Patent Grant
7608382
The present invention relates generally to controlling the dissolution rate of polymers used in forming photoresist compositions and more specifically to polymers having a cycloalkyl repeat unit for controlling the dissolution rate of such polymers in photoresist compositions and the compositions thereof.
Photoresists are photosensitive films used for transferring an image formed therein to an underlying layer or substrate. A layer of a photoresist is formed over a substrate and generally a layer of a material to which the image is to be transferred. The photoresist layer is then exposed through a photomask to a source of activating radiation where the photomask has some areas that are opaque to such radiation and other areas that are transparent. A photoinduced chemical transformation results in the areas exposed to the activating radiation which allows for the development of a relief image therein.
Photoresists can be either positive-tone or negative-tone. Generally, negative-tone photoresists undergo a crosslinking reaction within those portions of the photoresist layer that are exposed to activating radiation. As a result, the exposed portions become less soluble than unexposed portions in a solution used to develop the relief image. In contrast, for positive-tone photoresists, the exposed portions of the photoresist layer become more soluble, in a developer solution, than the portions unexposed to such radiation.
As microelectronic devices, such as integrated circuits, employ smaller and smaller device structures to effect their function, the need for photoresist compositions capable of resolving such device structures becomes increasingly important. While the ability of a particular photoresist composition to resolve a particular device structure is a function of many factors, one such factor is control of the difference in the dissolution rates of exposed and unexposed portions of the photoresist. While this factor has been studied previously, the thrust of such study has generally been to develop additives that might serve to increase the difference in the dissolution rate of such exposed and unexposed portions in a developer solution. However, such additives can affect other properties of the photoresist composition in a less than desirable manner, for example by increasing the optical density of the composition at the working wavelength of the activating radiation, and perhaps of more import, merely increasing the difference in the dissolution rates of exposed and unexposed regions does not always control the differential dissolution rate.
Thus it would be desirable to provide photoresist compositions with controlled differential dissolutions rates. That is to say, the difference between the dissolution rates of exposed and unexposed portions of the photoresist is controllable. It would also be desirable for such photoresist compositions to encompass a polymeric material that provides such control of the differential dissolution rate without the need for an additive. In addition, it would be desirable to provide such polymeric materials for use as base resins of such photoresist compositions and to provide methods of forming such desirable polymers.
The preparation of norbornene derivatives, hereinafter referred to as monomers that are useful for forming polycyclic olefin resins, generally results in a mixture of exo and endo isomers being formed (see
Advantageously, it has been found that the resultant polycyclic olefin resins exhibited unexpected variations in their dissolution rate. Unexpected because rather than observing the dissolution rate of such resins varying as a function of molecular weight (either expressed as Mn or Mw) as normally observed, the variations seem to be primarily a function of the ratio of exo to endo isomers in the monomer starting material (see,
For example a first resin with Mn=3560 polymerized from a monomer having an exo isomer mole percent (mol %) of 48, is found to have a dissolution rate (DR) of 3920 Angstroms per sec (Å/sec) while a second, analogous resin polymerized from the same starting monomer but with approximately twice the molecular weight (Mn=7520) is found to have a DR of 3850 Å/sec. Thus, unexpectedly, resins having very different molecular weights have essentially the same DR (see, Examples 21 and 22 in Table 1). Similarly, for a third resin with Mn=3270 and polymerized from a monomer having 22 mol % of the exo isomer, the DR is found to be 6627 Å/sec, while an analogous fourth resin with Mn=13700 again polymerized from the same starting monomer but having about four times the molecular weight is found to have essentially the same DR (DR=6543 Å/sec., see, Examples 16 and 20 in Table 1).
For each of the above examples, the resin is a homopolymer of, α,α-bis(trifluoromethyl)bicyclo[2.2.1]hept-5-ene-2-ethanol (HFANB), formed in essentially the same manner. Thus, for each of the pairs (21 and 22, 16 and 20), only the concentration of a chain transfer agent used for the polymerization is changed to provide polymers having different molecular weights.
Comparing the DR of the first pair of resins (21 and 22) to the second pair of resins (16 and 20), it is apparent that the second pair of resins has a DR of about twice that of the first pair of resins. As both pairs of resins are HFANB homopolymers differing only in the mole percent of exo isomer in the starting monomer, Applicants believe that this difference in dissolution rate is a function of this difference in exo isomer mole percent. Thus it seems that where the concentration of exo isomer in the starting monomer is decreased, for example from 48 mol % in the first pair of resins to 22 mol % in the second pair of resins, the dissolution rate is increased.
