Photoresists characteristics

In order to be successful as a photoresist the polymer must have three characteristics ... 

Preliminary Examination of PATE Imaging Characteristics. The data herein have shown that PATE resins are easily photolyzed in the deep UV region to form crosslinked films which are of sufficient integrity for photoresists. However, in addition to these film performance properties, a potential resist material must meet other equally important criteria. For example, the masked (unphotolyzed) portion of the resist film must be removed prior to etching, without damage to the cured film. Also, the cured films must withstand an etchant bath. Therefore, since PATE resins seem to meet the necessary requirements of solubility and solvent resistance, investigation of performance under crude simulated processing conditions was undertaken. 

Poly(methyl methacrylate) [PMMA] is an excellent polymer for studying photoresist dissolution because of its minimal swelling characteristic. For this work, PMMA molecules were labelled with phenanthrene (Phe) dye since its fluorescence is quenched by MEK. In addition, this dye has the advantage of forming few excimers (23-241 which results in self-quenching. Thus, the reduction in fluorescence intensity of PMMA-Phe is virtually solely due to MEK quenching. Consequently, the permeation of MEK into a PMMA film can be monitored from fluorescence intensity decay. 

The familiar positive photoresists. Hunt s HPR, Shipley s Microposit, Azoplate s AZ etc., are all two-component, resist systems, consisting of a phenolic resin matrix material and a diazonaphthoquinone sensitizer. The matrix material is essentially inert to photochemistry and was chosen for its film-forming, adhesion, chemical and thermal resistance characteristics. The chemistry of the resist action only occurs in the sensitizer molecule, the diazonaphthoquinone. A detailed description of these materials, their chemical structures and radiation chemistry will be discussed in Section 3.5.b. 

The photoactive compounds, or sensitizers, that are used in the formulation of positive photoresists, are substituted diazonaphthoquinones shown in Figure 17. The substituent, shown as R in Figure 17, is generally an aryl sulfonate. The nature of the substituent influences the solubility characteristics of the sensitizer molecule and also influences the absorption characteristics of the chromophor (79). The diazonaphthoquinone sulfonates are soluble in common organic solvents but are insoluble in aqueous base. Upon exposure to light, these substances undergo a series of reactions that culminate in the formation of an indene carboxylic acid as depicted in Figure 17. The photoproduct, unlike its precursor, is extremely soluble in aqueous base by virtue of the carboxylic acid functionality. 

Two component, positive photoresists (see Section 3.5.b) represent systems with unusual exposure characteristics caused by the standing wave effect (see Section 2.1.f) and "bleaching" or change in optical density during exposure (see Sections 3.5 and 3.9). Both of these phenomena result in nonlinear exposure throughout the thickness of the resist film, and result in uneven developing rates as a function of film thickness, making evaluation of these systems difficult. 

One attractive possibility is the use of the a-keto-oxime chromophore. It has a strong absorption at 220 nm whose tail, which extends to 240-250 nm, would improve the absorption characteristics of PMMA. Also, the esters possess a N-O bond which is photochemically labile yet sufficiently thermally stable so as to be compatible with the various processing steps. The solution degradation of a-keto oximino methacrylate esters upon irradiation with light of X365 nm has been reported by Delz-enne (2), and we proceeded to investigate the solid state photodegradation of similar copolymers and their possible utility as deep UV photoresists. 

Conventional positive photoresists only have limited utility in the mid-UV and deep-UV range. While it appears feasible to modify the structure of the o-quinonediazides to optimize their absorption characteristics in the mid-UV range, (8,9) or even to use appropriate sensitizers for conventional resists,... 

A mixture of three isomeric cresols is used in a commercially available cresol-formaldehyde Novolak resin. This mixed Novolak resin, Varcum resin (12), provides adequate properties as a host resin for near-UV- and mid-UV-photoresist applications. Gipstein and his co-workers prepared pure cresol-formaldehyde Novolak resin from each isomeric cresol and compared their spectroscopic and resist characteristics (13). Their data on the UV-absorption spectra of each cresol-formaldehyde Novolak resin together with the commercially available Varcum resin are as follows the absorbances of 0.2 jim thick Novolak films at 250 nm are 0.165(Varcum), 0.096(o-cresol), 0.092(m-cresol), and 0.055(p-cresol). The so-called "window" in the UV absorption at around 250 nm is a maximum with the p-cresol-formaldehyde Novolak resin, while the other isomeric cresol and formaldehyde Novolak resins yielded similar UV absorptions at this wavelength. The smallest UV absorption at 254 nm is an advantage for the p-cresol-formaldehyde Novolak when the resin is used for a deep UV photoresist with a suitable photoactive compound (14). 

A unique characteristic of polymers composed of extended chains of Group 14 elements is the delocalization of electrons through the cr-bond framework of the polymer backbone.7 These polymers are known to absorb in the ultraviolet, with absorption maxima dependent both on main chain substituents and on chain length. Several potential applications exist, such as photoconductors, photoresists in microelectronics, photoinitiators for radical reactions, and precursors to ceramic materials. 

The copolymers of type 67 exhibit the characteristic photochemical depolymerization noted for polysilanes, a source of their potential as photoresist materials. However, the presence of the ferrocenyl substituents results in a significant retardation of this depolymerization, presumably due to the ability of ferrocene to quench the triplet state responsible for the polysilane photochemistry164. Polymers of type 67 can be regarded as polysilanes with reversible redox behaviour. 

The great value of the unique characteristics of fluorinated polymers in the development of modern industries has ensured an increasing technological interest since the discovery of the first fluoropolymer, poly(chlorotrifluoro-ethylene) in 1934. Hence, their fields of applications are numerous paints and coatings [10] (for metals [11], wood and leather [12], stone and optical fibers [13, 14]), textile finishings [15], novel elastomers [5, 6, 8], high performance resins, membranes [16, 17], functional materials (for photoresists and optical fibers), biomaterials [18], and thermostable polymers for aerospace. 

The predictive value of the theoretical treatment described above was verified experimentally [88,90]. The experimental results were in excellent agreement with the calculated speed point and characteristic curve of cross-linking photoresist. 

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