Novel gallate-based oxide and oxyfluoride glasses with wide transparency,high refractive indices,and low dispersions

The glass-forming region of a BaO-La₂O₃-Ga₂O₃ ternary system was confirmed and BaF₂-BaO-La₂O₃-Ga₂O₃ new oxyfluoride glasses were prepared by a containerless processing. We also analyzed the physical, thermal, and optical properties of new oxide and oxyfluoride glasses. The direct effects of the substitution of oxygen by fluorine and the effect of BaO and La₂O₃ on the refractive index and Abbe number were discussed on the basis of electronic polarizability and resonance wavelength of oscillator. The refractive indices increased with increasing La₂O₃ concentration because La₂O₃ increased the electronic polarizabilities. Abbe number increased with increasing BaO and fluorine concentration because of the decrease in resonance wavelength of oscillator. By the combination of the BaO, La₂O₃, and fluorine in the gallate glass system, we could obtain novel oxide and oxyfluoride glasses with high refractive index (1.81-1.95) and high Abbe number (31-55). The absorption edge in UV region shifted to the shorter wavelength and IR cut-off wavelength shifted to the longer wavelength with increasing fluorine. Therefore, wide transparent glass was obtained from 262 nm to 11.3 μm.     

New class of bioinspired lenses with a gradient refractive index

The recognition that eye lenses in nature often employ a gradient refractive index to enhance the focusing power and to correct aberrations has motivated us to construct a synthetic lens using the layered concept encountered in biological lenses. The result is a highly flexible technology for the fabrication of gradient‐refractive index lenses that is based on a method of polymer forced assembly. Polymeric nanolayered films with incremental differences in the refractive index are assembled according to a prescribed design and molded into the desired shape. The exceptional flexibility of the process lies in the wide range of lens shapes and index profiles that can be realized. A lens with any refractive index distribution can be achieved within the refractive index range of available coextrudable optical materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1834–1841, 2007     

Magneto‐optical effects of Ge‐Ga‐Sb(In)‐S chalcogenide glasses with diamagnetic responses

The Faraday effects of Ge‐Ga‐Sb(In)‐S serial chalcogenide glasses were investigated at the wavelengths of 635, 808, 980, and 1319 nm, respectively. The compositional dependences were analyzed and associated influencing factors including the absorption edge, the concentration of Sb³⁺/In³⁺ ions, and the wavelength dispersion of refraction index were discussed. 80GeS₂·20Sb₂S₃ composition glass was found to have the largest Verdet constant (V=0.253, 0.219, 0.149, and 0.065 min·G^?1·cm^?1 for wavelengths 635, 808, 980, and 1319 nm, respectively) in these glasses, which is larger than that of commercial diamagnetic glasses (Schott, SF 6, V=0.069 min·G^?1·cm^?1@633 nm, for example). Sb³⁺ ions with high polarizability possessing s²‐sp electron jumps involving ¹S₀→¹P₁, ³P_0,1,2 transitions are responsible for large Verdet constant, and Becquerel rule is proved to be an effective guidance for estimating the Verdet constant and further optimizing the compositions in chalcogenide glasses.     

Large third-order optical nonlinearity of chalcogenide glasses within gallium-tin-selenium ternary system

We explore the third-order optical nonlinear properties of arsenic- and germanium-free chalcogenide glasses (ChGs) within a gallium-tin-selenium (Ga-Sn-Se, GSS) ternary system at wavelength of 1.064 μm in the picosecond region. A classical characterization showing the values of the absorption and the linear index will be given. Then, using D4σ-Z-scan technique, both nonlinear refractive index (n₂) and nonlinear absorption coefficient (β) of the GSS ChGs will be measured. A comparison of the results is made with other families of chalcogenide glasses considering the figure of merit calculation. The first results show that GSS system would give better NL performance promising high potential for n₂(β)-based photonic devices performed under clean production and green/sustainable chemistry.     

