boron nitride, but strain induced by the substrate can cause Raman shifts. Nevertheless, the Raman intensity of G band of atomically thin boron nitride can be used to estimate layer thickness and sample quality.

BN nanomesh observed with a scanning tunneling microscope. The center of each ring corresponds to the center of the pores
 
Top: absorption of cyclohexane by BN aerogel. Cyclohexane is stained with Sudan II red dye and is floating on water. Bottom: reuse of the aerogel after burning in air.

Boron nitride nanomesh

Boron nitride nanomesh is a nanostructured two-dimensional material. It consists of a single BN layer, which forms by self-assembly a highly regular mesh after high-temperature exposure of a clean rhodium or ruthenium surface to borazine under ultra-high vacuum. The nanomesh looks like an assembly of hexagonal pores. The distance between two pore centers is 3.2 nm and the pore diameter is ~2 nm. Other terms for this material are boronitrene or white graphene.

The boron nitride nanomesh is not only stable to decomposition under vacuum, air and some liquids, but also up to temperatures of 800 °C. In addition, it shows the extraordinary ability to trap molecules and metallic clusters which have similar sizes to the nanomesh pores, forming a well-ordered array. These characteristics promise interesting applications of the nanomesh in areas like catalysis, surface functionalisation, spintronics, quantum computing and data storage media like hard drives.

BN nanotubes are flame resistant, as shown in this comparative test of airplanes made of cellullose, carbon buckypaper and BN nanotube buckypaper.

Boron nitride nanotubes

Boron nitride tubules were first made in 1989 by Shore and Dolan This work was patented in 1989 and published in 1989 thesis (Dolan) and then 1993 Science. The 1989 work was also the first preparation of amorphous BN by B-trichloroborazine and cesium metal. 

Preparation of Amorphous Boron Nitride and Its Conversion to a Turbostratic, Tubular Form Ewan J. M. Hamilton1, Shawn E. Dolan1, Charles M. Mann1, Hendrik O. Colijn2, Clare A. McDonald2, Sheldon G. Shore, Science 30 Apr 1993: Vol. 260, Issue 5108, pp. 659–661 DOI: 10.1126/science.260.5108.659 Boron nitride nanotubes were predicted in 1994 and experimentally discovered in 1995. They can be imagined as a rolled up sheet of h-boron nitride. Structurally, it is a close analog of the carbon nanotube, namely a long cylinder with diameter of several to hundred nanometers and length of many micrometers, except carbon atoms are alternately substituted by nitrogen and boron atoms. However, the properties of BN nanotubes are very different: whereas carbon nanotubes can be metallic or semiconducting depending on the rolling direction and radius, a BN nanotube is an electrical insulator with a bandgap of ~5.5 eV, basically independent of tube chirality and morphology. In addition, a layered BN structure is much more thermally and chemically stable than a graphitic carbon structure.

Boron nitride aerogel

Boron nitride aerogel is an aerogel made of highly porous BN. It typically consists of a mixture of deformed BN nanotubes and nanosheets. It can have a density as low as 0.6 mg/cm3 and a specific surface area as high as 1050 m2/g, and therefore has potential applications as an absorbent, catalyst support and gas storage medium. BN aerogels are highly hydrophobic and can absorb up to 160 times their weight in oil. They are resistant to oxidation in air at temperatures up to 1200 °C, and hence can be reused after the absorbed oil is burned out by flame. BN aerogels can be prepared by template-assisted chemical vapor deposition using borazine as the feed gas.

Composites containing BN

Addition of boron nitride to silicon nitride ceramics improves the thermal shock resistance of the resulting material. For the same purpose, BN is added also to silicon nitride-alumina and titanium nitride-alumina ceramics. Other materials being reinforced with BN include alumina and zirconia, borosilicate glasses, glass ceramics, enamels, and composite ceramics with titanium boride-boron nitride, titanium boride-aluminium nitride-boron nitride, and silicon carbide-boron nitride composition.

Health issues

Boron nitride (along with Si3N4, NbN, and BNC) is reported to show weak fibrogenic activity, and to cause pneumoconiosis when inhaled in particulate form. The maximum concentration recommended for nitrides of nonmetals is 10 mg/m3 for BN and 4 for AlN or ZrN.

Holographic data storage

From Wikipedia, the free encyclopedia

Holographic data storage is a potential technology in the area of high-capacity data storage currently dominated by magnetic data storage and conventional optical data storage. Magnetic and optical data storage devices rely on individual bits being stored as distinct magnetic or optical changes on the surface of the recording medium. Holographic data storage records information throughout the volume of the medium and is capable of recording multiple images in the same area utilizing light at different angles.

