高折射率有机硅LED封装材料研究进展

封装材料是LED器件不可缺少的一部分,它将LED芯片保护起来,使其免受环境温度、湿度、辐射和外力等的影响。有机硅LED封装材料具有优异的热、紫外辐射稳定性,同时兼具高透明性、耐冷热循环性以及疏水性等,是较理想的大功率LED封装材料,但由于一般的有机硅封装材料折射率较低,与芯片材料折射率相差大,如何进一步提高有机硅LED封装材料的折射率、以提高光输出效率,是当前迫切需要解决的一个问题,也是相关领域的研究热点。目前,提高有机硅LED封装材料折射率的方法,一般可以分为三种,即分子中引入杂原子、引入硅苯基以及材料中引入无机纳米粒子的方法。本文通过检索近十年的LED封装材料的相关研究报道,分析了其发展变化趋势及分布,综述了国内外高折射率有机硅LED封装材料的研究进展。     

Synthesis of Siloxanes Containing Vinyl and Epoxy Group and its Enhancement for Adhesion of Addition-Cure Silicone Encapsulant

Three types of siloxanes containing vinyl and epoxy group, (3-glycidoxypropyl) allyloxydimethoxysilane (GAMS), [2, 2-bis (allyloxymethyl) butoxy] (3-glycidoxypropyl) dimethoxysilane (AGMS) and [3-allyloxy-2, 2-bis (allyloxymethyl) propoxy] (3-glycidoxypropyl) dimethoxysilane (AAGMS) were prepared by the transetherification of 3-glycidoxypropyltrimethoxysilane with allyl alcohol, trimethylolpropane diallyl ether and pentaerythritol allyl ether, respectively. The chemical structures were characterized by Fourier transform infrared (FTIR) spectroscopy and ¹H nuclear magnetic resonance (¹H-NMR) spectroscopy. GAMS, AGMS and AAGMS were used as adhesion promoter for addition-cure silicone encapsulant (ASE) with a large amount of alumina (Al₂O₃) as thermally conductive fillers. It was found that the adhesion promoters not only greatly improved the adhesion strength of ASE but also significantly enhanced the mechanical strength of ASE. Among them, AAGMS gave the best adhesion strength and mechanical strength of ASE. The shear strength and tensile strength of ASE were increased from 0.34 and 2.23 MPa to 1.14 and 3.27 MPa with addition of 1.5 phr AAGMS, which was about 335% and 147% higher than that of ASE without adhesion promoter, respectively. The scanning electron microscopy (SEM) results showed that the adhesion promoters could improve the compatibility between Al₂O₃ particles and ASE matrix. Additionally, the viscosity of ASE with less than 3.5 phr AAGMS did not exceed 5000 mPa?s, which could meet the requirements of electronic encapsulation.     

Nano- and micro-structured random copolymer modified cycloaliphatic epoxy resins for use as light-emitting diode encapsulation

Poly(2,2,3,4,4,4-Hexafluorobutylmethacrylate–random–glycidolmethacrylate) random copolymer (P(HFBMA-r-GMA)) was synthesized via free radical polymerization. The novel reactive random copolymer was incorporated to modify cycloaliphatic epoxy resins and obtain the nano- or micro- structured composites. The chemical structures of P(HFBMA-r-GMA) were confirmed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The morphology and light transmittance of the cured epoxy resins were observed by scanning electron microscopy (SEM), transmission electron microscope (TEM) and ultraviolet-visible spectrophotometry (UV-vis), respectively. It is indicated that the optical transmittance of composites were basically kept although the microphase separation occurred in the curing process, which has a profound influence on the mechanical properties and refractive indexes. The thermal properties, surface dewettability and water absorbency of the cured epoxy resins were examined by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), contact angle measurement and immersion test respectively. The experimental results revealed that the values of glass transition temperatures (Tg), surface dewettability and water resistance were effectively improved by the high cross-linking density and the enrichment of the fluorinated random copolymer dispersing in the composites. With respect to the corresponding properties of the neat epoxy resin, P (HFBMA-r-GMA)-0.25 hybrimer embraced the relatively good comprehensive properties, making the modified epoxy resins as good candidates for LED encapsulation.     

