Spallation effects caused by shock waves in optical components such as those used in the Laser MegaJoule facility during laser operation can lead to material fracture. One solution could be to use a viscoelastic thin film on these fused silica components to reduce the reflection of shock waves from the rear surface, but it must have excellent optical, mechanical, and power-handling properties. Among the viscoelastic materials investigated were Nafion and polydimethylsiloxane-based ormosil, with ormosil synthesized using a sol-gel process. The materials were characterized optically and especially tested for acoustic attenuation. These materials, as thin films deposited on a fused silica substrate, were studied under shock wave propagation using the laser shock technique. Preliminary results showed that these thin films have interesting properties that could help reduce mechanical damage to optical components.
The MegaJoule Laser (LMJ) for inertial confinement fusion experiments is currently in operation at CEA-CESTA in
France. All the lenses are coated by an antireflective (AR) layer to optimize the light power transmission. This AR layer
is manufactured by sol-gel process, a soft chemical process, associated with a liquid phase coating technique to realize
thin film of metal oxide. These optical components are hardened into ammoniac vapors in order to mechanically
reinforce the AR coating and to make them more handling. This hardening induces a thickness reduction of the layer so
an increase of the stiffness and sometimes a crazing of the layer. As these optical components undergo a high-power
laser beam, so, it is important to verify if the AR properties (optical and mechanical) influence the value of the threshold
laser damage. A series of coated samples have been manufactured having variable elastic moduli to discuss this point. In
that purpose, a homemade Laser Induced Damage Threshold (LIDT) setup has been developed to test the layers under
laser flux. We describe the used methods and different results are given. Preliminary results obtained on several coated
samples with variable elastic moduli are presented. We show that whatever are the elastic stiffness of the AR coating, an
overall decrease of the threshold appears with no noticeable effect of the mechanical properties of the AR coatings.
Some possible explanations are given.
Three-dimensional photonic crystals (PCs) are periodic materials with a modulated refractive index on a length scale
close to the light wavelength. This optical property allows the preparation of specific optical components like highly
reflective mirrors. Moreover, these structured materials are known to have a high laser-induced damage threshold
(LIDT) in the sub-nanosecond range compared to multi-layered dielectric mirrors. This property is obtained because only
one high LIDT material (silica) is used. The second material used in the layer stack is replaced by air. In this work, we
present the development of 3D PCs with narrow-sized colloidal silica particles, prepared by sol-gel process and
deposited with Langmuir-Blodgett technique. Different syntheses routes have been investigated and compared regarding
the optical properties of the PCs. Finally a numerical model based on an ideal opal network including defect influence is
used to explain these experimental results.
Fluorescent chemical sensors have been widely exploited for the detection and quantification of trace explosives. Their
performances are mainly dependent on the sensitive material. Fluorescent organic materials are very efficient in terms of
sensitivity, selectivity and response time but their degradation is a major drawback. Sol-gel materials offer a much longer
life span, especially in the case of inorganic sensitive coatings. The elaboration of sol-gel sensitive films is detailed in
this paper. Two examples of sol-gel fluorescent sensitive materials are presented: a hybrid organic-inorganic film and an
inorganic material.
The French Commission for Atomic Energy is currently involved in a project which consists in the construction of a
2MJ/500TW (351nm) laser, so called LMJ (Megajoule-class laser) devoted to Inertial Confinement Fusion (ICF)
research in France[1]. For this high power lasers, the sol-gel process[2] has been selected for 95% of laser optical coated
area because of room temperature and atmospheric pressure conditions with guarantee for high optical and laser induced
damage threshold (LIDT) performances at a low cost compared to conventional vacuum deposition processes.
The production rate of sol-gel coatings for the LMJ optical components will require an automated cleaning surface step
during sol-gel process. We are investigating a spraying system and wash cycles compatible with the two sol-gel
deposition methods: dip and laminar-flow coating. The challenge is to achieve the same cleaned optical surfaces as
manual process without using organic solvents. Therefore the main specifications of the cleaning quality are the
following ones: a high surface energy over all optical sides (up to 400×400 mm2 area) and no degradation of polished
sides (surface defects and LIDT).
