2 NEGATIVE PHOTORESISTS INTRODUCTION Chapter 1 briefly introduced the nomenclature of negative and positive resists. Here we describe the standard operations by which an image is formed in negative and positive working systems (see Fig. 2-1). ‘The material is coated on a substrate, dried, and exposed to a radiation pattern; it is then treated with a solvent termed the “developer.” In negative resists the photochemistry that occurs on irradiation renders the material less soluble in the developer; the unirradiated parts of the coating are washed away ‘and a negative polymer image of the original pattern remains on the substrate. In positive resists the photochemistry brings about an enhancement of solubil- ity or of dissolution rate and it is the irradiated areas that are removed by the developer. The early photomechanical materials such as bitumen of Judea, dichro- ‘mated gelatin, and other dichromated colloids were all negative resists. At the time of their discovery the mechanism by which they functioned was not ‘understood, Only in the 1920s was it recognized that gelatin and other natural colloids are macromolecules {1] and that rubber vulcanization is a crosslinking, process. At that point the idea began to take hold that the hardening and the insolubilization that occur on exposure of dichromated gelatin are brought about by radiation induced crosslinking, Exactly how crosslinks may be formed in dichromated coatings remained a mystery until Biltz and Eggert [2] established that the process involves the photoreduction of Cr(V1) to Cri). + 14H* + 66 2+ 7H,0 w INTRODUCTION 23, Radiation VELA a> Transarency Latent imsge —-[— Ty TI] resist 3, \'s, Support Developed __af image Negative Positive resis! resist Figure 2-1. Schematic of negative and postive resist functions Datta and Soller (3) have shown that the detailed fate of Cr(VI) depends somewhat on the colloidal medium, but that the final stage of the photopro- cess always leads to Cr?* ions. Since trivalent chromium is known to be a powerful coordination center, it was thought that crosslinks may be formed by the coordinative bonding of Cr?* with the amide groups of the protein ‘This view is supported by the fact that all polymers that have been used as gelatin substitutes, such as other proteins, starch, poly(vinyl alcohol), poly(vinyl pyrrolidone), and poly(vinyl butyral), carry ligands capable of forming com- plexes with Cr(III). More recently, coordinative bonding of gelatin to Cr(III) ‘was investigated by Duncalf and Dunn [4] who found that crosslinking occurs only in dry coatings of dichromated gelatin, but not in concentrated aqueous SUE Bac UR cP a RRR OP a,2A NEGATIVE PHOTORESISTS: and does not interact with the protein, Crosslinking in gelatin films can also be suppressed by the addition of chelating agents such as EDTA (ethylenedi- aminetetracetic acid). Furthermore, the addition of chromic chloride hexa- hhydrate does not have any effect on gelatin films, but when the films are heated high enough to drive off the water of crystallization, they become insoluble, as water in the coordination sphere of Cr(III) is being replaced by the amino and carbonyl ligands of the protein. This is convincing evidence that insolubilization is brought about by the reaction of substrate-bound ligands with a photogenerated coordination center. ‘Whatever the mechanistic detail, the most important conclusion from these studies is that polymer insolubilization can be achieved by crosslinking, and in fact, the great majority of negative resists are based on crosslink formation. However, this is not the only mechanism by which image and nonimage areas can be differentiated in negative resists. A number of materials have been designed on the principle of photoinduced polarity changes in polymer-bound functional groups. Such changes can have a profound effect on the solubility of the polymer. They are discussed in a later section of this chapter. ‘THE PHOTOCHEMISTRY OF CROSSLINKING In general, the reactions that have been used to generate crosslinks in poly- meric systems are of two types: Those where crosslinks are formed by the direct reaction of an excited molecule or group, and those where crosslinks arise through the action of a photogenerated reactive species in the ground state, Reactions of Excited Chromophores ‘The classic example of