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Silane

Silane is an with the SiH₄, representing the simplest of and serving as the silicon analogue of . Silane was first isolated in 1857 by the German chemists and Heinrich Buff, who obtained it from the reaction of aluminum silicide with . It is a colorless, pyrophoric gas that ignites spontaneously upon contact with air, exhibiting a sharp, repulsive odor and high toxicity by inhalation. With a , the central atom is bonded to four atoms at bond angles of approximately 109.5°, and a Si-H of 1.4798 . Silane is produced industrially through methods such as the reaction of (Mg₂Si) with (HCl), or by reducing (SiCl₄) with over a hot wire. These processes yield the gas, which must be handled under inert conditions due to its reactivity. Chemically, silane decomposes slowly in to form silicates and , and it reacts vigorously with oxidizing agents. The compound's primary applications lie in the , where it serves as a precursor for (CVD) to produce polycrystalline and films used in semiconductors, solar cells, and photovoltaic devices. Additionally, silane acts as a doping agent in solid-state devices and contributes to the synthesis of and carbide layers. Due to its extreme flammability and toxicity—classified with an LC50 of 9,600 in rats—strict safety protocols, including and protective equipment, are essential in its handling.

Structure and Properties

Molecular Structure

Silane has the SiH₄ and serves as the silicon analog of (CH₄), representing the simplest member of the family. The molecule adopts a around the central , with all four Si-H bonds equivalent and H-Si-H bond angles of approximately 109.5°. The Si-H is 1.48 . The Si-H bonds exhibit slight polarity due to the electronegativity difference between (1.90) and (2.20), resulting in a partial positive charge on the silicon atom and the reverse polarity compared to C-H bonds in . The systematic and accepted IUPAC name for SiH₄ is , with the monosilane also in common use. Isotopologues such as deuterated silane (SiD₄) are employed in spectroscopic studies to facilitate analysis of vibrational and rotational spectra; SiD₄ can be prepared via catalytic hydrogen-deuterium exchange reactions on silane or by analogous reduction methods using deuterated reagents.

Physical Properties

Silane is a colorless gas that is odorless in pure form but may exhibit a repulsive odor due to impurities at and . Its molecular weight of 32.117 g/ contributes to its gaseous state under standard conditions. Key thermodynamic properties of silane include a of -185.4 °C and a of -111.9 °C, indicating it liquefies only at very low temperatures. The critical temperature is approximately -3 °C, above which silane cannot be liquefied regardless of pressure. At (STP, 0 °C and 1 atm), its density is 1.44 g/L, roughly twice that of , which affects its behavior in mixtures and containment systems.
PropertyValueConditions
Melting point-185.4 °C1
Boiling point-111.9 °C1
Critical temperature-3 °C-
Density1.44 g/L (0 °C, 1 )
Silane is insoluble in , though it undergoes slow over time without rapid reaction under neutral conditions. It shows good solubility in organic solvents such as , reflecting its nonpolar nature and compatibility with non-aqueous media. At 25 °C, silane has a (Cp) of 42.8 J/mol·K for the gas phase, which is relevant for calculations in . Its thermal conductivity at similar conditions is approximately 0.018 W/m·K, typical for light diatomic-like gases but influenced by its tetrahedral . In comparison to (CH₄), silane displays a higher (-111.9 °C versus -161.5 °C for ) despite structural analogy, attributable to the larger atom increasing molecular and thus enhancing van der Waals intermolecular forces. This results in stronger attractions than might be anticipated from simple mass differences alone.

