Thermal and broadband infrared optics continues to see an increased demand from both the military and commercial market, while maintaining a desire for a reduction in size and weight and cost (SWaPc). This has led to the development of many new potential optical materials from various sources . Most of these new materials are chalcogenide glasses due to their broad transmission window and potential for hot forming such as precision glass molding. When evaluating these materials from an optical design perspective, there are a few optimal materials that continue to appear in different designs. This work demonstrates why these materials are attractive optically, and reports on the thermal and optical properties of these materials that affect their design and manufacturing.
With advances in optical material design, it is now possible to expand the waveband for IR imaging systems. This paper will focus on evaluating and comparing optical designs that use newer materials that have been developed from NRL (Naval Research Labs), and materials that are readily available material to design. A 3x zoom lens will be used for these comparisons to determine if there is a reduction in the size, weight and power of the lens system.
This presentation will examine the case study of a 3x zoom lens that was optimized to work in the MWIR and the LWIR wavelength region and the challenges that come with working in such a wide waveband.
The Research and Development group at Rochester Precision Optics LLC (RPO) is conducting a years-long survey of the optical properties of glasses in the Ge-As-Se family. The goal of this survey is to find compositions in this ternary space that are more appropriately suited to demanding DoD and advanced R&D needs. This talk will focus only on the As-Se binary tie line of the full family but will illustrate glass compositions and measurements never before achieved even in this simple system. In particular, the refractive index of each composition is measured using a minimum deviation system from 850 nm to 14 μm. By parameterizing the fits of these dispersion curves, we achieve a deterministic model for designing custom compositions over this tie line. We also discuss the completely novel As80Se20 glass, who’s properties have not been previously reported in literature.
This effort evaluates laser processing for one of the more simplistic laser functionalities, utilizing the absorption of the laser for surface heating, and relying on the surface tension of the material as a function of temperature to leave a polished surface. The laser polishing is investigated across different materials: oxide optical glass, non-oxide chalcogenide optical glass, and optical polymer. A continuous wave visible wavelength laser is used for the chalcogenide glass, while a pulsed 10.6µm laser is used for the oxide glass and the optical polymer. The laser polishing results are compared to a hot forced-air local surface heating technique and traditional polishing methods.
This talk will address the ideas of intelligent material design when applied to infrared-transparent glasses. By using literature data as a jumping-off point, glass properties can be reduced to mathematical equations whose simultaneous solution results in a material with specifically targeted optical properties such as index and dispersion, as well as targeted mechanical properties such as glass transition temperature and coefficient of thermal expansion. Using this design approach eliminates the need for the scattershot trial-and-error method by which novel chalcogenide glass compositions are currently designed. Examples relevant to current infrared optical systems and their SWaP reduction will be discussed.
Additive manufacturing has taken many industries by storm, bringing a revolution to prototyping and manufacturing lines. For the most part, Glass and Optical Materials have been left on the wayside during this insurgence of additive manufacturing. Initially, the processes had very significant barriers to create practical uses for glass and optical materials. The emergence of UV curing or crosslinking polymers from a bath has proven useful for some optical elements and component applications for organic polymers. The majority of inorganic glasses are already fully cross-linked and cannot be used in curing/crosslinking methods.
Rochester Precision Optics (RPO) is constantly developing and designing optical elements and assemblies, having a cheap and quick process to prototype optics for demonstrators and initial prototype systems would be extremely valuable. RPO has investigated a number of methods to incorporate additive manufacturing of glasses into the optics and photonics fields. Laser based approaches of additive manufacturing of chalcogenide glasses will be presented. Optical properties and performance is compared across various additive manufacturing approaches and compared against bulk traditional material and processes.
Chalcogenide glasses have been steadily advancing infrared imaging capabilities and systems since the mid 1900s. Rochester Precision Optics has recently invested in bolstering their infrared glass manufacturing capabilities. While vertically integrating to reduce costs and to support the current and expanding demand for their precision glass molding, diamond turning, and assemblies that use the classic chalcogenide glasses; the optical design team has been able to capitalize on the new infrared materials further expanding the infrared optical glass map for S.W.A.P. enhancement in their designs.
The focus of this work is to highlight some of the capabilities and recent innovations in chalcogenide glass manufacturing leading to low cost methods of producing optical materials, elements, unique or previously difficult geometries.
