THERMALLY STABLE POSITIVE RESIST

Abstract: A thermally stable, positive resist is provided which is useful in ultra violet lithography. The positive resist composi­ tion contains a polymer system, a sensitizer system, and a solvent for the polymer system and the sensitizer system. The polymer system contains a phenolic resin, and prefer­ ably a novolak-type resin compatible with the phenolic resin. The sensitizer system contains a photosensitive agent and a thermosensitive cross-linking agent for the phenolic resin. The photosensitive agent is a diazoketone compound insolu­ ble in aqueous alkaline solution that absorbs radiation in the near ultra violet region of the spectrum providing decom­ position products soluble in aqueous alkaline solution. The thermosensitive cross-linking agent is a bisarylazide com­ pound that absorbs radiation in the deep ultra violet region of the spectrum and that cross-links the phenolic compound when exposed to elevated temperatures.

Description: THERMALLY STABLE POSITIVE RESIST Field Of The Invention The present invention relates to thermally stable resist compositions useful in ultra violet lithography. More particularly, the present invention relates to a thermally stable, positive resist composition which has the ability to resolve micron size geometries in the fabrication of semiconductor devices. Background Of The Invention Resists are materials which, when exposed to high energy, such as an electron beam, or radiation of the proper wavelength, such as ultra violet radiation, are chemically changed in their solubility or removability characteristics in certain solvents or developers. To develop a resist generally means to remove, by whatever means, those areas of the resist which are more easily removable after the resist is exposed. A common and convenient means of development is through solvents which dissolve the more easily removed portion of the selectively exposed resist layer, but leave the remaining portions substantially intact. A material is "developable" if it is removable by any of the standard methods of development known to those skilled in the art. Two types of resists are available, negative-acting and positive-acting resists. Prior to exposure, negative-acting resists are soluble in developer, but with exposure they undergo chemical change and become insoluble in such developers. After selective exposure, the unexposed areas of the resist are selectively dissolved, softened, or washed away, leaving the desired resist pattern on a substrate. The remaining resist pattern is used to protect the substrate in, for example, etching processes, where surface etching of the substrate is desired only in the areas which underlie the unexposed resist. Positive-acting resists work in the opposite manner, with exposure making the resists soluble in the developer. In either case, the resist pattern that remains after development and, in some cases, post baking, is insoluble and chemically resistent to the cleaning, plating, etching or other solutions used in treating the substrate. Resists are used in the formation of integrated circuits, printed circuit boards, photolithographs, name plates and the like. Resists are particularly useful in the electronics industry where a typical operation might be the coating of a substrate, such as a silicon wafer with a thin film of a resist which is then exposed through either a positive or a negative of the desired image. If the resist used is a positive-acting material, the exposed areas of the resist layer are rendered soluble by the exposure, and are removed by washing with a developer to uncover the underlying metal layer. The areas surrounding the uncovered metal, which were not exposed remain and protect the portions of the metal layer which they overlie. An etchant to which the resist is impervious may then be used to etch away the uncovered metal areas, or selective plating or other processes may be accomplished, and there remains a layer of resist in the desired image pattern. Later in the manufacturing process, the remaining resist pattern may or may not be removed, as desired. Modern technology for processing semiconductors, such as plasma etching, sputtering, ion implantation, and the like, requires a photoresist having thermal stability at temperatures of at least about 2000C. A thermally stable photoresist is one which does not flow excessively at a given temperature and one in which images in the resist undergo little or no dimensional changes or distortion at a given temperature. Conventional photoresists are available which are thermally stable at about 1600C, and while they are useful at temperatures up to 1600C their thermal stability above l600C is such that they are not suggested for use in the high temperature processing described above. While negative-working resists have been proposed which are stated to have improved thermal properties, positive-working resists have inherent advantages over negative-working resists as is well known to those skilled in the art. Thus a positiveworking, thermally stable photoresist would be highly advantageous. One such thermally stable, positive acting photoresist composition known in the art contains a light-sensitive orthoquinone diazide or