Chemical Properties

Silane is thermodynamically unstable with respect to its constituent elements, and , possessing a (ΔH_f) of +34 kJ/mol at 298 K, yet it exhibits kinetic stability at owing to the high barrier for . This kinetic inertness under ambient conditions contrasts with its pronounced reactivity when activated by , , or oxidants. Due to its , silane undergoes spontaneous ignition upon exposure to air, combusting according to the equation: \ce{SiH4 + 2O2 -> SiO2 + 2H2O} This highly exothermic reaction underscores silane's sensitivity to atmospheric oxygen, limiting its handling to inert environments. Silane displays limited reactivity toward water, undergoing slow hydrolysis to yield silicic acid and hydrogen gas via the reaction: \ce{SiH4 + 2H2O -> SiO2 + 4H2} This process is sluggish at room temperature but can be accelerated by the presence of impurities or basic catalysts, such as alkali hydroxides, which facilitate Si-H bond cleavage. Upon heating above 400 °C, silane thermally decomposes into and , following the decomposition pathway: \ce{SiH4 -> Si + 2H2} This endothermic process is central to its use in silicon deposition and occurs without catalysts under controlled thermal conditions. Silane reacts vigorously with such as and , rapidly forming the corresponding halosilanes; for instance, with chlorine, it proceeds as: \ce{SiH4 + 4Cl2 -> SiCl4 + 4HCl} These halogenation reactions are highly exothermic and typically require careful control to avoid explosive outcomes. The Si-H bonds in silane exhibit weak acidity, attributable to the relatively low electronegativity of silicon and the polarizability of the Si-H linkage, enabling deprotonation by strong bases to afford silyl anions such as SiH₃⁻. This acid-base behavior facilitates the synthesis of organosilyl derivatives and highlights silane's role as a precursor in silyl chemistry.

Production

Laboratory Methods

One common laboratory method for silane synthesis involves the reaction of (Mg₂Si) with dilute , yielding silane gas according to the equation Mg₂Si + 4HCl → 2MgCl₂ + SiH₄. This approach is suitable for small-scale preparation and begins with the preparation of by heating magnesium powder with or silica. The reaction is typically conducted in a under inert conditions to manage the pyrophoric nature of the product, with the evolved gas collected over water or mercury. An alternative laboratory route utilizes the reduction of (SiCl₄) with lithium aluminum hydride (LiAlH₄) in an , producing silane via SiCl₄ + LiAlH₄ → SiH₄ + LiCl + AlCl₃. This method offers quantitative yields and high purity when performed at low temperatures, such as by adding SiCl₄ to a of LiAlH₄ in cooled to 0°C, followed by warming and gas collection. It is favored in research for its straightforward setup and avoidance of intermediates. Purification of laboratory-produced silane often involves trap-to-trap under vacuum to separate volatile impurities, or passage through concentrated to selectively remove (PH₃) contaminants arising from traces in starting materials. Common contaminants include (Si₂H₆), formed via side reactions or , which can be isolated by exploiting the difference (-112°C for SiH₄ versus -14°C for Si₂H₆).

Commercial Production

The primary commercial route for silane production involves the of (HSiCl₃) over heated , yielding silane and , followed by to separate the products. This operates according to the $4 \mathrm{HSiCl_3} \rightarrow \mathrm{SiH_4} + 3 \mathrm{SiCl_4}, typically conducted at elevated temperatures around 300–400°C with as a to drive the toward silane formation. The resulting mixture is then purified through to isolate high-purity silane gas. An alternative direct synthesis method starts from metallurgical-grade , reacting it with gas at high temperatures (above 1000°C) under or catalytic conditions to produce silane via \mathrm{[Si](/page/Si)} + 2 \mathrm{H_2} \rightarrow \mathrm{SiH_4}. This approach uses and metallurgical as primary feeds, but it suffers from low yields due to thermodynamic limitations and side reactions, making it less dominant than chlorosilane-based routes despite its potential for . In integrated polysilicon manufacturing, silane is often generated on-site as an intermediate in some variants of the process or silane-based methods, where purified undergoes redistribution reactions to silane, which is then pyrolyzed to deposit onto heated rods. This on-site minimizes transportation risks and aligns silane output with polysilicon demands in fabrication. For semiconductor applications, commercial silane achieves purity levels of 99.999% (5N), obtained through cryogenic that effectively removes critical impurities such as and to below 10 . Recent advancements include the adoption of fluidized-bed reactors in silane-related processes, which have reduced costs and improved by about 20% since 2015 through better and continuous operation compared to batch methods.

