Resist positive

Positive resists have as the photoreactive component a dissolution inhibitor that is destroyed in the regions exposed to the light. The resist is developed in an aqueous solution, where the exposed region dissolves away. The resists do not swell as much in the aqueous developer, allowing higher resolution. 

For positive resists, mixtures of 1,2-naphthoquinone diazides with phenolic resins, mainly the polymer from 3-cresol and formaldehyde (Novolac), are used. 

Sci. in press). In these studies, the PIQ (2.0 ym thick) was used as an underlayer. Thus, the film consisting of the polymer 11 and PIQ prepared on a silicon wafer was exposed to deep UV-light with the use of Canon contact aligner PLA-521 through a photomask for 5 to 6 s (UV intensity 72 mV/cm2 at 254 nm). The resulting film was then developed with a 1 5 mixture of toluene and isopropyl alcohol for 15 s and rinsed with isopropyl alcohol for 15 s. A positive resist pattern was obtained after treatment of the film pattern with 02 RIE under the condition of 0.64 W/cm2 (RF power 7 MHz, 02 pressure 3 mtorr). 

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. 

It has been noted previously that radiation exposure of a positive resist causes chain scission in its structure. As a result, its molecular weight decreases. According to Ku and Scala (3), the decrease in the number average molecular weight resulting from such irradiation is given by the expression ... 

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

Figure 3 Representative contrast curves for a) positive resists and b)...

Materials that exhibit enhanced solubility after exposure to radiation are defined as positive resists. The mechanism of positive resist action in most of these materials involves either main-chain scission or a polarity change. Positive photoresists that operate on the polarity change principle have been widely used for over three decades in the fabrication of VLSI devices and they exhibit high resolution and excellent dry etching resistance. Ordinarily, the chain scission mechanism is only operable at photon wavelengths below 300 nm where the energy is sufficient to break main chain bonds. 

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. 

The incorporation of PDMSX into conventional novolac resins has produced potential bilevel resist materials. Adequate silicon contents necessary for O2 RIE resistance can be achieved without sacrificing aqueous TMAH solubility. Positive resist formulations using an o-cresol novolac-PDMSX (510 g/mole) copolymer with a diazonaphthoquinone dissolution inhibitor have demonstrated a resolution of coded 0.5 pm L/S patterns at a dose of 156 mJ/cm2 upon deep-UV irradiation. A 1 18 O2 etching selectivity versus hard-baked photoresist allows dry pattern transfer into the bilevel structure. 

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. 

Figure 6. Exposure curves of positive resist Hitachi Chemical R1-7000P with and without the Dl-CEL. The contrast (r-value) of the Dl-CEL resist is three times of that of the non-CEL resist.

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. 

Fig. 8 Schematic representation of block copolymer nanolithography process, a Schematic cross-sectional view of a nanolithography template consisting of a uniform mono-layer of PB spherical microdomains on silicon nitride. PB wets the air and substrate interfaces, b Schematic of the processing flow when an ozonated copolymer film is used as a positive resist, which produces holes in silicon nitride, c Schematic of the processing flow when an osmium-stained copolymer film is used as a negative resist, which produces dots in silicon nitride, (taken from [44])...

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