Development and commercialization of ionic-type photosensitive polyimides

Toray's ionic-type photosensitive polyimide, “Photoneece”, is widely used as an interdielectric and as a protection layer for microelectronics, because of its properties, such as the removal of photoreactive groups at low temperature, excellent thermal, mechanical and electrical film properties and excellent adhesion to various substrates. Toray has developed a new type of “Photoneece”, UR-5100, which is a low-stress photosensitive polyimide. In addition to a low thermal expansion coefficient (25 ppm/°C), “Photoneece” UR-5100 also features high resolution with an aspect ratio of more than 2.0 in 40 μm imaged film, and excellent mechanical properties in the cured film such as high elongation (>20%) and tensile strength (>200 MPa), even after 60 hr heat treatment at 350°C. “Photoneece” UR-5100 can be applied in multichip modules (MCMs), hybrid circuits, ICs and LSIs. In this paper the characterization and processing of this “Photoneece” UR-5100 are described.     

A mechanism for the electron beam lithography of solvent-soluble photosensitive polyimides

Solvent-soluble and intrinsically photosensitive polyimides were prepared, and their electron beam reaction was investigated. Negative tone patterns were formed by the electron beam irradiation of PI(BTDA/DEDPM) and PI(BEDA/DEDPM). The mechanism for the pattern formation of PI(BTDA/DEDPM) was determined from transient absorption measurements, changes in the molecular weights, and IR spectrum measurements to be crosslinking via hydrogen abstraction by the triplet excited state benzophenone moiety. For the case of PI(BEDA/DEDPM), the pattern was formed by insolubilization due to chemical change in the polymer. These reactions are found to be so inhomogeneous that insolubilization of the polymer occurs at an early stage of gelation.     

Synthesis and properties of photosensitive polyimide-nanocrystalline titania optical thin films

In this study, synthesis, morphology, and properties of high refractive index photosensitive polyimide-nanocrystalline titania hybrid materials are reported. A soluble polyimide grafted with carboxylic acid or methacrylate groups (P1) was first synthesized from 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 3,5-diaminobenzoic acid (DABA), 4-aminobenzoic acid (4ABA), and 2-hydroxyethyl methacrylate (2HEMA). The residual carboxylic acid groups could undergo an esterification reaction with titanium butoxide to provide an organic-inorganic bonding. On the other hand, the grafted methacrylate groups rendered photosensitive property for photopatterning. A homogeneous hybrid solution was obtained through the formulation on different mole ratios of titanium butoxide/carboxylic acid, water/acid content in a mixed solvent. It was followed by spin-coating, photocuring and post-baking. The titania domain size in the hybrid materials analyzed by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) was around 4-7 nm. The prepared optically transparent films had tunable refractive index (1.583 < n < 2.029), relatively good surface planarity and high thermal stability. A fine pattern with a line width of 50 μm was produced by direct lithographic process on the hybrid films. The present study demonstrates a novel approach for preparing high refractive index hybrid photosensitive materials with patternability.     

Negative-type photosensitive polyimide precursors developable with aqueous alkaline solutions

New photosensitive polyimide precursors developable with aqueous alkaline solutions were synthesized. Among diamine monomers having a photofunctional group, 2′-(methacryloyloxy)ethyl 3,5-diaminobenzoate yields high molecular weight polyamic acid. A photosensitive polymer composition consisting of Michler's ketone and a thermally stable peroxide, 3,3′,4,4′-tetrakis(t-butyldioxycarbonyl)benzophenone, results in a high photosensitivity of 200 J/m². The photosensitive coating of the composition is soluble in aqueous alkaline solutions as well as in organic aprotic polar solvents, and both solvents can be used as developers. However, the resolution of patterns is quite different, especially in thick films. Solvent developers results in poor resolution, whereas aqueous alkaline developers give patterns of high aspect ratio even in thick films. This is probably due to the difference in the diffusion efficiency and swelling properties of the polymer compared to the developers.     

光敏聚酰亚胺的最新进展

综述光敏聚酰亚胺作为感光高分子的最新进展，着重叙述了有机硅改性光敏聚酰亚胺，自增感光敏聚酰亚胺和含氟光敏聚酰亚胺的制备方法和性能研究。     

Positive photosensitive polyimides with cyclobutane structure

A new family of positive photosensitive polyimide (PPI) systems composed of solvent soluble polyimides (Pls) with cyclobutane (CBDA) structures and diazonaphthoquinone compounds (DNQ) has been prepared. Heat and catalytic imidizations were carried out to obtain CBDA Pls; the former was better than the latter in controlling the molecular weight of the Pl. The ? OH groups in the Pls were easily acetylated during catalytic imidization, so ? COOH groups were selected as weak acidic groups in the Pls. The ? COOH groups were also effective in giving the Pls an alkaline solubility. Therefore, Pls having ? COOH groups were superior to those having ? OH groups for PPI systems. The photosensitive properties of various PPl systems containing ? COOH were found to vary with the fraction of ? COOH groups in the Pls, the content of DNQ in the systems, and the molecular weight of the Pls.     

