Fused quartz
Fused quartz, also known as fused silica, is a high-purity, amorphous form of silicon dioxide (SiO₂) produced by melting high-quality quartz sand or synthetic silica precursors at temperatures exceeding 1700°C and rapidly cooling the melt to form a glass-like material without crystalline structure.[1] This process yields a material with exceptional purity levels typically exceeding 99.98%, low metallic contamination (less than 1 ppm in synthetic variants), and no hydroxyl content in certain types, distinguishing it from lower-grade glasses.[1] Unlike crystalline quartz, fused quartz lacks a regular atomic arrangement, resulting in isotropic properties and superior performance in demanding environments.[2] Key properties of fused quartz include outstanding thermal stability, with a softening point up to 1710°C for electrically fused variants and a maximum continuous operating temperature of 1160°C, alongside a low coefficient of thermal expansion (CTE) of approximately 5.0 × 10⁻⁷/°C, which minimizes distortion under temperature fluctuations.[1] Mechanically, it features a density of about 2.2 g/cm³, tensile strength around 50 N/mm², and Mohs hardness of 5.5–6.5, providing durability while remaining lightweight.[1] Chemically, it resists most acids (except hydrofluoric and phosphoric) and offers high resistance to water, salts, and environmental factors, enabling use in corrosive settings.[1] Optically, fused quartz transmits light from the ultraviolet range (absorption edge at ~0.180 µm) to the near-infrared (up to 3.5 µm), with high clarity and low absorption, ideal for precision optics.[3] Electrically, it exhibits high resistivity (up to 10¹⁸ Ω·m at 20°C) and a dielectric constant of 3.7–3.81, supporting applications in insulation and low-loss dielectrics across broad frequencies.[1] These attributes make fused quartz essential in diverse industries, including semiconductor fabrication for wafer processing and deposition equipment due to its purity and thermal shock resistance; optical systems for UV lenses, fiber optics, and laser components owing to its transparency; and high-temperature processes like photovoltaic ingot growth and chemical crucibles for its stability up to 1400°C.[4] In lighting, it forms envelopes for halogen and metal halide lamps, leveraging its UV transmission and high-temperature endurance.[2] Additionally, its biocompatibility and low autofluorescence support medical and research applications, such as laboratory ware and biomedical optics.[3]Overview
Definition and composition
Fused quartz is a non-crystalline, amorphous form of silicon dioxide (SiO₂) created by melting high-purity quartz sand or crystalline silica at elevated temperatures followed by rapid cooling to prevent crystallization.[5] This process results in a glassy material with exceptional purity and homogeneity, distinguishing it from traditional silicate glasses that incorporate additional oxides.[1] The chemical composition of fused quartz is predominantly SiO₂, typically exceeding 99.9% purity, with trace impurities such as aluminum oxide (Al₂O₃) at levels around 20-30 ppm, iron oxide (Fe₂O₃) at 10-25 ppm, and hydroxyl (OH) groups varying by production method—often 1-20 ppm in synthetic variants.[1][6] These impurities arise from the raw materials or processing and can influence properties like transmission in the infrared spectrum, but high-grade fused quartz minimizes them to maintain optical and thermal performance.[7] A key distinction exists between fused quartz, derived from melting natural quartz crystals, and fused silica, which is produced from synthetic precursors such as silicon tetrachloride (SiCl₄) via chemical vapor deposition.[5] Both share the same base composition but differ in impurity profiles, with synthetic fused silica often achieving higher purity (e.g., lower metallic contaminants).[8] Unlike crystalline quartz, which features a ordered tetrahedral arrangement of SiO₄ units in a helical structure, fused quartz exhibits a disordered atomic network where silicon atoms are bonded to four oxygen atoms in continuous random tetrahedra, forming a three-dimensional glass structure without long-range order.[9] This amorphous nature arises during vitrification, where the material is cooled from its molten state—reached at approximately 1713°C, the melting point of quartz—faster than the rate allowing atomic reorganization into a crystal lattice, due to the melt's high viscosity.[10]Historical development