orthonaphthoquinone diazide and a polyamic acid condensation product of an aromatic dianhydride and an aromatic di-primary amine. Such polyamic acid condensation products are converted by heat to a thermally stable polyimide that is water-insoluble, and resistant to dilute acids and organic solvents. Such positive-acting photoresists are coated on a substrate, dried, exposed through a mask by a suitable actinic light source, such as a 200 watt medium or high pressure mercury arc lamp, developed to remove the exposed resist and then treated to develop the thermal properties of the unexposed resist. In order to fully develop these properties, the unexposed resist is given an allover exposure to actinic light to decompose the remaining diazide, such as for 60 to 180 seconds at about 3,000 microwatts/cm2, and the polyamic acid condensation product is converted to the polyimide form by heating the photoresist for about 30 minutes at 2200C or higher. The overall exposure step may be omitted if the photoresist is heated slowly during use to avoid rapid decomposition of the diazide. Thus, there currently exists a need for thermally stable positive resist systems with high resolution and good processing latitude. Summary Of The Invention Positive resist compositions are provided which are useful in ultra violet lithography. The compositions preferably have a total solids content of from about 15% to about 35% and contain a polymer system comprising a phenolic resin having a weight average molecular weight of at least about 2,000 and preferably a novolak-type resin compatible with the phenolic resin, a sensitizer system comprising a photosensitive agent, which is a diazoketone compound insoluble in aqueous alkaline solution and which absorbs radiation in the near ultra violet region of the spectrum providing decomposition products that are soluble in aqueous alkaline sou- tion, and a thermosensitive cross-linking agent for the phenolic resin, which is a bisarylazide compound that absorbs radiation in the deep ultra violet region of the spectrum and that cross-links the phenolic compound when exposed to elevated temperatures, and a solvent in which all components are readily soluble. The resist compositions of the present invention are developable in aqueous alkaline developers and produce a thermally stable resist which exhibits high resolution. Description Of The Preferred Embodiments The resist compositions of the present invention comprise a solution of a sensitizer system and a polymer system in a compatible solvent. The solids content of the composition is preferably between about 15% and about 35%, more preferably between about 20% and about 30%. The polymer system comprises a phenolic resin and may preferably also include a novolak-type resin compatible with the phenolic resin. The polymer system is present in an amount of from about 55% to about 90%, preferably about 65%, by weight of the total solids in the composition. The phenolic resin has a weight average molecular weight of at least about 2,000, preferably at least about 7,000, more preferably within the range of from about 10,000 to about 40,000, and even more preferably within the range of from about 15,000 to about 30,000, and is present in the composition in an amount of from about 40% to about 100%, preferably about 40% to about 95%, and more preferably about 85%, by weight of the polymer system in the composition. When employed in amounts less than about 100% of the polymer system, the phenolic resin has a weight average molecular weight of at least about 7,000 and the remainder of the polymer system comprises a novolak-type resin. Phenolic resins useful in the present invention are represented by the following structural formula: EMI6.1 wherein: A is a covalent bond, -0-, -C(O)O-, or -C(O)OCH2-, preferably a covalent bond or -O-, and more preferably a covalent bond; and R1 is -H, -F, -C1, -Br, or -I, preferably F. Particularly preferred as the phenolic resin are those resins represented by the following structural formula: EMI6.2 wherein R1 has its previously assigned meaning. The novolak-type resins useful in the present invention can be any such resin which is compatible with the phenolic resin both in coating characteristics, that is, which produces in combination with the phenolic resin a homogenous and uniform resist coating, and in rate of solubility in the aqueous alkaline developer. Preferred as the novolak-type resin is a cresol-formaldehyde novolak resin or a phenol-formaldehyde novolak resin. The cresol-formaldehyde novolak resins are particularly preferred and are preferably prepared as described in commonly assigned U.S. Patent 4,377,631. The novolak-type resin is present in an amount of from O to about 60%, preferably about 5% to about 60%, and more preferably about 15%, by weight of the polymer system in the composition. Novolak-type resins useful in the present invention are represented by the following structural formula: EMI7.1 wherein: R2 and RQ are independently monovalent C1 to C4 alkyl, preferably R2 and R3 are methyl. The thermosensitive cross-linking agent is a bisarylazide compound that absorbs radiation in the deep ultra violet region of the spectrum and that, when exposed to elevated