何謂氮化矽Silicon nitride？？
氮化矽（Si3N4）是一種很硬的固態物質，可由硅粉在氮气中加热或卤化硅与氨反应而制得。Si3N4是氮化矽陶瓷中的主要成份，比起其他陶瓷，有相對較高的抗震動特性。
因為材料的抗震動及抗高溫特性，高檔的滑板有時會用氮化矽來做成滑板的軸承。氮化矽也會用在家用瓦斯器具或熱表面點火裝置的點火器具。
在微電子領域中，常使用化學氣相沉積（CVD）或電漿輔助化學氣相沉積（PECVD）等方法來製備氮化矽。氮化矽通常會用做阻絕不同結構的絕緣體或微加工中蝕刻製程所需的保護層。氮化矽也常用在微晶片中的鈍化層，因為它比起二氧化矽，對水分子和鈉離子有更好的阻擋擴散的能力。而水分子和鈉離子是微電子領域兩大造成腐蝕和不穩定的因素。另外氮化矽也用在類比晶片中電容的多晶矽間的介電質。
因為氮化矽的硬度、熱穩定度及抗磨損特性，所以氮化矽也是常被用做切割工具的材料。它也常被用在高速的鑄鐵加工機器中。在鋼鐵加工機器中，氮化矽通會上一層氮化鈦層 (通常使用化學氣相沉積方法) 以增強它的抗化學特性。
晶體結構
氮化矽（Si3N4）存在有3種結晶結構，分別是α、β和γ三相。α和β兩相是Si3N4最常出現的型式，且可以在常壓下製備。γ相只有在高壓及高溫下，才能合成得到，它的硬度可達到35GPa
Silicon nitride (Si3N4) is a chemical compound of silicon and nitrogen. It is a hard ceramichaving high strength over a broad temperature range, moderate thermal conductivity, lowcoefficient of thermal expansion, moderately high elastic modulus, and unusually high fracture toughness
for a ceramic. This combination of properties leads to excellent
thermal shock resistance, ability to withstand high structural loads to
high temperature, and superior wear resistance. Silicon nitride is mostly used in high-endurance and high-temperature applications, such as gas turbines, car engine parts, bearings and metal working and cutting tools. Silicon nitride bearings are used in the main engines of the NASA's Space shuttles.
Thin silicon nitride films are a popular insulating layer in
silicon-based electronics and silicon nitride cantilevers are the
sensing parts of atomic force microscopes.
Silicon nitride was first produced in 1857 by Deville and Wohler but its active commercial production had started only in 1950s. In nature, Si3N4 was found in the 1990s as tiny inclusions in meteorites, and was named nierite after American physicist Alfred O. C. Nier
Silicon nitride was first produced in 1857 by Henri Etienne Sainte-Claire Deville and Friedrich Wöhler,[1]
but remained merely a chemical curiosity. It took almost hundred years
to bring it to applications. From 1948 to 1952, the Carborundum
Company, Niagara Falls, New York, applied for several patents on the manufacture and application of silicon carbide.[2] By 1958 Haynes (Union Carbide) silicon carbide was in commercial production for thermocouple tubes, rocket nozzles, and boats and crucibles for melting metals. British work on silicon nitride, started in 1953, was aimed at high-temperature parts of gas turbines and resulted in the development of reaction-bonded silicon nitride and hot-pressed silicon nitride. In 1971, the Advanced Research Project Agency of the US Department of Defense placed a US$17 million contract with Ford and Westinghouse for two ceramic gas turbines.[3]
Even
though the properties of silicon nitride were well known, its natural
occurrence was discovered only in the 1990s, as tiny inclusions (about
2×0.5 microns in size) in meteorites. The mineral was named nierite after a pioneer of mass spectroscopy Alfred O. C. Nier.[4] This mineral might have been detected earlier, again exclusively in meteorites, by Soviet geologists.[5]
Synthesis
Silicon nitride can be obtained by direct reaction between silicon and nitrogen at temperatures between 1300 and 1400 °C:[2]
3 Si(s) + 2 N2(g) → Si3N4(s)
by diimide synthesis:[2]
SiCl4(l) + 6 NH3(g) → Si(NH)2(s) + 4 NH4Cl(s) at 0 °C
3 Si(NH)2(s) → Si3N4(s) + N2(g) + 3 H2(g) at 1000 °C
or by carbothermal reduction in nitrogen atmosphere at 1400–1450 °C:[2]
3 SiO2(s) + 6 C(s) + 2 N2(g) → Si3N4(s) + 6 CO(g)
The
nitridation of silicon powder was developed in the 1950s, following the
"rediscovery" of silicon nitride and was the first large-scale method
for powder production. However, use of low-purity raw silicon caused
contamination of silicon nitride by silicates and iron.
