Photodegradable transient bilayered poly(phthalaldehyde) with improved shelf life

Metastable poly(phthalaldehyde) (PPHA) can be triggered to depolymerize under visible light by incorporation of photosensitive compounds, such as a photoacid generator (PAG), which can generate a strong acid in situ. However, photosensitive compounds can be thermally unstable and have limited shelf life, causing inadvertent device triggering. It can also be difficult to fabricate components that are photosensitive because special lighting conditions are needed. In this paper, nonphotosensitive PPHA films were formed and made photosensitive at the point of use. This improved the material shelf life and manufacturability by adding a second, PAG‐containing layer to the original nonphotosensitive layer at an optimal point before use. The catalytic photoacid was generated rapidly by exposure of the PAG‐containing layer to radiation. Depolymerization of PPHA via the acid catalyst was followed by diffusion of the acid into the nonphotosensitive layer causing it to depolymerize. Diffusion of the photoacid into the nonphotosensitive medium was quantified at various temperatures. Photoacid diffusion in a liquid, moving‐front caused depolymerization of the nonphotosensitive PPHA layer. The fabricated bilayer structure allowed for better stability of the structural material using PPHA while still achieving transience.     

双光子技术在光生酸剂中的应用研究

自2000年以来,双光子技术开始应用于光生酸剂体系中,并取得了一定的研究进展。双光子技术在光生酸剂中的应用主要有两种情况:一是单分子体系,即光生酸剂分子本身具有较高的双光子吸收截面,可以在双光子激发下产生光酸;二是双分子体系,由具有较高吸收截面的敏化剂分子和光生酸剂分子组成,通过分子间电子转移的方式产生光酸。本文就这一类具有特殊光学性质的有机分子体系的构成及其应用进行了综述,介绍了不同类型的可以利用双光子技术的光生酸剂体系,总结了双光子技术在光生酸剂发展中面临的一些关键问题,展望了双光子技术在光生酸剂中的发展方向。     

Vis‐sensitive photopolymer containing vinyl ether compound and pyrromethene dye

A visible light(vis)‐sensitive photoresist based on the concept of chemical amplification was developed utilizing poly(p‐hydroxystyrene) (PHS), 2,2‐bis[4‐(2‐(vinyloxy)‐ethoxy)phenyl]propane (BPA‐DEVE) as a crosslinking agent, N‐trifluoromethylsulfonyloxy‐1,8‐naphthalimide (NIT) as a photoacid generator (PAG) and pyrromethene dyes such as 1,3,5,7,9‐pentamethylbipyrromethene difluoroborate (PRH) and 2,8‐diethyl‐1,3,5,7,9‐pentamethylbipyrromethene difluoroborate (PRE) and 3,3′‐carbonylbis(7,7′‐diethylaminocoumarin) (KCD). On irradiation with an argon ion laser, the photopolymer comprising PRH and PRE exhibited a high sensitivity of 65 and 46 mJ cm^?2, respectively. It is suggested that the sensitization mechanism of the pyrromethene dye/PAG system involves singlet electron transfer. The sensitivity of the photoresist increased with the decreasing molecular weight of PHS because of the high dissolution rate. Copyright © 2002 John Wiley & Sons, Ltd.     

Zn(II)-induced ground-state pi-deconjugation and excited-state electron transfer in N,N-bis(2-pyridyl)amino-substituted arenes

The synthesis and X-ray crystal structures of two N,N-bis(2-pyridyl)amino (dpa)-substituted aromatic systems (Ar-dpa) 1 (Ar = 4,4'-disubstituted trans-stilbene) and 2 (Ar = 1,4-disubstituted benzene) and their ZnCl(2) complexes (1/ZnCl(2) and 2/ZnCl(2)) are reported. The fluoroionophoric behavior of 1-2 in response to Zn(II) in acetonitrile also has been investigated. In addition, compound 3DPA has been prepared and served as a pi-deconjugated model for 1DPA. The observed crystal structures for 1/ZnCl(2) and 2/ZnCl(2) could be divided into two distinct types, the planar and the twisted forms, depending on the aryl-dpa (C(ph)-NC(3)) dihedral angle. The twisted form is more favorable for these complexes unless the arene has a strong "push-pull" character. Nonetheless, the degree of pi-conjugation between the N-pyridyl and the N-aryl group is reduced in both complex forms when compared with the free ligands. Such a Zn(II)-induced pi-deconjugation not only directly affects the internal charge transfer (ICT) fluorescence of the dpa-substituted stilbenes but also facilitates the occurrence of photoinduced electron transfer (PET) from the stilbene donor to the dpa/Zn(II) acceptor. The PET process is particularly important in accounting for the observed Zn(II)-induced fluorescence quenching for 1DPA as well as 3DPA.     