temperatures, typically within the range of from about 800 to about 1600C for from about 10 to about 45 minutes, cross-links the phenolic resin establishing the thermal stability of the resist. Useful bisarylazide compounds are selected from the group consisting of EMI7.2 and mixtures thereof, wherein: L and M are independently a covalent bond, -CH2-, -C(CH3)2-, -CO-, -SO2, -O-, or -S-; and R4, R5, R6, and R7, are independently -H, -NH2 or -N3, provided that at least one of R4 and R5 is -N3 and at least one of R6 and R7 is -N3. Preferred are those compounds in which L is -C(CH3)2-, and R4 and R5 are -N3; and those in which M is -O-, and Rs and R7 are -N3. The photosensitive agent is a diazoketone which is insoluble in aqueous alkaline solution and sensitive to radiation in the near ultra violet region of the spectrum, providing, when exposed to such radiation, decomposition products which are soluble in aqueous alkaline solution. Diazoketone compounds useful in the present invention are compounds selected from the group consisting of EMI8.1 and mixtures thereof, wherein: : @ is -E-(CH2)2-O-W or -E-C@X' @@@@@ W is -CH3, -C2H5, (CB2)2-O-CH3 or -(CR2 )2-O-C2115; each X' is independently -H, -F, -Br, -C1 or -I, preferably each X' is -H or the same halogen ion; a is 1 or 2; b is 2, 3, 4, 5, 6, 7, 8 or 9; T is -(CO)-, -O-, -CH2-, -C(CH3)2)-, -S(O)2-, -S-, or -O-Z-O-, when a is 2; and T is H when a is 1; Z is -(CH2)2- or EMI8.2 D is -C(O)-, -O-, -CH2-, -C(CH3)2-, -S(O)2- or -S-; each R8, Rg and R10 is independently -H, -OH, -NH@, EMI9.1 provided: that at least one Rs, R9 or R10 is EMI9.2 that when T is -O-Z-O-, each Rlo is H, and that when a is 1, R10 is monovalent C1 to Cg alkyl, -H, -OH, NH2, EMI9.3 preferably monovalent C1 to C9 alkyl, more preferably -C(CHs ); and each E is independently -0- or -NH-, preferably -0-; when Z is erably -NH-. EMI9.4 E is pref Preferably, when a is 2, up to four of the R8, R9 and R10 substituents are selected from EMI9.5 The diazoketone is present in an amount of from about 50% to about 90%, preferably 70%, by weight of the sensitizer system in the composition. The compositions are formed by adding the components of the polymer system and the sensitizer system to a solvent in which all of the components are readily soluble. The order of addition is not critical. The solvent is preferably selected from the group consisting of aliphatic ketones, aliphatic esters, alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, and mixtures thereof. A particularly preferred class of aliphatic esters are the aliphatic alkylene glycol alkyl ethyl esters. More preferably, the solvent is selected from the group consisting of cyclohexanone, methylcellosolve acetate, ethylcellosolve acetate, butyl acetate and mixtures thereof. A particularly preferred solvent is a mixture of ethylcellosolve acetate, butylacetate and xylene. The choice of solvent will depend on the specific phenolic resin, novolak-type resin, diazoketone and bisarylazide employed. After the phenolic resin, the novolak-type resin, the diazoketone and the aromatic azide have been added to the solvent, the mixture is agitated until all solids are dissolved. The resultant resist solution is microfiltered, preferably using a millipore microfiltration system under about 30 pounds per square inch of pressure of nitrogen or other inert, oxygen-free, ambient atmosphere. Additives such as dyes, anti-striation agents, plasticizers, adhesion promoters, speed enhancers, and non-ionic surfactants may be added to the solution before it is filtered. Dye additives useful with the resist compositions of the present invention include Methyl Violet 2B (C.i No. 42535), Crystal Violet (C.I. No. 42555), Malachite Green (C.I. No. 42000), Victoria Blue B (C.I. No. 44045) and Neutral Red (C.I. No. 50040) at 0.1% to 3% weight levels, based on the weight of the positive resist composition. The dye additives may help provide increased resolution by inhibiting back scattering of light off the substrate. Anti-striation agents may be used up to a 5% weight level, based on the weight of the positive resist composition. Plasticizers which may be used include, for example, phosphoric acid tri-(-chloroethyl)- ester; stearic acid; dicamphor; acetal resins; phenoxy resins; and alkyd resins at 1% to 5% weight levels, based on the weight of the polymer sytem. The plasticizers improve the coating properties of the material and enable the application to the substrate of a film that is smooth and of uniform thickness. Adhesion promoters which may be used include, for example, - (3, ss-(3,4-epoxy-cyclohexyl3-ethyl- trimethoxysilane; p-methyl-disilane-methyl methacrylate; vinyltrichlorosilane; and y-amino-propyl triethoxysilane up to a 5% weight level, based on the weight of the positive resist composition. Speed enhancers that may be used include, for example, picric acid, nicotinic acid or nitrocinnamic acid at a weight level of up to 5%, based on the weight of the total solids. These enhancers tend to increase the solubility of the resist coating in both the exposed and unexposed areas, and thus they are used in applications where speed of development is the overriding consideration even though some degree of contrast may be sacrified. Thus while the