We present the metrologies carried out and the first results obtained from different wash cycles. These one mainly
consist in measurement of contact angles, defects inspections under specific lighting conditions and LIDT tests. Several
parameters of wash cycles have been investigated such as washing and rinsing temperatures, water quality, type and
concentration of detergents, wettability effects...
In the field of thin film coatings, sol-gel (SG) process is an alternative to the conventional Physical Vapor Deposition (PVD) techniques. Sol-gel process is particularly competitive on large-area or fragile substates by taking advantage of various liquid phase deposition techniques performed at room temperature and atmospheric pressure, coupled with the versatility of organo-metallic chemistry. Developed by the French Commission for Atomic Energy (CEA) since 1985 for its former high-power lasers generation, optimized sol-gel coatings proved also very resistant to laser energy.
In 1998, THALES Angenieux (TAGX) was selected by CEA to provide all the sol-gel coatings dedicated to the French Laser MegaJoule (LMJ) prototype, named Ligne d'Integration Laser (LIL).
In cooperation with Saint-Etienne Pole Optique et Vision (POV), TAGX initiated the building of a sol-gel technological platform (SGPF) aimed at demonstrating the feasibility of production of optical and functional coatings on large area substrates. A technology transfer was performed by CEA (Le Ripault) to TAGX focusing on the manufacture mainly of single-layer antireflective coatings (SLAR), but also of multi-layer AR-coatings and of multi-layered highly reflective (HR)-coatings.
Since beginning of 2001 and using SGPF equipments, TAGX successfully coated within specificaitons and schedule most of the 300 optics required for LIL activation. After this 2 years 1/2 production campaign in pre-industrial conditions, we can now analyse the advantages of each deposition technique used, the repeatability of the several processes, and the performance of the various coatings.
For fifty years, a considerable effort has been and is still being directed to the production of optical coatings using liquid deposition route. Sol-Gel is a chemical process widely used for oxide material preparation. Based on smooth chemistry (low temperature conditions), sol-gel allows nanoparticle and polymeric material synthesis dispersed in appropriate liquid medium. The process investigated at CEA (French Commission for Atomic Energy) is strongly developed to afford coatings onto mineral or metallic substrates using colloidal oxide-based and/or inorganic-organic hybrid materials. Such a chemical process is sufficiently adjustable to develop purpose-built materials and coatings for high power laser optical components, taking into account the high laser damage threshold requirement. Because the CEA megajoule-class pulsed laser is needing 7,000-m2 of coated area onto 10,000 large-sized optical components, we have developed to date, several optical coating procedures, each optical thin film being prepared from a specific material and deposition process. First need to fulfil was the antireflective (AR) coating required for transparent optics and used to increase laser light transmission and to suppress damaging residual reflection. The as-developed AR-coatings were made of nanosized particle-containing fragile single layer or abrasion-resistant polymeric-based broadband layer stack. For used on highly-reflective (HR) component, a specific unstressed multilayer coating has been developed and deposited onto deformable adaptative end-cavity mirror substrate. This HR-coating is made of quaterwave stack of colloidal-based low index and hybrid high index thin films.
Using such materials, first high ratio polarizing sol-gel coatings have been also produced. Apart optical coating preparation, sol-gel chemistry has been used to develop an hybrid dense protective thin film to enhance durability of oxidation-sensitive silver cavity reflectors. Each coating material preparation and room-temperature deposition process will be described. Because the sol-gel technology offers outstanding technical and economical advantages over the conventional vacuum techniques, this process has been transferred to one of THALES production plant for megajoule-class laser prototype supplying.