Patterning of single-wall carbon nanotubes via a combined technique (chemical anchoring and photolithography) on patterned substrates

Single-walled carbon nanotubes (SWNTs) have been chemically attached with high density onto a patterned substrate. To form the SWNT pattern, the substrate was treated with acid-labile group protected amine, and an amine prepattern was formed using a photolithographic process with a novel polymeric photoacid generator (PAG). The polymeric PAG contains a triphenylsulfonium salt on its backbone and was synthesized to obtain a PAG with enhanced efficiency and ease of spin-coating onto the amine-modified glass substrate. The SWNT monolayer pattern was then formed through the amidation reaction between the carboxylic acid groups of carboxylated SWNTs (ca-SWNTs) and the prepatterned amino groups. A high-density multilayer was fabricated via further repeated reaction between the carboxylic acid groups of the ca-SWNTs and the amino groups of the linker with the aid of a condensation agent. The formation of covalent amide bonding was confirmed by X-ray photoelectron spectroscopy (XPS) analysis. Scanning electron microscopy and UV-vis-near-IR results show that the patterned SWNT films have uniform coverage with high surface density. Unlike previously reported patterned SWNT arrays, this ca-SWNT patterned layer has high surface density and excellent surface adhesion due to its direct chemical bonding to the substrate.     

D‐π‐a‐type oxime sulfonate photoacid generators for cationic polymerization under UV–visible LED irradiation

Four D‐π‐A‐type nonionic oxime sulfonate photoacid generators (PAGs) have been designed and synthesized for use in light‐emitting diode (LED) excitable cationic photoinitiators, in which N,N‐diphenylamino was used as electron donor with trifluoroacetophenone‐based oxime sulfonates (trifluoromethanoesulfonate and p‐toluenesulfonate) as electron acceptor and substituted fluorene and biphenyl groups as the π‐conjugated systems. PAG‐Ben‐Tol (with biphenyl and p‐toluenesulfonate) and PAG‐Flu‐Tol (with fluorene and p‐toluenesulfonate) showed high quantum yields of photoacid generation (0.33–0.50) and very good thermal stability (over 250 °C). The absorbance spectra of these PAGs were consistent with the emission spectra of commercially gained UV–visible LED light sources. The potential of these PAGs for cationic photoinitiators was tested in two cationic monomer systems. These PAGs needed low light intensity and low concentration for photopolymerization with high conversions of monomer, for example, over 80%, gained at 3.0 mW cm⁻² from 365 to 470 nm LEDs. The photochemical mechanisms of these PAGs are comprehensively investigated and discussed in detail. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1146–1154     

Photoreactive fluorinated polyimide protected by tetrahydropyranyl (THP) group based on chemical amplification: Acid generation in polyimide film and lithographic properties

The photochemistry of photoacid generator (PAG), diphenyliodonium 9,10-dimethoxyanthracene-2-sulfonate (DIAS) and diphenyliodonium 8-anilinonaphthalene-1-sulfonate (DIANS) was investigated in both alkalinesoluble polyimide (6FDA-AHHFP) and novolak films. The quantum yields of photodissociation of DIAS and DIANS in both 6FDA-AHHFP and novolak films. The quantum yields of photodissociation of DIAS and DIANS in both 6FDA-AHHFP and novolak films were determined as 0.11, 0.21, 0.12 and 0.26, respectively. On the other hand, the quantum yields for acid generation from DIAS and DIANS in both of these films were 0.07, 0.18, 0.09 and 0.22, respectively, in the presence of an acid indicator. These results indicate that the values of the quantum yields of photodissociation and photoacid formation for DIAS and DIANS in 6FDA-AHHFP film are lower than those in novolak film. In order to elucidate the lowering of the quantum yields in 6FDA-AHHFP film, fluorescence quenchings of sodium 9,10-dimethoxy-anthracene-2-sulfonate and ammonium 8-anilinonaphthalene-1-sulfonate by a model compound of polyimide was carried out in acetonitrile. The fluorescences of these two salts were efficiently quenched by the model compound with the diffusion-controlled rate constant in acetonitrile, suggesting that a strong electron-accepting capability of the imide carbonyl group may hinder the electron transfer process within PAG molecules in 6FDA-AHHFP film. Although a polyimide (6F-THP) protected by tetrahydropyranyl group is insoluble in aqueous base, 6F-THP film containing PAG became soluble in a 2:1 mixture of 2.0 wt% tetramethylammonium hydroxide (TMAH) and methanol by exposure to 365 nm light and successive post-exposure baking (PEB) at 120°C for 10 min. The sensitivity and contrast of 6F-THP with DIANS after the PEB conditions mentioned above were 110 mJ/cm² and 3.7, respectively. A high-resolution pattern with a good profile was transferred into the 3 μm thickness of the 6F-THP film.     