exposed areas of the resist coating will be dissolved more quickly by the developer, the speed enhancers will also cause a larger loss of resist coating from the unexposed areas. Non-ionic surfactants that may be used include, for example, nonylphenoxy poly(ethyleneoxy) ethanol; octylphenoxy (ethyleneoxy) ethanol; and dinonylphenoxy poly(ethyleneoxy) ethanol at up to 0.5% weight levels, based on the weight of the positive resist composition. The filtered resist composition can be applied to a substrate by any conventional method used in the resist art, including dipping, spraying, whirling and spin coating. When spin coating is employed, the percent total solids content is selected to provide coatings of the desired thickness given the type of spinning equipment utilized and the spin speed and the amount of time allowed for the spinning process. The resist coatings produced by the abovedescribed procedure are particularly suitable for application to thermally grown silicon/silicon dioxide-coated wafers, such as are utilized in the production of microprocessors and other miniaturized integrated circuit components, aluminum/aluminum oxide wafers and other wafers typically employed in the art. After the resist composition is coated onto the substrate, the substrate is baked at about 800 to about 1100C until substantially all the solvent has evaporated and only a thin coating of the resist, on the order of a micron in thickness, remains on the substrate. Typically, the substrate is baked for about 20 to about 45 minutes. Preferably, the substrate is baked at about 900C for about 30 minutes. The coated substrate is then imagewise exposed to radiation in the near (about 440 to about 350 nm) to mid (about 360 to about 330 nm) ultra violet ranges of the spectrum, preferably the near ultra violet region, in any desired exposure pattern produced by use of suitable masks, stencils, templates, or the like. The resists can be exposed using commer cially available equipment, for example, a Perkin Elmer 1:1 Projection Micralign ill Model or a Kaspar Instruments contact exposure until Model 2001. The exposed, resist-coated substrates are then contacted with an aqueous alkaline developer, preferably by immersion in the developing solution in, for example, a Teflon tank until all of the resist coating has been dissolved from the imagewise exposed areas. The solution is preferably agitated, for example, by nitrogen burst agitation. The developer formulation is not critical and typical of the developers useful with the resists of the present invention is HPR-402, an aqueous alkaline positive resist developer manufactured by Philip A. Hunt Chemical Corporation. Typical development conditions are 23+2 C, with the development time depending largely on the exposure energy, developer strength and the developer mode such as spray, puddle, nitrogen burst submersion or mechanical agitation, and pre-bake temperature and time. For example, under mild (magnetic bar) agitation, using 40% HPR-402 developer in the immersion mode, the developing time is typically 60 seconds for 1 micron coatings pre-baked at about 900C for 30 minutes. After removal of the coated wafers from the developing solution, the wafers are typically rinsed for about one minute with deionized water, and then a post-development heat treatment or bake is employed which causes the thermosensitive agent to cross-link the phenolic resin, developing the thermal stability of the photoresist. The postbaking can be effected by oven baking of the coating and substrate. Typically, exposing the resist to temperatures within the range of from about 80 to about 1600C for from about 10 to about 45 minutes, cross-links the phenolic resin establishing the thermal stability of the resist. Preferably, the coating is baked at about 1250 to about 1500C for about 15 to about 45 minutes, more preferably at about 1280C for about 40 minutes. Particularly preferred is postbaking at about 1300C for about 30 minutes. In industrial applications, particularly in the manufacture of microcircuitry units on silicon/ silicon dioxide-type substrates, the developed substrates are typically treated with a buffered, hydrofluoric acid-based etching solution. The resists of the present invention are resistant to acid-based etching solutions and provide effective protection for the resist-coated areas of the substrate The resist compositions of the present invention produce a resist coating which exhibits the thermal stability required by the elevated temperatures employed in the plasma etching, ion milling, and sputtering processes used in the fabrication of semiconductor devices. The positive resist composition of the present invention does not require the use of deep ultra violet radiation as do currently employed positive resist systems, and develops its thermal stability at a relatively low postbake temperature without post-development exposure to actinic radiation. Examples The following examples present illustrative but non-limiting embodiments of the present invention. Comparative examples are also provided. Resist film thicknesses in the following examples were measured using a Sloan Dektak Profilometer (hereinafter, 'the Profilometer11). The resist coatings in the following