crosslinking by an excited chromophore occurs in poly(vinyl cinnamate), Be ees THE PHOTOCHEMISTRY OF CROSSLINKING 25 Minsk and co-workers conceived of the design of this polymer [5] while searching the literature for a potential crosslinking reaction. At the time the best known organic solid state photoreaction was the dimerization of cinnamic acid (6) Cinnamie seid Trnilic ald Poly(vinyl cinnamate) incorporates this reaction system. Crosslinks are formed by photoaddition between an excited (+) cinnamoyl group of one chain with a ground state cinnamoyl group belonging to another chain, —cH,—cHt A. 4 O) c ba beg cH 7 —CH,—CH is ont ne— lar - He— en 8 c=0 7 + —CH,—CH—26 NEGATIVE PHOTORESISTS “The nature of the crosslinks in poly(vinyl cinnamate) has been confirmed by direct product analysis [7]. At low temperature up to 80% of the reaction products are cyclobutanes, the rest are the result of radical mediated side reactions, [2 +2] Cycloaddition in the ground state of two C=C double bonds is forbidden by orbital symmetry (Woodward—Hoffmann), but it is symmetry allowed if one of the reactants is in the excited state. The reaction is therefore eminently suitable as a photocrosslinking mechanism. It is particularly effec- tive in the cinnamoyl group and its analogs where the carbonyl provides the desirable polarization of the reactive double bond, while the phenyl group increases the polarizability and enhances the light absorbing power of the chromophore. It is no coincidence that the cinnamoyl motif appears in the structures of a whole range of important photopolymers. ‘Minsk’s procedure for introducing cinnamoyl groups into hydroxylic poly- mers is indicated in Eq. (4) and serves as a model for the synthesis of other resists [5]. Photoreactive unit , Hydroxylic _ base , Photores ctive acid chloride polymer “ polymer ‘Although the crosslink-generating photoreaction is reasonably eficient (the quantum yield of crosslink formation is about 0.1), the practical photographie Performance of poly(vinyl cinnamate), when exposed to a medium pressure mercury lamp is poor. This is caused by the mismatch between the absorption Spectrum of the cinnamoyl group (its maximum absorbance is at 280 nm) and the spectral emission of the mercury arc (see Fig, 3-16). This difficulty can be overcome by spectral sensitization, or by the replacement of the cinnamoyl group with a chromophore that absorbs at longer wavelength. Spectral sensitization of poly(vinyl cinnamate) is rather successful [8]. For example, the addition of 5% of Michler’s ketone brings about a 300-fold enhancement of photographie speed. The reader i referred to Chapter 3 where the sensitization process is described in some detail oa ‘THE PHOTOCHEMISTRY OF CROSSLINKING 27 An example of the second strategy is poly(vinyl cinnamylidene acetate). Poly(vinyl Cinnamidene Acetate) ‘This material, inroduced by Leubuer and Unsul [9] in 1966, absorbs at 360 ram and has a photographic speed 200 times higher than that of unsensitized poly(vinyl cinnamate). It is noted that only the double bond adjacent to the carbonyl group is reactive [10]. Cycloaddition is here reversible, the cyclobu tanes formed on irradiation at 365 nm can be cleaved by irradiation with the 254 nm mercury Line [11].28 NEGATIVE PHOTORESISTS Other photoreactive chromophores of interest are the chalcones of the general structure [12] chat . and the phenylene diaerylates [13]. These can be used either as pendant groups, for example, attached by an ester linkage to poly(vinyl alcohol) (14), CH,—CH cH I CH c=o or J. or in the backbone of a polyester [15]. Particularly useful is a polyester of p-phenylenediacrylic acid (PPDA) with the not too flexible glycol shown in the following structure (13}. ° ‘ O pps This polyester is used on a very large scale as the photosensitive material of precoated lithographic plates (Eastman Kodak). The bifunctional chromo- phore absorbs strongly at 365 nm. The crosslinking reaction has a quantum yield of about 0.1. ‘THE PHOTOCHEMISTRY OF CROSSLINKING 29 ‘The physical properties of condensation polymers can be altered by changes in the nonphotosensitive components [16, 17]. For example, the introduction ‘of a rigid glycol component such as bisphenol A leads to heat-resistant materials [16]. Recently, Li et al, [18] have described a group of polyesters based on