TW201406798A - A self-imageable layer forming polymer and compositions thereof - Google Patents

Abstract

Copolymers and compositions thereof useful for forming self-imageable films encompassing such copolymers are disclosed. Such copolymers encompass norbornene-type repeating units and maleic anhydride-type repeating units where at least some of such and maleic anhydride-type repeating units have been ring-opened. The films formed from such copolymer compositions provide self imageable, low-k, thermally stable layers for use in microelectronic and optoelectronic devices.

Description

a polymer that forms a self-imageable layer and a composition thereof [Related application cross-reference]

U.S. Provisional Patent Application No. 61/507,685, filed on Jan. 4, 2011, and U.S. Provisional Patent Application No. 61/548,832, filed on Jan. The priority of the number, both of which are incorporated herein by reference in their entirety.

The present invention generally relates to copolymers and compositions thereof comprising norbornene-type repeat units and non-norbornene-type repeat units suitable for forming self-imageable layers, and more particularly, the invention relates to inclusions from a repeating unit of a norbornene-type monomer and a copolymer derived from a repeating unit of a maleic anhydride type monomer and a composition thereof for imaging a layer produced therefrom in the layer It is self-imageable when exposed to actinic radiation.

In the past few years, microelectronics (such as semiconductors) and the optoelectronics industry have needed to make device geometries smaller and smaller. Although in some device manufacturing fields, submicron device geometries have been commonplace for many years, in other fields, such as liquid crystal displays (LCDs), organic light emitting diodes (OLEDs), and a variety of radio frequency (Rf) and microwave devices (eg, RFIC/MMIC, switches, couplers, phase shifters, SAW filters and SAW duplexers), these device geometries It has only recently approached the sub-10 micron level.

These smaller geometries require a dielectric material having a low dielectric constant to reduce or eliminate any crosstalk caused by capacitive coupling between adjacent signal lines or between signal lines and device features (e.g., pixel electrodes). While many low dielectric (low K) materials can be used in microelectronic devices, for optoelectronic devices, such materials must also be substantially transparent in the visible spectrum, without the need for high temperatures incompatible with other components in the photovoltaic device. Treatment (over 300 ° C) and low cost and feasibility when manufacturing large scale photovoltaic devices.

Therefore, there is a need for materials that are capable of forming self-imageable layers without the need to deposit separate imaging layers. The material should also be easy to apply to the substrate, having a low dielectric constant (3.9 or less) and thermal stability at temperatures in excess of 250 °C.

Specific examples of the invention are described below with reference to the drawings and/or images. When a schema is provided, it is a drawing of a simplified portion of the device provided for illustrative purposes only.

1 is a flow chart depicting a method of making a specific example of a (DRM) ROMA copolymer of the present invention; FIGS. 2a, 2b, 2c, and 2d are a portion of an infrared spectrum showing a specific example of a dissolution rate improving treatment that has been subjected to the present invention. Carbonyl stretching frequency before and after the copolymer Figure 3 is a graphical representation of the dissolution rate change of the ROMA copolymer subjected to the dissolution rate modification treatment of the present invention and the reaction time; Figures 4a and 4b are specific examples of the (DRM) ROMA copolymer film of the present invention. Micrographs of lines and spaces of 10 μm and 5 μm obtained after imagewise exposure of the formed film.

Specific examples of the invention relate to copolymers comprising at least one repeating unit derived from a norbornene-type monomer and at least one repeating unit derived from a maleic anhydride type monomer, as defined below, and comprising such copolymers The composition of the object. The copolymer compositions are capable of forming self-imageable films suitable for use in the fabrication of layers of microelectronics and optoelectronic devices. That is, after imaging exposure to actinic radiation, the layers (or films) can be developed to form a patterned layer (or film) that reflects the image used to expose the layer (or film). It is thus possible to provide a structure that is or will be part of such microelectronic and/or optoelectronic devices.

As used herein, the articles "a", "the"

Because all numbers, values, and/or expressions relating to the amounts of ingredients, reaction conditions, and the like, as used herein and in the scope of the accompanying claims, are subject to various measurement uncertainties, unless otherwise stated. All should be understood to be modified by the term "about" in all cases.