Turning to
It should be noted that while the Applicants advance no specific theory to explain the unexpected results observed (see above and
Not withstanding the above, it is also well known that understanding the dissolution rate behavior of binder resins, is both important in the development of high performance photoresist formulations and complex. For example, Ito, et al., Proceedings of SPIE, 2003, 5039, 70 reported that homopolymers of HFANB made with both Ni and Pd catalysts exhibited “no straightforward relationship . . . between dissolution rate [in 0.26 N TMAH] and Mn or Mw” when investigated using quartz crystal microbalance methods. Ito also investigated the dissolution rate behavior of the same polymers using a more dilute, 0.21 N, TMAH solution but found the dissolution behavior complex and seemingly dependant on the molecular weight polydispersity of the polymer. Hoskins et al, Proceedings of SPIE, 2003, 5039, 600, reported the dissolution rate behavior of HFANB homopolymers in a 0.19 N TMAH solution where the homopolymers were made using only Pd catalysts. Using optical interferometric methods to measure dissolution rates, Hoskins reported that the HFANB homopolymers were found to “exhibit an atypical dependence of dissolution rate on molecular weight”. Thus Hoskins found that low molecular weight HFANB homopolymers (Mw<10,000) exhibited decreasing dissolution rates with increasing molecular weights while homopolymers with Mw>10,000 but <100,000 exhibited increasing dissolution rates with increasing molecular weight. However, it should be noted that the molecular weight polydispersity of the Hoskins samples were quite broad, ranging from 1.91 to 9.21, thus potentially complicating interpretation of the dissolution rate behavior.
Therefore, to simplify the investigation of dissolution rate behavior, Applicants elected to prepare HFANB homopolymers using only Pd catalysts and process conditions that would result in relatively narrow molecular weight polydispersities (i.e., 1.50 to 2.50). In addition, and to further avoid complexities, Applicants measured the dissolution rate behavior of such homopolymers using only a standard 0.26 N TMAH solution and quartz crystal microbalance methods.
Thus, by and through obtaining this increased understanding of dissolution rate behavior, Applicants believe that it is possible to create binder resins for photoresist compositions, both positive-acting and negative-acting, that take advantage of this understanding and hence allow for the difference between the dissolution rate of exposed and unexposed portions of photoresist layers (the differential dissolution rate) to be controlled. Additionally, it is believed and shown herein that this understanding can lead to better imaging results over a broader range of polymer parameters, for example variations in molecular weight. It should be further noted that the selection of HFANB monomers for the homopolymers studied, was also influenced by the use of such monomers in a large number of photoresist binder resin formulations that have been reported and thus the understanding obtained would be more readily applied.
In addition, the homopolymers used in the dissolution rate study were prepared using both olefinic and non-olefinic chain transfer agents (CTAs). Analysis of the homopolymers so formed, indicates that physical characteristics of the polymers, for example Mw, Mn, OD (optical density) and the like, can be varied by the choice of the CTA employed during the polymerization.
While the above observations were of homopolymers formed by vinyl addition polymerization, it has been shown that polymers formed using more than one type of monomer will exhibit similar dissolution rate effects that should also lead to enhanced imaging. Therefore, the monomers that will be useful in the practice of embodiments in accordance with the present invention are described below where the polymers formed from such monomers will encompass at least one monomer having a desired exo isomer mol %.
Embodiments in accordance with the present invention include repeat units derived from norbornene-type monomers having an acid labile protected pendant group. Such monomers are represented by Formula A, below:
where m and Z are defined above and where at least one of R1, R2, R3, or R4, independently, is an acid labile protected pendant group that is cleavable by, for example, an acid generated from a photoacid generator. Any known acid labile group known to the literature and to the art can be utilized in the present invention such as those set forth herein with regard to Formula A.
The remaining one or more R1, R2, R3, or R4, groups, independently, can be hydrogen, or a hydrocarbyl having from 1 to about 20 carbon atoms, or halogens selected from F, Cl or Br, or a hydrocarbyl having from 1 to about 20 carbon atoms substituted at any hydrogen atom with an O, S, N, or Si, and the like, or a fluorinated hydrocarbyl having from 1 to about 20 carbon atoms wherein each carbon atom, independently, is substituted with 0, 1, 2, or 3 fluorine atoms.