examples were exposed using a Perkin-Elmer 1:1 Projection Micralign 111 Model (hereinafter, the "P-E exposure unit") or a Kaspar Instruments contact exposure unit Model 2001 (hereinafter, "the Kaspar exposure unit"). Image dimensions were determined using an I.T.P. Videomicrometer System No. 148 (hereinafter, "the I.T.P. unit"). The Novolak resins employed in the examples were prepared as set forth in U.S. patent 4,377,631. Example 1 Sample compositions A through N were prepared as summarized in Table 1. The precentages are by weight of the total solids. The solvent employed in samples A through E and I through M was cyclohexanone; in sample F, a mixture of 41% cyclohexanone and 59% ethylcellosolve acetate; in sample G a mixture of about 60% cyclohexanone, about 38% ethylcellosolve acetate, about 1% butyl acetate and about 1% xylene; in sample H, a mixture of about 70% cyclohexanone, about 26% ethylcellosolve acetate, about 2% butyl acetate and about 2% xylene; and in sample N, a mixture of 85% ethylcellosolve acetate, 7.5% butyl acetate, and 7.5% xylene. Sample compositions E and N are comparative. Samples A through H were tested for photospeed and image quality and were found to be relatively slow, whereas samples I through M had a relatively faster photospeed. Microscopic examination of postbaked imaged resists of formulations A through M showed insignificant flow or no flow after l700C postbake for 30 minutes whereas the comparative compositions exhibited excessive flow. Example 2 Sample compositions I through L were evaluated as follows. The samples were spin coated on Si/SiO2 wafers providing a film thickness of about TABLE 1 Sample Composition PVP,% Novolak,% Diazoketone,% Bisarylazide.% Total Solide,% N15 N26 N37 D18 D29 D310 B111 B212 B313 A 65Ú 10 - - 10 - - - 15 - 25 B 70Ú 5 - - 10 - - 15 - - 25 C 70Ú 5 - - 10 - - - - 15 25 D 70ê 5 - - - - - 15 - - 26 E14 70ê 10 - - - 20 - - - - 27 F 33.75ê 33.75 - - - - 15.63 16.87 - - 30.5 G 39.59 37.82 - - 13.16 - - 9.43 - - 27 H 67.54 7.48 - - 10.0 - - 15.02 - - 27 I 60Ú 5 - - - - 20 - - 15 25 J 60Ú 5 - - - - 20 - 15 - 25 K 60Ú - 5 - - - 20 - - 15 25 L 55Ú 5 - - - - 20 - - 15 25 M 50Ú 5 - - - - 20 - - 15 25 N14 - - - 75 - - 20 - - - 27.75 1. A 30,000 Mw polyvinylphenol. 7. A novolak resin prepared from a 45% m-cresol, 2. A 10,000 Mw polyvinylphenol. 55% p-cresol mixture and having a solftening 3. A 7,400 Mw polyvinylphenol. point of about 145 C. 4. A 4,000 Mw polyvinylphenol. 8. A sensitizer prepared by reacting one mole of 5. A novolak resin prepared from a 60% m-cresol, abielamine with one mole of 2-diazo-1-naphthol40% p-cresol mixture and having a softening 5-sulfochloride. point of about 136 C. 9. Naphthoquinone (1,2)diazide(2)-5-sulfonic acid 6. A novolak resin prepared form a 60% m-vresol O-cresol ester. 40% p-cresol mixture and having a softening 10. A sensitizer prepared by reacting about two moles point of about 136 C. of 2-diazo-1naphthol-5-sulfochloride with one mole of trihydroxybenzophenone. 11. 3,3'-biazidodiphenylsulfone. 12. 4,4'-biazidodiphenylmethylene. 13. 4,4'-biazidooxydiphenyl. 14. Comparative. 1 micron, and then prebaked at 700, 1000 or 1300C for 30 minutes. The coatings were exposed for 20 seconds on the Kaspar exposure unit through a multi-density mask to ultra violet radiation at an intensity of 3.2 m.wt./cm2 measured at 380 n.m. and then developed for about 60 seconds, after which the percent film loss and percent transmission of complete development were determined. The processing parameters and results are summarized in Table 2. Example 3 Compositions I, J, K and N were evaluated to determine their thermal stability. The samples were spin coated on Si/SiO2 wafers, providing a film thickness of about 1 micron, prebaked at 1000C for 30 minutes, exposed through a resolution mask on the P-E exposure unit to ultra violet radiation at constant intensity measured at 356 n.m. The wafers were developed for about 60 seconds using an aqueous alkaline developer, postbaked and then subjected to electron microscopic examination and examination on the I.T.P. unit. Exairiination of the samples showed some changes in image slope and top roundness with increasing postbake temperature. The greatest change in profile was seen at.1500C suggesting thÅat at this temperature or lower, cross-linking of the resist occurred yielding a more thermally stable geometry. This was confirmed by the observed stability in image dimensions after postbaking at 1280C for 30 minutes. Generally, window dimensions appeared to increase after postbaking at 1280 to 130 c but to decrease after postbaking at 150 c. Whensamples I, J, K were postbaked at 1280C for 30 minutes and then at 2000C for 30 minutes, no dimensional changes were observed between these two postbake temperatures, whereas comparative sample N TABLE 2 Sample Film Soft Bake DeveloperÚ Film Transmission of Composition Thickness, Temp., C, Conc.,% Loss,% Complete Development,% I 1.09 70 20 6.4 20 1.09 70 21 6.4 20 1.09 70 22 6.4 20 1.09 70 25 19.3 14 1.09 70 27 28.4 12 J 1.1 70 25 5.45 30 1.1 70 27 5.45 30-35 1.1 70 27 3.64 30 1.04 100 25 3.85 40 1.04 100 27 5.77 35-40 1.04 100 27 3.85 40 0.98 130 25 0 > 100 K 1.08 70 25 9.26 22 1.08 70 27 14.81 22 1.08 70 30 16.67 18 0.98 100 25 2.04 35-40 0.98 100 27 4.08 #35 0.98 100 30 10.2 #25 0.93 130 25 1.08 > 100 0.93 130 27 0 > 100 0.93 130 30 0 > 100 Lê 1.02 70 30 1.96 22 1.02 70 33 5.88 20 1.02 70 35 1.96 18 0.96 100 30 2.08 35-40 0.90 130 35 0 > 100 ÚLSI developer; a metal ion-containing aqueous alkaline developer available from Philip A. Nuat Chemical Corporation. ê All of the developer wafers exhibited surface hazo. TABLE 3 Sample Film Thick- Scan DeveloperÚ Film Composition mess, Setting Conc.,% Loss,% D.I.D.