The production of fused quartz, a high-purity form of amorphous silica glass, traces its origins to early 19th-century experiments with high-temperature melting techniques. In 1839, French scientists first succeeded in melting quartz using an oxyhydrogen combustion flame, marking the initial creation of quartz glass on a small scale.[11] This breakthrough laid the groundwork for later advancements, though practical applications remained limited due to challenges in scaling and purity. Significant progress occurred in the late 19th and early 20th centuries with the advent of electric heating methods. In 1899, Richard Küch at Heraeus in Germany established the industrial production of fused quartz glass using an oxyhydrogen flame, enabling consistent manufacturing for laboratory and early industrial uses.[12] By 1902, British researchers employed a graphite rod in a single-rod electric furnace to fuse quartz sand into glass, further refining the process for tubular forms.[11] A pivotal application emerged in 1906 when Peter Cooper Hewitt's mercury vapor lamp design was improved by Küch and Retschinsky, incorporating a quartz tube to withstand high temperatures and ultraviolet radiation; this innovation pioneered the use of quartz in mercury vapor lamps and influenced later commercial developments, including General Electric's acquisition of related mercury lamp patents in 1913.[13] During the 20th century, fused quartz gained strategic importance, particularly in World War II, where it was essential for optical instruments and radar systems due to its thermal stability and transparency.[14] The invention of the electric fusion furnace in the 1940s facilitated larger-scale production, supporting wartime demands.[11] Post-war, commercialization accelerated in the 1950s, driven by needs in semiconductors and lighting; companies like Heraeus expanded global supply, while General Electric's quartz division (later evolving into Momentive Technologies) advanced high-purity variants for electronics.[15][16] Modern developments since the 1980s shifted toward ultra-pure synthetic fused quartz, with plasma-enhanced chemical vapor deposition (PECVD) and related methods enabling impurity levels below 1 ppm for applications in optics and semiconductors; remote PECVD systems, developed in the late 1970s to early 1980s, allowed precise deposition on substrates at lower temperatures.[17] This evolution emphasized high-impact techniques like outside vapor deposition for optical fibers, prioritizing purity over traditional melting.[11]Production
Raw materials and preparation
The primary raw materials for fused quartz are natural quartz crystals or quartz sand derived from low-iron vein deposits, which provide high-purity silicon dioxide (SiO₂) essential for the material's transparency and thermal stability.[3] These natural sources, such as those from pegmatite formations in regions like Spruce Pine, North Carolina, or Drag, Norway, are selected for their minimal fluid inclusions and low levels of metallic impurities to ensure the final product's quality.[18] Alternatively, synthetic silica is produced through chemical vapor deposition using gaseous precursors like silicon tetrachloride (SiCl₄), offering superior control over composition for applications requiring extreme purity.[19] Preparation begins with rigorous selection of raw materials to achieve impurity levels below 50 ppm for metallic contaminants such as aluminum (Al), iron (Fe), and alkali metals (Na, K), which can otherwise compromise optical and electrical properties.[3] Natural quartz is sourced from sustainable deposits to minimize environmental impact, deliberately avoiding hydrothermal quartz varieties that contain inclusions leading to defects.[18] Selected crystals or sand are then crushed using mechanical or electro-dynamic methods to produce fine particles, typically in the range of 10-800 mesh, liberating the quartz from gangue minerals.[18] Following crushing, the material undergoes washing and purification steps, including water rinsing, magnetic separation, and acid leaching with hydrochloric or sulfuric acid to remove surface contaminants like iron oxides and alkali metals, targeting overall impurity reduction to under 10 ppm.[20] For optical-grade fused quartz, synthetic silica is preferred as it enables impurity levels below 1 ppm through precise precursor refinement, far surpassing natural sources in consistency.[3] These preparatory processes emphasize beneficiation techniques such as flotation and calcination to enhance purity while adhering to sustainable practices that limit resource depletion from finite high-quality deposits.[18] However, the reliance on a few key deposits, such as Spruce Pine, exposes the supply chain to risks, including temporary production halts due to Hurricane Helene in September 2024.[21]Manufacturing processes