With new detectors that are capable of imaging across multiple wavelength bands, new methods need to be developed to reduce the lens count and improve performance across these multiple bands while minimizing the SWAP-c (Size, Weight, power and cost) of the system. One method that was proposed was using an update to the classical γν-ν diagram. This method which, uses instantaneous Abbe number and minimum dispersion wavelength to select materials that minimize the chromatic and thermal focal shift over the desired spectral region. A MWIR/LWIR lens was designed using this method to minimize the lens count. The lens has a continuous 3x zoom range. The lens was manufactured to determine the validity of the method that was used and to evaluate the new materials that are being developed. A comparison of the nominal design to the manufactured design is discussed. This includes a comparison of MTF performance.
One of the difficulties in designing infrared optical systems is the comparative lack of glasses from which to design lenses. In visible optical systems, the designer has a palette of hundreds of glass options with varying dispersions and mechanical properties. In contrast, the designer of infrared optical systems has perhaps a dozen materials options from which to choose.
Instead, what if the infrared transparent materials were designed specifically for various applications? Using a material with a targeted index dispersion profile, the designer can complete a system using fewer lens surfaces and in many cases with increased functionality such as athermalization.
Next comes the question of how to obtain such a material. One approach is somewhat scattershot: to melt series of glasses, measure each of their properties, and settle on one composition for scale-up to production volumes. This approach is both time- and resource-consuming, as the measurements for many properties require specialized equipment and sample preparation.
In contrast to this scattershot method, the principle of intelligent material design allows glass scientists to design glasses with intentionally chosen mechanical and optical properties, and greatly reduces the number of test melts required to obtain a final production solution. Intelligent material design consists of leveraging the existing literature data to make informed decisions about which glass compositions are likely to exhibit the desired properties. By describing the variation of the properties over the glass family with mathematical functions, the material design problem is reduced to the simultaneous solution of a set of equations.
Due to changes in the fictive temperature as a result of the precision glass molding process there is an induced change in the index of refraction. This can be on the order of 0.001 in oxide glasses and as high as 0.02 in the chalcogenide glasses. It is important to accurately define the expected index of refraction and the tolerance of it after molding as there may be an impact on the optical design tolerances and system performance. We report on the measured change in index of refraction in common chalcogenide glasses due to the Rochester Precision Optics (RPO) precision glass molding process. We will compare the change in index of refraction between as advertised, as measured, as molded, and we will look at post mold annealing recovery. Utilizing an upgraded M3 refractometer we will be able to measure the index from the visible to the LWIR.
We show successful printing of chalcogenide glass using two different techniques. Additive manufacturing is still a fairly new field, but is increasing rapidly. We compare some of the first tests of selective laser melting and direct laser processing techniques to chalcogenide glass.
Advanced photonic devices require novel optical materials that serve specified optical function but also possess
attributes which can be tailored to accommodate specific optical design, manufacturing or component/device
integration constraints. Multi-component chalcogenide glass (ChG) materials have been developed which exhibit
broad spectral transparency with a range of physical properties that can be tuned to vary with composition, material
microstructure and form. Specific tradeoffs that highlight the impact of material morphology and optical properties
including transmission, loss and refractive index, are presented. This paper reports property evolution in a
representative 20 GeSe2-60 As2Se3-20 PbSe glass material including a demonstration of a 1D GRIN profile through
the use of controlled crystallization.
Conventional photonic integration technologies are inevitably substrate-dependent, as different substrate platforms stipulate vastly different device fabrication methods and processing compatibility requirements. Here we capitalize on the unique monolithic integration capacity of composition-engineered non-silicate glass materials (amorphous chalcogenides and transition metal oxides) to enable multifunctional, multi-layer photonic integration on virtually any technically important substrate platforms. We show that high-index glass film deposition and device fabrication can be performed at low temperatures (< 250 °C) without compromising their low loss characteristics, and is thus fully compatible with monolithic integration on a broad range of substrates including semiconductors, plastics, textiles, and metals. Application of the technology is highlighted through three examples: demonstration of high-performance mid-IR photonic sensors on fluoride crystals, direct fabrication of photonic structures on graphene, and 3-D photonic integration on flexible plastic substrates.