When a range of values is disclosed herein, the range is continuous, including the minimum and maximum values within the range, and each value between the minimum and the maximum. Also, when the range is an integer, then each integer between the minimum and maximum of the range is included. In addition, when a plurality of ranges are provided to describe features or characteristics, the ranges can be combined. That is, unless otherwise All ranges disclosed herein are to be understood as being inclusive of any and all sub-ranges. For example, the range "1 to 10" should be considered to include any and all subranges between a minimum value of 1 and a maximum value of 10. Exemplary subranges of ranges 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

As used herein, the terms "copolymer composition" or "polymer composition" are used interchangeably herein and are intended to include at least one synthetic polymer or copolymer and from the initiation associated with the synthesis of such copolymers. Residues of agents, solvents or other elements, wherein such residues are understood to be not incorporated into the composition in a covalent form. The residue and other elements considered to be part of the polymer composition are typically mixed or co-stirred with the polymer such that it tends to remain with the polymer as it is transferred between the containers or between the solvent or dispersion medium. The copolymer composition may also include materials added after the copolymer is synthesized to provide or improve the specific properties of the composition.

As used herein, "hydrocarbyl" refers to a radical containing a group of carbon and hydrogen atoms, non-limiting examples of which are alkyl, cycloalkyl, aryl, aralkyl, alkaryl and alkene. base. The term "halohydrocarbyl" refers to a hydrocarbon group in which at least one hydrogen has been replaced by a halogen. The term perhalohydrocarbyl refers to a hydrocarbyl group in which all hydrogens are replaced by halogen.

As used herein, "alkyl (alkyl)" means methyl or ethyl and carbon chain length of C ₃ to, for example, an appropriate C ₂₅ linear or branched group of non-cyclic or cyclic saturated hydrocarbon group. Non-limiting examples of suitable alkyl groups include, but are not limited to, -(CH ₂ ) ₃ CH ₃ , -(CH ₂ ) ₄ CH ₃ , -(CH ₂ ) ₅ CH ₃ , -(CH ₂ ) ₉ CH ₃ , -(CH ₂ ) ₂₃ CH ₃ , cyclopentyl and cyclohexyl.

As used herein, "aryl" refers to an aromatic group including, but not limited to, phenyl, biphenyl, benzyl, xylyl, naphthyl, anthryl and the like. group The group.

The term "alkyl aryl group (alkaryl)" or "arylalkyl (aralkyl)" herein used interchangeably and refers to an aryl group with at least one (e.g., phenyl) and substituted alkyl carbon chain length of C ₁ to an appropriate a straight chain or branched non-cyclic alkyl group of C _25. Furthermore, it is to be understood that the above acyclic alkyl group may be a haloalkyl group or a perhaloalkyl group.

As used herein, the term "alkenyl group (alkenyl of)" means ethylene or having at least one double bond and alkenyl carbon chain length of a suitable linear C ₃ to C _25, or of a non-cyclic branched or cyclic hydrocarbon group. Non-limiting examples include, inter alia, vinyl, propenyl, butenyl, and the like.

As used herein, the term "heterohydrocarbyl" refers to any of the previously described hydrocarbyl, halohydrocarbyl and perhalohydrocarbyl groups wherein at least one of the carbon chains is replaced by N, O, S, Si or P. Non-limiting examples include heterocyclic aromatic groups such as pyrrolyl, furyl and the like, as well as non-aromatic groups such as ethers, thioethers and decyl ethers. The term "alkylol" refers to an alkyl group comprising at least one hydroxyl group.

It is further understood that any of the above hydrocarbyl, halohydrocarbyl, perhalohydrocarbyl and heterohydrocarbyl moieties may be further substituted as desired. Non-limiting examples of suitable substituents include, in particular, hydroxyl, benzyl, carboxylic acid and carboxylate groups, decylamines and quinone imines.

Specific examples of the invention include copolymers having at least one repeating unit derived from a norbornene-type monomer as defined below and at least one repeating unit derived from a maleic anhydride type monomer as defined below.