Applications

Semiconductor Manufacturing

Silane serves as a critical precursor in manufacturing due to its ability to decompose into high-purity under controlled conditions, enabling the fabrication of silicon-based devices essential for and . In (CVD) processes, silane undergoes at temperatures between 600°C and 700°C, following the reaction \mathrm{SiH_4 \to Si + 2H_2}, to deposit films. These films are widely used in production for applications such as electrodes and interconnects in integrated circuits, providing uniform, low-stress layers with thicknesses typically ranging from 100 to several micrometers. Doping applications leverage silane as the primary source, combined with dopant gases like for n-type semiconductors or for p-type semiconductors, to introduce controlled levels during CVD. This in-situ doping method ensures precise carrier concentrations, often in the range of $10^{15} to $10^{20} atoms/cm³, which is vital for creating p-n junctions in transistors and diodes. For instance, -silane mixtures yield n-type films with enhanced , while -silane combinations produce p-type layers suitable for devices, improving overall device performance in . In solar cell production, plasma-enhanced CVD (PECVD) utilizes silane to deposit layers at lower temperatures around 200–300°C, forming intrinsic or doped films for thin-film photovoltaic modules. This process enables the creation of p-i-n structures with bandgaps tailored for light absorption and is used in niche applications, including some tandem configurations integrating with other materials. Epitaxial growth employs low-pressure CVD (LPCVD) with to produce single-crystal layers on substrates, essential for high-performance integrated circuits. Operating at pressures of 10–100 and temperatures of 800–1100°C, this method achieves growth rates up to 10 μm/h, yielding defect-free films with thicknesses of 1–10 μm for advanced nodes. Silane's high reactivity allows selective epitaxial growth in device fabrication, minimizing defects like stacking faults and supporting the scaling of transistors in logic chips. The market impact of silane underscores its importance in silicon precursor applications, driven by demand from advanced chips and emerging perovskite-silicon tandem cells that rely on high-purity silicon substrates produced via silane CVD; as of 2024, record efficiencies exceeding 33% have been achieved in such tandems. Global silane consumption in these areas is projected to grow at a CAGR of over 9% through 2033, reflecting its indispensable role in enabling and gains in and renewables.

Chemical and Other Uses

Silane serves as a key precursor in the of organosilicon compounds, particularly through hydrosilylation reactions where it adds to alkenes to form alkyl-substituted silanes. These reactions typically require catalysts and proceed by inserting the unsaturated bond across a Si-H linkage, enabling the production of intermediates for siloxanes and polymers. A representative example is the hydrosilylation of , yielding ethylsilane: SiH_4 + C_2H_4 \to C_2H_5SiH_3. This methodology is widely applied in industrial routes to functionalize for adhesives, coatings, and lubricants. In and rocketry, silane acts as an effective additive owing to its exceptionally low ignition energy, approximately 0.01 mJ in air, which facilitates spontaneous and reliable ignition under high-energy conditions. demonstrations have shown silane- mixtures with oxygen providing robust ignition for rocket engines, reducing startup delays in propulsion systems. Similarly, its pyrophoric nature supports ignition aids in s, enhancing combustion efficiency at concentrations as low as 2.5% in . Silane is also employed in the thermal oligomerization to generate higher silanes, starting with the formation of (Si_2H_6) via at elevated temperatures around 400–500°C. This process involves dehydrogenative of silane molecules and serves as a foundational step for synthesizing polysilanes, which are catenated polymers used in photoresists, optical materials, and precursors for ceramics. The reaction kinetics favor disilane as the primary product under controlled conditions, with further oligomerization yielding chains up to several silicon units. In , silane finds application in for calibrating and resolving silicon isotopes, leveraging its volatility to generate ion beams from gaseous samples. Commercial silane is ionized to separate isotopes such as ^{28}Si, ^{29}Si, and ^{30}Si in magnetic sector analyzers, achieving enrichments beyond 99.9998% for specialized uses like . This technique provides high-precision isotopic ratios essential for geochemical and studies. Emerging roles for silane include its function as a in the synthesis of nanoparticles for lithium-ion battery anodes, where thermal decomposition of silane gas produces discrete nanoscale particles that improve . Patents on silane-derived materials for batteries have shown an increasing trend, with annual growth of approximately 15% since 2020, driven by demands for higher-capacity electrodes in electric vehicles.