Additionally, whereas magnetic and optical data storage records information a bit at a time in a linear fashion, holographic storage is capable of recording and reading millions of bits in parallel, enabling data transfer rates greater than those attained by traditional optical storage.

Recording data

Holographic data storage contains information using an optical interference pattern within a thick, photosensitive optical material. Light from a single laser beam is divided into two, or more, separate optical patterns of dark and light pixels. By adjusting the reference beam angle, wavelength, or media position, a multitude of holograms (theoretically, several thousands) can be stored on a single volume.

Reading data

The stored data is read through the reproduction of the same reference beam used to create the hologram. The reference beam's light is focused on the photosensitive material, illuminating the appropriate interference pattern, the light diffracts on the interference pattern, and projects the pattern onto a detector. The detector is capable of reading the data in parallel, over one million bits at once, resulting in the fast data transfer rate. Files on the holographic drive can be accessed in less than 0.2 seconds.

Longevity

Holographic data storage can provide companies a method to preserve and archive information. The write-once, read many (WORM) approach to data storage would ensure content security, preventing the information from being overwritten or modified. Manufacturers believe this technology can provide safe storage for content without degradation for more than 50 years, far exceeding current data storage options. Counterpoints to this claim are that the evolution of data reader technology has – in the last couple of decades – changed every ten years. If this trend continues, it therefore follows that being able to store data for 50–100 years on one format is irrelevant, because you would migrate the data to a new format after only ten years. However, claimed longevity of storage has, in the past, proven to be a key indicator of shorter-term reliability of storage media. Current optical formats – such as CD – have largely lived up to the original longevity claims (where reputable media makes are used) and have proved to be more reliable shorter-term data carriers than the floppy disk and DAT media they displaced.

Terms used

Sensitivity refers to the extent of refractive index modulation produced per unit of exposure. Diffraction efficiency is proportional to the square of the index modulation times the effective thickness. 

The dynamic range determines how many holograms may be multiplexed in a single volume data.

Spatial light modulators (SLM) are pixelated input devices (liquid crystal panels), used to imprint the data to be stored on the object beam.

Technical aspects

Like other media, holographic media is divided into write once (where the storage medium undergoes some irreversible change), and rewritable media (where the change is reversible). Rewritable holographic storage can be achieved via the photorefractive effect in crystals: 

Hologram maken (1).svg
  • Mutually coherent light from two sources creates an interference pattern in the media. These two sources are called the reference beam and the signal beam.
  • Where there is constructive interference the light is bright and electrons can be promoted from the valence band to the conduction band of the material (since the light has given the electrons energy to jump the energy gap). The positively charged vacancies they leave are called holes and they must be immobile in rewritable holographic materials. Where there is destructive interference, there is less light and few electrons are promoted.
  • Electrons in the conduction band are free to move in the material. They will experience two opposing forces that determine how they move. The first force is the coulomb force between the electrons and the positive holes that they have been promoted from. This force encourages the electrons to stay put or move back to where they came from. The second is the pseudo-force of diffusion that encourages them to move to areas where electrons are less dense. If the coulomb forces are not too strong, the electrons will move into the dark areas.
  • Beginning immediately after being promoted, there is a chance that a given electron will recombine with a hole and move back into the valence band. The faster the rate of recombination, the fewer the number of electrons that will have the chance to move into the dark areas. This rate will affect the strength of the hologram.
  • After some electrons have moved into the dark areas and recombined with holes there, there is a permanent space charge field between the electrons that moved to the dark spots and the holes in the bright spots. This leads to a change in the index of refraction due to the electro-optic effect.
Hologram lezen.svg

When the information is to be retrieved or read out from the hologram, only the reference beam is necessary. The beam is sent into the material in exactly the same way as when the hologram was written. As a result of the index changes in the material that were created during writing, the beam splits into two parts. One of these parts recreates the signal beam where the information is stored. Something like a CCD camera can be used to convert this information into a more usable form.

Holograms can theoretically store one bit per cubic block the size of the wavelength of light in writing. For example, light from a helium–neon laser is red, 632.8 nm wavelength light. Using light of this wavelength, perfect holographic storage could store 500 megabytes per cubic millimeter. At the extreme end of the laser spectrum, fluorine excimer laser at 157 nm could store 30 gigabytes per cubic millimeter. In practice, the data density would be much lower, for at least four reasons:
  1. The need to add error-correction
  2. The need to accommodate imperfections or limitations in the optical system
  3. Economic payoff (higher densities may cost disproportionately more to achieve)
  4. Design technique limitations—a problem currently faced in magnetic Hard Drives wherein magnetic domain configuration prevents manufacture of disks that fully utilize the theoretical limits of the technology.
Despite those limitations, it is possible to optimize the storage capacity using all-optical signal processing techniques.