The terms "norbornene-type", "polycycloolefin" and "poly(cyclic) olefin" are used interchangeably herein and are meant to include at least one drop. Monomer (or resulting repeating unit) of the borneol moiety, such as the moiety shown below:

This portion is the simplest norbornene-type or poly(cyclic) olefin monomer, bicyclohept-2-ene, commonly referred to as norbornene. As described above, the term "norbornene-type" monomer or repeating unit is used herein to include norbornene itself, as well as any substituted norbornene, and any substituted or unsubstituted higher order ring thereof. derivative. Formulas I and Ia shown below represent the norbornene-type monomer and the norbornene-type repeating unit, respectively, which are included in the specific examples of the present invention:

Wherein m is an integer in the range of 0 to 5 and R ¹ , R ² , R ³ and R ⁴ independently represent hydrogen or a hydrocarbyl group at each occurrence.

As used herein, it is to be understood that the term "maleic anhydride-type" refers to a monomer comprising at least one maleic anhydride type moiety (such as shown in Formula II below) and obtained therefrom. Repeating units (such as shown by Formulas IIa, IIb, and IIc below):

Wherein R ⁵ and R ⁶ are the same or different hydrocarbyl groups.

It should also be understood that the term "maleic anhydride type monomer" includes the monomer of formula III.

Wherein R ⁷ and R ^{8 are the} same or different and are selected from the group consisting of hydrogen, methyl and ethyl. In addition, it is to be understood that the repeating units of the formulae III, IIb and IIc may be the same as the monomers of the formula II, and the similar repeating units may be derived from the maleic anhydride type monomer of the formula III and are included in the specific examples of the invention. .

Monomers suitable for use in the specific examples of the invention are generally described herein and are further described by the monomers and substituent structures provided herein. With regard to specific examples of the polymer composition of the present invention, it should be noted that the compositions may comprise a single copolymer comprising at least one norbornene-type repeating unit and at least one maleic anhydride-type repeating unit. In other embodiments, the polymer composition may comprise: a single copolymer comprising two or more different types of norbornene-type repeating units and at least one maleic anhydride-type repeating unit, or at least A single copolymer of a norbornene-type repeating unit and two or more different types of maleic anhydride-type repeating units.

In still other embodiments, the polymer composition may comprise a blend of polymers comprising a blend of at least two polymers (such as the polymers described above) or homopolymers of the copolymer and norbornene. One or more of them.

When any of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a hydrocarbyl group, the group may alternatively be described as any C ₁ to C ₃₀ alkyl, aryl, aralkyl group. , alkaryl, cycloalkyl or heteroalkyl. Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, tert-butyl, pentyl, neopentyl, hexyl, g. Base, octyl, sulfhydryl and sulfhydryl. Representative cycloalkyl groups include, but are not limited to, adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl. Representative aryl groups include, but are not limited to, phenyl, naphthyl, and anthracenyl. Representative aralkyl groups include, but are not limited to, benzyl and phenethyl. Further, it should be noted that the above-mentioned hydrocarbon group may be substituted, that is, at least one hydrogen atom may be replaced by, for example, a C ₁ -C ₁₀ alkyl group, a haloalkyl group, a perhaloalkyl group, an aryl group and/or a cycloalkyl group. Representative substituted cycloalkyl groups include, inter alia, 4-tert-butylcyclohexyl and 2-methyl-2-adamantyl. A non-limiting representative substituted aryl group is 4-tert-butylphenyl.

Further, any one or more of R ¹ to R ⁶ may also be a halohydrocarbyl group, wherein the group includes any of the above-mentioned hydrocarbyl groups, wherein at least one, but not all, of the hydrogen atoms in the hydrocarbyl group is halogen (fluorine) , chlorine, bromine or iodine). Further, any one or more of R ¹ to R ⁶ may be a perhalohydrocarbyl group, wherein the group includes any of the above-mentioned hydrocarbyl groups, wherein all hydrogen atoms in the hydrocarbyl group are replaced by halogen. Representative perfluorinated substituents include, but are not limited to, perfluorophenyl, perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, and perfluorohexyl.

