New aqueous base developable photoresist for lithographic printing plates applications

Negative photoresists are materials that become insoluble in developing solution when exposed to optical radiation. This work describes the production of simple negative‐working resists, demonstrating aqueous development, for potential printing plate applications. The copolymers comprised glycidyl methacrylate (GMA) and acrylic acid (AA) via free‐radical solution polymerization in methyl ethyl ketone as a solvent using azobisisobutyronitrile as initiator at 60°C. Characterization of the copolymers prepared was carried out via IR, ¹H‐NMR, and thermal analysis techniques. The copolymers of GMA/AA were successfully prepared over a wide range of composition. It was found that the copolymer containing 15 mol % of AA unit in the feed was developed with NaOH on copper plate rather than zinc plate and crosslinked in the presence of photogenerated acid (PAG) caused by acid‐initiated ring‐opening polymerization of pendant epoxide groups. Exposure of the resist films to UV radiation at λ_max = 365 nm results in the generation of acid, and the subsequent baking process at 80°C for 1 min promotes the diffusion of the PAG, which initiates the cationic crosslinking of the epoxide rings. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Solvent penetration and photoresist dissolution: A fluorescence quenching and interferometry study

A novel method, based upon fluorescence quenching measurements, is described for the study of the mechanistic details of solvent penetration into thin polymer films. Here poly(methyl methacrylate) (PMMA) labelled with phenanthrene (Phe) groups was coated as a film (0.8 μm thick) onto quartz disks. Diffusion of solvent (1 : 1 2-butanone/2-propanol) into the film was followed by a decrease in Phe fluorescence, while film dissolution was monitored simultaneously by laser interferometry. In the case of PMMA (M_w = 411,000, films annealed at 160°C) both processes occur at approximately the same rate and exhibit non-Fickian (relaxation-controlled) diffusion behavior. Correlating the results of these two experiments shows that, once the steady state is reached, the dissolution rate is controlled by the advance of the solvent front into the PMMA film. The “transition layer,” an important dissolution parameter, increases its thickness from 50 to 90 nm during the plasticization stage of solvent penetration and maintains its thickness until the solvent front reaches the quartz substrate.     

The role of the latent image in a new dual image,aqueous developable,thermally stable photoresist

A new dual image, aqueous developable photoresist can be processed to yield either positive or negative images that are crosslinked and thermally stable to temperatures >300°C. Positive images have similar resolution and processing parameters to conventional positive novolak resists. Negative resists from this system have a number of new and interesting properties that surpass the capabilities of their positive counterparts. In addition to producing highly resolved submicron images, thick coatings of resist can be used to form images with high aspect ratios. By adjusting the exposure of the resist, images with inward sloping wall profiles can be realized. As a result of the images being crosslinked and Insoluble in the resist coating solution, images can be recoated and new images formed over the top of existing patterns to form structures. A hypothetical mechanism that suggests that resist defects caused by dust on the mask or photoresist surface can be reduced In negative mode processing is also presented.     

Flash exposure system for thin photoresist films

The formation of an image in a photoresist during photolithographic processing requires the exposure of the photoresist through a mask to a light source in the spectral region to which the photoresist is sensitive. The functional advantage of the flash exposure of photoresist is presented, which includes the elimination of oxygen effects, the reduction of diffraction and standing wave effects, and the enhancement of pattern-edge acuity. The effects of both broad and narrow band sources are also shown with emphasis on proximity printing techniques. Finally, the optical, electrical and physical design parameters for a practical flash exposure system are discussed.     

A water‐developable negative photoresist based on the photocrosslinking of N‐phenylamide groups with reduced environmental impact

A water‐developable negative photoresist based on the photocrosslinking of N‐phenylamide groups was prepared by the copolymerization of 4‐styrenesulfonic acid sodium salts (SSS) with N‐phenylmethacrylamide (copolymer A) or p‐hydroxy‐N‐phenylmethacrylamide (copolymer B), and its properties such as solubility changes, photochemical reaction, and photoresist characteristics were studied. The copolymer containing a relatively higher amount of SSS units was soluble in water. Solubility changes of the copolymers in the various buffer solutions of pH 4 ～ 11 and in water upon irradiation were observed by the measurement of insoluble fraction. The copolymers were soluble in water before irradiation, whereas they became insoluble upon irradiation with the UV light of 254 nm. The photochemical reaction of the copolymer studied by the UV and IR absorption spectroscopies indicated that a photo‐Fries rearrangement was favored for copolymer A, whereas a photocrosslinking reaction was predominate for copolymer B. Resist properties of the copolymers were studied by measurement of the normalized thickness and by development of the micropattern. Negative tone images with a resolution of 1 μm were obtained with these materials that have a sensitivity (D) of ～ 1100 mJ/cm² with an aqueous developing process.© 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1172–1180, 2002     

