Recently, there are lots of interest in using chemical amplification (CA) on electron beam lithography for application to photo mask fabrication, direct writing, and projection printing. E-beam resists introducing chemically amplification concepts provide superior lithographic performance in comparison with traditional non CA E-Beam resist in particular high resolution and sensitivity. In first approach, we applied CA concepts to acetyl polymer based E-beam resist (resist thickness: 4,000Å), which can print fine images (<100nm), meet sensitivity (10μC/cm2), and have stability against post exposure delay (PED)(>10hrs) using 50KeV E-beam exposure tool. But, there is vacuum delay problem (40nm CD shrinkage/5hrs) due to thermally unstable blocking group in polymer. To prevent this vacuum delay problem due to polymer-inherent thermal instability in low-activation-energy-acetal polymer, we newly designed various poly(hydroxystyrene-acrylate) copolymer derivatives that contained thermally stable (acrylate) acid-blocking group. In this presentation, first we will discuss the chemistry of newly designed copolymer derivatives, and second, vacuum delay effects and other lithographic performances (resolution, sensitivity, line edge roughness) of these resist systems.
Recently, KrF lithography has extended to 100nm technical node using various techniques and pushed ArF lithography to sub-100nm application. To enhance resolution, there are many problems to be solved, like dark erosion (dark film loss), sloped profile, line edge roughness (LER), and so on. Also, thin resist film must be used to prevent pattern collapse. In general, the aspect ratio is less than 2.5 for sub 100nm. For this reason, chemically amplified resist has to get high etch resistance, low dark film loss and vertical profile shape at maximum resolution. Many efforts have been made to solve these problems and to improve resist performance. In this study, we tried to resolve some of these problems using various acid-quenching systems. We estimated the quencher ability using acid diffusion depth in resist film by sandwich method and pKb values of amines. The changes of lithographic properties according to the application of different amines were investigated. It was found that acid-quenching ability of an amine was not related to its basicity from sandwich experiment results. In fact, quenching efficiency was more closely related to the amine molecular structure and bulkiness of a substituent attached to nitrogen atom. We observed that pattern shape and process margin were not directly related to the basicity of an amine, but more related to quenching efficiency. The amines having higher quenching ability show wider process margin. However, other lithographic properties such as LER and dark erosion were not affected by acid-quenching ability. It is believed that they are determined by other components including polymer, protection groups, and PAGs.
Various derivatives of modified poly(4-hydoxystyrene-co-4-(1-ethylethoxystyrene))(M-EEPHS) were synthesized by insertion of third monomer unit such as styrene, 4-acetoxystyrene, 4-methoxycarbonyloxystyrene, tertbutoxycarbonyloxystyrene, tert-butyl acrylate, and 4-(1-cyclohexylethoxy)styrene. Their dissolution rate behavior was investigated with different blocking level. From the average dissolution rate of M-EEPHS in a 2.38wt% TMAH solution as a function of the total protection%, hydrophobicity was proven as more influential factor for the dissolution inhibition rather than hydrogen bonding by ester or carbonate functionality in a blocking group. To study structural effect on KRF lithographic performance, resists containing M-EEPHS were formulated and testified. Defects that are found in EEPHS based resist, such as LER (Line Edge Roughness) and top surface erosion at defocus can be solved by incorporation of carbornate, bulky acetal functionality or dissolution inhibition group. When hybrid system, which contained both M-EEPHS and poly[4-hydroxystyrene-co-tert-butyl acrylate-co-4-(3-cyano-1,5-di-tert-butyl carbonyl pentyl styrene)](P(HS-TBA-CBPS)) as an annealing type resin, were compared with the lithographic results of single polymeric system (M-EEPHS only), their performances were directly projected to those of blends of high activation type and low activation type resin.
We prepared ter-polymer of hydroxystyrene, tert-butyl acrylate and 4-(3-cyano-1,5-di-tert-butyl carbonyl pentyl styrene) (P(HS-TBA-CBPS)) and discussed a characteristic of prepared polymer. As TBA, newly introduced monomer increases, contrast of resist is improved. And the prepared polymer was blended with poly(4-hydroxystyrene-co-4-(1-ethylethoxystyrene)) (EE-PHS). The synergic effect on a resist performance in KrF lithography by the combination of high and low activation energy system was shown. A resist using blending polymer was shown a good performance on resolution and LER(Line Edge Roughness) than resist using polymer separately. Based on the results, it was found that high performance KrF resist could be obtained by optimization of polymer blending.
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