The interest of the antireflective coatings applied onto large-area glass components increases everyday for the potential application such as building or shop windows. Today, because of the use of large size components, sol-gel process is a competitive way for antireflective coating mass production. The dip-coating technique commonly used for liquid-deposition, implies a safety hazard due to coating solution handling and storage in the case of large amounts of highly flammable solvent use. On the other hand, spin-coating is a liquid low-consumption technique. Mainly devoted to coat circular small-size substrate, we have developed a spin-coating machine able to coat large-size rectangular windows (up to 1 x 1.7 m2). Both solutions and coating conditions have been optimized to deposit optical layers with accurate and uniform thickness and to highly limit the edge effects. Experimental single layer antireflective coating deposition process onto large-area shielding windows (1000 x 1700 x 20 mm3) is described. Results show that the as-developed process could produce low specular reflection value (down to 1% one side) onto white-glass windows over the visible range (460-750 nm). Low-temperature curing process (120°C) used after sol-gel deposition enables antireflective-coating to withstand abrasion-resistance properties in compliance to US-MIL-C-0675C moderate test.
The CEA/DAM megajoule-class pulsed Nd:glass laser devoted to Inertial Confinement Fusion (ICF) research is requiring 240 cavity-end mirrors. The mirror design is based on 44-cm square highly-reflective (HR)-coated deformable substrates. Such large dielectric mirrors are using interference quarterwave stacks of SiO2 and ZrO2-PVP (PolyVinylPyrrolidone) thin films starting from sol-gel colloidal suspensions (sols). The colloidal/polymeric ratio of the ZrO2-PVP composite system has been optimized regarding refractive index value, laser damage threshold and chemical interactions have been studied using FT-IR spectroscopy. Therefore a promising deposition technique so- called Laminar Flow Coating (LFC) has been associated to sol-gel chemistry for HR sol-gel coating development. The as-designed LFC prototype machine has been used for coating solution wave deposition by transportation of a tubular dispense unit under the substrate flat surface. Thin film so created by the solvent evaporation was then dried at room temperature or using short wavelength UV-curing built-in station. Optimization of parameters such as optical layer number, coating uniformity, coating edge effect, 1053-nm reflectance and laser damage threshold is discussed. Demonstration has been made that this novel coating method is a competitive way for large-area optical deposition compared to dipping or spinning techniques. Association of sol-gel colloidal suspensions to LFC process appear to be a promising cheap way of producing high power laser optical coatings.
The French Commission for Atomic Energy is currently involved in a project which consists of the construction of a 2 MJ/500TW (351-nm) pulsed Nd:glass laser and which will be devoted to Inertial Confmement Fusion (ICF) research in France. With 240 laser beams and almost 10,000 m2 in coated area required, the proposed megajoule-class laser will be the largest laser system ever built in the world. Room temperature and atmospheric pressure deposited coatings such as sol-gel for antireflective (AR) applications and silicone for environmental protective coatings, with high optical and laser-included damage performance, can be applied at a low cost compared to conventional vacuum deposition processes. Today, we are using such a technology to AR-coat prototypes of lenses, windows, blast-shields, debris-shields, flashlamps and harmonic converters required by our proposed megajoule-class laser. This technology has also been selected for the preparation of multilayer highly reflective (HR) coatings for use as cavity-end deformable mirrors in the laser system. Due to their suitability to ensure appropriate deposited optical thickness, room-temperature deposition techniques such as dip-, spin- or laminar-flow-coating have been optimized for such laser coating production.
A novel optical coating devoted to reduction of CRT panel specular reflection has been developed using the sol-gel route. The sol-gel antireflective (AR) coating is made from tantalum and silicon oxide-based solutions. First layer is an hybrid material based on polymeric mixture of tantalum with silicon oxide. Second and third layers are respective containing tantalum oxide and silica polymeric matrix, since they correspond to the high and low index thin film in the optical stack. Sol-gel synthesis has been carried out starting from cheap precursors in order to produce metallic alkoxide-based solution, each one suitable for liquid- deposition technique use such as dip or spin-coating. After layer deposition, a curing step is required. Both thermal and UV-curing could include layer densification and generate final coating properties. UV-curing is performed using short wavelength irradiation and thermal baking step does not exceed 150 degrees C temperature. CRT front panel prototypes have been produced with sol-gel AR-coat for test measurements. The process time including deposition by dip- coating and curing, is about one hour. This three-layer antireflective coating has been optimized to offer scratch- resistance, easy-clean and broadband antireflection properties on CRT panels.