Y3NbO7 transparent ceramic series for high refractive index optical lenses

A₂B₂O₇ and A₃BO₇ transparent ceramic families are potential materials for optical lenses because of their high refractive index. Although nonstoichiometry is widely present in these material families, its effect on refractive index and optical properties has not yet been fully studied. In this study, optical properties are reported for the Y₃NbO₇ transparent ceramic series, Y_1−xNb_xO_1.5+x (x = 0.20, 0.22, 0.24, 0.25, 0.26), which were fabricated by a pressureless pre-sintering and a hot isostatic pressing post-sintering treatment. The refractive index increases from 2.04 to 2.10 (at 587.6 nm) as the Nb content x increases, which is mainly attributed to the variation in the oxygen ion/vacancy ratio. The Abbe number is larger than 40, showing a decreasing trend as the Nb content x increases. The specimen with x = 0.24 has the highest inline transmittance, which were 62% and 76% at 587.6 and 2000 nm, respectively, for a 1-mm-thick specimen. Through the approach of nonstoichiometry, Y_1−xNb_xO_1.5+x series exhibit balanced properties of refractive index, Abbe number, and transmittance, which can be considered as a promising candidate for high refractive index optical lenses.     

Fabrication of a gradient refractive index preform using laminar shear mixing

A gradient refractive index rod was successfully prepared by a new fabrication method using laminar shear mixing, and a graded index polymer optical fiber that satisfied IEEE1394b was obtained from the method. To fabricate the gradient refractive index rod, a liquid monomer mixture with a relatively low refractive index was placed in a prepared cylindrical glass reactor and a transparent polymer rod with a higher refractive index was introduced at the center of the reactor. The reactor and the polymer rod were then rotated concurrently with a small rotating speed difference to generate a Couette flow in the liquid phase. The centrifugal force generated by rotation and the polymer diffusion into the liquid monomer mixture developed a graded concentration profile in a radial direction. The Couette flow could reduce the concentration fluctuation in a tangential direction. In addition, the graded index profile could be controlled by the copolymer composition of the rod and its diameter. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1100–1104, 2005     

Interpreting the optical properties of oxide glasses with machine learning and Shapely additive explanations

Due to their excellent optical properties, glasses are used for various applications ranging from smartphone screens to telescopes. Developing compositions with tailored Abbe number (V_d) and refractive index at 587.6 nm (n_d), two crucial optical properties, is a major challenge. To this extent, machine learning (ML) approaches have been successfully used to develop composition–property models. However, these models are essentially black boxes in nature and suffer from the lack of interpretability. In this paper, we demonstrate the use of ML models to predict the composition-dependent variations of V_d and n_d. Further, using Shapely additive explanations (SHAP), we interpret the ML models to identify the contribution of each of the input components toward target prediction. We observe that glass formers such as SiO₂, B₂O₃, and P₂O₅ and intermediates such as TiO₂, PbO, and Bi₂O₃ play a significant role in controlling the optical properties. Interestingly, components contributing toward increasing the n_d are found to decrease the V_d and vice versa. Finally, we develop the Abbe diagram, using the ML models, allowing accelerated discovery of new glasses for optical properties beyond the experimental pareto front. Overall, employing explainable ML, we predict and interpret the compositional control on the optical properties of oxide glasses.     

Intrinsic second-order nonlinearity in chalcogenide glasses containing HgI2

Frequency conversion using nonlinear optical (NLO) crystals is widely used in advanced photonic technologies to produce coherent light in the spectral regions where the available laser sources are missing. Isotropic glasses usually do not show second order nonlinear processes like second harmonic or difference frequency generation (SHG, DFG) except for temporarily induced anisotropy under external stimuli. Here, we show that a HgI₂–Ga₂S₃–GeS₂ homogeneous glass exhibits a strong intrinsic SHG response comparable with that of the well-known NLO single crystal LiNbO₃. The origin of this extremely rare phenomenon seems to be noncentrosymmetric bent HgI₂ molecules embedded in a sulfide glassy host. Taking into account the unique properties of chalcogenide glasses (wide IR transmission, low phonon density, unlimited ability to be modified changing the appropriate glass properties, fiber drawing and thin layer design), the observed phenomenon opens up the possibility of creating fundamentally new devices for mid-IR photonics.     