In some embodiments, the perhalohydrocarbyl group can include a perhalogenated phenyl group and a perhalogenated alkyl group. In other embodiments, the perfluorinated group can include perfluorophenyl, perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, and perfluorohexyl. The cycloalkyl, aryl and aralkyl groups of these specific examples may also be substituted by any C ₁ -C ₅ alkyl group, C ₁ -C ₁₂ haloalkyl group, aryl group and/or cycloalkyl group in addition to a halogen substituent. Replace.

As mentioned above, a specific example of the present invention relates to a copolymer comprising a norbornene-type repeating unit and a maleic anhydride-type repeating unit, and a composition obtained therefrom. The copolymer compositions are capable of forming films suitable for use in the fabrication of self-imageable layers of microelectronics and optoelectronic devices. That is, when imaging exposure to actinic radiation, the layers (or films) can be developed to form a patterned film, wherein the pattern reflects the image used to expose the film.

Thus available or will be part of such microelectronic and/or optoelectronic devices The structure of the points. For example, the films can be used as low-k dielectric layers in liquid crystal displays or microelectronic devices. It should be noted that these examples are only a few of the many uses of the self-imageable film, and such examples are not intended to limit the scope of such films or polymers and polymer compositions used to form such films.

Thus, specific examples of the invention comprise copolymers comprising repeating units derived from the above monomers and which are obtainable by free radical polymerization using methods known to those skilled in the art to form at least one type A copolymer intermediate of a norbornene-type repeating unit and a maleic anhydride repeating unit. Non-limiting examples of initiators that can be used in the free radical polymerization include, for example, azo compounds and organic peroxides. Non-limiting examples of azo compounds include azobisisobutyronitrile (AIBN), ( E )-dimethyl 2,2'-(diazene-1,2-diyl) bis(2-propionic acid) Ester) (AMMP), ( E )-2,2'-(diazepine-1,2-diyl)bis(2,4-dimethylvaleronitrile) (ADMPN) and 1,1'-azo Bis(cyclohexanecarbonitrile) (ABCN). Non-limiting examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide, phenylhydrazine peroxide, and methyl ethyl ketone peroxide.

Specific examples of some of the polymers of the present invention are made by contacting the copolymer intermediate with an agent sufficient to cause ring opening of the maleic anhydride repeating unit and thereby forming a repeating unit of Formula IIa and/or IIb. Object formation. A specific example of the polymer is represented by the formula IVa, wherein the norbornene-type repeating unit is generally found to have an alternating relationship with the maleic anhydride-type repeating unit.

Specific examples of other copolymers of the invention comprise at least one norbornene-type repeating unit of formula Ia, at least one ring-opening maleic anhydride-type repeating unit of formula IIa and/or IIb, and a repeating unit of formula IIc, Shown in IVb. It has also been found that the norbornene-type repeating unit and the maleic anhydride-type repeating unit in the specific examples of the copolymer represented by the formula IVb have an alternation.

Wherein for Formulas IVa and IVb, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as previously defined and although not specifically shown, it is understood that Formulas IVa and IVb are derived from Formula III. A monomeric maleic anhydride type repeating unit.

In addition to the polymer specific examples, the polymer composition of the present invention typically also includes at least one casting solvent, at least one photoactive compound (PAC), and at least one epoxy resin, wherein the epoxy resin comprises at least two Epoxy groups.

Exemplary casting solvents include, but are not limited to, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl methanol (MIBC), gamma butyrolactone ( GBL), N-methylpyrrolidone (NMP) and methyl n-amyl ketone (MAK) And mixtures thereof.

Exemplary PACs include, but are not limited to, PAC-5570 (St. Jean Photochemicals, Inc., Quebec, Canada), SCL6 (Secant Chemicals, Inc., Winchendon, MA, USA), Tris-P 3M6C-2-201 (also referred to herein). For TrisP), TS-200, TS-250, TS-300 and 4NT-300 (both from Toyo Gosei Co., Ltd., Chiba, Japan), the structure is as follows:

For TS-200, 67% D is DNQ, for TS-250, 83% D is DNQ, and for TS-300, 100% D is DNQ; and where "D" or "Q" refers to DNQ, which is the following One of the diazonaphthoquinone-type structures is either a hydrogen atom.