sipryipyridine, which are thermally stable up to 450°C (see also OL io o-(O)-crmat © tuacn{O)-o-L-al Oy. ™sR 0 While most earlier photopolymers were prepared by the functionalization of fa preexisting polymer, Baumann and Zweifel [27] found that bifunctional monomers containing dimethylmaleimide and another group, for example, an acrylate, can be polymerized via the acryloyl group without affecting the maleimide. (The steric hindrance of the methyl groups protects the double bond of maleimide from radical attack in the thermal polymerization process.) This allows much greater flexibility in the synthesis of polymers and copoly= mers. Accordingly, Berger and Zweifel, and co-workers [28] have incorporated ddimethylmaleimide as a side chain in various acrylic copolymers and prepared resists of the general structure. ‘C(CH,)—CH, | ©) Dimethylmaleimide Photographie sensitivities as high as 1 mJ/em® have been achieved in some of these systems. ‘An interesting photopolymer was discovered by De Boer in 1973 when he introduced diphenyleyclopropene as a side chain into substituted poly(vinyl alcohol) (29) THE PHOTOCHEMISTRY OF CROSSLINKING 31 TABLE 21 Water Processable Crosslinking Photoresists Contents of R Relative Photosensitive Group R (mol) Sensitivity Reference [-se-arar- ©] rn =o G)-arer (Opes Soe —06)-aeen Qa 08 5 —N{O)-cn=cx(O) a ms c-c Ho ton Sh on pho Ph al pao (19) on CH,CH, cH, Acetone pinacot THE PHOTOCHEMISTRY OF CROSSLINKING 41 ‘Smets et al, [48] have used this process in photocrosslinking copolymers of vinylbenzophenone and 4-dimethylaminostyrene. The reaction, in this case, passes through an exciplex (see Chapter 3), which the authors were able to detect by fluorescence spectrometry. —CH,—CH— —CH—CH,— Vinyibenzophenone 4.Dimethylaminostyrene Recently, a photoreactive polyimide has been reported [49, 50], where crosslinking is brought about by photogenerated radicals, The repeat unit of this material has the structure2 NEGATIVE PHOTORESISTS where the R groups may be methyl or other alkyl substituents. The key step i the functional mechanism is hydrogen abstraction by the carbonyl group of the benzophenone moiety from nearby alkyl substituents and the formation of two radicals, The recombination of these radicals on neighboring chains leads then to the formation of crosslinks [51 ‘The photoreactive polyimide has fairly high photographie speed (a typica exposure requirement is 25 mJ/em?), good contrast, and high resolution ‘There are no volatile products on heating and the images are dimensionally stable up to 400°C. Finally, the resist can be coated and imaged in thick layers, which is important for its use as an a-particle barrier, as well as for other applications. It is of some interest to note that the hydrogen abstraction reaction, which is so efficient in fluid solution, (@ = 0.6), is reversible in the rigid polymer ané Teads to a low net quantum yield of crosslink formation ( = 0.03), Sono st Ph I : (22} tl eae "Seon + ¢-O : A Hybrid System. An interesting new crosslinking system based on the reac- ‘tion of radicals was recently disclosed by Plambeck et al. [52]. It is a hybrid ‘THE PHOTOCHEMISTRY OF CROSSLINKING 43 AnnN - any c ro " \ = \ \ © ana ARAN Scheme 1 system that combines the photographic speed of silver halide photography with the desirable physical properties of @ polymer. It makes use of the catalytic development of exposed silver halide to generate reactive inter mediates capable of forming crosslinks in a high molecular weight polymer. The idea was realized by designing polymers with pendant color coupler groups and using bifunctional color developers to act as crosslinking agents in the presence of a silver latent image. The process is illustrated in Scheme 1 ‘The reaction between developer and silver ions is described by reaction (23) [53]. ‘The diimine cation reacts with the active methylene of a color coupler to form a dye. Og ee N RN NH + | + 2A8t =N 0 . 