Fluoride glass is a class of non-oxide optical glasses composed of fluorides of various metals. They can contain heavy metals such as zirconium, or be combined with lighter elements like aluminium and beryllium. These heavier elements cause the glass to have a transparency range extended into the infrared wavelength. [1]
Thus, the goal for heavy metal fluoride glasses (HMFG) is to create ultra-low loss optical fiber communication systems for commercial and defense applications as well as bulk components that can be used in invasive medical treatment. However, the heavier elements also cause the glass to have a low viscosity and make them vulnerable to crystallization during the glass transition or processing. This makes the glass more fragile and have poor resistance to moisture and environmental attacks. [2]
Fluoride glasses' best attribute is that they lack the absorption band associated with the hydroxyl (-OH) group (3.2–3.6 micrometers) which is present in nearly all oxide-based glasses. [3]
Fluoride fiber's optical properties can be determined by the intrinsic and extrinsic sources of loss. There are three sources of intrinsic loss for fluoride glass: UV absorption edge, Rayleigh scattering, and multiphonon absorption. [1]
At short wavelengths within the UV and visible spectrum, the UV absorption edge is the dominant effect. The UV absorption edge occurs when a wavelength of energy matches the electron transition or ionization potential and is absorbed into the material as an electron is ejected into another quantum state. However, this absorption only occurs at short wavelengths and rapidly decreases as the wavelength increases. [2]
In the visible to the near-infrared range of light, Rayleigh scattering is the dominant effect. Rayleigh scattering is the dispersion or elastic scattering of particles far smaller than the wavelength of energy. It is the reason the sky is blue as light from the sun is scattered by the molecules in the air. [4] Since glass is an amorphous solid and has minor variations in density across a fiber, Rayleigh scattering occurs and energy dissipates. However, the Rayleigh scattering scales inversely with wavelength so as the wavelength increases, the Rayleigh scattering decreases. [5]
Compared to silica glass, fluoride glasses undergo multiphonon scattering at longer wavelengths which is why they stay transparent into the infrared spectrum. This is where multiple phonons are created with the absorption and conjunction of a single phonon. This is important specifically in glass because neighboring ions vibrating against each other in phase can cause multiphonon scattering to occur. Since fluoride glasses have heavier ions than their silica counterpart, there are lower vibration frequencies that correspond to a longer infrared absorption edge. [6] [7]
The extrinsic sources of loss come mainly from crystallite scattering and impurity absorption. The main extrinsic source of loss comes from crystallite scattering. Crystallite scattering results from the directional ordering of a set of atoms that reflect and absorb wavelengths of energy differently. Since fluorite glasses tend to devitrify very readily, it can be difficult to avoid crystallization during processing. Impurity absorption arises from the many transitions and some rare earth elements that can be contained in the glass. Since these elements are absorptive in the mid-infrared range, there needs to be less than 1ppb levels of contamination so that the extrinsic loss is less than the intrinsic loss.
An example of a heavy metal fluoride glass is the ZBLAN glass group, composed of zirconium, barium, lanthanum, aluminum, and sodium fluorides. These materials' main technological application is as optical waveguides in planar and fiber form. They are advantageous especially in mid-infrared (2000-5000 nm) range. [8]
The first step in fluoride glass synthesis is batch preparation. The most important criteria of this step are the purity requirements which are specific for cation is desired. In general, many different diamagnetic cations can be tolerated so the things that should be monitored are the optically absorbent impurities and anionic impurities, such as nitrates, carbonates, and sulfates. One major impurity that should be avoided is water. The anionic impurities and water can cause anionic oxygen to arise in the final product. To avoid this, each individual material should be dehydrated or heated to prevent water contamination during synthesis. [1] [9]
After mixing the initial materials, the batch is heated to its melting temperature within a crucible. This raw glass often has high devitrified areas when the glass is dried in the crucible. This is tuned through the fining process that heats the melt above the liquidus temperature. As the heat increases, the viscosity decreases and the melt becomes homogenized without stirring and defects are removed. [9]
The result is a homogeneous, clear glass after cooling. There are many methods for cooling but the classical method involved cooling to just above the liquidus temperature and then melting into a cast and quench. When using a mold, there may be non-uniform cooling depending on the mold shape and weight. This casting method is fast, flexible, and can create many different shapes and sizes. However, it is limited because it exposes the glass to atmospheric contamination. There may be micro-crystalline phases still present in the glass at the top of the mold due to condensates. Additionally, bubbles may not reach the surface because the glass is frozen in the mold. Another method of cooling is through the mold-crucible method where the sample is cooled inside the crucible it was melted in. This means there is no exposure to the atmosphere or outside contamination, but the resulting glass is limited to the shape of the crucible. The last method of cooling is rapid quenching and is reserved for less stable glasses. [1]
The main goal in fluoride glass research and development is an ultra-low loss optical fiber communication system. Since fluoride glass fibers are transparent in the infrared range, they can transmit wavelengths of energy across a large area.