Preparation and characterization of photoreactive copolymers containing curable pendants for positive photoresist

tert‐Butyl methacrylate (TBMA) was copolymerized with various comonomers that were selected from methyl methacrylate (MMA), n‐butyl acrylate (NBA), acrylic acid (AA), and 2‐hydroxyethyl methacrylate (HEMA). From film physical properties, poly(TBMA‐co‐HEMA) and poly(TBMA‐co‐AA‐co‐NBA), were selected as resin binders. To introduce unsaturated double bonds onto the side chain of copolymers, they were further functionalized with acryloyl chloride and glycidyl methacrylate. Copolymers synthesized in this investigation were all identified by using FTIR and NMR. The thermal decomposition temperature of functionalized poly(TBMA‐co‐HEMA) showed obvious difference before and after crosslinking. Adding a small amount of EGDMA as the crosslinking agent could increase the degree of crosslinking and obviously improve the physical properties. Functionalized poly(TBMA‐co‐HEMA) was used as a binder resin and composed with a photoacid generator for positive photoresists. From exposure characteristics, the optimal lithographic condition was achieved when exposed for 90 s, PEB at 100°C for 2.5 min, and developed in 10 wt % Na₂CO₃ developer for 30 s. After completing the lithography process, the residual pattern of positive photoresist was further treated at 140°C for 30 min to cure the pendant unsaturated groups. The resolution of the positive photoresist was analyzed by an optical microscope and SEM technique. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 328–333, 2001     

Integrated energy storage system based on triboelectric nanogenerator in electronic devices

The emergence of electronic devices has brought earth-shaking changes to people's life.However,an extemal power source may become indispensable to the electronie devices due to the limited capacity of batteries.As one of the possible solutions for the extermal power sources,the triboelectric nanogenerator(TENG)provides a novel idea to the increasing mumber of personal electronic devices.TENG is a new type of energy ollector,which has become a hot spot in the field of nanotechnology.It is widely used at the acquisition and conversion of mechan-ical enegy to electrice energy through the principle of electrostatic induction.On this basis,the TENG could be integrated with the energy stonage system into a self-powered system,W hich can supply power to the electronic devices and make them work continuously.In this review,TENG's basic structure as well as its working process and working mode are firstly discussed.The integration method of TENGs with enegy storage systems and the related research status are then introduced in detail.At the end of this paper,we put forward some problems and discuss the prospect in the future.     

Preparation of photoresist polymer by a photoreactive monomer containing N,N-diethyldithiocarbamate group

A novel photosensitive monomer with a pendant photoreactive diethyldithiocarbamoyl group, VBDC, was synthesized and copolymerized with some vinyl monomers by AIBN. The copolymers obtained have efficient photocrosslinking abilities, and are thermally stable. Therefore, there was no loss of dithiocarbamoyl group during radical polymerization, and the polymerization proceeded through vinyl group. The degree of photocrosslinking was proportional to the concentration of the photosensitive group, but photosensitivity of the polymer was not. Water-soluble photoreactive copolymers, VBDC with AAm or MA, were also prepared. AAm copolymer has a good photosensitivity by only 3 mol % VBDC incorporation. Photocrosslinking yields of these polymers depend on the viscosity of original polymers except in the case of low concentration of VBDC. The relation between copolymer composition and glass transition temperature was also investigated. From the investigation of T_g, it was concluded that the copolymer structure largely affected on ΔT_g. The mechanism of photocrosslinking was studied by photodecomposition of benzyl N, N-diethyldithiocarbamate, and the result that the decreases of sulfur content clearly related to photocrosslinking points was also obtained.     

Novel one-component molecular glass photoresist based on cyclotriphosphazene containing t-butyloxy carbonyl group for i-line lithography

Hexakis(4-formylphenoxy) cyclotriphosphazene (HAPCP), substitution reaction product of hexachlorotriphosphazene (HCTP) with p-hydroxybenzaldehyde, was reduced by sodium borohydride to afford hexakis[4-(hydroxymethyl) phenoxyl] cyclotriphosphazene (HHPCP). The hydroxyl group of this compound was then protected by the reaction with di-tert-butyl dicarbonate ester (DBDC) in the presence of 4-dimethylaminopyridine (DMAP) as catalyst to give t-butyloxy carbonyl (tBOC) protected HHPCP. Fourier-transform infrared spectroscopy (FT-IR) and proton nuclear magnetic resonance (¹H NMR) were employed to characterize the chemical structure, indicating that the synthesis was successful. Thermal behavior was characterized by thermogravimetric analysis (TGA), the results showed that the initial thermal decomposition temperature occurred at approximately 170 °C, X-ray diffraction analysis (XRD) results showed that the tBOC protected HHPCP derivatives had amorphous form, and performed excellent film-forming property. Upon irradiation to 365 nm exposure, the photoacid generated proton H⁺, which can catalyze the deprotection of acid labile tBOC group. This type of novel molecular glass photoresist based on hexachlorotriphosphazene showed high sensitivity, making it possible to fabricate 1 μm line and space pattern under i-line exposure.     