4 ‘The first reaction is strongly catalyzed by the silver nuclei of an exposed silver hhalide emulsion, The practical problem is to design a polymer that will disperse silver halide grains. Coupler polymers compatible with silver halide were prepared by copo- lymerization of acrylates with methacrylates and with polymerizable coupler te RN NH, + 2Ag* > R.44 NEGATIVE PHOTORESISTS coupler was found to be particularly useful. A typical copolymer composition is shown in the following formula, oa, c CH cH fo OB thas ‘The bifunctional color developer was modeled on the Kodak CD4 developer. tO penny) ie oh oh on on To prepare a negative working lithographic plate, equal amounts of coupler copolymer and sensitized silver halide are mixed together at a carefully controlled pH of 9.5 to form a combined emulsion, This is coated on anodized aluminum at a dry coating weight of between 10 to 40 mg/dm:. The plates are exposed in a process camera and developed, subjected to a conventional spray washout, and rinsed in 2% acetic acid. Good quality images are obtained and the plates are not visibly degraded after 100,000 impressions [52] Resists Based on Photoinduced Polar Photoinduced changes in the polarity of polymer-bound functional groups can profoundly affect the solubility of the polymer, To be effective, polarity changes have to be quite dramatic to transform the resist from a material soluble in organic solvents to one that dissolves in an aqueous medium. This idea has been used extensively in the design of electron resists (see Chapter 8), but it can be applied equally to photopolymers sensitive in the visible and near uv. The classical example of a photoinduced polarity change is the photode- composition of diazoquinones, which transforms a moderately polar com- pound, the diazoquinone, into an ionizable compound, the indene carboxylic acid. This reaction is the basis of the important positive working photoresists described in Chapter 5. If diazoquinone units are attached to a polymer backbone, for example via acrylic side groups, the polymer will be soluble in organic solvents before exposure and become soluble in dilute aqueous alkali after exposure. Changes THE PHOTOCHEMISTRY OF CROSSLINKING 45 Schwalm et al. have used the photochemical transformation of N-imino- pyridinium ylides (1) to 1,2-diazepins (II) as the basis of a negative working resist [54]. (nay (max) = 230 nm ‘The polymer-bound ylides are water soluble while the diazepins are hydro- phobic. The system works well as a negative resist with an aqueous developer. The positive tone function expected on development with organic solvents is less satistactory because of some adventitious crosslinking [54]. In diazoquinone chemistry the driving force of the photoreaction is th great stability of N,, which makes the —=N, substituent such an effective leaving group. A rather popular negative photoresist is based on the same principle [55~57]. This so-called diazoresin is a low molecular weight polymer Produced by the diazotization of an anilin—formaldehyde resin. Its structure follows near Nel NH \ NH | NH cH cH, cH, gD Hy cH, cH, cH, NH | NH |46 NEGATIVE PHOTORESISTS n irradiation the diazonium ion eliminates nitrogen, leaving behind a carbo- cation that then reacts by substitution with the chloride ion. ‘The chlorinated resin is no longer water soluble and will act as a negative resist with an aqueous developer. The material is widely used in the printing industry for negative lithographic plates and for the preparation of silverless negatives. In the diazoresin material some crosslinks are also formed on exposure, which make the image mechanically and thermally more resistant. This occurs at sites where a diazonium ion is located near a secondary amine and where the substitution reaction may produce a quarternary ammonium jon and lead to a crosslink. | NH car (26) of diazonium salts was used in a different way to produce a negative working resist (58). An aqueous acetic acid solution of 4-dimethylaminophenyldiazonium chloride, zinc chloride, and the binder poly- N-vinyl pyrrolidone is coated over a cresol novolac film on a silicon wafer. The diazonium compound diffuses into the phenolic layer and is eventually parti- tioned between the top layer and the phenolic resin; a uniform two-layer resist is formed. On exposure, the diazonium compound in the top layer bleaches and acts as a contrast enhancing dye (see Chapter 6). In the bottom layer it decomposes to the nonpolar 4-dimethylaminochlorobenzene, which acts as a dissolution inhibitor of the phenolic resin on development in aqueous alkali. A resolution of 0.5 jm, lines and spaces, was achieved with this material, ‘THE PHYSICAL CHEMISTRY OF CROSSLINKING In crosslinking resists the irradiated