A series of novel copolymers [p (AOBHA-co-NPMA)] containing 2-Allyloxy-N-benzylidene hexadecylamine (AOBHA) as film formation material and β-naphtayl methacrylate (NPMA) as photosensitive group were synthesized by free-radical polymerization. The copolymers could form stable condensed monolayer at air/water interface and be transformed onto solid substrates. Positive-tone patterns with the resolution of 0.75 μm of the copolymers Langmuir-Blodgett (LB) films with 35 layers were fabricated by deep UV irradiation, followed by developing with acetone. The etched gold patterns with resolution of 0.75 μm were also obtained, showing that the copolymer has enough resistance to wet etching suitable for fabricating photomask. The mechanism of photolysis was also investigated by UV and GPC, in which showed that the scission of main and side chain of p (AOBHA-co-NPMA) LB films occurred at the same time.
A series of copolymer containing photoactive anthracene group, poly(N-dodecylmeth- acrylamide-co-anthrylmethylacrylate) p(DDMA-co-AnMA) were synthesized. Their molecular arrangement and photolithographic properties in Langmuir–Blodgett (LB) films were investigated. The copolymer p(DDMA-co-AnMA) could form stable monolayer at air/water interface and could be transferred onto solid supports, giving Y-type uniform LB films. The result showed that the irradiation with difference light wavelength leaded to changes of copolymer LB films in their chemical structure, concerning only the anthracence unit. When irradiated at 248 nm, the anthracene acted as photodecomposition group because of the peroxides. On the other hand, the main photoreaction induced by 365 nm is dimerization of anthracene. As a result, posotive-tone and negative-tone pattern could get by choosing a suittable irradiation light wavelength. Etching resistance of p(DDMA-AnMA) LB films was also investigated in a nanometer regime permitting etching of gold.
A new application of polymer Langmuir-Blodgett (LB) films which contain a photoacid generator introduced into polymer main chain as a co-monomer to draw photo patterns as a photolithographic is described here. The chemically positive-tone resist system terpolymers p (DDMA-DNMMA-AOPTs) s used here contains N-dodecylmeth acrylamide (DDMA), 1,4-dioxaspiro [4.4] nonane-2-methylmeth acrylate and 4-(allyloxy) phenyl-4-toluenesulfonate (AOPTs), which was prepared by free radical polymerization. In the terpolymers system, the acid generated by the PAG catalyzed the ketal moiety liberates cyclopentanone and regenerating derivative of glyceryl alcohol in an exposed region during the postexposure baking process. The rending moiety is dissolved into alkaline aqueous to form a positive tone in the expose region. The decompose mechanism of [p (DDMA-DNMMA-AOPTs) s] LB films irradiated by deep UV light was investigated. The photopatterning properties were also investigated. Results showed that the resolution of patterns with p (DDMA-DNMMA-AOPTs) s b LB films with 40 layers were 0.75μm which is the limit resolution of the photo-mask employed in the experiment. The effect of photogenerated acid from the photo-acid generator after irradiated by deep UV light on a typical chemically amplified resist system was studied by thermogravimetric analysis, which showed that the existence of the photoacid generator of AOPTs in terpolymer can improve the sensitivity of ketal-protected polymers without decreasing resolution.
In the paper, an approach for introducing a photoacid generator (PAG) into Langmuir- Blodgett (LB) films to draw photopatterns is described. The chemically amplified positive-tone resist system used here consisted of two components: a copolymer, poly(iso-pentylmethacrylamide- co-4-t-butyloxylvinylphenylcarbonate) [poly(iPMA-t-BVPC39)] and a photoacid generator (PAG), tri(2,3-dibrompropyl)iso-cyanvrate (TDBPIC). In the two-component system, the acid generated by the photoacid generator (PAG) catalyzes the deprotection reaction of poly(iPMA-t-BVPC39) to re- move the tert-butoxycarbonyl group (t-BOC) in the exposed region during the post exposure baking process, thus rendering the exposure region soluble to alkali aqueous to form a positive tone. Phhot- olithographic properties of the LB films have been evaluated. The patterns can be resolved with a resolution of 1 μm line width by UV irradiation,followed by development with an alkali solution. Quantum yield is determined to be 0.065 and catalytic chain length is also calculated to be 2460. The LB films used above can be used to generate etched gold patterns on a glass substrate using an aqueous iodide, ammonium iodide in alcohol /water,as the etchant. The etch resistance of such LB films is sufficiently good, allowing patterning of a gold film suitable for photomask fabrication.
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