Preparation and application of photosensitive copolymers for PDP barrier ribs formed by photolithography

In this work, the photosensitive paste was prepared. It was comprised of inorganic particles and a photosensitive organic component. The inorganic particles included glass, ceramics, and metals. The organic component should contain at least the following photosensitive materials: photosensitive monomers, photoreactive copolymer and photopolymerization initiators. The photoreactive copolymer played a role of an adhesive in the photosensitive paste. Meanwhile in the development stage, the carboxyl groups of the copolymer reacted with the alkalescent developer. Following this, the unexposed part must be removed and an excellent pattern can be formed. A series of three-component acrylic copolymers (MAA/St/MMA) were designed, and then synthesized via free radical polymerization. Subsequently glycidyl methacrylate (GMA) was employed to modify the prepared copolymers through ring-opening reactions between the carboxyl groups and the epoxide groups. Eventually the photosensitive copolymers were obtained and used to form the barrier ribs of PDPs. The chemical structure, glass transition temperature, acid value and molecular weight of photosensitive copolymers had different effects on the structure and pattern of PDP barrier ribs. Through analyzing effects of different polymer performance parameters on the patterns of barrier ribs, the optimal photosensitive copolymer was acquired.     

Recent advances in analytical chemistry--a material approach

Advancements of materials research have profound direct impacts on developments in analytical chemistry and may hold the key to improvement of existing or new techniques at present times and near future. Applications of materials in analytical chemistry are reviewed, with focus on sensors, separations and extraction techniques. This review aims to survey examples of interesting works carried out in the last five years over a broad spectrum of materials classified as hybrids, nanomaterials and biomolecular materials.     

Photosensitive polyimides for applications in electrical and optical interconnection technology

The application of photosensitive polyimides in electrical and optical interconnection technology is discussed. Critical properties of two photosensitive polyimide formulations with significantly different structural chemistries have been compared. Polyamic ester based formulations such as Selectilux® HTR3 show significant distortions in the photopatterned features upon high-temperature baking, which can be ascribed to anisotropic shrinkage. A BTDA-alkylated diamine based preimidized formulation (Probimide®), on the other hand, shows a more uniform shrinkage of the photopatterned features. HTR3 films interacts strongly with metals such as copper, which adversely affect the photopatternability of these materials. Planarization behavior in multiple layer structures has also been investigated. We explored the viability of these materials for applications in optical interconnection. Probimide® materials exhibit low scattering losses and appear to be promising candidates for the development of a MCM-compatible optical interconnection technology. We also describe here a novel technique for optical recording of refractive index patterns in Probimide® films.     

电感耦合等离子体质谱技术最新进展

对1998年以来电感耦合等离子体质谱技术（ICP－MS）的最新进展作一简要回顾。内容包括同位素比值分析、双聚焦扇形磁场高分辨ICP－MS、多接收器磁扇形等离子体质谱仪（MC－ICP－MS）、飞行时间等离子体质谱仪（ICP－TOF－MS）、“冷”等离子体及屏蔽炬技术以及动态碰撞／反应池技术等进展。     

Synthesis and mechanical properties of novel photosensitive polyimides

This paper surveys novel photoimageable polyimides (PHIMPI), with emphasis on synthesis. Details of the chemistry and synthesis techniques on PHIMPI are discussed. A number of associated issues such as swelling, storage stability, shrinkage, photospeed, solvent developability, moisture absorption, thermal expansion and mechanical properties are presented. Most of the photoimageable polyimides that are commercially suitable to date are negative-acting, although recent developments in positive-acting PHIMPI are included.     

Recent advances in immobilized enzymatic reactors and their applications in proteome analysis

Immobilized enzymatic reactors recently have drawn much attention because of the striking advantages, such as high substrate turnover rate and ease in coupling with the separation and detection systems. Carrier materials, which have great effects on the development of the immobilized enzymatic reactors, have always being the focus of study. In this paper, the contributions, mainly in the last 5 years, on the enzymatic reactors and their applications in proteome study are reviewed, with some newly developed inorganic and organic carriers for enzyme immobilization described in details. Moreover, the hyphenation of immobilized enzymatic reactors with the separation and identification systems is also summarized. By reviewing these achievements, it could be seen that enzymatic reactors have very bright future, especially in proteome analysis.     

Photochemical reactivities of photosensitive polymers containing chalcone derivatives

Monomeric vinyl chalcone derivatives were prepared by the condensation reaction of p-hydroxybenzaldehyde with acetophenone derivatives in the presence of sodium ethoxide as a base, followed by esterification of their hydroxy groups with methacryloyl chloride. The monomers, 4-(methacryloyloxy)chalcone derivatives, have been polymerized by a free radical technique. Copolymers containing the chalcone groups with different ratios of p-nitrophenylmethacrylate as photosensitizer group have also been prepared. The photosensitivities of the polymeric chalcone derivatives were investigated through their photochemical reaction on exposure to UV light, and by measuring the changes in their UV spectra before and after irradiation. The results obtained from the disappearance rates of the C?C bonds indicate that the photoreactivities of the polymers are largely affected by the position of the substituent in the phenyl ring of the chalcone, the photosensitizer group ratio, and the irradiation time.     