Microencapsulation of Bioactive Ingredients for Their Delivery into Fermented Milk Products: A Review

The popularity and consumption of fermented milk products are growing. On the other hand, consumers are interested in health-promoting and functional foods. Fermented milk products are an excellent matrix for the incorporation of bioactive ingredients, making them functional foods. To overcome the instability or low solubility of many bioactive ingredients under various environmental conditions, the encapsulation approach was developed. This review analyzes the fortification of three fermented milk products, i.e., yogurt, cheese, and kefir with bioactive ingredients. The encapsulation methods and techniques alongside the encapsulant materials for carotenoids, phenolic compounds, omega-3, probiotics, and other micronutrients are discussed. The effect of encapsulation on the properties of bioactive ingredients themselves and on textural and sensory properties of fermented milk products is also presented.     

大尺寸高质量GaSb单晶研究

采用垂直布里奇曼法(VB法)生长2英寸GaSb单晶,分析了GaSb多晶产生的原因,即GaSb原料与覆盖剂中残留水分发生化学反应生成氧化镓残渣,残渣吸附在坩埚内壁导致GaSb多晶形成.通过增加覆盖剂除水工艺,成功生长出2英寸高质量GaSb单晶.此外,研究了单晶内部位错分布特点,结果显示GaSb晶体具有较低的位错密度,EPD≤500 cm-2;同时,对晶体进行XRD摇摆曲线测试,其FWHM值为27 arcsec,表明晶体质量较高;此外,对晶体进行了电学性能测试,结果显示制备的GaSb晶体呈P型导电,晶体迁移率为610 cm2/V·s,载流子浓度达到了1.68×1017cm-3.     

A comparative study of calorimetric methods to determine the crosslinking degree of the ethylene‐Co‐vinyl acetate polymer used as a photovoltaic encapsulant

EVA copolymer foils are widely used as encapsulants for photovoltaic (PV) cells in PV modules. These foils need to be crosslinked during module manufacturing, to enhance their properties. Accurate and reliable methods for the determination of their crosslinking degree are thus very important. In this work, two semi‐empirical calorimetric methods are considered and compared to a scientifically sound rheological method used as a reference. The main purpose of this work is to reveal the chemical and physical fundamentals on which the two calorimetric methods are based, to allow for a scientific understanding of their advantages, and limitations. For one of these calorimetric methods, the so‐called “Melt‐Freeze” method, we have sought for a deeper understanding of the underlying crystallization physics through the use of successive self‐nucleation and annealing experiments, which give access to the crystallite size distribution of EVA, and to the influence of crosslinking upon it. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 866–876     

Recent Development of Advanced Functional Polymers for Semiconductor Encapsulants of Integrated Circuit Chips and High-temperature Photoresist for Electronic Applications

A new polymer system of semiconductor devices was studied in response to the multifunctional systems evolved. A variety of functional polymers have been developed in the manufacture of semiconductor and integrated circuit (IC) packaging devices by R&D of high-temperature polymers. With the increase in integration of electronic devices and the need to reduce overall size, market needs are moving to multilevel metallization. Toray's core polymer technologies for electronic devices in the past 35 years (1961–95) are reviewed. The new technology of IC encapsulants of biphenyl type epoxy compounds is described for the new generation 16 megabits dynamic randon accessory memory (DRAM) electronic memory device, with good heat dissipation characteristics and low stress with an anti-flammability UL V-0 property of halogen-free formulation. As core functions are built into devices, packaging and mount technologies become more important. A new photosensitive high-temperature polymer stable up to 500°C with photosensitivity and high resolution has been developed. The trend toward a high degree of integration in solid-state technology requires the use of new high-temperature photosensitive insulating materials. Toray's "Photoneece" system provides such versatile polyimide pattern-generation techniques, containing a unique photosensitive polyimide precursor which can be spun or coated on the substrate. The main components of polyimide consist of poly(amic acid), a tertiary amine having methacrloyl group and a sensitizer. Through analyses of visible, fluorescence and electron spin resonance (ESR) spectroscopy, and flash photolysis and quantitative analyses, a new reaction mechanism is proposed. By photo-irradiation, the stable ion radical is formed without vinyl radical polymerization. The polymer is excited to form an excited singlet state. An anion radical of pyromellitic diamide moiety in a polymer chain is generated after intersystem crossing to an excited triplet state. The resultant relief of the photosensitive polyimide precursor, after exposure to UV light with a mask, development and cure processing, is transformed into a cyclized aromatic polyimide. The new system has higher photosensitivity and resolution and eliminates three steps in the conventional pattern-making process for integrated circuits, resulting in a significant cost reduction. The characterization of pattern generation, the conversion to polyimide patterns, and the properties of both Photoneece and the patterns are discussed. Initial photoreaction of an ionic-bonded photosensitive polyimide was studied by fluorescence, ESR and flush photolysis. A charge transfer complex between a polyamic acid (polyimide precursor) and an aromatic amine (sensitizer) was formed by UV irradiation from fluorescence measurement. Photo-induced radical was observed by ESR measurement. The photo-induced radical was an anion radical of polyamic acid from flush photolysis. From these results, a new photo-induced charge separation in an ionic bonded photosensitive polyimide film was found. Photo-induced electron transfer from an aromatic amine (sensitizer) to acid part of the polyamic acid occurs. © 1997 John Wiley & Sons, Ltd.     