Intrinsic high refractive index polymers

As the ubiquity and complexity of optical devices grows, our technology becomes more dependent on specialized functional materials. One area of continued interest is in high refractive index polymers as lightweight, processable and inexpensive alternatives to silicon and glass. In addition to a high refractive index, optical applications require these polymers to be transparent and have a low optical dispersion. Both nanocomposite and intrinsic high refractive index polymers offer particular advantages and disadvantages. While nanocomposite high refractive index polymers have refractive indices above 1.80, the nanoparticle type, content and size can negatively affect storage stability and processability. Alternatively, intrinsic high refractive index polymers are prepared by introducing an atom or substituent with a high molar refraction into a polymer chain; the resultant polymers are easier to store, transport, tune and process. Polymers containing aromatic groups, halogens (except fluorine), phosphorus, silicon, fullerenes and organometallic moieties have all shown significant promise. Many factors can affect intrinsic high refractive index polymer performance including molecular packing, molar volume, chain flexibility and substituent content. This mini‐review summarizes the principles behind and recent developments in intrinsic high refractive index polymers. © 2014 Society of Chemical Industry     

Preparation,characterization, and mechanical-optical properties of telluro-borate glasses containing tungsten

The current work is interested in the preparation, characterization, and mechanical-optical properties of the glasses in the (75-x)B₂O₃–10SrO–8TeO₂–7ZnO−xWO₃ system, with (x = 0 (BSTZW0), 1 (BSTZW1), 5 (BSTZW2), 10 (BSTZW3), 22 (BSTZW4), 27 (BSTZW5), 34 (BSTZW6), and 40 mol% (BSTZW7). The preparation of the glasses has involved the melt-quenching route. The new glasses are characterized by different characterization techniques using densimeter, microhardness, Raman spectroscopy, UV–visible absorption and emission, and X-ray diffraction. Photoluminescence can determine the impact of substituting B₂O₃ with WO₃ on the mechanical-optical parameters and the structure of the present glasses. The prepared samples’ X-ray patterns showed amorphous states. The density value rises from 2.88 to 4.50 g/cm3, with the amount of WO₃ rising from 0 to 40 mol% as a result of the difference in molecular weight between WO₃ and B₂O₃. The Vickers microhardness (Hv) rises as the amount of WO₃ increases as a result of a decrease in free volume and the formation of covalent bonds. The elastic moduli were found to increase when the WO₃ concentrations increased from 0 to 40 mol%. This increase depends on the formation of bridging oxygen atoms. The Raman bands are designed to correspond to the bonds that form the structure of the current glass and detect the insertion of WO₃ content by the attribution of the new W–O–W and W–O bonds. The UV–Visible spectroscopy analysis showed no band characteristic for the reduced species of W⁵⁺ ions identified by dark blue. However, the photoluminescence spectra showed emission bands (under excitation at 300 nm) that are associated with the active centers of W⁴⁺, W⁵⁺, and W⁶⁺ ions.     

Synthesis of carbazole‐substituted poly(dimethylsiloxane) and its improved refractive index

A series of substituted 9‐vinylcarbazole polysiloxane was synthesized followed by room temperature vulcanization to afford a crosslink network via trimethoxysilane crosslinker. Structural confirmation was made using FTIR, one and two‐dimensional ¹H‐ and ²⁹Si‐NMR spectroscopy. Quantitative estimation of the amount of substituted carbazole was made based on NMR data. These were related to the refractive index whose values were in the range of 1.4370–1.4625 at increasing carbazole content. These values are higher than uncrosslink series, attributable to the tightness of the systems. They displayed an improved thermo‐optic coefficient compared to linear unsubstituted polydimethylsiloxane (PDMS). The synergistic effect of substituted carbazole unit with the crosslink network of PDMS presents a viable choice of encapsulant for opto‐electronic devices. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41654.     