The diimide decomposition results in amorphous silicon nitride, which
needs further annealing under nitrogen at 1400–1500 °C to convert it to
crystalline powder; this is now the second-most important route for
commercial production. The carbothermal reduction was the earliest used
method for silicon nitride production and is now considered as the
most-cost-effective industrial route to high-purity silicon nitride
powder.[2]
Electronic-grade silicon nitride films are formed using chemical vapor deposition (CVD), or one of its variants, such as plasma-enhanced chemical vapor deposition (PECVD):[2][6]
3 SiH4(g) + 4 NH3(g) → Si3N4(s) + 12 H2(g)
3 SiCl4(g) + 4 NH3(g) → Si3N4(s) + 12 HCl(g)
3 SiCl2H2(g) + 4 NH3(g) → Si3N4(s) + 6 HCl(g) + 6 H2(g)
For deposition of silicon nitride layers on semiconductor (usually silicon) substrates, two methods are used:[6]
1.
Low pressure chemical vapor deposition (LPCVD) technology, which works
at rather high temperature and is done either in a vertical or in a
horizontal tube furnace,[7] or
2. Plasma-enhanced chemical vapor deposition (PECVD) technology, which works at rather low temperature and vacuum conditions.
The lattice constants of silicon nitride and silicon are different. Therefore tension or stress
can occur, depending on the deposition process. Especially when using
PECVD technology this tension can be reduced by adjusting deposition
parameters.[8]
Silicon nitride nanowires can also be produced by sol-gel method using carbothermal reduction followed by nitridation of silica gel, which contains ultrafine carbon particles. The particles can be produced by decomposition of dextrose in the temperature range 1200–1350 °C. The possible synthesis reactions are:[9]
SiO2(s) + C(s) → SiO(g) + CO(g) and
3 SiO(g) + 2 N2(g) + 3 CO(g) → Si3N4(s) + 3 CO2(g) or
3 SiO(g) + 2 N2(g) + 3 C(s) → Si3N4(s) + 3 CO(g).
Silicon nitride is difficult to produce as a bulk material—it cannot be heated over 1850 °C, which is well below its melting point, due to dissociation to silicon and nitrogen. Therefore, application of conventional hot press sintering
techniques is problematic. Bonding of silicon nitride powders can be
achieved at lower temperatures through adding additional materials
(sintering aids or "binders") which commonly induce a degree of liquid
phase sintering.[10] A cleaner alternative is to use spark plasma sintering
where heating is conducted very rapidly (seconds) by passing pulses of
electric current through the compacted powder. Dense silicon nitride
compacts have been obtained by this techniques at temperatures
1500–1700 °C
There exist three crystallographic structures of silicon nitride (Si3N4), designated as α, β and γ phases.[13] The α and β phases are the most common forms of Si3N4,
and can be produced under normal pressure condition. The γ phase can
only be synthesized under high pressures and temperatures and has a
hardness of 35 GPa.[14][15]
The α- and β-Si3N4 have trigonal and hexagonal structures, respectively, which are built up by corner-sharing SiN4 tetrahedra. They can be regarded as consisting of layers of silicon and nitrogen atoms in the sequence ABAB... or ABCDABCD... in β-Si3N4 and α-Si3N4,
respectively. The AB layer is the same in the α and β phases, and the
CD layer in the α phase is related to AB by a c-glide plane. The Si3N4 tetrahedra in β-Si3N4
are interconnected in such a way that tunnels are formed, running
parallel with the c axis of the unit cell. Due to the c-glide plane
that relates AB to CD, the α structure contains cavities instead of
tunnels. The cubic γ-Si3N4 is often designated as c modification in the literature, in analogy with the cubic modification of boron nitride (c-BN). It has a spinel-type
structure in which two silicon atoms each coordinate six nitrogen atoms
octahedrally, and one silicon atom coordinates four nitrogen atoms
tetrahedrally.[12]
The
longer stacking sequence results in the α-phase having higher hardness
than the β-phase. However, the α-phase is chemically unstable compared
with the β-phase. At high temperatures when a liquid phase is present,
the α-phase always transforms into the β-phase. Therefore, β-Si3N4 is the major form used in Si3N4ceramics.[16]
In
general, the main issue with applications of silicon nitride has not
been technical performance, but cost. As the cost has come down, the
number of production applications is accelerating.[17]
[edit]Automobile industry
One
of the major applications of sintered silicon nitride is in automobile
industry as a material for engine parts. Those include, in Diesel engines, glowplugs for faster start-up; precombustion chambers (swirl chambers) for lower emissions, faster start-up and lower noise;turbocharger for reduced engine lag and emissions. In spark-ignition engines, silicon nitride is used for rocker arm pads for lower wear, turbocharger for lower inertia and less engine lag, and in exhaust gas control valves
for increased acceleration. As examples of production levels, there is
an estimated more than 300,000 sintered silicon nitride turbochargers
made annually.[2][10][17]
[edit]Bearings
Si3N4 bearing parts
Silicon nitride bearings are both full ceramic bearings and ceramic hybrid bearings with balls in ceramics and races in steel. Silicon nitride ceramics have good shock resistance compared to other ceramics. Therefore, ball bearings made of silicon nitride ceramic are used in performance bearings. A representative example is use of silicon nitride bearings in the main engines of the NASA's Space Shuttle.[18][19]
Silicon
nitride ball bearings are harder than metal which reduces contact with
the bearing track. This results in 80% less friction, 3 to 10 times
longer lifetime, 80% higher speed, 60% less weight, the ability to
operate with lubrication starvation, higher corrosion resistance and
higher operation temperature, as compared to traditional metal bearings.[17]
Silicon nitride balls weigh 79% less than tungsten carbide balls.