Fused quartz is primarily manufactured through high-temperature melting processes that transform quartz sand or granules into a viscous glass state, followed by shaping into desired forms. The main methods include electric fusion, flame fusion, and chemical vapor deposition (CVD), each suited to specific purity requirements and product geometries. These processes operate at temperatures typically ranging from 1700°C to over 2000°C to achieve melting, with the material's high viscosity governing its flow and formability.[19][22] Electric fusion is the most widely used method for producing fused quartz, involving the heating of refined quartz granules or sand in a vacuum or inert atmosphere to prevent contamination. In continuous electric fusion, the material is melted in a vertical furnace equipped with a refractory metal crucible and resistance heating elements, allowing the viscous melt to be drawn into rods, tubes, or plates. Alternatively, batch fusion occurs in a vacuum chamber where quartz is heated to form large boules that can be further processed. These processes utilize temperatures of 1700–2000°C, achieved via resistance or arc furnaces, ensuring high purity with low hydroxyl (OH) content.[19][22][23] Flame fusion, a variant adapted from early 20th-century techniques similar to the Verneuil process, employs an oxy-hydrogen (H₂/O₂) or oxy-fuel flame to melt quartz sand continuously. The refined sand is fed through the high-temperature flame (exceeding 2000°C), where it forms a viscous ingot that is slowly withdrawn and shaped, often into rods or tubes via a die. This method, introduced in the early 1900s, produces material with stable OH content around 150 ppm and is valued for its bubble-free optical quality.[19][22] For applications demanding ultra-high purity, such as semiconductor components, chemical vapor deposition (CVD) synthesizes fused silica by depositing SiO₂ from gaseous precursors like silicon tetrachloride (SiCl₄) or tetraethyl orthosilicate (TEOS), which are oxidized in a flame or plasma. In one-step CVD, the reaction directly yields molten silica that can be formed into tubes; in two-step variants like outside vapor deposition (OVD), porous soot is first deposited and then sintered at high temperatures to densify the glass. This approach achieves OH contents below 1 ppm and is particularly used for high-purity tubes.[19] Once melted, the viscous fused quartz is shaped using techniques such as continuous drawing, where the melt is pulled through dies to form tubes or rods, or molding in graphite crucibles for items like laboratory ware. Electric cylinder fusion involves rotating the melt in a heated cylinder to coat the inner walls centrifugally, producing large-diameter tubes. To relieve internal stresses from rapid cooling, the formed products undergo annealing at controlled temperatures around 1000–1200°C. The material's viscosity during these steps follows an approximate Arrhenius temperature dependence, given by \eta \approx A \exp\left(\frac{B}{T}\right), where \eta is viscosity, T is temperature in Kelvin, and A and B are material constants reflecting activation energy for flow (typically B \approx 450 kJ/mol for silica). This behavior ensures precise control over shaping at elevated temperatures.[19][22][24]Quality assessment
Quality assessment of fused quartz involves evaluating its purity, structural integrity, and freedom from defects to ensure suitability for optical, thermal, and industrial applications. Purity metrics primarily focus on detecting metallic impurities, which can degrade transmission properties; spectroscopic techniques such as ultraviolet-visible (UV-Vis) spectroscopy are used to identify iron (Fe) content by measuring absorption bands around 240-270 nm, as iron impurities introduce coloration and reduce UV transparency.[25] For broader trace element analysis, inductively coupled plasma mass spectrometry (ICP-MS) quantifies metallic impurities like aluminum (Al), titanium (Ti), and alkali metals at parts-per-million (ppm) levels or below, enabling precise control of contamination that affects electrical resistivity and optical clarity.[26] Structural quality is assessed through tests for internal stress and hydroxyl (OH) content, as these influence mechanical stability and spectral performance. Birefringence testing, often via polariscopic or interferometric methods, detects residual stress by measuring phase retardation differences, with low-birefringence values (e.g., <0.1 nm/cm) indicating minimal stress-induced anisotropy.[27] Hydroxyl content, which impacts UV transmission by causing absorption below 200 nm, is measured using infrared (IR) spectroscopy at the 2.7-2.8 μm band, with high-purity grades targeting <5 ppm OH for vacuum UV applications.[28] Impurities like OH groups can limit deep-UV performance, as detailed in property analyses.