ê I.D.1 I.D.24 I.D.35 I.D.46 I.D.57 I 1.06 200 22 4.9 4.89 5.06 5.04 5.03 5.07 4.49 225 22 4.9 4.89 5.19 -- -- -- 4.56 250 22 4.9 4.82 -- -- -- -- - 290 22 4.9 4.48 -- -- -- -- - 350 25 12.5 5.03 -- -- -- -- - J -- 225 27 8.6 5.12 -- -- -- -- - 250 27 8.6 5.08 5.27 -- -- -- 4.62 250 27 8.6 5.08 5.27 5.27 -- -- - 290 27 8.6 4.78 -- -- -- -- - K 1.07 250 25 10.2 5.06 5.21 5.16 5.17 5.15 4.5 270 25 10.2 5.22 -- -- -- -- - 300 25 10.2 4.98 5.12 -- -- -- 4.43 350 25 10.2 4.66 -- -- -- -- - N -- 350 50 -- 5.03 5.23 -- -- -- 4.48 350 50 -- 4.97 5.08 4.61 Excessive flow 4.51 1. LSI developer; a metal ion-containing aqueous alkaline developer available from Philip A. Hunt Chemical Corporation. 2. D.I.D. = developer image dimension; nominal of 5 window. 3. I.D.1 = image dimension after postbake at 128 C. for 30 min., nominal of 5 window. 4. I.D.2 = image dimension after postbake at 128 C. for 30 min., then at 150 C. for an additional 30 min,; nominal of 5 window. 5. I.D.3 = image dimension after postbake for 30 min. at 128 C., 30 min. at 150 C., and then 30 min. at 175 C.; nominal of 5 window. 6. I.D.4 = final image dimension after postbake for 30 min. at each of the following temperature: 128 C., 150 C., 175 C. and 200 C.; nominal of 5 window. 7. I.D.5 = image dimension after postbake for 30 min. at 150 C.; nominal of 5 window. exhibited excessive flow. The results are summarized in Table 3. Example 4 Sample compositions 0 through X were prepared as summarized in Table 4. The percentages are by weight of the total solids and the solvent employed was a mixture of 85% ethylcellosolve acetate, 7.5% butyl acetate and 7.5% xylene. Sample X is comparative. Example 5 Sample compositions P, v and W were spin coated on Si/SiO2 wafers providing a film thickness of about 1 micron, prebaked at about 1000C for about 30 minutes, and then developed for about 60 seconds, without having been exposed to ultra violet radiation, to determine the ability of the unexposed films to withstand aqueous alkaline developers. The process parameters and film loss are summarized in Table 5. Example 6 Sample compositions P, V and W were spin coated on Si/sio2 wafers providing a film thickness of about 1 micron, prebaked as summarized in Example 5, exposed through a resolution mask on the P-E exposure unit to near ultra violet radiation at the energies indicated in Table 6 (measured at 356 n.m.), developed for about 60 seconds, postbaked at either 1300C for 30 minutes, or at 1300C for 30 minutes followed by 2000C for 30 minutes, and then examined using the I.T.P. unit to determine image dimensions. These dimensions were compared to image dimensions measured before postbaking. The process parameters and the results are summarized in Table 6. TABLE 4 Sample Composition PVP,% Novolak,% Diazoketone,% Bisarylazide,% Total Solide,% N4 N54 N65 D46 D57 E48 0 55 10 - - 20 5 10 26 P 55 10 - - 25 - 10 24.5 Q 55 - 10 - 20 - 10 26 R 59.15 10.85 - - 20 - 10 26 S 45 25 - - 20 - 10 26 T 45 25 - - 16 4 10 26 U 46 - - 25 20 - 10 26 V 55 10 - - 20 5 10 26 W 55 10 - - 25 - 10 26 XÚ - 75 - - 25 - - 27.75 1. Comparative. 2. A 24,000 Mw polyvinylphenol. 3. Novolak prepared from a mixture of 60% m-cresol and 40% p-cresol and having a softening point of about 130 to 133 C. 4. Novolak prepared from a mixture of m-cresol and catechol and having a softening point of about 171 C. 5. Novolak prepared from a mixture of 50% m-cresol and 50% p-cresol and having a softening point of about 140 C. 6. A sensitizer prepared by reacting about two moles of 2-diazo-1-naphthol-5-sulfochloride with one mole of trihydroxybenzophenone. 7. Naphthoquinone (1,2)diazide(2)-4-sulfonic acid cumylphanol ester. EMI21.1 Example 7 Sample compositions P through V, and X were spin coated on Si/SiO2 wafers to provide the film thicknesses indicated below in Table 7, prebaked at 1000C for 30 minutes, exposed through a resolution mask on the P-E exposure unit, to near ultra violet radiation at the energies indicated in Table 7 (measured at 356 n.m.) then developed for about 60 seconds. The resists were evaluated for film loss and developed image dimension employing the I.T.P. unit, the Profilometer, and a scanning electron microscope. The process parameters and results are summarized in Table 7. Example 8 The plasma etch rates of sample composition 0 and comparative sample compositions X, Y and Z were determined using a CEF3 plasma environment as is typically employed for Sio, etching and an SF6 plasma environment as is typically employed for nitride and polysilicone etching. As controls, uncoated SiO2, nitride, and polysilicone surfaces were also etched. The compositions were spin coated on Sioz wafers at a thickness of about 1 micron, prebaked at 1000C for 30 minutes, postbaked at the temperàture indicated in Table 8 and then etched in either the CHF3 or SF6 plasma environment. The etch rate was determined at different settings. The process parameters and results are summarized below in Table 8. TABLE 5 ------- Film Loss Sample Spin Spced, Prebaked film Developer 1 Developed film (unerposed) Composition rpm thickness, Conc., % thickness, ---------- ----------- ----------- ------------- ------------ --------------- @ % P 3700 1.0073 44 0.9133 940 9.3 V 5000 0.94 42 0.90 400 4.3 W2 5000 0.986 44 0.879 1070 10.9 1 HPR-402; an aqueous alkaline positive resist developer available from Philip A. Hunt Chemical Corporation. 