Multilayered chalcogenide glass with gradient index for reduced SWaP IR optical system

Gradient index (GRIN) lens could promote the lightweight and miniaturization of optical imaging system, but the development of IR GRIN lens is still in its infancy. A new series of As–S–Se chalcogenide glasses (ChGs) possessing similar glass transition temperature, excellent thermal stability, and large refractive index variation was developed, and these properties enabled them to become a good glass material catalog for co-molding multilayered GRIN IR lens. By employing precision molding, layer-stacked GRIN ChG was co-molded with a maximum refractive index variation of 0.47 at 4 μm, which was correlated to the variation of Raman intensity and elemental content. A mid-IR optical imaging system was designed and fabricated using the GRIN ChGs, and IR images were obtained. This multilayered GRIN ChG could lead to 18% smaller and 35% lighter SWaP IR optical system.     

Preparation and characterization of novel ZnS/sulfur-containing polymer nanocomposite optical materials with high refractive index and high nanophase contents

A series of novel transparent bulk ZnS-polymer nanocomposites with high refractive index were successfully prepared via in-situ bulk polymerization in the presence of 2-mercaptoethanol (ME)-capped ZnS NPs. The polymerization mechanism combined the step-growth and free radical polymerization of different monomers of episulfide, m-xylylene diisocyanante (XDI), 2-hydroxyethyl methacrylate (HEMA) and N,N-dimethylacrylamide (DMAA). The high refractive index of episulfide compounds, including ESGMES, ESDGEBA and MPS, were synthesized and used as monomers in polymerization systems. The cured nanocomposites with 30 wt% nanoparticles show high refractive index and good transparency. The refractive index of the nanocomposites could be continuously regulated in the range from 1.59 to 1.65 by the content of ZnS NPs and the pencil hardness is round about 5H. The content of ME-ZnS NPs can affect the thermal stability, mechanical and optical properties of the resulting nanocomposites, and the relationship between them were studied by TGA, DMA, pencil hardness test, Charpy impact test.     

The relationship between refractive index and optical properties of absorbing nanoparticle

This article represents an analytical formulation for optical properties of absorbing metallic nanoparticles in visible region of electromagnetic spectrum based on Mie theory, in order to find a clear relationship between fundamental characteristics of nanoparticles with their spectral behavior and color coordinate in CIELAB color space. Calculations were performed on nanoparticles with various diameters (d = 50, 100, and 200 nm), as well as complex refractive index with different real (n = 1.5, 2.0, 2.5, and 3.0) and imaginary (k = 0.001 and 0.1) parts. Obtained results reveal that scattering phenomena in nanoparticles are strongly linked to the particle size parameter and complex index of refraction. The results indicate that the reflectance and lightness (L*) of nanoparticles increases as a result of increase in their size and real part of complex refractive index and decrease with increasing the imaginary part of complex refractive index. The CIELAB colorimetric system was used for analysis the color of nanoparticles. According to obtained results, all nanoparticles have greenish‐blue color, and undergo color change as a result of varying in their size and the complex refractive index. © 2015 Wiley Periodicals, Inc. Col Res Appl, 41, 477–483, 2016     

Preparation and characterization of high refractive index thin films of TiO2/epoxy resin nanocomposites

By using sol–gel method, amorphous titania was introduced into epoxy matrix to prepare a series of high refractive index TiO₂/epoxy resin nanocomposite films. To increase the refractive index of the hybrid films, triethoxysilane‐capped trimercaptothioethylamine (TCTMTEA), a new kind of high refractive index coupling agent was synthesized from trimercaptothioethylamine (TMTEA). In the experiment, TCTMTEA acted as the solidification agent together with TMTEA except being used as the coupling agent. The hybrid films have been characterized via FTIR, AFM, DSC, TGA, etc. The experimental results showed that the amorphous TiO₂ had been dispersed uniformly in the organic polymer matrix with the size smaller than 100 nm in each sample. More importantly, the refractive index of this kind of materials can be continuously adjusted from 1.61 to 1.797 with the content of TiO₂ increasing from 0% to 65% in mass, and the continuously adjusted refractive index is very important for the applications in optical antirefractive films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1631–1636, 2006     