[29] Fused quartz adheres to international standards for optical and thermal grades, including ISO 10110 for specifying optical homogeneity and defect classes. Materials are also classified by production method into types like Type I (electric fusion, low OH content) and Type II (flame fusion, higher OH content), both typically transparent for optical and thermal uses.[3] These standards ensure consistent performance, with requirements for near-zero striae and bubbles in precision optics, while tolerating higher defect levels for refractory uses.[30] Defect detection targets inclusions like bubbles and striae, which scatter light and compromise homogeneity. Bubble count is evaluated per ISO 10110 classes (e.g., N_x A_y, where x denotes size and y the obscured area fraction), using microscopic inspection or light scattering techniques to quantify total cross-sectional area obscured, typically aiming for <0.1% in optical grades.[3] Striae, or refractive index variations, are assessed via interferometry or schlieren imaging, measuring wavefront distortion to classify homogeneity, with low-striae materials showing <0.01 waves deviation over the aperture.[31] To minimize batch variability, modern production facilities employ statistical process control (SPC), monitoring key parameters like impurity levels and defect densities in real-time using control charts and capability indices (e.g., C_pk >1.33), ensuring consistent quality across lots and reducing rejection rates.[32]Physical and chemical properties
Mechanical and thermal characteristics
Fused quartz exhibits a density of 2.20 g/cm³ at 25°C, which contributes to its lightweight nature in structural applications.[33] Its Young's modulus measures 72 GPa, indicating high stiffness suitable for precision components under load.[34] Despite this rigidity, fused quartz is brittle, with a compressive strength of 1.1 GPa, allowing it to withstand significant pressure before failure.[35] However, its fracture toughness is low at approximately 0.7 MPa·m¹/², making it susceptible to crack propagation under tensile stress or impact.[36] The material's thermal properties are particularly advantageous for high-temperature environments. Fused quartz has a low coefficient of thermal expansion (CTE) of 0.55 × 10⁻⁶ /K over the range of 20–1000°C, resulting in near-zero expansion that prevents cracking during thermal cycling.[37] Its thermal conductivity is 1.4 W/m·K, enabling efficient heat dissipation without excessive thermal gradients.[35] At elevated temperatures, fused quartz maintains stability, with a softening point of 1600–1700°C (varies by grade) and a maximum continuous use temperature of approximately 1000–1100°C, with short-term use up to 1200°C before risking devitrification.[1] These characteristics collectively ensure its reliability in refractory roles where thermal shock resistance is critical.Chemical properties
Fused quartz demonstrates excellent chemical stability, resisting attack by most acids except hydrofluoric and phosphoric acids, and showing high resistance to water, salts, and alkalis at elevated temperatures. It has negligible solubility in water and is inert to most environmental factors, making it suitable for corrosive environments.[1]Optical and electrical attributes
Fused quartz exhibits excellent optical transparency across a broad spectrum, making it ideal for applications requiring high light transmission. Its refractive index is approximately 1.458 at a wavelength of 589 nm, with dispersion described by the Sellmeier formula n^2 - 1 = \frac{0.6961663 \lambda^2}{\lambda^2 - 0.0684043^2} + \frac{0.4079426 \lambda^2}{\lambda^2 - 0.1162414^2} + \frac{0.8974794 \lambda^2}{\lambda^2 - 9.896161^2} where \lambda is in micrometers; this allows precise modeling of wavelength-dependent behavior in optical designs.[38] The material transmits light from approximately 0.2 to 3.5 \mum, spanning ultraviolet (UV) to near-infrared (IR) regions, with over 90% transmittance through a 1 mm thickness in the visible spectrum (400-700 nm). For high-hydroxyl (OH) grades, the UV cutoff occurs around 220 nm due to absorption by OH groups, limiting deep-UV performance compared to low-OH variants.[9][39] Electrically, fused quartz acts as an outstanding insulator, with volume resistivity exceeding $10^{18} \Omega \cdotcm at 25°C, enabling its use in high-voltage environments without significant leakage. Its dielectric constant is 3.8 at 1 MHz, reflecting low polarization response and minimal energy loss in alternating fields.[40][41] As an amorphous material, pure fused quartz shows negligible inherent birefringence, ensuring isotropic light propagation unless mechanical stresses induce anisotropy. However, impurities such as metallic ions can cause fluorescence under UV excitation, typically emitting blue light, which must be minimized for sensitive optical systems.[9][3] Fused quartz's superior UV transparency, extending below 200 nm in low-impurity grades, outperforms borosilicate glass (cutoff near 310 nm) and supports critical applications like excimer laser optics at wavelengths such as 193 nm and 248 nm.[39][42]Applications and uses