A novel optical coating developed to reduction of specular reflection has been developed using the sol-gel route. The sol-gel antireflective (AR) coating is made from tantalum and silicon oxide-based solutions. First layer is deposited from a solution based on polymeric tantalum oxide. Second layer is containing silica polymeric matrix in order to get a double-layer optical stack. Sol-gel synthesis have been carried out starting from cheap precursors in order to produce metallic alkoxide-based solution, each one suitable for liquid-deposition technique use such as dip-coating. After layer deposition, a curing step is required. Both thermal and UV-curing could induce layer densification and generate final coating properties. Thermal baking step does not exceed 150 degrees C temperature. This two-layer antireflective coating has been optimized to offer scratch- resistance allowing easy-cleaning and also broadband anti- reflection property onto various substrate. Experiments of AR-coating deposition onto large-area high-power laser glass plates is described. Based on calculations, the amplification yield using such a sol-gel coating onto LMJ- blastshields is evaluated to be ca. 7 percent.
The CEA/DAM megajoule-class pulsed Nd:glass laser devoted to Inertial Confinement Fusion (ICF) research will require 240 cavity-end mirrors. The approved laser design necessitates 44cm X 44cm X 6cm highly-reflective (HR)-coated substrates representing more than 50m2 of coated area. Prototypes of these dielectric mirrors were prepared with interference quarterwave stacks of SiO2 and ZrO2-PVP thin films starting from sol-gel colloidal suspensions. Low reflective index materials was based on nanosized silica particles and high refractive index coating solution was made of a composite system. The colloidal/polymeric ratio in the composite system has been optimized regarding refractive index value, laser damage threshold and chemical interactions have been studied using FTIR spectroscopy. A promising deposition technique so-called 'Laminar Flow Coating' has been associated to sol-gel chemistry for HR laser damage-resistant sol-gel coating development. This novel coating method confirmed its main advantages compared to dipping or spinning processes: coating large flat square substrates at room temperature with small solution consumption, good thickness uniformity, weak edge-effects, induced stress-free coating, good optical properties and laser damage resistance.
CEA Limeil-Valenton has embarked in a project called 'laser megajoule' (LMJ) consisting of the construction of a 2-MJ/500- TW (351-nm) pulsed Nd:glass laser and devoted to inertial confinement fusion research in France. Room temperature and atmospheric pressure deposited sol-gel coatings for antireflective (AR), highly reflective (HR) and polarizer uses, and silicone films for environmental protection have displayed remarkable optical and laser strength performance. Such coatings can be applied onto large area and at a low cost compared to conventional vacuum deposition techniques. CEA Limeil-Valenton is also maintaining sustained efforts to promote the sol-gel technology in other areas.
The Centre d'Etudes de Limeil-Valenton is currently involved in a project which consists of the construction of a 2 MJ/500TW pulsed Nd:glass laser devoted to inertial confinement fusion research. With 240 laser beams, the proposed megajoule-class laser conceptual design necessitates 44-cm X 44-cm X 6-cm cavity-end mirrors representing more than 50-m2 of coated area. These dielectric mirrors are made of quarterwave stacks of SiO2 and ZrO2-PVP and are prepared from colloidal suspensions using the sol-gel route. After a sustained search effort, we have prepared (SiO2/ZrO2- PVP)10 mirrored coatings with up to 99 percent reflection at 1053-nm and for different incidence use. Adequate laser-conditioned damage thresholds ranging 14-15 J/cm2 at 1053-nm wavelength and with 3-ns pulse duration were achieved. Large-area mirrors with good coating uniformity and weak edge-effect were produced by dip-coating at room temperature and atmospheric pressure.