Fluorine-contained photoacid generators (PAGs) and corresponding polymer resists

A new series of fluorinated anionic photoacid generators (PAGs) (F4-MBS-TPS, F4VBzBS-TPS, F4-IBBS-TPS, CF3 MBS-TPS, MTFBS-TPS and VBzTFBS-TPS), and corresponding PAG bound polymeric resists (HS-EA-PAG) based on hydroxystyrene (HOST) and 2-ethyl-2-adamantyl methacrylate (EA), (GB-EA-PAG) based on γ-butyrolactone methacrylate (GBLMA) and 2-ethyl-2-adamantyl methacrylate (EA) were prepared and characterized. The acid generating efficiency of PAG bound polymers (HS-EA-PAG) series was in the range of 54-81%, which agrees well with the electron withdrawing effect of the substituents. With regard to the referenced F4-PAG bound polymer with 68% acid generating efficiency, and our previously reported EUVL results of F4-MBS-TPS bound polymer photoresists, these new PAG bound polymers should be effective resists for 193 nm or EUV lithography.     

Thermal and acid-catalyzed reaction of bifunctional vinyl ether urethane in nonionic and ionic polymer matrices

A bifunctional vinyl ether urethane derivative (BVU) was synthesized and characterzed. Photoresist systems consisting of BVU and a photoacid generator (PAG) along with various matrix polymers were prepared and the photoresist characteristics were evaluated. In the presence of BVU and a PAG, poly(methylmethacrylate-co-acrylic acid) and poly(methylmethacrylate) exhibited positive and negative tone behavior, respectively, where as poly(p-hydroxystyrene) showed both positive and negative working properties depending on the prebake temperature of the system. The depandence of the photoresist behaviors on these matrix polymers was studied. The mechanism of the thermal and photochemical reactions was revealed.     

Multifunctional photo acid generator for fluorescence imaging based on self-contained photoreaction

We present N-(p-anilinesulfonyloxy)-1,8-naphthalimide (ASNI) as fluorescence imaging material based on a novel fluorescence imaging mechanism. ASNI is composed of two functional moieties in one molecule: an acid-reactive fluorescence probe and a photoacid generator (PAG). When ASNI is photoirradiated, a bond in the PAG moiety breaks and an acid is generated. The fluorescence probe moiety then detects the acid and fluoresces. We call this novel mechanism a self-contained photoreaction (SCP). The photophysical properties and photoreactivity of ASNI were measured and compared with those of a prototype PAG, N-(phenylsulfonyloxy)-1,8-naphthalimide. These were well represented by density functional theory calculations. SCP permits one-step fluorescence imaging without any wet or dry developing process.     

含碘鎓盐光产酸剂和增感染料的化学增幅型i-线正性光致抗蚀剂

4,4’-二甲苯基三氟甲磺酸碘鎓盐可以被染料增感,在365 nm光照时分解产酸.尽管产生的酸与染料的胺基发生作用,依然能在后烘过程中催化缩醛聚合物酸敏基团的分解,但需要稍高的后烘温度和稍长的后烘时间.基于此,本文将酚醛树脂、缩醛聚合物、碘鎓盐产酸剂和染料组成了一种新型的化学增幅型i-线正性光致抗蚀剂材料,在曝光量为10...     

Effect of diphenylamine on photodissociation of aryl azides

The charge-transfer complexes of aromatic azides with diphenylamine (DPA) were studied. Irradiation of 4-nitrophenyl azide in the presence of DPA was found not to give rise to the dissociation of the azido group in the azide radical anionvia intracomplex electron transfer. The photodissociation slows down due to both the static (the formation of a photostable complex with diphenylamine) and dynamic quenching. When 4-azidoacetophenone is irradiated in the presence of DPA, the amine-sensitized decomposition of azide and the photodecomposition of the azide—DPA complex occur along with the direct photolysis of azide, which results in acceleration of the photodissociation due to an increase in the efficiency of the light absorption by the reaction system. A possible sensitization of photodecomposition of aromatic azidesvia an electron transfer mechanism by irradiation of the azide-donor complex is shown.     

Dipeptide hydrogelation triggered via ultraviolet light

UV irradiation of a dipeptide gelator in solution with a photoacid generator (PAG) results in the formation of a hydrogel. We demonstrate that photopatterning of these gels using a UV mask is possible.     