Returning to descriptions of acid labile protected groups, in some embodiments, such groups are a fluorinated carbinol moiety having from 1 to about 20 carbon atoms wherein each carbon atom, independently, is substituted with 0, 1, 2, or 3 fluorine atoms and the oxygen atom is protected by an acid labile group (i.e., blocking or protective groups) that are cleavable by acids generated from a photoacid generator. Exemplary fluorinated groups include, among others, —(CR2)nOR′, —(O—(CH2)n)n—C(CF3)2—OR′, —(CH2O)n—C(CF3)2—OR′, —((CH2)nO)n—CH2—C(OR′)(CF3)2 where each occurrence of n is an independently selected integer from 0 to about 5, each occurrence of R is independently a hydrogen or a halogen (i.e., F, Cl, Br, I) and where R′ is the acid labile group. R′ includes, but is not limited to, —CH2OCH3 (dimethyl ether), —CH2OCH2CH3 (methyl ethyl ether), —C(CH3)3, —Si(CH3)3, —CH2C(O)O(t-Bu), 2-methylnorbornyl, 2-methylisobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, 3-oxocyclohexanonyl, mevalonic lactonyl, dicyclopropylmethyl (Dcpm), or dimethylcyclopropylmethyl (Dmcp) groups, or R′ is —C(O)OR″ where R″ is —C(CH3)3, —Si(CH3)3, 2-methylnorbornyl, 2-methylisobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, 3-oxocyclohexanonyl, mevalonic lactonyl, Dcpm, or Dmcp groups, or combinations thereof.
In some embodiments of the present invention, Formula A is also represented by Formula A1, below
where n and R′ are as previously defined. More specifically, exemplary monomers encompassing an acid labile protected pendant group in accordance with Formula A1 encompass:
Additionally, norbornene-type monomers in accordance with Formula A are represented by Formula A2, below:
where n′ is an integer from 0 to 5 and Ra, Rb, and Rc, independently, represent linear or branched hydrocarbyl groups from C1 to about C20 or Ra and Rb taken together along with the common carbon to which they are attached represent a saturated cyclic group containing 4 to 12 carbon atoms. An exemplary norbornene-type monomer in accordance with Formula A2 encompasses:
where tBu is a tertiary butyl group
Some embodiments of the present invention include repeat units derived from norbornene-type monomers having a crosslinking capable pendant group. Such monomers are represented by Formula B, below:
where m and Z are defined as above, and where each of R5, R6, R7 and R8, independently, are H, a halogen, a linear, branched or cyclic C1 to C30 alkyl, an alkylol, an aryl, an aralkyl, an alkaryl, an alkenyl or an alkynyl; with the proviso that at least one of R5, R6, R7 and R8 is a functional group that is capable of crosslinking. Suitable crosslinking capable functional groups include, but are not limited to, hydroxy alkyl ethers according to Formula I:
-A-O—[—(CR**2)q—O—]p—(CR**2)q—OH Formula I
where A is a linking group selected from C1 to C6 linear, branched, or cyclic alkylene, each occurrence of R** is independently selected from H, methyl and ethyl, q is independently an integer from 1 to 5, in some cases from 2 to 5, and p is an integer from 0 to 3.
Other suitable crosslinking capable functional groups are represented by Formulae II, III, IV and V:
—R***-Q Formula II
—(CH2)nC(O)OR# Formula III
—(CH2)t—C(CF3)2—O—(CH2)t—CO—(OR##) Formula IV
where for Formula II, R*** is a linear, branched or cyclic C1 to C30 alkylene, arylene, aralkylene, alkarylene, alkenylene or alkynylene linking group that is optionally partially or completely halogenated, and Q is a functional group selected from hydroxyl, carboxylic acid, amine, thiol, isocyanate and epoxy. For Formula III, n is as previously defined and R# represents an acid labile group cleavable by a photoacid generator. Finally for Formula IV, each occurrence of t is independently an integer from 1 to 6 and R∩# is a C1-C8 linear or branched alkyl moiety, and in some instances a t-butyl group.
In addition, some embodiments in accordance with the present invention include repeat units derived from norbornene-type monomers having pendant groups that are exclusive of acid labile protected groups and crosslinking capable groups. Such monomers are represented by Formula C, below:
where m and Z are as previously defined, and where substitutents R9, R10, R11 and R12, are each an independently selected neutral substituent selected from the group of substituents consisting of halogens (i.e., F, Cl, or Br), —(CH2)n—C(O)OR21, —(CH2)n—(CM2)n—OR18, —(CM2)n-OC(O)R17, —(CH2)n—OC(O)OR17, —(CH2)n—C(O)R18, —(CH2)nC(R19)2CH(R19)(C(O)OR20), —(CH2)n—NH—(SO2)—CF3, —(CH2)nC(R19)2CH(C(O)OR20)2, —C(O)O—(CH2)n—OR18 and —(CH2)n—O—(CH2)n—OR18, —(CH2)n—(O—(CH2)n)n—C(CF3)2OR21 where each occurrence of n is independently an integer from 0 to 5, M can be hydrogen or a halogen (i.e., F, Cl, or Br), R19 can independently be hydrogen, a halogen, a linear or branched C1 to C10 alkyl group or cycloalkyl group or a linear or branched C1 to C10 halogenated alkyl group or halogenated cycloalkyl group, R18 can independently be hydrogen, a linear or branched C1 to C10 alkyl group or cycloalkyl group or a linear or branched C1 to C10 halogenated alkyl group or halogenated cycloalkyl group, R20 is not readily cleavable by a photoacid generator and can independently be a linear or branched C1 to C10 alkyl group or cycloalkyl group or a linear or branched C1 to C10 halogenated alkyl group or halogenated cycloalkyl group, R17 is not readily cleavable by a photoacid generator and can independently be linear or branched C1 to C10 alkyls or halogenated alkyls, a monocyclic or polycyclic C4 to C20 cycloaliphatic or halogenated cycloalkyl moiety, a cyclic ether, a cyclic ketone or a cyclic ester (lactone), where each of the cyclic ether, ketone and ester can be halogenated or not and R21 is defined as R17 plus hydrogen. Exemplary cycloaliphatic moieties include, but are not limited to, unsubstituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl groups as well as 1-adamantyl and 1-norbornyl moieties. Additionally, R9, R10, R11 and R12 can each be an independently selected neutral substituent represented by Formula I:
-A-O—[—(CR**2)q—O—]p—(CR**2)q—OH Formula I
where A and q are as defined before, but R** is selected from a halogen.