A secondary goal for fluoride glasses is infrared transmitting optical fibers and bulk components in the medical field. Fluoride optical fibers may transmit a laser beam into the body during surgery for less invasive procedures. They can also be used as gas or liquid sensors within the body by putting a light produced through the fiber via laser or LED on one side of the fiber and detecting the change on the other. Additionally, it allows for molecules with absorption bands in the infrared range to be detected through infrared spectroscopy. [2] [10]
Rayleigh scattering, named after the 19th-century British physicist Lord Rayleigh, is the predominantly elastic scattering of light or other electromagnetic radiation by particles much smaller than the wavelength of the radiation. For light frequencies well below the resonance frequency of the scattering particle, the amount of scattering is inversely proportional to the fourth power of the wavelength.
In physics, attenuation is the gradual loss of flux intensity through a medium. For instance, dark glasses attenuate sunlight, lead attenuates X-rays, and water and air attenuate both light and sound at variable attenuation rates.
Fluorite (also called fluorspar) is the mineral form of calcium fluoride, CaF2. It belongs to the halide minerals. It crystallizes in isometric cubic habit, although octahedral and more complex isometric forms are not uncommon.
UV spectroscopy or UV–visible spectrophotometry refers to absorption spectroscopy or reflectance spectroscopy in part of the ultraviolet and the full, adjacent visible regions of the electromagnetic spectrum. Being relatively inexpensive and easily implemented, this methodology is widely used in diverse applied and fundamental applications. The only requirement is that the sample absorb in the UV-Vis region, i.e. be a chromophore. Absorption spectroscopy is complementary to fluorescence spectroscopy. Parameters of interest, besides the wavelength of measurement, are absorbance (A) or transmittance (%T) or reflectance (%R), and its change with time.
Circular dichroism (CD) is dichroism involving circularly polarized light, i.e., the differential absorption of left- and right-handed light. Left-hand circular (LHC) and right-hand circular (RHC) polarized light represent two possible spin angular momentum states for a photon, and so circular dichroism is also referred to as dichroism for spin angular momentum. This phenomenon was discovered by Jean-Baptiste Biot, Augustin Fresnel, and Aimé Cotton in the first half of the 19th century. Circular dichroism and circular birefringence are manifestations of optical activity. It is exhibited in the absorption bands of optically active chiral molecules. CD spectroscopy has a wide range of applications in many different fields. Most notably, UV CD is used to investigate the secondary structure of proteins. UV/Vis CD is used to investigate charge-transfer transitions. Near-infrared CD is used to investigate geometric and electronic structure by probing metal d→d transitions. Vibrational circular dichroism, which uses light from the infrared energy region, is used for structural studies of small organic molecules, and most recently proteins and DNA.
In the field of optics, transparency is the physical property of allowing light to pass through the material without appreciable scattering of light. On a macroscopic scale, the photons can be said to follow Snell's law. Translucency allows light to pass through, but does not necessarily follow Snell's law; the photons can be scattered at either of the two interfaces, or internally, where there is a change in index of refraction. In other words, a translucent material is made up of components with different indices of refraction. A transparent material is made up of components with a uniform index of refraction. Transparent materials appear clear, with the overall appearance of one color, or any combination leading up to a brilliant spectrum of every color. The opposite property of translucency is opacity.
Absorption spectroscopy refers to spectroscopic techniques that measure the absorption of radiation, as a function of frequency or wavelength, due to its interaction with a sample. The sample absorbs energy, i.e., photons, from the radiating field. The intensity of the absorption varies as a function of frequency, and this variation is the absorption spectrum. Absorption spectroscopy is performed across the electromagnetic spectrum.
Fused quartz,fused silica or quartz glass is a glass consisting of almost pure silica (silicon dioxide, SiO2) in amorphous (non-crystalline) form. This differs from all other commercial glasses in which other ingredients are added which change the glasses' optical and physical properties, such as lowering the melt temperature. Fused quartz, therefore, has high working and melting temperatures, making it less desirable for most common applications.
Diffuse reflection is the reflection of light or other waves or particles from a surface such that a ray incident on the surface is scattered at many angles rather than at just one angle as in the case of specular reflection. An ideal diffuse reflecting surface is said to exhibit Lambertian reflection, meaning that there is equal luminance when viewed from all directions lying in the half-space adjacent to the surface.
An optical filter is a device that selectively transmits light of different wavelengths, usually implemented as a glass plane or plastic device in the optical path, which are either dyed in the bulk or have interference coatings. The optical properties of filters are completely described by their frequency response, which specifies how the magnitude and phase of each frequency component of an incoming signal is modified by the filter.
