Electron beam resists chain

Other investigations dealt with straight-chain molecules (oi-tricosenoic acid) in which the penultimate and final carbon atoms at the hydrophobic end are connected by a double bond [91, 92]. The material does not polymerize as rapidly as those described before when irradiated by UV light, however, but it is readily polymerized when bombarded with an electron beam. It was thus thought to be an optimal material for the fabrication of electron beam resists. 

In this article we will describe two different types of positive electron-beam resists, which were briefly reported in our previous communications (2,3). One is the homopolymer or copolymer with methyl methacrylate and a-substituted benzyl methacrylate, which forms methacrylic acid units in the polymer chain on exposure to an electron-beam and can be developed by using an alkaline solution developer. In this case, the structural change in the side group of the polymer effectively alters the solubility properties of the exposed polymer, and excellent contrast between the exposed and unexposed areas is obtained. The other is a self developing polyaldehyde resist, which is depolymerized into a volatile monomer upon electron-beam exposure. The sensitivity was extremely high without using any sensitizer. 

In summary, the side-chain radical of the structure -COOCH2 is the direct precursor and plays a key role in the radiation-induced scission of PMMA main-chain. Therefore, the main-chain scission can be suppressed by inhibiting the formation of the side-chain radical or by killing it with an adequate scavenger. On the contrary, the enhancement of the formation of the side-chain radical will be a guiding principle to increase the sensitivity of PMMA as an electron-beam resist. 

The radiation degradation of poly(2-octyne) occurs only in the presence of oxygen. Its degradation products contain carbonyl and hydroxyl groups, and so dissolve in polar solvents (e.g., acetone). Such solubility change is essential to resist materials. The Gs value (number of main-chain scission per 100 eV of absorbed dose) of poly(2-octyne) is ca. 12. It is noteworthy that this value is higher than that of poly-(methyl methacrylate) (Gs ca. 2)118) which is being used as electron-beam resists. 

Since polymers with tetrasubsltuted centers are difficult to synthesize, two main types of positive resists have been dlsclosed. Polymethylmethacrylate r polymethyl Isopropenyl ketone hich undergo side chain elimination and subsequent main chain fracture have been used as positive electron beam resists (cf. 

However conventional positive electron beam resists like PMMA(4) or PBS(5.) do not have excellent dry etching resistance. The electron beam sensitivities of these positive resists primarily result from radiation-induced degradation of polymer main chains. If the main chain bonding force of these polymers is weakened in order to improve sensitivities, the dry etching resistances of these polymers will decrease. In such cases, sensitivity to electron beam exposure and dry etching resistance are in a trade-off relationship. 

Photoresists and electron-beam resists are the key to the success of VLSI electronic circuits. Without these resists, most electronic equipment would not exist. These polymers are spun onto the semiconductor and exposed to the circuit pattern leading to main chain scission or crosslinking. Subsequently, unpolymerised sections are removed. This process is employed either in wet or in dry conditions. This is known as the photolithographic process, which is part of the semiconductor fabrication technology. Further treatment includes diffusion of various semiconductor elements and metallisation for conduction lines. Layer by layer, the total package is developed. Current research is now directed toward finer features in the patterns and changes in the surface characteristics for subsequent layers. 

Concerning the design of positive electron-beam resists [228,229], anionic polymerization was used to introduce 2-phenylallylgroups at the end of poly(a-MeSt) chains. 

A number of new resist materials which provide very high sensitivities have been developed in recent years [1-3]. In general, these systems owe their high sensitivity to the achievement of chemical amplification, a process which ensures that each photoevent is used in a multiplicative fashion to generate a cascade of successive reactions. Examples of such systems include the electron-beam induced [4] ringopening polymerization of oxacyclobutanes, the acid-catalyzed thermolysis of polymer side-chains [5-6] or the acid-catalyzed thermolytic fragmentation of polymer main-chains [7], Other important examples of the chemical amplification process are found in resist systems based on the free-radical photocrosslinking of acrylated polyols [8]. 

Electron Beam Lithography. LB PMMA films with thicknesses of 6.3 nm (7 layers) are sufficient for patterning a Cr film suitable for photomask fabrication. For ultrathin PMMA films the resolution (see Fig. 1) is limited by the smallest spot diameter available on MEBES I (1/8 pm). However, it is not possible to obtain this resolution if a thicker resist (>100 nm) is used under the same exposure and development conditions, which demonstrates that ultrathin resists are able to minimize the proximity effect. Also, since the radius of gyration of 188,100 Mw PMMA is about 10 nm in the bulk, and the thickness of the 7 layer film (6.3 nm) is less than 10 nm, it is reasonable to assume there must be an alteration of chain configuration in the ultrathin films. This will be particularly true when the post-deposition baking temperature of the multilayer films is less than the glass transition temperature (115°C), as is the case for the present experiments. In such a case, interdiffusion of PMMA chains between the deposited layers may not result in chain configurations characteristic of the bulk. 

Ito has also extended this type of photochemistry to the electron-beam-induced catalytic acidolysis of acid-labile main chain acetal linkages in polyphthaldehyde. These polymers, like the poly(2-methylpentene-l-suIfone) (PMPS) sensitizer in NPR resist described earlier have ceiling temperatures on the order of -40 °C. As normally used, the polyaldehydes are end-capped by acylation or alkylation and are thus quite stable. The main chain bonds are very sensitive to acid-catalyzed cleavage which in turn allows the whole chain to revert to monomer in an unzipping sequence similar to that occuring in irradiated PMPS. Irradiation of polyphthaldehyde containing 10% of a suitable sensitizer such as triphenylsulfonium hexafluoroarsenate with either deep UV... 

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