Therefore it will be appreciated that polymers in accordance with embodiments of the present invention encompass repeat units derived from polycyclic olefin monomers in accordance with any one of Formulae A, B and C. Such monomers can be produced by a variety of methods where such methods, as well as catalyst systems for the polymerization of such monomers are discussed in detail in U.S. Pat. Nos. 5,468,819, 5,569,730, 6,136,499, 6,232,417 and 6,455,650, the disclosures of which are incorporated, in pertinent part, herein. Exemplary methods of forming polycyclic olefin monomers include, Diels-Alder condensations employing cyclopentadiene and an appropriate dienophile or the reaction of an appropriately substituted polycyclic olefin with a desired exo isomer mol %, with a reagent appropriate for forming the final monomer desired.
As disclosed herein above, it has been found that monomers having a desired exo isomer mol % affect the dissolution rate of polymers made therefrom advantageously. In some embodiments, this desired exo isomer mol % is greater than the exo isomer mol % that would be expected for a polycyclic olefin monomer based on the thermodynamic equilibrium of the isomers of the monomer obtained from a Diels-Alder reaction. In other embodiments, the desired exo isomer mol % is less than the exo isomer mol % that would be expected for a polycyclic olefin monomer based on the thermodynamic equilibrium of the isomers of the monomer obtained from a Diels-Alder reaction. Such desired exo isomer mol % monomers can be obtained by selecting appropriate portions of monomer during purification using, for example, fractional distillation methods. However, obtaining such monomers is not limited to fractional distillation or any other purification method. Rather, such desired exo isomer mol % monomers useful for embodiments of the current invention can be obtained by any appropriate method and these appropriate methods and the monomers obtained therefrom are within the scope and spirit of the present invention.
It should be understood that the polymers in accordance with embodiments of the present invention encompass at least one polycyclic olefin repeat unit derived from a polycyclic olefin monomer having a desired exo isomer mol %. However such polymers can also encompass repeat units derived from a variety of other types of monomers. For example, such polymers can include repeat units derived from maleic anhydride monomers, acrylate monomers, trifluoromethylacylate monomers and the like, as well as mixtures of such various types of monomers. In addition, polymers in accordance with the present invention can be formed using any appropriate polymerization method including vinyl addition, ring opening metathesis polymerization (ROMP) and free radical methods with the proviso that the polymerization method does not significant alter the exo isomer mol % of the polycyclic olefin monomer employed. It should also be understood that polymers in accordance with the present invention are not limited to having a single repeat unit having a desirable exo isomer mol %. Thus, polymers encompassing two or more such repeat units are also within the scope and spirit of the present invention.
Advantageous polymers produced in accordance with the present invention encompass addition polymerized polycyclic repeat units linked via 2,3-enchainment. Such polymers include at least one monomer encompassed by Formula C, as defined above, and optionally one or more monomers encompassed by Formulae A and/or B and of any of the other monomer types mentioned above. At least one of such monomers has a desired exo isomer mole % such that the resulting polymer will have a desired dissolution rate or imaging property. Advantageously, the desired exo isomer mol % of the at least one monomer can be obtained by, for example, selecting an appropriate cut or fraction from a fractional distillation of the monomer. However other methods for obtaining a monomer with the desired exo isomer mol % can also be employed, for example by preparing the monomer in a manner that results directly in the desired exo isomer mol %.