应用低水分熄焦工艺改造焦炉熄焦系统

低水分熄焦工艺具有熄焦均匀、焦炭整粒、改善环境及延长设备寿命等诸多优点。文中介绍了低水分熄焦工艺的先进性与可实施性,并根据本钢焦化厂实际情况,将低水分熄焦工艺用于原湿法熄焦工艺的改造,设备选型全部国产化。改造后焦炭水分指标由改造前的平均5.3%下降到4.4%,熄焦操作时间由原160s缩短为70s。     

Poly(Schiff's bases)–bifluorophores: Synthesis,photophysical properties,nonradiational transfer of energy of electronic excitation

A method of the synthesis of a new generation of polymers with intrinsic fluorescence—poly(Shiff's bases)–bifluorophores—was developed. These polymers contain two different fluorophores in each unit of the main polymer chain. One of the fluorescent fragments is a donor of electron excitation energy and the second one is an acceptor. The photophysical properties of poly(Shiff's bases)–bifluorophores were investigated. It was shown that in poly(Shiff's bases)–bifluorophores nonradiation energy transfer along the polymer chain in the solid and liquid solutions of polymers takes place. The influence of the disposition of fluorophores in the polymer chain and the distance between them on nonradiation energy transfer were investigated. It was shown that the maximum nonradiation energy transfer is realized in polymers–bifluorophores with a statistical distribution of the fluorophore fragment in the polymer chain. The influence of the distance between a donor and an acceptor of the electron excitation energy on the nonradiation energy transfer was investigated. It was established that nonradiation energy transfer is not observed if the distance between a donor and an acceptor of energy exceeds 10 nm. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 398–406, 2001     

Synthesis, characterization and fluorescence quenching of conjugated polymer containing triphenylamine group

Poly(triphenylamine-p-phenylenevinylene)s with two different end-groups were obtained through a Wittig polycondensation. The structures of two copolymers were characterized. Ultraviolet and visible spectroscopy (UV-Vis) and photoluminescence (PL) spectra show the end-capped polymer emits intensive green light in both solution and film state. Their applications in the detection of nitro compounds were investigated, and the results show high fluorescence quenching sensitivity of the end-capped polymer towards o-nitrotoluene (o-NT). When the concentration of o-NT was 21.5 × 10⁻³ mol/L, the fluorescence quenching reached 96%. Additionally, after the exposure of polymer film in three different quenchers such as dinitrotoluene (DNT), p-nitrobenzoquinone (p-BQ) and p-nitrotoluene (p-NT) for 600 s, its fluorescence quenching reached 93.6%, 11.5% and 77.9%, respectively. This kind of polymer has great advantages in preparation and may find applications in the detection of nitro explosives. __________ Translated from Journal of Functional Polymers, 2008, 21(1): 11–16 [译自: 功能高分子学报]     

Synthesis,characterization and fluorescence quenching of conjugated polymer containing triphenylamine group

Poly(triphenylamine-p-phenylenevinylene)s with two different end-groups were obtained through a Wittig polycondensation. The structures of two copolymers were characterized. Ultraviolet and visible spectroscopy (UV-Vis) and photoluminescence (PL) spectra show the end-capped polymer emits intensive green light in both solution and film state. Their applications in the detection of nitro compounds were investigated, and the results show high fluorescence quenching sensitivity of the end-capped polymer towards o-nitrotoluene (o-NT). When the concentration of o-NT was 21.5 × 10^-3 mol/L, the fluorescence quenching reached 96%. Additionally, after the exposure of polymer film in three different quenchers such as dinitrotoluene (DNT), p-nitrobenzoquinone (p-BQ) and p-nitrotoluene (p-NT) for 600 s, its fluorescence quenching reached 93.6%, 11.5% and 77.9%, respectively. This kind of polymer has great advantages in preparation and may find applications in the detection of nitro explosives.     

Electrochemical etch-stop control for silicon structures containing electronic components

A predictive analysis of the feasibility of electrochemical etch-stop control in the fabrication of some silicon sensors was validated experimentally. The application is for sensors with thin silicon structures containing electronic components, such as cantilever accelerometers and diaphragm pressure gauges with strain gauges in the surface to detect deflection. Such structures are formed by deep anisotropic etching of silicon. Since the depth of the etch determines the thickness of the cantilever or diaphragm, the ability to stop the etching precisely is critical. Accurate etch-stop control can be accomplished by electrochemical passivation of an n-type epitaxial layer on a p-type silicon wafer, where the epi layer thickness becomes that of the diaphragm or cantilever. The analysis shows that passivation of the epi layer can be maintained even underneath the electronic components for conditions which allow etching of the p-type silicon substrate. Therefore, electrochemical etch-stop control appears feasible in most practical sensor designs.     

