Polymer electron beam sensitive

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. 

In 2000, the dark-brown cluster polymer 6.23, obtained from the polycondensation of the hexanuclear ruthenium carbido species RU(sC(CO)i5 with the diphos-phinoalkyne Ph2PC = CPPh2 in refluxing THF, was reported [57]. The stmcture was assigned on the basis of IR, NMR, and elemental analysis, and an estimated degree of polymerization of up to 1000 was reported based on electron microscopy techniques. Polymer 6.23 has been shown to be electron-beam sensitive and this allows the creation of Ru-based nanoparticle chains and, ultimately, conducting wires [57-59]. 

Babich ED, Paraszcak J, Hatzakis M et al. (1985) A comparison of the electron beam sensitivities and relative oxygen plasma etch rates of various otganosilicon polymers Microelectronic Eng 3 279-291... 

A disadvantage of AES is that the intense electron beam easily causes damage to sensitive materials (polymers, insulators, adsorbate layers). Charging of insulating samples also causes serious problems. 

Overall a customer needs to know under what circumstances it is best to use either the electron-beam techniques of EDS and WDS or the X-ray technique of XRF for an analysis problem. If both are equally available, the choice usually resides in whether high spatial resolution is needed, as would be obtained only with electron-beam techniques. If liquids are to be analyzed, the only viable choice is XRF. If one s choice is to use electron-beam methods, the further decision between EDS and WDS is usually one of operator preference. That is, to commence study on a totally new sample most electron-beam operators will run an EDS spectrum first. If there are no serious peak overlap problems, then EDS may be sufficient. If there is peak overlap or if maximum sensitivity is desired, then WDS is usually preferred. Factored into all of this must be the beam sensitivity of the sample, since for WDS analysis the beam current required is lO-lOOx greater than for EDS. This is of special concern in the analysis of polymer materials. 

Silicone acrylates (Fig. 5) are again lower molecular weight base polymers that contain multiple functional groups. As in epoxy systems, the ratio of PDMS to functional material governs properties of release, anchorage, transfer, cure speed, etc. Radiation induced radical cure can be initiated with either exposure of photo initiators and sensitizers to UV light [22,46,71 ] or by electron beam irradiation of the sample. 

X-ray photoelectron spectroscopy is frequently applied in the fields of catalysis and polymer technology. It has poor spatial resolution, and is generally limited to homogenous samples. Radiation sensitive materials are more appropriate for XPS analysis, as the X-ray beam is less damaging to the specimen surface than the electron beam used in AES, partly due to the lower flux densities that are used. 

Negative resists generally exhibit high sensitivity but low contrast. For instp.ncin our laboratory, polymers containing thiirane groups / g v ere found to be extremely sensitive (o = 6 x 10 T C/cm2) to electron beam irradiation at a 20 kV... 

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]. 

Figure 13. Outline of the pattern generation for integrated circuits provided by electron beam writing on chemically suitable polymer films, which are thus sensitized for development.

Key words electron diffraction, beam sensitive materials, polymers, sample preparation... 

As we mentioned before, G(s) is a structure dependent constant that describes the number of scissions per unit absorbed dose and in that sense can be compared to a photochemical quantum efficiency. The G(s) of a radiation-sensitive polymer is a figure of merit that can be used in comparing one material with another. There is a very high correlation between G(s) values to gamma radiation (the radiation most commonly used for determining G(s)) and high sensitivity for lithographic materials used in either electron beam, ion beam or x-ray exposure. 

An early commercial interest in poly (olefin sulfones) was sparked by the low raw materials cost, but this interest waned when it became apparent that thermal instability is a general characteristic of this class of materials. In 1970 Brown and O Donnell reported that poly (butene-1-sulfone) is degraded by gamma radiation with a G(s) approaching 10, making it one of the most radiation-sensitive polymers known (38-39). The potential for use of this radiation sensitivity in the design of electron beam resists was quickly realized by several members of the electronics industry. Bell Laboratories, RCA, and IBM published studies demonstrating the potential of poly (alkene... 

The incorporation of small percentages (<10%) of 3-oximino-2-butanone methacrylate (4) into poly(methyl methacrylate) (PMMA) (Scheme I) results in a four fold increase in polymer sensitivity in the range of 230-260 nm flO.l 11. Presumably, the moderately labile N-O bond is induced to cleave, leading to decarboxylation and main chain scission (Scheme II). The sensitivity is further enhanced by the addition of external sensitizers. Also, preliminary results indicated that terpolymerization with methacrylonitrile would effect an additional increase. These results complement those of Stillwagon (12) who had previously shown that copolymerization of methyl methacrylate with methacrylonitrile increased the polymer s sensitivity to electron beam irradiation. The mole fraction of the comonomers was kept low in order to insure retention of the high resolution properties of PMMA (3.41. 

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