It will of course be realized that the resulting dissolution rate and/or imaging property of a polymer employing a repeat unit having the desired exo isomer mol % is also dependent on the relative amount of such repeat unit incorporated within the polymer. Thus, where a polymer incorporates a relatively low concentration of the repeat unit having the desired exo isomer mol %, such low repeat unit concentration can correlate to little or no effect on the dissolution rate or imaging property of the polymer. However where the concentration of the desired exo isomer mol % repeat unit is high, a significant effect on the dissolution rate or imaging property of the resulting polymer is observed. For example, referring to Table 2, below, it is seen that for the polymers of Examples 24, 25 and 26 (about 87% HFANB), the dissolution rate of the polymer behaves in essentially the same manner as is observed for the HFANB homopolymers of Examples 1-23. Where however, the amount of HFANB is reduced, such as in blends of HFANB homopolymer with other materials such as the P(TBTFMA-VENBHFA) copolymer discussed below, the observed effect can be reduced.
Embodiments of the present invention can also include polymers formed from more than one polycyclic olefin monomer having a reactive pendant group (where “reactive” refers to a protected acid labile pendant group or a pendant group involved in the dissolution of the resulting polymer). Thus for each of these monomers there can be a different desired exo isomer mol %. While the combination of such different monomers into a single polymer can require some experimentation to determine the appropriate exo isomer mol % for each monomer and the relative concentration of each monomer within the polymer, Applicants believe that such experimentation is straight forward and well within the ability of one having ordinary skill.
It should be realized by now, that embodiments in accordance with the present invention include both the polymers formed by vinyl addition polymerization, as well as the cyclic olefin monomers employed for forming such polymers, where at least one of such cyclic olefin monomers has a desired exo isomer mol %. In addition, it will be understood that the polymers of some embodiments in accordance with the present invention encompass at least one monomer selected from those in accordance with each of Formulae A, B and C. Such polymers, as well as others in accordance with the present invention, are useful for forming photoresist compositions having a desired dissolution rate and imaging property. Some embodiments in accordance with the present invention will encompass positive tone (positive acting) polymers and the photoresist compositions made therefrom. Other embodiments will encompass negative tone (negative acting) polymers and the photoresist compositions made therefrom. It should be appreciated that the specific monomers having a desired exo isomer mol % that are selected, will include pendant groups that are appropriate for the type of photoresist composition (positive or negative) desired. It should also be apparent that where some embodiments of the present invention will encompass monomers and the resulting repeat units having an enhanced exo isomer mol %, other embodiments of the present invention will encompass monomers and the resulting repeat units having an enhanced endo isomer mol %. It should also be noted that the pendant groups of monomers, and the resulting repeat units, in accordance with the present invention may or may not be protected with acid labile groups. Finally, embodiments in accordance with the present invention include the selection of monomers having a desired exo isomer mol % for combination with any of the various additives used in formulating photoresist compositions. For example, such additives can include photoacid generators, photoinitiators, dissolution rate modifiers and the like, where any of such additives can be monomeric, oligomeric or polymeric in nature.
The various aspects of the invention will be appreciated more fully in light of the following illustrative examples and exemplary formulas for polymers in accordance with the present invention. Such examples are for illustrative purposes only and are not to be construed as limiting the scope and spirit of the present invention. Unless specifically noted otherwise, the molecular weight of the resulting polymers prepared in the following examples, where reported, was determined using GPC methods in THF with a poly(styrene) standard.
α,α-bis(trifluoromethyl)bicyclo[2.2.1]hept-5-ene-2-ethanol ((HFANB) 80.0 g, 0.292 mol, endo/exo ratio was 44/56), N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate ((DANFABA) 0.0468 g, 0.0584 mMol) and sufficient toluene to bring the total volume to 200 mL were added to a glass pressure reactor. The mixture was purged with hydrogen gas for 30 min then charged with hydrogen (90 psig). The reaction mixture was heated to 80° C. The pressure was relieved and the palladium catalyst, palladium bis(di-isopropylphenylphosphine) diacetate (0.0071 g, 0.012 mMol) was added. The reactor was immediately repressurized with hydrogen gas (90 psig) and allowed to react for 18 h. The reaction mixture was cooled and then filtered through a 0.22 micron Teflon® filter to remove black palladium metal. The resulting filtrate was added to heptane to precipitate the polymer as a white powder. The powder was collected by filtration and dried in a vacuum oven at 90° C. Yield 52.5 g (66%). Mw=11,300; Mn=5440.
HFANB (19.2 g, 0.701 mol, endo/exo ratio was 70/30), DANFABA (0.0112 g, 0.0140 mMol) and sufficient toluene to bring the total volume to 47 mL were added to a glass pressure reactor. The reactor was charged with 17 psig ethylene and then heated to 80° C. The pressure was relieved and the palladium catalyst, palladium bis(di-isopropylphenylphosphine) diacetate (3 mL of a 0.93 mMol solution in methylene chloride) was added. The reactor was immediately repressurized with ethylene (17 psig) and allowed to react for 20 h. The reaction mixture was cooled and added to an excess of hexane in order to precipitate the polymer. The polymer was collected by filtration and dried in a vacuum oven at 80° C. Yield 9.5 g (50%).