Chalcogenide glasses are increasingly used in infrared-transparent optical systems for space applications due to their relatively low density (compared to Ge or ZnSe), tunable spectral and thermo-mechanical properties, and molding capability. Remaining challenges include their application to thin-film optics and coatings. The high refractive indices of chalcogenide glasses (n ˃ 2.7) suggest the possibility for high reflecting coatings based on few periods of alternating layers with high index contrast. As2Se3 thin film deposited by thermal evaporation is investigated using ellipsometry which show optical properties consistent with bulk material. Also we demonstrate a novel method for fabrication of antireflection coating using porous chalcogenide. Possibility of negligible extinction coefficient and low refractive index of this porous coating promises broadband suppression of undesired Fresnel reflections at the interface from infrared optics.
High-index-contrast optical devices form the backbone of densely integrated photonic circuits. While these devices are
traditionally fabricated using lithography and etching, their performance is often limited by defects and sidewall
roughness arising from fabrication imperfections. This paper reports a versatile, roll-to-roll and backend compatible
technique for the fabrication of high-performance, high-index-contrast photonic structures in composition-engineered
chalcogenide glass (ChG) thin films. Thin film ChG have emerged as important materials for photonic applications due
to their high refractive index, excellent transparency in the infrared and large Kerr non-linearity. Both thermally
evaporated and solution processed As-Se thin films are successfully employed to imprint waveguides and micro-ring
resonators with high replicability and low surface roughness (0.9 nm). The micro-ring resonators exhibit an ultra-high
quality-factor of 4 × 105 near 1550 nm wavelength, which represents the highest value reported in ChG micro-ring
resonators. Furthermore, sub-micron nanoimprint of ChG films on non-planar plastic substrates is demonstrated, which
establishes the method as a facile route for monolithic fabrication of high-index-contrast devices on a wide array of
unconventional substrates.
Chalcogenide glasses, namely the amorphous compounds containing sulfur, selenium, and/or tellurium, have emerged as a promising material candidate for mid-infrared integrated photonics given their wide optical transparency window, high linear and nonlinear indices, as well as their capacity for monolithic integration on a wide array of substrates. Exploiting these unique features of the material, we demonstrated high-index-contrast, waveguide-coupled As2Se3 chalcogenide glass resonators monolithically integrated on silicon with a high intrinsic quality factor of 2 × 105 at 5.2 micron wavelength, and what we believe to be the first waveguide photonic crystal cavity operating in the mid-infrared.
Here we show our ability to fabricate two-dimensional (2D) gratings on chalcogenide glasses with peak-to-valley amplitude of ~200 nm. The fabrication method relies on the thermal nano-imprinting of the glass substrate or film in direct contact with a patterned stamp. Stamping experiments are carried out using a bench-top precision glass-molding machine, both on As2Se3 optically-polished bulk samples and thermally-evaporated thin films. The stamps consist of silicon wafers patterned with sub-micron lithographically defined features. We demonstrate that the fabrication method described here enables precise control of the glass’ viscosity, mitigates risks associated with internal structural damages such as dewetting, or parasitic crystallization. The stamping fidelity as a function of the Time-Force-Temperature regime is discussed, and further developments and potential applications are presented.
This study explores the structural relaxation behavior of As2Se3 by thermo mechanical analysis in order to characterize and eventually predict volume change in As2Se3 upon relaxation during cooling after precision glass molding (PGM) and annealing. A vertical beam of As2Se3 was placed in a thermo mechanical analyzer (TMA) and fully relaxed at a given temperature. The temperature was then quickly changed a given amount and the 1-D relaxation of the beam was measured until it reached equilibrium at the new temperature. The resultant curve was then fit with a Prony series which captured the relaxation data. The mathematical representation of the relaxation is then analyzed as a function of time, temperature, and quench rate and can be used to predict one dimensional (1-D) length change upon relaxation. A maximum of three terms is needed to describe the relaxation behavior and that number declines with an increase in temperature. This decay of the number of Prony terms needed to describe relaxation points to a structure that relaxes with less complexity as it approaches Tg. These trends can be converted to 3-D due to the amorphous and therefore typically isotropic nature of As2Se3 glass. This volume change information as a function of vital processing parameters can then be used to predict the change in shape of a work piece during cooling or post process annealing within a precision molding cycle. The mathematical representation of volume relaxation can then be applied to finite element models (FEM) of As2Se3 lenses or other optical elements.