关于湿法熄焦系统中水锤现象防护的比较

介绍了水锤现象的成因、危害、机理及防护措施,通过对比分析国内几种典型湿法熄焦工艺中水锤现象的防护措施,发现在熄焦水泵出口选用缓闭止回阀,在熄焦水输送管道中部选用自动液力阀,可防止湿法熄焦系统中水锤现象发生。     

Plasma quenching reactions with laser pyrolysis of graphite and coal in helium or hydrogen

Laser pyrolysis of graphite in hydrogen resulted in about three orders of magnitude more products than were produced by laser pyrolysis of the same material in helium. The percentage of acetylene produced increased directly with the percentage of hydrogen in the carrier gas. Laser pyrolysis of coal in hydrogen yielded 10 times more low molecular weight hydrocarbon products than were produced by laser pyrolysis of coal in helium. A model to explain the results is given.     

Phosphorus‐containing epoxy resin for an electronic application

A phosphorus‐containing epoxy resin, 6‐H‐dibenz[c,e][1,2] oxaphosphorin‐6‐[2,5‐bis(oxiranylmethoxy)phenyl]‐6‐oxide (DOPO epoxy resin), was synthesized and cured with phenolic novolac (Ph Nov), 4,4′‐diaminodiphenylsulfone (DDS), or dicyandiamide (DICY). The reactivity of these three curing agents toward DOPO epoxy resin was found in the order of DICY > DDS > Ph Nov. Thermal stability and the weight loss behavior of the cured polymers were studied by TGA. The phosphorus‐containing epoxy resin showed lower weight loss temperature and higher char yield than that of bisphenol‐A based epoxy resin. The high char yields and limiting oxygen index (LOI) values as well as excellent UL‐94 vertical burn test results of DOPO epoxy resin indicated the flame‐retardant effectiveness of phosphorus‐containing epoxy resins. The DOPO epoxy resin was investigated as a reactive flame‐retardant additive in an electronic encapsulation application. Owing to the rigid structure of DOPO and the pendant P group, the resulting phosphorus‐containing encapsulant exhibited better flame retardancy, higher glass transition temperature, and thermal stability than the regular encapsulant containing a brominated epoxy resin. High LOI value and UL‐94 V‐0 rating could be achieved with a phosphorus content of as low as 1.03% (comparable to bromine content of 7.24%) in the cured epoxy, and no fume and toxic gas emission were observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 353–361, 1999     

Synthesis of naphthalene containing aralkyl novolac epoxy resins for electronic application

Naphthalene containing aralkyl novolac epoxy resins were synthesized by the condensation of p‐xylylene glycol with 2,7‐dihydroxynaphthalene or 2‐naphthol followed by the epoxidation of the resulting aralkyl novolacs with epichlorohydrin. The mechanical and dynamic viscoelastic properties of cured aralkyl novolac epoxy resins were investigated. Comparisons of mono‐ and di‐functional naphthalene containing aralkyl novolac epoxy resins based on thermal and moisture absorption properties were also studied. The results indicate that a naphthalene containing aralkyl epoxy resin made from the difunctional naphthol has a low coefficient of thermal expansion, high heat resistance, and low moisture absorption.     

Preparation and characterization of copolymers containing (+)‐bornyl methacrylate and their racemate for positive‐tone photoresist

This study investigated the chemical behavior of polymers bearing cycloaliphatic bornyl units along with the steric difference of the chiral (+)‐bornyl methacrylate [(+)‐BMA] and racemic (±)‐BMA, expressed in the physical properties of the copolymers and the resist characteristics. To do this, a series of copolymers containing (+)‐bornyl methacrylate [(+)‐BMA] and (±)‐BMA] units was synthesized. Comonomers of tert‐butyl methacrylate (TBMA), methyl methacrylate (MMA), and maleic anhydride (MA) were used. The thermogravimetric curves, glass‐transition temperature (T_g), and molecular weight (MW) of the copolymers were evaluated. Exposure characteristics of chemical‐amplified positive photoresists comprising various copolymers were investigated. It was found that copolymers bearing (±)‐BMA have higher T_g and better thermostability than those of copolymers containing (+)‐BMA units. The copolymers with (±)‐BMA units, however, revealed an inert photochemical behavior on the positive‐tone photoresist. The patterning properties of the positive photoresist, composed of copolymers bearing (+)‐BMA and (±)‐BMA, and the photoacid generator (PAG) were also investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3538–3544, 2001