areas are made resistant to solvent by the interconnection of polymer chains into a network. In the preceding sections we have presented the chemical mechanisms by which this is brought about; here ‘we are concerned with the physical consequences of the chemical process. Let us start with a qualitative description [59]. Crosslinks are formed at the sites of individual chromophores. In the early stages this leads only to an increase in the average molecular weight of the polymer, but it has a dramatic effect on the molecular weight distribution in the system. Since all chromo- 7 THE PHYSICAL CHEMISTRY OF CROSSLINKING 47 phores (polymer repeat units) have a priori the same probability of excitation, in a polydisperse system large molecules are more likely to react than smaller ones. As a consequence, the largest molecule in the ensemble will rapidly outstrip all others. When this many-branched supermolecule permeates the whole irradiated area, it forms there a continuous three-dimensional network that the solvent may penetrate, but which it can no longer disperse: An insoluble residue or gel has been formed. This gel constitutes the image in polymer photography. Image formation in crosslinking resists is thus identified as a process of photoinduced gelation, ‘The point at which the gel makes its first appearance is called the gel point of the system. At the gel point only an infinitesimally small fraction of the material is part of the network. If crosslinking continues, more and more of the original molecules become linked to the network and the weight fraction of gel gradually increases. A plot of the gel fraction against the exposure (radiation dose) that caused it is termed the gel curve of the photopolymer. Fig. 2-3 shows the gel curve of a resist film of low optical density, In Fig. 2-3 the weight fraction of gel (IV) is plotted as a function of incident exposure in terms of photons per square centimeter. These so-called quantum exposures are often expressed in cinsteins per square centimeter, an einstein being one mole of quanta (or photons). Since the gel constitutes the image in crosslinking resists, the gel curve is also the photographic characteris, tic curve of the resist. The progress of the crosslinking process can be expressed by the weight fraction of the gel, or more commonly by the relative (or normalized) thickness of the film remaining in the exposed areas after development. Following the custom in silver halide photography, the normal- ized thickness is often plotted as a function of the decadic logarithm of the exposure dose, measured in millijoules per square centimeter. Such a plot is Figure 23_Gel curve of a polyester of pphenylenediacrlic acid, sensitized with 3% Michler’s ketone radiated at 395 nm. fis the dspersity ofthe molecular weight of the polymer, W the gl fraction, E the exposure dose in photons/em*, (Reproduced with permission from J. Chim. Phys. 79, 469 (1980)48 NEGATIVE PHoToRESISTS 10 09 08 07+ Kodak 747 os ost oat 7 eb 1 Wayant © 900 Le ee) t be (ee ee etry 2 3400 Exposure dose in mitem? Figure 24. Sensitometsc curves of @ group of commercial negative photoresist, (Reproduced vith permission from L. F. Thompson and R. E. Kerwin, Annu. Rev. Maver. Sci, 6,272 976)] oa or ; ar | shown in Fig. 6-2. Equation (27) may be used to convert einsteins per square centimeter into millijoules per square centimeter. (sem) = 296% 10 + icine) (7) Sensitometric curves for a few typical negative resists [59a] are shown in Fig. 2d, Gel Point Exposure and Photographic Sensitivity In Fig. 2-3 the curve originates abruptly at the gel point, which marks the minimum exposure required for incipient image formation {60}. The gel point exposure or gel dose E,, is a measure of the inherent photographic sensitivity of the system without reference to any particular application, The exposure that satisfies the requirements of a specitic application is higher than E,, and defines a work point on the gel curve. For example, in Fig. 2-3 the work point might be reached when about half of the resist in the exposed areas has been insolubilized. The position of the work point varies with the application; i is higher for etching masks, lower for photolithography. Because gel point and work point differ, the practical speed of a resist depends not only on the position ofthe gel curve, but