2 Identical components to P but higher percentage of total solids. TABLE 6 Postbaked image dimension, Exposure Sample Energy, DeveloperÚ Developed 130 C/30 min. Composition mj/cmê Conc.,% image dimension, 130 C/30 min. + 200 C/30 min. P 143 44 4.96 4.97 4.94 V 230 42 5.03 4.99 5.06 W 110 44 5.03 5.00 4.95 TABLE 7 Exposure Developed Sample Film Energy, Developer Developed Film Image Composition Thickness, mj/cmê Concentration,% Thickness, Dimension5 Film Loss, A DvÚ Dvê P 1.03 120 - 44 0.93 5.04 1033 Q 1.167 135 - 42 1.05 5.03 700 R 1.09 149 - 40 0.983 4.96 1067 S 0.99 281 - 40 0.96 5.01 367 T 1.0 245 - 46 0.94 5.06 600 U 1.01 315 - 36 0.965 4.93 450 V 0.98 96 27 - 0.89 5.05 900 0.98 165 - 42 0.93 5.00 500 X 0.9757 35 50 - 0.903 4.914 734 1. MIF; a metal ion-free aqueous alkaline developer available from Philip A. Hunt Chemical Corporation. 2. HPR-402; an aqueous alkaline positive resist developer available from Philip A. Hunt Chemical Corporation. 3. Comparative. 4. Pronounced foot. 5. Nominal of 5 . TABLE 8 Sample Postbake Etch Rate, @/min., at Composition Temp., C Gas 20watts 25watts 30watts 50watts 100watts ControlÚ - CHF3 - 700 - - Controlê - SF6 - - 800 - Control - SF6 2000 - - 0 200 CHF3 - 250 - 320 360 0 130 SF6 - 1670 - 3220 4390 0 90 SF6 - 1670 - 4000 -7 X4 250 CHF3 - 150 - 240 400 X4 130 SF3 - 1660 - 3015 -7 X4 250 SF6 - 1790 - 3015 4020 X4 90 SF6 - 1670 - -7 -7 Y5 130 SF6 - 1855 - 4020 4825 Z6 130 SF6 - 1670 - 3015 -7 1. Uncoated SiO2 water. 5. KTI-802; a positive resist composition available 2. Uncoated nitride surface. from Kodak; comparative 3. Uncoated polysilicone surface. 6. OFPR-800; a positive resist composition 4. Comparative. available from Dynachem; comparative. 7. Severely attacked.

Claims: CLAIMS: 1. A positive resist composition, comprising a sensitizer system, a polymer system, and a solvent for the sensitizer system and the polymer system, the polymer system comprising a phenolic resin having a weight average molecular weight of at least about 2,000, the sensitizer system comprising a photosensitive agent and a thermosensitive cross-linking agent for the phenolic resin, the photosensitive agent comprising a diazoketone compound insoluble in aqueous alkaline solution that absorbs radiation in the near ultra violet region of the spectrum providing decomposition products soluble in aqueous alkaline solution, the thermosensitive agent comprising a bisarylazide compound that absorbs radiation in the deep ultra violet region of the spectrum and that cross-links the phenolic resin when exposed to elevated temperatures. 2. The composition of claim 1 wherein the polymer system includes a novolak-type resin and the phenolic resin has a weight average molecular weight of at least about 7,000. 3. A positive resist composition, comprising a sensitizer system, a polymer system, and a solvent for the sensitizer system and the polymer system, the polymer system comprising, by weight, about 40% to about 100% of a phenolic resin having a weight average molecular weight of at least about 2,000 and from 0% to about 60% of a novolak-type resin compatible with the phenolic resin, the polymer system comprising about 55% to about 95%, by weight, of the total solids in the composition, the sensitizer system comprising, by weight, from about 50% to about 90% of a photosensitive agent and from about 10% to about 50% of a thermosensitive-cross- linking agent for the phenolic resin, the photosensitive agent is a diazoketone compound insoluble in aqueous alkaline solution that absorbs radiation in the near ultra violet region of the spectrum providing decomposition products soluble in aqueous alkaline solution, and the thermosensitive crosslinking agent is a bisarylazide compound that absorbs radiation in the deep ultra violet region of the spectrum and that cross-links the phenolic resin when exposed to elevated temperatures. 4. The composition of claim 3 wherein the bisarylazide compound is selected from the group consisting of EMI28.1 and mixtures thereof, wherein: L and M are independently a covalent bond, -CH2-, -C(CB3)2-, -SO2-, -CO-, -O-, or -S and R4, R5, R6, and R7 are selected independently from -H, -NH2 and -N3, provided that at least one of R4 and Rs is -N3, and at least one of R6 and R7 is -N3. 