Sensitivity positive resist

Scheme I. Photolysis of a diazonaphthoquinone (DNQ) positive-resist sensitizer. The reaction leads to a carbene (1), which undergoes a Wolff rearrangement to give a ketene (2). Finally, this ketene can react with water present in the resin to give an indenecarboxylic acid (ICA) (3).

Other positive resists sensitive to these wavelengths include the alkyl and aryl sulfones. 

One method for obtaining a high masking speed and resolution with X-ray lithography is use of highly sensitive positive resists. This paper reports some investigations on such sensitive positive X-ray resists. 

Thus it can be seen that X-ray sensitivity for a positive resist... 

Another class of "chain scission" positive resists is the poly(olefin sulfones). These polymers are alternating copolymers of an olefin and sulfur dioxide. The relatively weak C-S bond is readily cleaved upon irradiation and several sensitive resists have been developed based on this chemistry (49,50). One of these materials, poly(butene-l sulfone) (PBS) has been made commercially available for mask making. PBS exhibits an e-beam sensitivity of 1.6 pC cm-2 at 20 kV and 0.25 pm resolution. 

The most widely used positive resists are those that operate on the basis of a dissolution inhibition mechanism. Such resists are generally two-component materials consisting of an alkali soluble matrix resin that is rendered insoluble in aqueous alkaline solutions through addition of a hydrophobic, radiation-sensitive material. Upon irradiation, the hydrophobic moiety may be either removed or converted to an alkali soluble species, allowing selective removal of the irradiated portions of the resist by an alkaline developer. 

A 0.4 m thick SPP layer was exposed to X-rays followed by a flood exposure using near UV radiation. The resist was then dip-developed in a 0.8 wt% TMAH solution for 60 s at 25 °C. We used two x-ray exposure systems to evaluate the characteristics of the SPP resist. One is SR-114 which has a source composed of a molybdenum rotating anode with a 0.54 nm Mo-La characteristic line. The exposure was carried out in air. The other has a synchrotron radiation source with a central wavelength of 0.7 nm (KEK Photon Factory Beam Line, BL-1B). The exposure was carried out in vacuum (<10-4 Pa). A positive resist, FBM-G,15) was used as a standard, because its sensitivity only weakly depends on the ambient. 

Some sensitivities with 364 nm irradiation are as follows DMA/PEMA, 0.0059 DPA/PEMA, 0.0057 DPA/PPSQ, 0.0092 cm2/mJ. (This value is the initial rate dA/dt divided by the intensity see ref. 15.) A comparable datum for DMA/PPSQ is not available, but by comparing the doses required to reach a specified absorbance, one finds that DMA/PPSQ is slightly faster than DMA/PEMA the ratio is about 1.5 (+/-20%). These numbers are a little smaller than those for conventional positive resist (49). With deep UV irradiation, however, they will be 7-20 times larger due to the larger extinction coefficient, which helps fulfill one of the key prerequisites of a CEL (or PIE) material for the deep UV. 

Radiation-sensitive polymers are used to define pattern images for the fabrication of microelectronic devices and circuits. These polymers, called resists, respond to radiation by either chain scission (positive resists) or by crosslinking (negative resists). In positive resists, the exposed areas dissolve selectively by chemical developers in negative resists, the exposed areas are insoluble and remain after development. 

Poly(methyl methacrylate) (PMMA) is a classical one-component, positive resist system. PMMA is a single, homogeneous material that combines the properties of excellent film-forming characteristics, resistance to chemical etchants and intrinsic radiation sensitivity. 

The positive resist materials evolved from discoveries made by the Kalle Corporation in Germany who developed the first positive-acting photoresist based on the use of a novolac matrix resin and a diazoquinone photoactive compound or sensitizer. The original materials were designed to produce photoplates used in the printing industry. These same materials have been adopted by semi-conductor fabrication engineers and continue to function effectively in that more demanding application. 

Figure 17. A schematic representation of positive resist action in diazonaphthoquinone-novolac resists. Photolysis of the sensitizer inhibitor) produces acid which allows the exposed areas of the resist to be selectively dissolved (developed) in aqueous base.

Figure 31. NPR, Bell Laboratories "New Positive Resist for e-beam applications. The sensitizer is a radiolabile polysulfone and the matrix resin is...

Figure 34. The Polystyrenes. Polystyrene is a low sensitivity negative resist, poly (a-methylstyrene) is a low sensitivity positive resist and the para-substituted analogs listed are all sensitive negative resists.

Another interesting positive-tone polyacrylate DUV resist has been reported by Ohno and coworkers (82). This material is a copolymer of methyl methacrylate and glycidyl methacrylate. Such materials are negative e-beam resists, yet in the DUV they function as positive resists. Thermal crosslinking of the images after development provides relief structures with exceptional thermal stability. The reported sensitivity of these copolymers is surprising, since there are no obvious scission mechanisms available to the system other than those operative in PMMA homopolymer, and the glylcidy side-chain does not increase the optical density of the system. 

The resolution capability of a resist is directly related to resist contrast (7) which, for a negative resist, is related to the rate of crosslinked network formation at a constant input dose. It is somewhat more complicated for a positive resist being related to the rate of chain scission and the rate of change of solubility with molecular weight with the latter being markedly solvent dependent. Contrast, like sensitivity, is governed by the type of chemical reactions that occur in the polymeric resist and is affected by molecular parameters such as molecular weight distribution and chemical composition. 

---