also on its initial slope, | “THE PHYSICAL CHEMISTRY OF CROSSLINKING 49 Figure 2-5. Unit area of a cesist lm of thickness ‘exposed toa photon MX I oor more generally, on its shape. The initial slope of the gel curve is related to the photographic contrast of the resist. The two parameters, gel dose and initial slope of the gel curve, provide in most respects an adequate characte zation of the photographie performance of a resist. ‘A relation between gel point exposure E', and the molecular properties of the photopolymer can be derived from gelation theory [61] (see Fig. 2-5). ‘Consider unit area of a resist film of thickness r and specific gravity d. If the molecular weight of the monomer unit is My, the number of moles of photoreactive groups in unit area of the film is rd/M,. In the process of irradiation a fraction p of the available groups has become crosslinked and the umber of crosslinked groups in unit area is therefore, rdp/My. If during, irradiation a fraction of the incident photons is absorbed, the photochem- ical balance equation can be written in the form rdp ~ Mb (28) where £ is the incident radiation dose in einsteins per square centimeter and. ® is the quantum yield of erossink formation. This quantum yield is defined as the number of groups or chromophores taking part in intermolecular crosslinks, for each photon absorbed in the film.” Equation (28) relates the crosslink density p to exposure energy at any stage of the crosslinking process. At the gel point the crosslink density is such that con the average every macromolecule carries one crosslink. This is expressed by Stockmayer’s rule Mg mn (29) where M, is the weight average molecular weight of the polymer. The ‘minimum’ exposure that brings the photopolymer to the gel point is obtained ‘only intermolecular exosstinks contbute to network formation and hence tothe polymer gel. Intramolecular links between to groups on the same chain produce loops and do not connect with another macromolecule,50 NEGATIVE PHOTORESISTS by combining Eqs. (28) and (29). rd a AM,® ~ 2.303emM,0 (0) On the right of Eq, (30) the absorbed fraction of radiation, A, has been approximated, for D < 1 by the following expression. A=1~ 10°? = 2,303D = 2.303emr (i) In Eqs. (30) and (31) ¢ is the molar extinction coefficient of the chromophore (reactant group), which can be determined from the absorption spectrum, and m is here the molarity of the chromophore in the solid film. The weight average molecular weight M, may be obtained either by gel permeation chromatography (GPC) or from light scattering experiments Equation (30) is the fundamental equation of crosstinking resists. It relates photographic characteristic, namely, the gel dose Eg, to molecular properties of the polymer. It shows that the photographic sensitivity is proportional to the quantum yield of the crosslinking reaction, to the weight average molecular weight M, of the polymer. and to the light-gathering power. em, of the chromophores. In opticaly thin films the gel point exposure Eis independent of film thickness and becomes an intrinsic property of the material, Equation (30) allows an estimate of the maximum photographic speed that can be achieved with a crosslinking resist. In the absence of a chain mecha- nism the maximum value of ® is 2. Assuming realistic values for e and m and for the molecular weight a value of M, = 10%, the minimum gel dose required in an optically thin film is found as 0.25 x 10°? einsteins /em? for UV radiation of 360 nm. This corresponds to an energy density of 1X 10° J/em? = 0.1 mJ/em®. This value constitutes an absolute benchmark in the evaluation of resist performance. In Table 2-5 it is compared with the practical exposure requirements of several Kodak resists. It can be seen that the sensitivity of commercial crosslinking resists has not yet reached the theoretical maximum. Equation (30) applies to optically thin films. In many practical applications, however, comparatively thick films are used. Under these conditions an image is formed only when the gel point has been reached in the resist layer adjacent to the support. For that case, @ minimum image exposure E, is readily derived from Eq. (30). It is noted first, that the absorption of the critical sublayer is low and can be approximated by Eq. (31). Furthermore, the fraction of light reaching