CsCl对GeS2-Sb2S3硫系玻璃光学及析晶特性的影响

通过熔融-淬冷法制备了(100-x)(0.9GeS2-0.1Sb2S3.)-xCsCl(x=5,10,15,20,以摩尔计)系列硫卤玻璃.测试了样品的折射率和吸收光谱.根据Tauc方程计算了间接允许光学带隙和直接允许光学带隙.通过差热分析对微晶玻璃析晶动力学进行了研究.利用析晶活化能(E)和频率因子(v),并结合动力学因素和热力学因素分析了玻璃的稳定性.结果表明:随着CsCl含鼍的增加,样品的线性折射率变小,短波截止波长蓝移,光学带隙逐渐增大,玻璃稳定性变差:85(0.9GeS2-0.1Sb2S3)15CsCl玻璃样品较适合制备透明的微晶玻璃,可用于研究硫系基质玻璃与微晶玻璃之间的三阶非线性效应.     

Preparation of low refractive index fluorinated materials for antireflection coatings

Novel low refractive index fluorinated polymers were prepared from perfluoroalkylsilane and polyethoxysiloxane by a sol‐gel technique for antireflection applications. Perfluoroalkylsilane having low refractive index fluoroalkyl groups incorporate polyethoxysiloxane by condensation of their siloxane groups to improve the adhesion and hardness of the fluorinated polymers. Syntheses and characteristics of the fluorinated polymers were investigated by the studies of FTIR, GPC, UV–vis, ellipsometry, and mechanical tests. The experimental results reveal that the refractive index and hardness of the coating using the optimal fluorinated polymer were about 1.39 and 3H, respectively, which meet the requirements in practical applications. It was also found that the fluorinated polymer made from polyethoxysiloxane had a better hardness than that made from tetraethyl orthosilicate. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and properties of polythiourethane/ZnS nanocomposites with high refractive index

The inorganic–organic crosslinking polythiourethane/ZnS (PTU/ZnS) nanocomposites with high refractive index and transmittance were successfully prepared. The thiol‐capped ZnS nanoparticles with a diameter of about 5 nm were fabricated into the molecular chains of PTU via the formed covalent bonds between the capped ZnS and the matrix. The investigations demonstrated the ZnS nanoparticles were uniformly dispersed in the PTU matrix even at high contents. The optical studies showed the refractive index of the highly transparent nanocomposite films linearly increased from 1.643 to 1.792 with the increase of the ZnS content. The structure, morphology, and other properties were also characterized by FTIR, NMR, AFM, XRD, DSC, TGA, etc. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

高折射率含硫环氧树脂的合成与表征

利用间接法以巯基乙醇和环氧氯丙烷 (ECH)为原料通过 3步反应得到 2 ,3 二 (2 ,3 环氧丙硫乙硫基 )丙基·2 ,3 环氧丙基硫醚型环氧树脂 (TGEBES) ,其折射率和环氧值分别达 1.5 85 0和 0 .5 3;在没有任何催化剂的条件下 ,按以三元硫醇 (BES)和ECH物质的量比为 1∶3.6、在温度为 0～ 5℃下反应 3～ 4h ,环氧化反应的产率达到84 .5 %。并利用红外光谱和核磁共振对含硫高折射率环氧树脂的结构进行了表征 ;利用高效液相色谱对TGEBES和BES的纯度进行了测定 ,结果表明TGEBES和BES纯度分别达 96 %和 97.7%以上。     

Raman Study of the Interface between Hot-Pressed Silica Parts

We present a Raman spectroscopy study of silica glasses prepared by hot-pressing of gels. Our particular interest is the structure at the interfaces formed during hot-pressing of small parts to obtain large pieces, such as silica tubes for optical-fiber preforms. A specific feature of the interface that distinguishes this layer from the bulk is its fractal structure. The parameters of the fractal units, including their maximum dimensions in real space, are determined by the pre-hot-pressing mechanical processing. We attribute this structure to residual microcracks inherent in the surface layer of polished plates. There are no fractals at the interfaces sintered at temperatures higher than the glass transition temperature.