Safety and Precautions

Health and Fire Hazards

Silane is highly toxic by , acting as a severe irritant to the and mucous membranes upon exposure. Inhalation of silane gas can cause symptoms including , , coughing, and chest tightness, with high concentrations leading to due to the formation of siliceous particles during or . The lethal concentration (LC50) for silane in rats via is 9600 over 4 hours, indicating its at relatively low concentrations. Chronic exposure to silane primarily poses risks through its products rather than the gas itself, which is not directly classified as carcinogenic. However, of silica dust generated from silane can lead to , a progressive , and is associated with increased risk. Crystalline silica, a key byproduct, is classified by the International Agency for Research on Cancer (IARC) as a , meaning it is carcinogenic to humans based on sufficient evidence from occupational exposure studies. Silane exposure is regulated to minimize these risks; the (OSHA) has no (PEL) for silane, while the National Institute for Occupational Safety and Health (NIOSH) (REL) is 5 as an 8-hour time-weighted average (TWA); the NIOSH immediately dangerous to or health (IDLH) value is not determined (N.D.). Silane presents extreme fire and explosion hazards due to its pyrophoric nature and wide flammability range. It is pyrophoric, igniting spontaneously in air at temperatures at or below 54°C, and can form explosive mixtures with lower and upper explosive limits of approximately 1% and 96% by volume, respectively, allowing ignition over nearly the entire concentration range in air. Combustion of silane produces silica dust and hydrogen gas, both of which exacerbate hazards: the fine silica particles can disperse and cause respiratory issues, while hydrogen contributes to secondary explosions due to its own flammability. These properties necessitate stringent controls in environments where silane is present to prevent ignition from sparks, static electricity, or even elevated ambient temperatures.

Handling and Storage

Silane is typically stored in high-pressure cylinders constructed from passivated to minimize decomposition reactions with the cylinder walls. These cylinders must maintain a slight positive of an , such as or , to prevent air ingress and spontaneous ignition. Storage areas should keep temperatures below 50°C and segregate silane from oxidizers or incompatible materials to avoid hazardous interactions. Safe handling of silane requires operations in controlled environments like glove boxes or fume hoods equipped with explosion-proof ventilation and electrical systems to mitigate ignition risks. Personnel must use non-sparking tools and ground all equipment to prevent static discharge. For transportation, silane is often diluted with inert gases to concentrations below 1% to reduce flammability hazards during transit. In the event of a spill, immediately evacuate the area and ventilate to disperse vapors while monitoring for autoignition, particularly for small releases where controlled may be safer than suppression attempts. must not be used on spills or leaks, as it can react to produce gas, exacerbating the risk. Silane is classified by the U.S. (DOT) as a 2.1 flammable gas under UN 2203, requiring specific labeling, , and shipping protocols. In the , silane falls under REACH registration requirements for industrial manufacturers and importers exceeding one ton per year, ensuring compliance with assessments. Waste silane streams should be disposed of via flaring or catalytic combustion, converting the gas to silica and water vapor, in accordance with EPA emission control guidelines for hazardous gases. Operators handling silane must receive specialized training, including the use of leak detection systems with silane sensors set to alarm at thresholds as low as 0.5 ppm to enable early response to potential releases.

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