this layer is determined by the overall transmittance of the film, T = 10-. Thus, for frontal irradiation of a resist layer coated on a nonre- ‘THE PHYSICAL CHEMISTRY OF CROSSLINKING SI TABLE 2-5 Exposure Requirements of Photoressts and of Other Photographic Materials [59] Photographic Material E (al fon Positive AZ resist 100 Kodak Photo Resist (KPR 11) 70 Diazo paper 30 Kodak Thin Film Resist (KTFR) 20 Kodak Ortho Resist (KOR) 4 Equation (30) oa Day silver @M Company) 0.02 flecting support the minimum exposure given by [61] dod AM T (32) If the resist is coated on a transparent support and irradiated through that support, the minimum image exposure and the gel point exposure coincide and Eq. (30) applies directly. This method of irradiation is convenient if the quantum yield of crosslinking of the polymer is to be determined [62] Resist Contrast. The photographic contrast of a resist film is related to the initial slope of the gel curve. Gelation theory makes it possible to link this to molecular properties of the polymer. The starting point of the argument is a general expression derived by Flory [63], which connects gel fraction W with crosslink density p. 1- Yo) - ew? (33) Here y is the degree of polymerization (y tion function in the system, It so happens that in the majority of crosslinking photopolymers the distribution of molecular weight, and hence of the degree of polymerization, y, is well approximated by a so-called lognormal distribution. That is distribution, which on a logarithmic scale has the bell-shaped appearance of the classic Gaussian or normal distribution (see Fig. 2-8). It can be represented by a distribution function of the form M/My), and f(s its distibu- In yo)" | ! (332)52 NEGATIVE PHOTORESISTS pen pete . 2 ru (Protens em?) Figure 2.6 Gel curves of two photopolymers with snilar gel point exposure doses, but diferent Aispersites of molecular weight. (Repredvced with permission from J. Photogr Sci, 28, 187 (asi) Here fis the half-width or dispersity of the distribution andy, is the most probable value of y' located at the apex of the distribution curve. If this distribution function is introduced into Eq. (33), the initial slope of the gel curve is obtained by differentiation [59] as shown below. (* M, MyA® = at 34) dE} My rd a) Introducing the customary expression for resist contrast (y) with respect to a log E scale one finds aw log E ' M, = 2x 2203exp(~B) = 7 2% 220 (AF) = 065° It can be seen from Eq. (35) that resist contrast depends only on the width of the molecular weight distribution, measured here by the ratio M,/M, [see Eq. (36). This point is illustrated in Fig. 2-6; it shows the gel curves of two Photopolymers that have similar gel point exposures, but differ in the disper- sity of molecular weight Shape of the Gel Curve. The behavior of the resist film at all stages of exposure is described implicitly by the Flory function, Eq. (33). If the distribution function of molecular weight is known, the relation between 1 and p or between W and E can be made explicit and the gel curve established. Figure 2-7 shows the Flory functions for lognormal distributions of molecular THE PHYSICAL CHEMISTRY OF CROSSLINKING 53 06 [ ro Pt |i2 — Cpe | + . [| + iz = SS} i i 3 tala 5 | + 2 22 £ | 4 [+ 5 Bos | 03 : 02 01 12 3 4 8 6 7 8 9 WW 1s 6 15 Fyure 27 Generated, dimensiones chart ofthe Flory function W'= (E/E, A). Ym this equation 1 i identical with the normalized film thickness 1m, E and Bate the exposure dose and the gel point exposure dose, respectively, nd ft 8 he dxpersity of moleclar weight of the ‘ginal polymer weight in a generalized dimensionless plot where the gel fraction W is plotted as a function of the ratio p/p, or E/E, for a range of values of the dispersity B. The dispersity, which is again defined as the half-width of the bell-shaped lognormal distribution function of molecular weight, can be obtained direct! from Gel Permeation Chromatography, as it is shown in Fig. 2-8. It is also related to the ratio of weight average to number average molecular weight by the expression -xp(B*) (36) Since the molecular weight distributions of most resists is adequately repre- sented by a lognormal distribution, the Flory function in Fig. 2-7 may quite generally be used to predict resist performance if the dispersity of molecular weight of the material is known,