Optics and lighting
Fused quartz serves as a critical material for envelopes in halogen and mercury lamps due to its ability to withstand high operating temperatures. In tungsten-halogen lamps, the fused quartz envelope maintains structural integrity at temperatures ranging from 400°C to 1000°C, enabling efficient light emission while tolerating internal pressures up to 50 atmospheres.[43] Similarly, mercury vapor lamps utilize fused quartz arc tubes to contain the high-pressure plasma, supporting temperatures around 700–800°C and allowing transmission of ultraviolet radiation essential for applications like germicidal lighting.[44] These properties make fused quartz ideal for demanding illumination technologies where thermal stability and optical clarity are paramount. In fiber optics, fused quartz forms the foundational core material for early silica-based optical fibers, providing the high-purity silica needed for low-loss light transmission over long distances in telecommunications.[9] Additionally, fused quartz windows are employed in laser systems, such as those using CO₂ (10.6 μm) and Nd:YAG (1.06 μm) wavelengths, where their broad transmission spectrum from ultraviolet to near-infrared—extending up to 3.5 μm—ensures minimal attenuation and resistance to thermal shock during high-power operation.[45] Fused quartz excels in ultraviolet applications, particularly as lenses and prisms in photolithography systems and sterilization lamps, leveraging its superior UV transmission down to 170 nm.[46] In photolithography, these components facilitate precise light patterning for microfabrication, while in UV sterilization devices, they enable effective transmission for disinfection processes in water and air purification. A notable example is its role in excimer lasers operating at 193 nm for semiconductor patterning, where high-purity fused quartz requires extremely low absorption—on the order of 2 × 10⁻³ cm⁻¹—to minimize energy loss and prevent material degradation during prolonged exposure.[47] This low absorption, combined with the material's UV transparency, underscores its precision in photonics. Overall, optics and lighting applications account for approximately 20% of global fused quartz demand, driven by the sector's need for reliable, high-performance materials.[48]Electronics and semiconductors
Fused quartz plays a critical role in semiconductor fabrication due to its high purity, thermal stability, and chemical inertness, enabling the production of contamination-free environments essential for integrated circuit (IC) manufacturing. In the Czochralski process, fused quartz crucibles are used to contain molten silicon at approximately 1420°C, allowing the growth of high-quality single-crystal silicon ingots that serve as the foundation for silicon wafers.[49] These crucibles must withstand extreme temperatures and minimize impurities to prevent defects in the resulting crystals, with their opaque or translucent forms optimized for uniform heat distribution during pulling.[4] Diffusion tubes and bell jars made from fused quartz are integral to doping and deposition steps in IC production, where they facilitate precise control of gaseous precursors in high-temperature furnaces. Diffusion tubes enable uniform dopant distribution across wafers during thermal diffusion processes, while large bell jars enclose chemical vapor deposition (CVD) setups to deposit thin films without introducing contaminants.[50][51] Their low thermal expansion and resistance to thermal shock ensure reliability in repeated cycles up to 1200°C. In plasma etching chambers, fused quartz serves as windows and liners that transmit radio frequency (RF) fields while resisting corrosion from halogen-based plasmas, such as those containing fluorine or chlorine. These components maintain vacuum integrity and optical clarity for process monitoring, enduring aggressive etching environments that would degrade lesser materials.[52] The material's low sodium content, typically below 0.2 ppm in semiconductor-grade variants, is vital for preventing mobile ion contamination in complementary metal-oxide-semiconductor (CMOS) processes, where even trace alkali metals can cause threshold voltage shifts and reliability failures.[53][54] Emerging applications include fused quartz substrates for microelectromechanical systems (MEMS) and photonic integrated circuits, leveraging its optical transparency and dimensional stability for precise patterning and integration of optical and mechanical elements. These substrates support advanced fabrication techniques, such as ion implantation for waveguides, enabling compact devices in sensing and communication technologies.[55]Industrial and refractory roles