Five chalcogenide glasses in the GeAsSe ternary glass system were melted, fabricated into flats, and molded between planar, uncoated, binderless WC molds using a laboratory-scale precision glass molding machine. The five glasses originate at the binary arsenic triselenide (As40Se60) and are modified by replacing As with Se in 5 mol% increments, or by locking the As:Se ratio and adding Ge, also in 5 mol% increments. The glasses are separated into two groups, one for the Ge-free compositions and the other for the Ge-containing compositions. This effort analyzes the differences between the Ge-containing and the Ge-free glasses on the post-molded glass and mold surface behavior, as well as the mold lifetime. Fabrication features, such as scratch and/or dig marks were present on the glass and mold surfaces prior to the PGM process. White light interferometry analysis of the surfaces shows an overall reduction in the RMS roughness of the glass after molding, and an increase of the roughness of the molds, after 15 molding cycles. After molding, the quantity of observable defects, primarily deposits and dig marks are increased for both the glass and mold surfaces. Deposits found on the WC molds and glasses were analyzed using Electron Dispersive X-ray Spectroscopy (EDS) and showed no evidence of being due to material transfer between the WC molds and the glass constituents. In general the main observable difference in the analysis of the two post molded sets, despite the changes in chemistry, is the quantity of molding induced defects near the edge of the GeAsSe samples.
The structural and optical properties of AsSe chalcogenide glass, starting with As40Se60, were studied as a function of Ge or Se additions. These elements provide broad glass forming options when combined with the host matrix to allow for compositional tuning of properties. Optimization of glass composition has been shown to produce bulk glasses with a thermoptic coefficient (dn/dT) equal to zero, as well as a composition which could demonstrate a net zero change in index after precision glass molding (PGM). The bulk glass density, coefficient of thermal expansion (CTE), refractive index, and dn/dT were measured for all bulk compositions, as was the refractive index after PGM. For the bulk glasses examined, both the refractive index (measured at discrete laser wavelengths from 3.4 to10.6 μm) and dn/dT were observed to decrease as the molecular percentage of either Ge or Se is increased. Compared to the starting glass’ network, additions of either Ge or Se lead to a deviation from the “optimally constrained” binary glass’ average coordination number <r> = 2.4. Additions of Se or Ge serve to decrease or increase the average coordination number (CN) of the glass, respectively, while also changing the network’s polarizability. After a representative PGM process, glasses exhibited an “index drop” consistent with that seen for oxide glasses.1 Based on our evaluation, both the Gecontaining and Ge-free tielines show potential for developing unique compositions with either a zero dn/dT for the unmolded, bulk glass, as well as the potential for a glass that demonstrates a net zero “index drop” after molding. Such correlation of glass chemistry, network, physical and optical properties will enable the tailoring of novel compositions suitable for prototyping towards targeted molding behavior and final properties.
Precision glass molding (PGM) is an optical manufacturing process used to hot press optical glass into a specified lens shape. This is done by taking the glass to a temperature above Tg and exerting force using an upper and lower mold. These molds will, together, give the pressed lens its shape. This study focuses on the high temperature interactions between the mold tooling material and two optical oxide glasses, Ohara’s L-BAL35 and Schott’s N-FK5. Flat molds were used to press flat glass work pieces at high temperature and force; key post process parameters such as sample and mold surface contamination using EDS and visible degradation via SEM were catalogued and analyzed. The molds used were bare tungsten carbide (WC) and silicon carbide (SiC) with an amorphous SiC chemical vapor deposition (CVD) coating. The results showed that raw WC molds suffered the most degradation including physical damage as well as chemical adherence and reaction. The Ti binder used in the WC as well as some the tungsten itself transferred to both glasses and caused a white reflective layer to appear on the molded glass surface. Severe damage was evident after only 2 pressing cycles with potassium from N-FK5 being the most prominent chemical contaminant. N-FK5 proved to be the more corrosive of the two glasses in all occasions. The SiC coated molds fared better in terms of degradation than the WC, however sticking of glass to mold was a problem.
Chalcogenide glasses, namely the amorphous compounds containing sulfur, selenium, and/or tellurium, have emerged as a promising material candidate for integrated photonics given their wide infrared transparency window, low processing temperature, almost infinite capacity for composition alloying, as well as high linear and nonlinear indices. Here we present the fabrication and characterization of chalcogenide glass based photonic devices integrated on silicon as well as on flexible polymer substrates for mid-IR sensing, optical interconnect and nonlinear optics applications.