Silicon nitride ball bearings can be found in high end automotive
bearings, industrial bearings, wind turbines, motorsports, high-end MTBs, racebikes, rollerblades andskateboards.
Silicon carbide bearings are especially useful in applications where
corrosion, electric or magnetic fields prohibit the use of metals. For
example, in tidal flow meters, where seawater attack is a problem, or
in electric field seekers.[10]
Si3N4
was first demonstrated as a superior bearing in 1972 but did not reach
production until nearly 1990 because of challenges associated with
reducing the cost. Since 1990, the cost has been reduced substantially
as production volume has increased. Although Si3N4
bearings are still 2–5 times more expensive than the best steel
bearings, their superior performance and life are justifying rapid
adoption. Around 15–20 million Si3N4 bearing
balls were produced in the U.S. in 1996 for machine tools and many
other applications. Growth is estimated at 40% per year, but could be
even higher if ceramic bearings are selected for consumer applications
such as in-line skates and computer disk drives
Silicon nitride
has long been used in high-temperature applications. In particular, it
was identified as one of the few monolithic ceramic materials capable
of surviving the severe thermal shock and thermal gradients generated
in hydrogen/oxygen rocket engines. To demonstrate this capability in a
complex configuration, NASA scientists used advanced rapid prototyping
technology to fabricate a one-inch-diameter, single-piece combustion
chamber/nozzle (thruster) component. The thruster was hot-fire tested
with hydrogen/oxygen propellant and survived five cycles including a
5-minute cycle to a 1320 °C material temperature.[20]
[edit]Metal working and cutting tools
The first major application of Si3N4
was abrasive and cutting tools. Grinding, milling, and boring of metals
constitute the major cost of manufacturing. A study in the early 1970s
estimated that there were 2,692,000 metal-cutting machine tools in the
United States with an annual operating cost of $64 billion.[17]
Bulk, monolithic silicon nitride is used as a material for cutting tools, due to its hardness, thermal stability, and resistance to wear. It is especially recommended for high speed machining of cast iron.
Hot hardness, fracture toughness and thermal shock resistance mean that
sintered silicon nitride can cut cast iron, hard steel and nickel based
alloys with surface speeds up to 25 times quicker than those obtained
with conventional materials such as tungsten carbide.[10] The use of Si3N4
cutting tools has had a dramatic effect on manufacturing output. For
example, face milling of gray cast iron with silicon nitride inserts
doubled the cutting speed, increased tool life from one part to six
parts per edge, and reduced the average cost of inserts by 50%, as
compared to traditional tungsten carbide tools
Electronics
Example of local silicon oxidationthrough a Si3N4 mask
Silicon nitride is often used as an insulator and chemical barrier in manufacturing integrated circuits, to electrically isolate different structures or as an etch mask in bulk micromachining. As a passivation layer for microchips, it is superior to silicon dioxide, as it is a significantly better diffusion barrier against water molecules and sodium ions, two major sources of corrosion and instability in microelectronics. It is also used as a dielectric between polysilicon layers in capacitors in analog chips.[21]
Si3N4 cantilever used in atomic force microscopes
Silicon nitride deposited by LPCVD contains up to 8% hydrogen. It also experiences strong tensile stress, which may crack films thicker than 200 nm. However, it has higher resistivity and dielectric strength than most insulators commonly available in microfabrication (1016Ω·cm and 10 MV/cm, respectively).[6]
Not only silicon nitride, but also various ternary compounds of silicon, nitrogen and hydrogen (SiNxHy) are used insulating layers. They are plasma deposited using the following reactions:[6]
2 SiH4(g) + N2(g) → 2 SiNH(s) + 3 H2(g)
SiH4(g) + NH3(g) → SiNH(s) + 3 H2(g)
These SiNH films have much less tensile stress, but worse electrical properties (resistivity 106 to 1015 Ω·cm, and dielectric strength 1 to 5 MV/cm).[6][22]
Silicon nitride is also used in xerographic process as one of the layer of the photo drum.[23] Silicon nitride is also used as an ignition source for domestic gas appliances.[24]
Because of its good elastic properties, silicon nitride, along with
silicon and silicon oxide, is the most popular material for cantilevers — the sensing elements of atomic force microscopes.[
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