The polymer was then dissolved in 48 mL of toluene. To this mixture was added 24 mL of glacial acetic acid, 12 mL of hydrogen peroxide (30%), and 12 mL of water. The mixture was heated to 80° C. for 3 h. The organic layer was separated and washed four times with water. The organic layer was then concentrated by rotary evaporation then poured into heptane to precipitate the polymer. The polymer was collected by filtration and dried in a vacuum oven at 80° C. Yield 8.8 g. The polymer was redissolved in methanol and precipitated by addition to water. Mw=6400; Mn=3630.
Synthesis Example 2 was repeated except that a pressure of 5 psig ethylene was used. Yield 11.4 g (59%). The polymer was treated with glacial acetic acid and hydrogen peroxide as in Synthesis example 2. Yield 10.5 g. Mw=12900; Mn=5930.
Synthesis examples 4, 5, and 6 were made in a manner identical to Synthesis example 3, but different levels of ethylene were used to access different molecular weights. Yields are found in Table 1, below. The polymers were treated with glacial acetic acid and hydrogen peroxide as in Synthesis example 3. The polymer's molecular weights are found in Table 1, below.
HFANB (19.2 g, 0.701 mol, endo/exo ratio was 70/30), DANFABA (0.0112 g, 0.0140 mMol) and sufficient toluene to bring the total volume to 47 mL were added to a glass pressure reactor. The mixture was charged with hydrogen gas (90 psig). The reaction mixture was heated to 80° C. The pressure was relieved and the palladium catalyst, palladium bis(di-isopropylphenylphosphine) diacetate (3 mL of a 0.93 mMol solution in methylene chloride) was added. The reactor was immediately repressurized with hydrogen (90 psig) and allowed to react for 18 h. The reaction mixture was cooled and then filtered through a 0.22 micron Teflon® filter. The resulting filtrate was added to heptane to precipitate the polymer as a white powder. The powder was collected by filtration and dried in a vacuum oven at 80° C. Yield 11.6 g (61%). Mw=17,860; Mn=7270.
Synthesis Example 7 was repeated except that hydrogen was sparged through the reaction mixture for 15 min prior to pressurizing the reactor with 90 psig hydrogen. Yield 9.95 g (52%). Mw=7900; Mn=4150.
Synthesis example 1 was repeated except that the endo/exo ratio of the monomer was 85/15. The polymer was isolated by precipitation into hexane. Yield 65.1 g (80%). Mw=8870; Mn=4880.
Synthesis example 9 was repeated except that the endo/exo ratio of the monomer was 85/15 and the hydrogen pressure was 50 psig. The polymer was isolated by precipitation into hexane. Yield 60.6 g (76%). Mw=13600; Mn=5700.
Synthesis example 9 was repeated except that the endo/exo ratio of the monomer was 85/15 and the hydrogen pressure was 50 psig. The polymer was isolated by precipitation into hexane. Yield 61.9 g (77%). Mw=11600; Mn=5820.
HFANB (40.0 g, 0.146 mol, endo/exo ratio was 90/10), DANFABA (0.0351 g, 0.0438 mMol), triethylsilane (2.31 mL, 14.4 mMol), ethanol (0.940 mL, 16.2 mMol), and toluene (68 mL) were added to a glass vial. The bottle was capped with a septum and mixture was sparged with nitrogen for 15 min. The mixture was then heated to 80° C. and the catalyst, [palladium bis(triisopropylphosphine)(acetonitrile)(acetate)][tetrakis(pentafluorophenyl)borate] (0.017 g, 0.0146 mMol) was added in a minimum of 1,2-dichloroethane. The mixture was allowed to react for 18 h. The reaction mixture was cooled and added to heptane to precipitate the polymer as a white powder. The powder was collected by filtration, washed with heptane and dried in a vacuum oven at 100° C. Yield 30.7 g (77%). The polymer was redissolved in toluene and reprecipitated into heptane, filtered and dried in a vacuum oven at 100° C. Mw=4670; Mn=3120.
Synthesis example 12 was repeated except that only 0.28 mL (0.177 mol) of triethylsilane was employed. Yield and molecular weights are reported in Table 1, below.
Synthesis example 12 was repeated except that 1.1 mL (0.0069 mol) of triethylsilane was employed. Yield and molecular weights are reported in Table 1, below.
Synthesis example 12 was repeated except that only 0.55 mL (0.0034 mol) of triethylsilane was employed. Yield and molecular weights are reported in Table 1, below.