Novel soluble thermally stable silane-containing aromatic polyimides with reduced dielectric constant

Bis(p-aminophenoxy)diphenylsilane (BPS), bis(m-aminophenoxy)diphenylsilane (BMS) and bis(5-amino-1-naphthoxy)diphenylsilane (BAS) as three silane-diamines were prepared by the reactions of 4-aminophenol, 3-aminophenol, and 5-amino-1-naphthol respectively, with dichlorodiphenylsilane in the presence of triethylamine. The related silane-containing polyimides were prepared by two-step polycondensation reactions of these diamines with three different aromatic dianhydrides. All the polymers were characterized and their physical and thermal properties were studied. The polymers showed high thermal stability while their solubility was greatly increased in polar aprotic solvents. Wide angle X-ray diffraction showed that all the polyimides were almost amorphous. Also their dielectric constants were decreased due to the incorporation of softening and low-polarizing siloxane units into the polymer backbone.     

Synthesis of novel aromatic polyimides containing bulky side chain for vertical alignment liquid crystals

In this study, a novel 4-（4-octyloxybenzoyloxy）biphenyl-3′,5′-diaminobenzoate and polyimides based on it were synthesized. The polyimide with mesogenic unit side chain exhibited excellent vertical alignment for nematic liquid crystal （LC）. The pretilt angles of LCs above 89° were kept after the rubbing process with 220 mm rubbing strength. The polyimide films as the alignment layer were baked at 120℃ for 12 h, the vertical alignment of LCs was still uniform and stable. Meanwhile, the UV-vis spectra of the noyel polyimide films showed the high transparency in a visible wave length.     

Synthesis and electrochromic properties of polyimides with pendent benzimidazole and triphenylamine units

Five novel near-infrared electrochromic aromatic polyimides(PIs) with pendent benzimidazole group were synthesized from 4,4'-diamino-4'-(1-benzylbenzimidazol-2-yl)triphenylamine(named as DBBT) with five different dianhydrides via two-step polymerization process, respectively. The maximum UV-Vis absorption bands of these PIs locate at about 335 nm for solid films due to the π-π* transitions. A reversible pair of distinct redox peaks, that were associated with a noticeable color change from original yellow to blue, was observed in the cyclic voltammetry(CV) test. A new absorption peak emerged at 847 nm in near-infrared(NIR) region with increasing voltage in UV-Vis-NIR spectrum, which indicates that PI can be used as NIR electrochromic material. These novel PIs have good electrochemical stability, appropriate energy levels for the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital(LUMO), in the range of-5.17 e V to-5.20 e V and-2.14 e V to-2.26 e V(versus the vacuum level) determined by cyclic voltammetry method. These values basically consisted with the results of quantum chemical calculation. These polyimides can be used as novel electrochromic and hole transportation materials.     

Synthesis and properties of novel diisocyanate based optically active polyimides

A new optically active diisocyanate was prepared from the reaction of l-leucine and pyromellitic dianhydride (PMDA) and subsequent transformation of intermediate imide-containing diacid to diisocyanate via Weinstock modification of Curtius rearrangement. Solution polycondensation reaction of the prepared diisocyanate with PMDA, 3,3,4,4-benzophenonetetracarboxylic dianhydride, and hexafluoroisopropylidene 2,2-bis(phthalic anhydride) resulted in the preparation of novel optically active polyimides. The optimal conditions for polyimidations (reaction duration and temperature programming) were obtained via study of the model compound. The monomer, model compound and polymers were characterized by FTIR, ¹HNMR, mass spectroscopy and elemental analysis and their optical and physical properties were studied as well.     

Synthesis and characterization of polyimides based on novel isomeric perfluorinated naphthylenediamines

Novel highly fluorinated polyimides containing hexafluoronaphthylene fragment in the main chain were prepared by the two-stage polymerization of 2,7- and 2,6-diaminohexafluoronaphthalenes with 4,4′-oxydiphthalic anhydride: polycondensation in a solution at 80 °C followed by high-temperature solid-state chain extension. The influence of hexafluoronaphthylene fragment isomerism on the key polyimide features - molecular weight, thermal stability, solubility, optical properties - was characterized. Polyimides based on 2,7-diaminohexafluoronaphthalene or easily accessible mixture of isomeric diamines formed the flexible, transparent, and thermostable films.     

Soluble polyimides from a semi-aliphatic diamine containing ester,amide and ether groups

A diamine was synthesized by two successive reactions.Nucleophilic reaction of 4-hydroxybenzoic acid with terephthaloyl chloride yielded terephthaloyl bis(4-oxybenzoic) acid.Then reaction of this compound with 1,8-diamino-3,6- dioxaoctane via Yamazaki method resulted in preparation of diamine named terephthalic acid bis(4-{2-[2-(2-amino ethoxy)ethoxy]ethyl carbamoyl}phenyl) ester.After fully characterization it was used to prepare new polyimides through polycondensation with different dianhydrides using trimethylchlorosilane.Characterization of polymers was achieved by common methods and their physical properties including inherent viscosity,thermal behavior,thermal stability,crystallinity and solubility were studied.Prepared polyimides showed improved solubility and good thermal stability.