Synthesis and Characterization of Ethylhydrosilicone Fluids as Liquid Cross-Linking Agents for the Encapsulant of Light Emitting Diodes

We report a series of ethylhydrosilicone fluids synthesized through the ring-opening copolymerization of mixed cyclosiloxanes and end-capped with the 1,1,3,3-tetramethyl-1,3-dihydrosiloxane using anionic exchange resin as catalyst. The mixed cyclosiloxanes consisted of methylphenylcyclosiloxane (D_n ^Me,Ph, n = 3, 4), tetramethylhydrogencyclosiloxane (D₄ ^H), and tetramethylethylcyclosiloxane (D₄ ^Me,Et). The refractive indices of the obtained silicone fluids were determined, and these products were further characterized by SEC, ¹H NMR, TGA, and DSC. The DSC results indicated that the cold resistance of the silicone fluids obtained was improved with the increase of (MeEtSiO) unit content. Therefore, the silicone fluids with good cold resistance can be used as liquid cross-linking agents for LED encapsulants to enhance the cold tolerance of LED devices.     

Modification of Epoxy Resin with Cycloaliphatic-Epoxy Oligosiloxane for Light-Emitting Diode (LED) Encapsulation Application

A novel cycloaliphatic-epoxy oligosiloxane (EHDM) was incorporated into 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (ERL-4221) for use as a light-emitting diode (LED) encapsulant. EHDM, with reactable epoxy groups and flexible Si-O-Si chains, was obtained by the hydrolytic condensation reaction between 2-(3,4-epoxycyclo-hexyl)ethyl-trimethoxysilane (EHETMS) and dimethyldiethoxylsilane (DMDES). The results of Fourier transform infrared spectroscopy, ²⁹Si nuclear magnetic resonance, and gel permeation chromatography indicated that EHDM had a narrow molecular weight distribution and high epoxy graft degree. The thermal and mechanical properties, morphologies, and light transmittance of the cured neat epoxy resin and EHDM-modified epoxy were investigated by differential scanning calorimetry, thermogravimetric analysis, tensile and impact testing, scanning electron microscopy, and ultraviolet-visible spectrophotometry. The experimental results demonstrated that the cured EHDM-10 hybrimer with 10 pph of EHDM relative to ERL-4221 maintained the neat ERL-4221 epoxy transmittance of 85% at 450 nm. With respect to the corresponding properties of the neat epoxy resin, EHDM-10 hybrimer possessed a higher glass transition temperature, better thermal stability, better fracture toughness, and lower water absorption ratio, indicating EHDM effectively improved the properties of ERL-4221 for LED packaging applications.     

磷化铟单晶生长中的传热和流动分析

用有限元法对轴向磁场存在下3英寸磷化铟单晶液封提拉法生长中的传热和流动进行了求解．结果表明:液封改变了晶体表面被封部分的换热,进而影响生长界面的形状．增加磁场强度能有效减弱熔体和封层内的流动,并使生长界面形状发生变化。增加提拉速度,生长界面形状由凸变凹．随晶体转速的增加,多涡胞流动出现．