HFANB (100 g, 0.365 mol, endo/exo ratio was 78/22), DANFABA (0.088 g, 0.110 mMol), triethylsilane (5.8 mL, 36 mMol), ethanol (2.3 mL, 40 mMol), and toluene (171 mL) were added to a glass vial. The vial was sealed with a septum and heated to 80° C. and the catalyst, [palladium bis(triisopropylphosphine)(acetonitrile)(acetate)][tetrakis(pentafluorophenyl)borate] (1.0 mL of a 0.0025 M solution in methylene chloride) was added. The mixture was allowed to react for 18 h. The reaction mixture was cooled and a small amount of acetone was added to reduce the viscosity of the solution. The reaction mixture was added to a ten-fold excess of hexane to precipitate the polymer as a white powder. The powder was collected by filtration and dried in a vacuum oven at 90° C. Yield 30.1 g (73%). Mw=5350; Mn=3270.
Synthesis example 16 was repeated except that 3.1 mL (19 mMol) of triethylsilane was employed. Yield and molecular weights are reported in Table 1, below.
Synthesis example 16 was repeated except that 1.8 mL (11 mMol) of triethylsilane was employed. Yield and molecular weights are reported in Table 1, below.
Synthesis example 16 was repeated except that 1.2 mL (7.5 mMol) of triethylsilane was employed. Yield and molecular weights are reported in Table 1, below.
Synthesis example 16 was repeated except that 0.89 mL (5.6 mMol) of triethylsilane was employed. Yield and molecular weights are reported in Table 1, below.
HFANB (41.1 g, 0.150 mol, endo/exo ratio was 58/42), DANFABA (1.0 mL of a 0.0075 M solution in methylene chloride), triethylsilane (1.73 g, 0.0148 mol), ethanol (0.77 g, 0.017 mol) and sufficient toluene to bring the total volume to 100 mL were added to a glass vial. The reaction mixture was heated to 80° C. The palladium catalyst, bis(di-isopropylphenylphosphine) diacetate was added (1 mL of a 0.0025 M solution in methylene chloride) to the monomer solution. After 18 h, the reaction mixture was cooled and then added to hexane to precipitate the polymer as a white powder. The powder was collected by filtration and dried in a vacuum oven at 90° C. Yield 30.2 g (73%). Mw=5770; Mn=3560.
Synthesis example 21 was repeated except that 0.54 mL (4.6 mMol) of triethylsilane was employed. Yield and molecular weights are reported in Table 1, below.
Synthesis example 21 was repeated except that 0.27 mL (2.3 mMol) of triethylsilane was employed. Yield and molecular weights are reported in Table 1, below.
HFANB (51.0 g, 0.186 mol, endo/exo ratio was 90:10), 5-norbornene-2-hydroxyethylether ((HEENB) 2.36 g, 0.0140 mol), triethylsilane (2.58 g, 0.0222 mol), ethanol (1.02 g, 0.0222 mol) and sufficient toluene to bring the total volume to 133 mL were added to a glass vial. The reaction mixture was heated to 80° C. DANFABA (1.0 mL of a 0.06 M solution in methylene chloride) and [palladium bis(triisopropylphosphine)(acetonitrile)(acetate)] [tetrakis-(pentafluorophenyl)borate] (1.0 mL of a 0.02 M solution in methylene chloride) was added. After 18 h, the reaction mixture was cooled and then added to 40 mL of Amberlite GT-73 (Rohm and Haas) and Diaion CRBO2 (Mitsubishi Chemical) resin beads. This slurry was shaken overnight. The resin beads were removed by filtration to give a colorless filtrate. The filtrate was concentrated by rotary evaporation and then added to a 10-fold volumetric excess of hexane to precipitate the polymer. The polymer was collected by filtration and dried in a vacuum oven at 90° C. Yield 24.6 g (46%). Mw=4610; Mn=3260. The molar ratio of HFANB:HEENB was found to be 88:12 by 13C NMR measurements.
Synthesis example 24 was repeated except that the monomer's endo/exo ratio was 70:30. Yield 19.9 g (37%). Mw=6740; Mn=4580. The molar ratio of HFANB:HEENB was found to be 86:14 by 13C NMR measurements.
Synthesis example 24 was repeated except that the monomer's endo/exo ratio was 58:42. Yield 20.9 g (39%). Mw=7140; Mn=4590. The molar ratio of HFANB:HEENB was found to be 87:13 by 13C NMR measurements.