Fused quartz serves as a critical material in industrial furnaces due to its ability to withstand extreme temperatures and thermal cycling. Components such as muffles, tubes, and boats are commonly fabricated from fused quartz for heat treatment processes, operating reliably up to 1400°C while maintaining structural integrity and minimizing contamination.[56] These parts benefit from the material's low thermal expansion, which enhances resistance to thermal shock during rapid heating and cooling cycles.[57] In chemical processing, fused quartz is employed for pipes and vessels that handle corrosive substances, offering superior resistance to most acids at elevated temperatures. For instance, it demonstrates excellent durability against hydrochloric, sulfuric, and nitric acids, except hydrofluoric acid, which attacks it at all temperatures, and is attacked by hot phosphoric acid above 150°C.[56][23][58] This inertness makes it ideal for transporting or containing aggressive chemicals in industrial settings without significant degradation.[58] Within metallurgy, fused quartz crucibles are widely used for melting precious metals such as gold, silver, and platinum, leveraging the material's high purity and thermal stability to prevent alloy contamination during high-temperature operations.[59] Additionally, fused quartz forms injection molds for glass processing, enabling precise shaping under high-heat conditions due to its non-reactivity and dimensional stability.[60] A notable application is in solar cell diffusion furnaces, where fused quartz tubes and liners endure repeated cycles at 1200°C, facilitating dopant diffusion into silicon wafers while resisting oxidation and devitrification.[61] In aggressive chemical environments, such as those involving phosphoric acid, fused quartz exhibits low erosion rates, ensuring long-term performance in refractory roles.[56]Distinctions and variants
Comparison to related materials
Fused quartz, an amorphous form of nearly pure silicon dioxide, exhibits a coefficient of thermal expansion (CTE) approximately 10 times lower than that of borosilicate glass, at 0.55 × 10⁻⁶ /K compared to 3.3 × 10⁻⁶ /K for borosilicate, enabling superior thermal shock resistance in high-temperature environments.[35][62] Additionally, fused quartz offers broader ultraviolet (UV) transmission, extending down to wavelengths as low as 0.18 µm, whereas standard borosilicate glass typically transmits UV light only above 0.30 µm, though specialized UV-grade variants reach 0.25 µm.[35][63] However, fused quartz incurs significantly higher production costs due to its purity requirements and manufacturing complexity, making borosilicate a more economical choice for less demanding applications.[64] In contrast to crystalline quartz, which is a naturally occurring or synthesized trigonal mineral with anisotropic properties, fused quartz is amorphous and thus isotropic, providing uniform mechanical and thermal behavior without direction-dependent variations.[5][65] The crystalline form exhibits piezoelectricity, generating electric charge under mechanical stress, a property absent in the non-crystalline fused quartz due to its lack of ordered atomic structure.[66] This amorphous nature also facilitates easier shaping and fabrication through melting and molding processes, unlike the rigid crystalline quartz, which requires precise cutting and polishing.[67] Compared to alumina ceramics, which are polycrystalline aluminum oxide with high mechanical strength, fused quartz provides superior optical clarity and chemical purity, as it is composed of over 99.9% SiO₂ without metallic impurities that can scatter light or react in harsh environments.[68][69] However, alumina offers greater hardness on the Mohs scale (9 versus 5.5-6.5 for fused quartz), contributing to better wear resistance in abrasive conditions.[70][1] Fused quartz is preferred over soda-lime glass in applications requiring high purity, as soda-lime glass contains alkali oxides (such as Na₂O and CaO) that can leach out in aqueous or humid conditions, leading to surface degradation and contamination, whereas fused quartz's pure SiO₂ composition prevents such alkali leaching.[71][64]| Material | Density (g/cm³) | Max. Service Temperature (°C) |
|---|---|---|
| Fused Quartz | 2.20 | 1100 |
| Borosilicate Glass | 2.23 | 500 |
| Crystalline Quartz | 2.65 | 573 (phase transition) |
| Alumina Ceramic | 3.90 | 1700 |
| Soda-Lime Glass | 2.50 | 300 |