Chalcogenide glasses, namely the amorphous compounds containing sulfur, selenium, and/or tellurium, have emerged as
a promising material candidate for integrated photonics given their wide infrared transparency window, low processing
temperature, almost infinite capacity for composition alloying, as well as high linear and nonlinear indices. Here we
present the fabrication and characterization of chalcogenide glass based photonic devices integrated on silicon as well as
on flexible polymer substrates for sensing, optical interconnect and nonlinear optics applications.
KEYWORDS: Silica, High power lasers, Chalcogenide glass, Laser systems engineering, Selenium, Fiber lasers, Semiconductor lasers, Near infrared, Thermal optics, Absorption
Chalcogenide samples with varying selenium concentrations, As10Se90, As30Se70, As40Se60, and As50Se50, were
characterized for high power transmission using a Tm:fiber laser system. The Tm:fiber laser oscillator consists of a
LMA fiber with 25/400 μm core/cladding diameters pumped by 793 nm diode. The output beam was collimated to
a 3 mm beam diameter, and transmitted through the chalcogenide samples at CW powers up to 23 W. We measure
the transmission as a function of incident power, as well as some initial characterization of surface damage from
nanosecond pulses at 2 μm. Furthermore, we utilize a wavefront sensor to characterized the thermal lens induced by
the Tm:fiber laser.
This paper discusses the use of chalcogenide phase change materials to create tunable metamaterials as potential
candidates for application to adaptive coded aperture control in the infrared. Phase change materials exhibit large and
reversible changes in optical properties (Δn, Δk) when switched between the amorphous and crystalline phases.
Thermally-induced phase transitions from the insulating amorphous to the conductive crystalline state can be controlled
through external means, facilitating the design of reconfigurable metamaterial devices that operate with ultrafast
response times. In this work, robust global stochastic optimization algorithms were combined with full-wave
electromagnetic simulation tools to design periodic subwavelength chalcogenide nanostructured arrays to meet the
specified device performance goals in each phase. The measured optical properties (n, k) of deposited chalcogenide thin
films and nanofabrication constraints were incorporated into the optimization algorithm to guarantee that the designed
nanostructures could be manufactured. By choosing the appropriate cost functions, adaptive metamaterials were
designed to switch between transmissive and reflective, transmissive and absorptive, and reflective and absorptive states.
These design demonstrations represent a significant step forward in the development of adaptive infrared metamaterials.
Nano-cavity photothermal spectroscopy is a novel technique for ultra-sensitive chem-bio detection. We illustrate that
through simultaneous localization of optical and thermal interactions in a planar nano-cavity, detection sensitivity can be
improved by > 104 compared to state-of-the-art. Key to nano-cavity photothermal sensing is the use of novel infraredtransparent
chalcogenide glasses for resonant cavity fabrication, as these glasses feature a photothermal figure-of-merit
over two orders of magnitude higher than conventional materials. We demonstrate planar optical resonant cavity devices
in these glasses with record cavity quality factors up to 5 × 105, leading to high photothermal detection sensitivity.
Physical properties of chalcogenide glass, including broadband infrared transparency, high refractive index, low
glass transition temperature, and nonlinear properties, make them attractive candidates for advanced mid-infrared (3 to
12 μm) optical designs. Efforts focused at developing new chalcogenide glass formulations and processing methods
require rapid quantitative evaluation of their optical constants to guide the materials research. However, characterization
of important optical parameters such as optical dispersion and thermal coefficient remains a slow and costly process,
generally with limited accuracy. The recent development of a prism coupler at the Pacific Northwest National
Laboratory (PNNL) now enables rapid, high precision measurement of refractive indices at discrete wavelengths from
the visible to the mid-infrared. Optical dispersion data of several chalcogenide glass families were collected using this
method. Variations in the optical dispersion were correlated to glass composition and compared against measurements
using other methods. While this work has been focused on facilitating chalcogenide glass synthesis, mid-infrared prism
coupler analysis has broader applications to other mid-infrared optical material development efforts, including oxide
glasses and crystalline materials.
In this paper, we review the design, processing, and characterization of novel planar infrared chemical sensors.
Chalcogenide glasses are identified as the material of choice for sensing given their wide infrared transparency as well as
almost unlimited capacity for composition alloying and property tailoring. Three generations of on-chip spectroscopic
chemical sensor devices we have developed: waveguide evanescent sensors, micro-disk cavity-enhanced sensors and
micro-cavity photothermal sensors are discussed.
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