光致酸发生剂——对甲基苯磺酸三苯基硫盐的合成

以二苯亚砜为起始反应物,通过改进反应溶剂,首先合成了溴化三苯基硫盐,大大缩短了反应时间,提高了该盐的反应收率.再运用银盐置换法,合成了光致酸发生剂——对甲基苯磺酸三苯基硫盐,并对其进行了红外和核磁共振表征.     

一种新型深紫外正型光致抗蚀剂材料的研究

通过松香酸和丙烯酸的Diels-Alder反应得到了一种二酸——丙烯海松酸.丙烯海松酸有大的脂环结构和良好的成膜性,在固体膜层中,它可以和二乙烯基醚,如1,3-二乙烯氧基乙氧基苯,在加热条件下(80℃以上)发生反应,产物在稀碱水中难溶.这样形成的产物在光产酸剂产生的强酸催化下,在温度高于100℃时,可以迅速分解,从而变成稀碱水易溶.因此,用此二酸、二乙烯基醚和产酸剂可组成一种正型的光致抗蚀剂,当用254 nm的低压汞灯曝光时,其感度在30 mJ/cm²以下.     

Polymeric photoacid generators for direct photochemical modification of surface

To achieve easy spin coating and enhanced efficiency in the photolithographic process for the direct photochemical modification of surface, we incorporated photoacid generator (PAG) into polymer backbone. Bis‐(4‐hydroxy‐phenyl)‐(4‐methoxy‐3,5‐dimethyl‐phenyl)‐sulfonium chloride was synthesized as a monomer, and was polymerized with sebacoyl chloride and terephthaloyl chloride. The resulting polymeric PAG in chloride salt form was converted to the p‐toluenesulfonate and 1‐naphthol‐5‐sulfonate forms with ion‐exchange reactions. By the photolithographic process with the polymeric PAG, the protecting groups of the linker molecules self‐assembled onto a glass plate were micropatterned to produce an amine pattern for the microarray of oligonucleotides. The acids generated from the polymeric PAG effectively deprotect the acid‐labile protecting groups of the linker molecules through a chemical amplification process in the exposed region. After the treatment of the patterned amino groups with a fluorescent dye, the pattern profiles were observed with a fluorescence scanner. The fluorescence image reveals a well‐defined pattern at a micro level, which clearly indicates that the polymeric PAGs have a great potential in photochemical surface modification for the microarray of oligonucleotides. Copyright © 2007 John Wiley & Sons, Ltd.     

非离子型产酸剂——N-羟基邻苯二甲酰亚胺对甲苯磺酸酯的合成与性能研究

以邻苯二甲酸酐、盐酸羟胺和对甲苯磺酰氯为起始原料,合成了非离子型光致产酸剂——N-羟基邻苯二甲酰亚胺对甲苯磺酸酯,对其进行了红外、核磁共振和紫外表征,测定了其化学结构、溶解性和紫外吸收等性能.结果表明,这种非离子型产酸剂较离子型产酸剂在常用溶剂中有非常良好的溶解性,并在248 nm处有好的透明性,可用于深紫外光刻工艺体系.     

A New Method of Photopatterning with LB Films Based on a Chemically Amplified Mechanism

IntroductionDeep-UV lithography is generally recognized asthe most promising lithographic technology, for the pro-duction of high-resolution devices. However, lithogra-phy requires high sensitivity, high resolution, and highresistance. To make this techno…     

X-ray absorption spectroscopy to probe surface composition and surface deprotection in photoresist films

Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) is utilized to provide insight into surface chemical effects in model photoresist films. First, NEXAFS was used to examine the resist/air interface including surface segregation of a photoacid generator (PAG) and the extent of surface deprotection in the film. The concentration of PAG at the resist-air interface was higher than the bulk concentration, which led to a faster deprotection rate at that interface. Second, a NEXAFS depth profiling technique was utilized to probe for compositional gradients in model resist line edge regions. In the model line edge region, the surface composition profile for the developed line edge was dependent on the post exposure bake time.     

Retrospective of work at Bell Laboratories on the effect of fluorine substitution on the properties of photoacid generators

An overview is given on the work done at Bell Laboratories in which fluorine substitution was employed to tune the structure property relationships of chemically amplified resists. In particular, this paper will detail how structural changes in 2-nitrobenzyl photoacid generator (PAG) affect molecular properties such as quantum yield, thermal stability, and in turn also influence the lithographic characteristics of photoresist formulations such as sensitivity and post-exposure bake (PEB) and post-exposure delay (PED) latitude.