Unlike current storage technologies that record and read one data bit at a time, holographic memory writes and reads data in parallel in a single flash of light.

Two-color recording

Set up for holographic recording
 
For two-color holographic recording, the reference and signal beam fixed to a particular wavelength (green, red or IR) and the sensitizing/gating beam is a separate, shorter wavelength (blue or UV). The sensitizing/gating beam is used to sensitize the material before and during the recording process, while the information is recorded in the crystal via the reference and signal beams. It is shone intermittently on the crystal during the recording process for measuring the diffracted beam intensity. Readout is achieved by illumination with the reference beam alone. Hence the readout beam with a longer wavelength would not be able to excite the recombined electrons from the deep trap centers during readout, as they need the sensitizing light with shorter wavelength to erase them.

Usually, for two-color holographic recording, two different dopants are required to promote trap centers, which belong to transition metal and rare earth elements and are sensitive to certain wavelengths. By using two dopants, more trap centers would be created in the lithium niobate crystal. Namely a shallow and a deep trap would be created. The concept now is to use the sensitizing light to excite electrons from the deep trap farther from the valence band to the conduction band and then to recombine at the shallow traps nearer to the conduction band. The reference and signal beam would then be used to excite the electrons from the shallow traps back to the deep traps. The information would hence be stored in the deep traps. Reading would be done with the reference beam since the electrons can no longer be excited out of the deep traps by the long wavelength beam.

Effect of annealing

For a doubly doped lithium niobate (LiNbO3) crystal there exists an optimum oxidation/reduction state for desired performance. This optimum depends on the doping levels of shallow and deep traps as well as the annealing conditions for the crystal samples. This optimum state generally occurs when 95 – 98% of the deep traps are filled. In a strongly oxidized sample holograms cannot be easily recorded and the diffraction efficiency is very low. This is because the shallow trap is completely empty and the deep trap is also almost devoid of electrons. In a highly reduced sample on the other hand, the deep traps are completely filled and the shallow traps are also partially filled. This results in very good sensitivity (fast recording) and high diffraction efficiency due to the availability of electrons in the shallow traps. However, during readout, all the deep traps get filled quickly and the resulting holograms reside in the shallow traps where they are totally erased by further readout. Hence after extensive readout the diffraction efficiency drops to zero and the hologram stored cannot be fixed.

Development and marketing

In 1975, Hitachi introduced a video disc system in which chrominance, luminance and sound information were encoded holographically. Each frame was recorded as a 1mm diameter hologram on a 305mm disc, while a laser beam read out the hologram from three angles.

Developed from the pioneering work on holography in photorefractive media and holographic data storage of Gerard A. Alphonse, InPhase conducted public demonstrations of the a prototype commercial storage device, at the National Association of Broadcasters 2005 (NAB) convention in Las Vegas, at the Maxell Corporation of America booth. 

The three main companies involved in developing holographic memory, as of 2002, were InPhase and Polaroid spinoff Aprilis in the United States, and Optware in Japan. Although holographic memory has been discussed since the 1960s, and has been touted for near-term commercial application at least since 2001, it has yet to convince critics that it can find a viable market. As of 2002, planned holographic products did not aim to compete head to head with hard drives, but instead to find a market niche based on virtues such as speed of access.

InPhase Technologies, after several announcements and subsequent delays in 2006 and 2007, announced that it would soon be introducing a flagship product. InPhase went out of business in February 2010 and had its assets seized by the state of Colorado for back taxes. The company had reportedly gone through $100 million but the lead investor was unable to raise more capital.

In April 2009, GE Global Research demonstrated their own holographic storage material that could allow for discs that utilize similar read mechanisms as those found on Blu-ray Disc players.

Video game market

Nintendo filed a Joint Research Agreement with InPhase for holographic storage in 2008.

Nintendo is also mentioned in the patent as a joint applicant: "... disclosure is herein made that the claimed invention was made pursuant to a Joint Research Agreement as defined in 35 U.S.C. 103 (c)(3), that was in effect on or before the date the claimed invention was made, and as a result of activities undertaken within the scope of the Joint Research Agreement, by or on the behalf of Nintendo Co., and InPhase Technologies, Inc.".

In fiction

In Lego Star Wars: The Yoda Chronicles, the Jedi use the holocrons, holographic crystals, to store data about their history. 

In 2010: The Year We Make Contact, a tapeworm had to be employed to erase HAL’s holographic memory as “chronological erasures would not work.” 

In Robot and Frank, Robot has a holographic memory which can be half erased but, will be in half the resolution.

Black Wednesday

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