The Centre d'Etudes de Limeil-Valenton is currently involved in a project which consists of the construction of a 2 KJ/500TW pulsed Nd:glass laser and which will be devoted to inertial confinement fusion research in France. With 240 laser beams and almost 10 000 m2 in coated area required, the proposed megajoule-class laser will be the largest laser system ever built in the world. The proposed laser conceptual design necessitates 44-cm by 44-cm by 6-cm cavity-end mirrors representing more than 50-m2 of coated area. These dielectric mirrors are made of quarterwave stacks of SiO2 and ZrO2-PVP and are prepared from colloidal suspensions. After a sustained search effort, we have prepared mirrored coatings with up to 99 percent damage thresholds ranging 8-10 J/cm2 at 1053- nm wavelength and with 3-ns pulse duration were achieved. Mirrors with good coating uniformity and weak edge-effect could be produced by dip-coating and laminar-flow coating at room temperature and atmospheric pressure. To satisfy the coating demand, coating equipments and a 1000-m2 sol-gel coating production plant are planned to be built at REOSC- Group SFIM company in order to start producing within schedule and cost goal.
It is well established by manufacturers and users that optical coatings are generally prepared by the well known Physical Vapor Deposition (PVD) technology. In the authors' opinion sol-gel technology is an effective and competitive alternative. The aim of this paper is to emphasize on the sol-gel thin film work carried out at CEA Limeil-Valenton and concerning the technology for high power lasers. We will briefly discuss the chemistry of the sol-gel process, the production of optical coatings and the related deposition techniques. Finally, the paper describes performance of sol-gel optical coatings we have developed to fulfill the requirements of a future 1.8 MJ I500TW (351 nm) pulsed Nd:glass laser so-called << LMJ << (Laser MegaJoules). This powerful laser is to be used for our national Inertial Confinement Fusion (ICF) program, to demonstrate at the laboratory scale, ignition of deuterium-tritium fusion fuel. Moreover, the aim of this article is, hopefully, to provide a convincing argument that coatings and particularly optical coatings, are some of the useful products available from sol-gel technology, and that exciting developments in other areas than high power laser technology are almost certain to emerge within the coming decade.
Keywords : sol-gel, oxides, colloidal suspensions, optical coatings, laser damage
It is well established by manufacturers and users that optical coatings are generally prepared by the well known physical vapor deposition (PVD) technology. In the authors' opinion sol-gel technology is an effective and competitive alternative. The aim of this paper is to emphasize the sol-gel thin film work carried out at Centre d'Etudes de Limeil-Valenton (CEL-V) and concerning the technology for high power lasers. We briefly discuss the chemistry of the sol- gel process, the production of optical coatings, and the related deposition techniques. Finally, the paper describes the preparation and performance of sol-gel optical coatings we have developed to fulfill the requirements of a future 2 MJ/500 TW (351 nm) pulsed Nd:glass laser so-called LMJ (Laser MegaJoules). This powerful laser is to be used for our national inertial confinement fusion (ICF) program, to demonstrate at the laboratory scale, ignition of deuterium-tritium fusion fuel. Moreover, the aim of this article is, hopefully, to provide a convincing argument that coatings and particularly optical coatings, are some of the useful products available from sol-gel technology , and that exciting developments in other areas are almost certain to emerge within the coming decade.
We investigate an innovative sol-gel method that allows coating of mineral or plastic substrates with colloidal oxide-based materials and/or inorganic-organic composites and/or hybrids. To date, we have developed narrow and broadband antireflective coatings, multilayered dielectric mirrors, and a few polarizing thin films. These sol-gel optical coatings have demonstrated adequate performance for use in our proposed 2MJ/600TW (351 nm_ Nd:glass laser. To prepare such optical thin films, sol-gel technology offers outstanding technical and economic advantages over physical vapor deposition. Sol-gel technology opens new prospects in a variety of coating applications, and few areas offer greater payoff for interaction across disciplines than that of sol-gel-derived thin films.