5. The composition of claim 3 wherein the diazoketone compound is selected from the group consisting of EMI28.2 and mixtures thereof, wherein: Q is -E-(CH2)2-O-W or -E-CbX' (2b+1); W is -CH3, -C2H5, -(CH2)2-O-CH3 or -(CH2)2-O-C2H5 ; each X' is independently -H, -F, -Br, -Cl or -I; a is 1 or 2; b is 2, 3, 4, 5, 6, 7, 8 or 9; T is -(CO)-, -O-, -CH2-, -C(CH3)2)-, -S(O)2-, -S-, or -0-Z-O-, when a is 2; and T is H when a is 1; EMI29.1 D is -C(O)-, -O-, -CH2-, -C(CH3)2-, -S(O)2-= or -S-; each R8, Rg and Rlo is independently -H, -OH, EMI29.2 provided: that at least one R8, R9 or Rlo is EMI29.3 that when T is -O-Z-O-, each R10 is H, and that when a is 1, R10 is monovalent C1 to Cg alkyl, -C(CH3)3, -H, -OH, -NH2, EMI29.4 each E is independently -0-, or -NH-. 6. The composition of claim 3 wherein the phenolic resin is represented by the following structural formula: EMI30.1 wherein: A is a covalent bond, -0-, -C(O)O-, or -C(O)OCH2-; and R1 is -H, -F, -C1, -Br or -I. 7. The composition of claim 3 wherein the novolak-type resin is represented by the following structural formula: EMI30.2 wherein: R2 and R3 are independently monovalent C1 to C4 alkyl. 8. The composition of claim 3 wherein the phenolic resin has a weight average molecular weight of at least about 7,000, the phenolic resin is present in the composition in an amount of from about 40% to about 95% by weight of the polymer system in the composition, and the novolak-type resin is present in an amount of from about 5% to about 60% by weight of the polymer system in the composition. 9. The composition of claim 3 wherein the total solids content of the composition is within the range of from about 15% to about 35%. 10. A positive resist composition, comprising a polymer system, a sensitizer system, and a solvent for the polymer system and the sensitizer system, the composition having a total solids content of from about 15% to about 35%, the polymer system comprising, by weight, about 40% to about 95% of a phenolic resin having a weight average molecular weight of at least about 7,000, and about 5% to about 60% of a novolak-type resin compatible with the phenolic resin, the polymer system comprising about 55% to about 95%, by weight, of the total solids in the composition, the phenolic resin is represented by the following structural formula: EMI31.1 wherein: A is a covalent bond, -0-, -C(O)O-, or -C(O)OCH2-, and R1 is -H, -F, -C1, -Br or -I, the novolak-type resin is represented by the following structural formula: : EMI31.2 wherein: R2 and R3 are independently monovalent C1 to C4 alkyl, the sensitizer system comprises, by weight, from about 10% to about 50% of a thermosensitive crosslinking agent for the phenolic resin and from about 50% to about 90% of a photosensitive agent, the thermosensitive cross-linking agent is a bisarylazide compound selected from the group consisting of EMI32.1 and mixtures thereof, wherein: : L and M are independently a covalent bond, -CE2-, -C(CH3)2-, -SO2-, -CO-, -O-, or -S-, and R4, R5, R6, and R7 are selected independently from -H, -NH2 and -N3, provided that at least one of R4 and R5 is -N3 and at least one of R6 and R7 is -N3, the photosensitive agent is a diazoketone compound selected from the group consisting of EMI32.2 and mixtures thereof, wherein: Q is -E-(C112)2-O-W or W is -CH3, -C2H5, - (CH2)2-O-CH3 or (cH2 )2-O-C2H5; each X' is independently -H, -F, -Br, -Cl or -I; a is 1 or 2; b is 2, 3, 4, 5, 6, 7, 8 or 9; T is -(CO)-, -O-, -CH2-, -C(CH3)2)-, -S(0)2-, -S-, or -O-z-o-, when a is 2 and T is H when a is 1; Z is -(CH2)2- or EMI33.1 D is -C(O)-, -O-, -CH2-, -C(CH3)2-, -S(O)2- or -S-; each R8, R9 and R10 is independently -H, -OH, NH2 EMI33.2 provided: that at least one R8, R9 or Rio is EMI33.3 that when T is -O-Z-O-, each Rio is H, and that when a is 1, R10 is monovalent C1 to Cg alkyl, -C(CH3)3, -H, -OH, -NH2 EMI33.4 each E is independently -0-, or -NH 11. The composition of claim 3 or 10 wherein the solvent is selected from the group consisting of aliphatic ketones, aliphatic esters, alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, and mixtures thereof. 12. The composition of claim 3 or 10 wherein the solvent is a mixture of ethylcellusolve acetate, butyl acetate and xylene. 13. The composition of claim 3 or 10 wherein the polymer system comprises, by weight, about 15% of the novolak-type resin and about 85% of the phenolic resin. 14. The composition of claim 3 or 10 wherein the sensitizer system comprises, by weight, about 70% of the diazoketone compound and about 30% of the bisarylazide compound. 15. The composition of claim 3 or 10 wherein the polymer system comprises about 65% by weight of the total solids in the composition. 16. A photosensitive material, comprising a support having coated thereon a layer comprising the composition of claim 1, 3 or 10. 17. A method of forming a thermally stable photoresist image, comprising imagewise exposing the photosensitive material of claim 16 to near ultra violet radiation, developing a positive relief image by contacting the exposed layer with an aqueous alkaline developer thereby removing the imagewise exposed areas, and then exposing the remaining photosensitive material to elevated temperature to develop the thermal stability of the photoresist. 18. The method of claim 17 wherein the remaining photoresist material is exposed to a temperature within the range of from about 800 to about 1600C for from about 10 to about 45 minutes.

Inventors: TOUKHY, MEDHAT A.
Applicants: OLIN HUNT SPECIALTY PRODUCTS INC.
Application year: 1984
Main classification: G03F7
IPC codes: C08L61, G03F7, C08L33, G03C1