Dissolution Rate Method 1 for Examples 1-23
A quartz crystal microbalance (QCM) was employed to study the kinetics of dissolution of the polymer films formed from the several polymers of Examples 1-23 in an aqueous base developer. The quartz crystals employed in this study had an inherent frequency of about 5 MHz. A Maxtek TPS-550 sensor probe and PI-70 driver were used in conjunction with a Phillips PM6654 programmable high resolution frequency counter and an IBM PC. The instrument was controlled and data were collected by a custom-made LabView software program. The polymer was dissolved in propylene glycol methyl ether acetate (1/5 wt/wt) and the solution was filtered down to 0.2 μm. Polymer films were prepared by spin-casting on 1″ quartz discs and baked at 130° C. for 60 sec and then the coated discs were mounted on a QCM probe. In 0.26 N tetramethylammonium hydroxide (TMAH) (CD-26), the dissolution of the polymer is more or less linear with time, allowing the calculation of the rates (Å/sec) from the slopes of the thickness-development time plots.
The results of these measurements are shown in
Dissolution Rate Measurements Example 2.
The copolymers from Synthesis Examples 24, 25, and 26 were dissolved in PGMEA to between 20-25% solids.
A clean silicon wafer (Silicon Quest, <1,0,0>) was spin coated with 1 mL of hexamethyldisilazine (HMDS), 500 rpm for 10 seconds and 2000 rpm for 60 seconds, then baked at 130° C. for 90 seconds. Approximately 1 mL of the filtered (0.2 micron) polymer solution was applied to the center of the wafer and spun as described above. The Wafer was soft baked at 130° C. for 120 seconds to ensure the removal of all of the casting solvent.
Cauchy parameters and film thickness of the samples were determined using a J. A. Woollam M2000 ellipsometer.
Dissolution rate measurement was performed using a reflectometry based Dissolution Rate Monitor, collected and controlled using a custom made Lab-View system, using single wavelength versus time, interferometry data. The developer was aqueous tetramethyl ammonium hydroxide (Shipley, TMAH 2.38%). Samples were developed using a puddle technique in which aliquots of developer are placed upon the film, and film thickness was measured vs. time. The slope of the line of a thickness vs. time plot yields dissolution rate and was expressed as Å/second. Results of these measurements are presented in Table 2.
As in DR data plotted in
Polymer Blend Formulation and Imaging
poly(t-butyl 2-trifluoromethylacrylate-co-5-[(1,1′,1′-trifluoro-2′-trifluoromethyl-2′-hydroxy)propyl]norbornan-2-yl vinyl ether) (P(TBTFMA-VENBHFA) copolymer) and an HFANB homopolymer (1/1 wt/wt) (one of Examples 12, 15, 16, 19, 21 and 23) were blended by dissolving equal weights of each in propylene glycol methyl ether acetate to make a 10 wt % polymer solution. Di-t-butylphenylidodonium perfluorooctanesulfonate (4%) and tetrabutylammonium hydroxide (0.15%) were added to the polymer solution. The solution was filtered (0.2 μm). The solution was then spin-cast and the resulting films baked at 130° C. for 60 sec, exposed to 193 nm radiation through a binary chrome-on-glass mask, post exposure-baked at 130° C. for 90 sec, and then developed with a commercially available 0.26 N tetramethylammonium hydroxide solution.
Referring to
The copolymer is represented by the structure below where the percentages are the relative concentration of the individual monomers in the copolymer.
Thus, it can be said from the imaging results presented above, that when the molecular weight of HFANB homopolymer is high (see,
Where the molecular weight of the HFANB starting monomer is low (
This application is a continuation of U.S. patent application Ser. No. 10/783,174, filed Feb. 20, 2004, which claims the benefit of U.S. Provisional Patent Application No. 60/449,785, filed Feb. 24, 2003, which is hereby incorporated by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 6143472 | Sumino et al. | Nov 2000 | A |
| 6165672 | Jung et al. | Dec 2000 | A |
| 6284429 | Kinsho et al. | Sep 2001 | B1 |
| 6358675 | Boardman et al. | Mar 2002 | B1 |
| 6503686 | Fryd et al. | Jan 2003 | B1 |
| 6624335 | Tachibana et al. | Sep 2003 | B2 |
| 6723486 | Goodall et al. | Apr 2004 | B2 |
| 6790579 | Goodall et al. | Sep 2004 | B1 |
| 6866984 | Jung et al. | Mar 2005 | B2 |
| 20020004570 | Zampini et al. | Jan 2002 | A1 |
| 20020136982 | Goodall et al. | Sep 2002 | A1 |
| 20030004289 | Shin et al. | Jan 2003 | A1 |
| 20030232276 | Poss et al. | Dec 2003 | A1 |
| Number | Date | Country |
|---|---|---|
| 1004568 | May 2000 | EP |
| Number | Date | Country | |
|---|---|---|---|
| 20080124651 A1 | May 2008 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60449785 | Feb 2003 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10783174 | Feb 2004 | US |
| Child | 11981617 | US |