In physics, backscatter is the reflection of waves, particles, or signals back to the direction from which they came. It is usually a diffuse reflection due to scattering, as opposed to specular reflection as from a mirror, although specular backscattering can occur at normal incidence with a surface. Backscattering has important applications in astronomy, photography, and medical ultrasonography. The opposite effect is forward scatter, e.g. when a translucent material like a cloud diffuses sunlight, giving soft light.
Many ceramic materials, both glassy and crystalline, have found use as optically transparent materials in various forms from bulk solid-state components to high surface area forms such as thin films, coatings, and fibers. Such devices have found widespread use for various applications in the electro-optical field including: optical fibers for guided lightwave transmission, optical switches, laser amplifiers and lenses, hosts for solid-state lasers and optical window materials for gas lasers, and infrared (IR) heat seeking devices for missile guidance systems and IR night vision.
ZBLAN is the most stable, and consequently the most used, fluoride glass, a subcategory of the heavy metal fluoride glass (HMFG) group. Typically its composition is 53% ZrF4, 20% BaF2, 4% LaF3, 3% AlF3 and 20% NaF. ZBLAN is not a single material but rather has a spectrum of compositions, many of which are still untried. The biggest library in the world of ZBLAN glass compositions is currently owned by Le Verre Fluore, the oldest company working on HMFG technology. Other current ZBLAN fiber manufacturers are Thorlabs and KDD Fiberlabs. Hafnium fluoride is chemically similar to zirconium fluoride, and is sometimes used in place of it.
An optical fiber, or optical fibre in Commonwealth English, is a flexible, transparent fiber made by drawing glass (silica) or plastic to a diameter slightly thicker than that of a human hair. Optical fibers are used most often as a means to transmit light between the two ends of the fiber and find wide usage in fiber-optic communications, where they permit transmission over longer distances and at higher bandwidths than electrical cables. Fibers are used instead of metal wires because signals travel along them with less loss; in addition, fibers are immune to electromagnetic interference, a problem from which metal wires suffer. Fibers are also used for illumination and imaging, and are often wrapped in bundles so they may be used to carry light into, or images out of confined spaces, as in the case of a fiberscope. Specially designed fibers are also used for a variety of other applications, some of them being fiber optic sensors and fiber lasers.
A fiber-optic sensor is a sensor that uses optical fiber either as the sensing element, or as a means of relaying signals from a remote sensor to the electronics that process the signals. Fibers have many uses in remote sensing. Depending on the application, fiber may be used because of its small size, or because no electrical power is needed at the remote location, or because many sensors can be multiplexed along the length of a fiber by using light wavelength shift for each sensor, or by sensing the time delay as light passes along the fiber through each sensor. Time delay can be determined using a device such as an optical time-domain reflectometer and wavelength shift can be calculated using an instrument implementing optical frequency domain reflectometry.
Low-dispersion glass is a type of glass with a reduction in chromatic aberration. Crown glass is an example of a relatively inexpensive low-dispersion glass.
The technique of vibrational analysis with scanning probe microscopy allows probing vibrational properties of materials at the submicrometer scale, and even of individual molecules. This is accomplished by integrating scanning probe microscopy (SPM) and vibrational spectroscopy. This combination allows for much higher spatial resolution than can be achieved with conventional Raman/FTIR instrumentation. The technique is also nondestructive, requires non-extensive sample preparation, and provides more contrast such as intensity contrast, polarization contrast and wavelength contrast, as well as providing specific chemical information and topography images simultaneously.
Gallium lanthanum sulfide glass is the name of a family of chalcogenide glasses, referred to as gallium lanthanum sulfide (Ga-La-S) glasses. They are mixtures of La2S3, La2O3, and Ga2S3, which form the basic glass with other glass modifiers added as needed. Gallium-lanthanum-sulfide glasses have a wide range of vitreous formation centered around a 70% Ga2S3 : 30% La2S3 mixture, and readily accept other modifier materials into their structure. This means that Ga-La-S composition can be adjusted to give a wide variety of optical and physical properties.
When optical fibers are exposed to ionizing radiation such as energetic electrons, protons, neutrons, X-rays, Ƴ-radiation, etc., they undergo 'damage'. The term 'damage' primarily refers to the additional loss of the propagating optical signal leading to decreased power at the output end which could lead to premature failure of the component and or system.
Jacques Lucas is Professor Emeritus at the University of Rennes 1. Jacques Lucas is a solids-based chemist who specializes in the discovery of new lenses, contributing to their analysis, knowledge of their optical properties and their use in various fields. He is a member of the French Academy of sciences.