The adhesion of sol-gel antireflective porous silica coatings on vitreous optical substrates has been dramatically improved by exposure to ammonia vapors or a dip in basic solutions. The approximately 70 to 270-nm thick coatings consisted of monolayers of spherical, 20-nm diameter amorphous silica particles deposited from ethanolic colloidal suspensions by conventional liquid coating techniques. Although, the as-deposited coatings had only low adhesion and were easily damaged when cleaned by standard drag-wiping procedures, coatings exposed over 5 hours to ammonia vapors passed both adhesive-tape and moderate abrasive- resistance tests. The increase in strength was accompanied by a roughly 20% shrinkage of the original coating thickness but the antireflective properties were retained. Our explanation of this chemical effect is a base-catalyzed phenomenon leading to surface silanol condensation and hydrogen-bonding of neighbor silica particles. In addition, since this basic treatment enhanced the laser damage resistance, such strengthened antireflective coatings have been successfully evaluated on flashlamps used on Phebus, Europe's most powerful laser. This allows an increase of the laser-disk pumping efficiency.
The cost of a large laser system is a strong function of the overall electrical to final photon efficiency. To improve the stored energy and therefore the pumping efficiency of sophisticated and costly laser-glass amplifiers, we have developed a novel two-layer broadband antireflective coating for the blast-shield component. The blast-shield is an optic placed between the flashlamps and the laser disk amplifiers to prevent damage of laser disks by possible explosion of a flashlamp. The sol-gel antireflective coating was dip-coated at room temperature onto 8-cm diameter glass samples. The coating basically consisted of a halfwave- thick high-index material such as ZrO2-PVP (PolyVinyl Pyrrolidone) and a quarterwave- thick low-index material such as SiO2-siloxane. To improve the abrasion resistance of the coated part, a lubricating and water-repellent material was applied as a very thin overcoat. In addition to a 6.5 to 7.2% transmission gain over the spectrum of interest, the coating was moderately abrasion resistant and chemically durable. Flashlamp-induced damage to the antireflective coating for 1000 glow discharges at 10 to 12 J/cm2 were minimal and similar to uncoated parts.
We describe a new coating method `laminar flow coating' (LFC) technique developed to obtain highly reflective (HR) laser damage resistant sol-gel multidielectric coatings. Such coatings are used in high-power lasers for inertial confinement fusion experiments (ICF). This technique uses substrates in an upside-down position and a travelling wave of coating solution is laminary transported under the substrate surface with a tubular dispense unit. This creates a thin-film coating by the solvent evaporation. Satisfactory results have been obtained onto 20 cm square glass substrates regarding the optical performances, the thickness uniformity, the edge-effects and the laser damage resistance. This deposition technique combines the advantages of both classical techniques: the substrate non-exclusive geometry such as in dip- coating and the small solution consumption such as in spin-coating. The association of sol-gel colloidal suspensions and LFC coating process has been demonstrated as a promising way to produce cheap specific optical coatings.
A novel quarterwave-thick narrow-bandwidth antireflective coating has been developed for both plastic and vitreous substrates by a sol-gel route. This coating has revealed pronounced scratch- and climatic-resistances under adverse conditions. The single-layer coating consists basically of a composite material made of silica as the discontinuous phase and of a polytetrafluoroethylene-derived (TeflonTM) organic polymer as the continuous phase. This leads to a fluorine-containing silica-based product so-called Fluosil-coating. The coating is applied by spin or dip from specific solutions at room temperature followed by a mild and short heat treatment. In addition to remarkable abrasion and environmental resistance properties, such coatings have displayed excellent laser-induced damage threshold levels surpassing uncoated substrates. We hope such a product might open new perspectives concerning household articles, architectural optical thin-films, ophthalmic uses and so on.
We describe a new coating method "Laminar Flow Coating"* (LFC) technique developed to obtain highly reflective (HR) laser damage resistant sol-gel multidielectric coatings. Such coatings are used in highpower lasers for inertial confinement fusion experiments (ICF). This technique uses substrates in an upsidedown position and a travelling wave of coating solution is laminary transported under the substrate surface with a tubular dispense unit. This creates a thin-film coating by the solvent evaporation. Satisfactory results have been obtained onto 20-cm square glass substrates regarding the optical performances, the tickness uniformity, the edge-effects and the laser damage resistance. This deposition technique combines the advantages of both classical techniques : the substrate non-exclusive geometry such as in dip-coating and the small solution consumption such as in spin-coating. The association of sol-gel colloidal suspensions and LFC coating process has been demonstrated as a promising way to produce cheap specific optical coatings1.
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