Exemplary PACs also include, but are not limited to, the PACs disclosed in U.S. Patent No. 7,524,594, from col. 13, line 39, to col. 9z in column 20. These PACs are provided below.

Exemplary epoxy resins and other crosslinking additives as mentioned above include, but are not limited to, bisphenol A epoxy resins (LX-1-Daiso Chemical, Inc., Osaka, Japan), 2, 2'-((( (1-(4-(2-(4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl) bis (4 , 1-phenylene))bis(oxy))bis(methylene))bis(ethylene oxide) (Techmore VG3101L-Mitsui Chemical), trimethylolpropane triglycidyl ether (TMPTGE-CVC) Specialty Chemicals) and 1,1,3,3,5,5-hexamethyl-1,5-bis(3-(oxiran-2-ylmethoxy)propyl)trioxane ( DMS-E09-Gelest), as shown below:

Still other exemplary epoxy resins or crosslinking additives include, inter alia, Araldite MT0163 and Araldite CY179 (manufactured by Ciba Geigy); and EHPE-3150, Epolite GT300 and (manufactured by Daicel Chemical).

Some specific examples of the invention include the following structures, such as photovoltaic structures, which are packaged A self-imageable layer formed from at least one film of a specific example of the copolymer composition of the present invention. As mentioned above, the copolymer of the specific embodiment of the composition contains at least one repeating unit derived from a norbornene-type monomer and at least one repeating unit derived from a maleic anhydride-type monomer. The polymer composition specific example further comprises at least one casting solvent, at least one photosensitive compound (PAC), and at least one epoxy resin.

With respect to specific embodiments of the compositions of the present invention, such specific examples provide a "positive tone" self-imageable film. Generally, for a positive composition, the exposed portion of the layer formed from the composition becomes more soluble in the developer solution than the portion not exposed to the radiation. In each case, the more soluble portion is washed away with an aqueous alkali solution during the development process. The solubility of the above exposed portion in the aqueous alkali solution is caused by at least one PAC added to the composition, the at least one PAC producing a carboxylic acid such that the exposed portion is in an aqueous alkali solution compared to any unexposed portion in which the PAC remains unchanged. The solubility in the solution is improved.

The above structural specific examples of the present invention can be easily formed by first casting a polymer composition on a suitable substrate to form a layer of a polymer composition, and then heating the substrate to an appropriate temperature for a suitable time, wherein the time and temperature are sufficient to shift Essentially all of the casting solvent in the composition. After this first heating, the layer is imagewise exposed with actinic radiation of the appropriate wavelength. As is known to those skilled in the art, the above-described imagewise exposure causes a chemical reaction of the PAC contained in the exposed portion of the layer, which chemically reacts the exposed portion in an aqueous alkali solution (usually a tetramethylammonium hydroxide (TMAH) solution). The dissolution rate is increased. In this way, the exposed portions are removed and the unexposed portions are retained. A second heating is then carried out to cause partial crosslinking of the polymer with the epoxy resin additive, thereby substantially "cure" the polymer of the unexposed portions to form the above-described structural specific examples of the present invention.

The following examples, which are essentially non-limiting, illustrate the methods of making the specific examples of the copolymers of the present invention. These examples illustrate the formation of the previously mentioned copolymer intermediates, referred to herein as cyclic olefin maleic anhydride (COMA) copolymers. Moreover, these examples describe ring-opening analogs that form intermediates of such COMA copolymers, referred to herein as ROMA copolymers, and such embodiments further disclose ROMA copolymers that form dissolution rate improvement (DRM).

Referring now to Figure 1, a general process flow suitable for forming the (DRM) ROMA copolymer is provided. Specifically, step 100 is a polymerization of a norbornene-type monomer and maleic anhydride in a suitable polymerization solvent to form the above COMA copolymer. In step 110, the solution of the COMA copolymer is first treated with a mixture of strong bases to ring the anhydride ring to an alcohol (e.g., methanol or butanol) to form a ROMA copolymer having a monoester and a salt moiety. The ROMA copolymer is then treated with an acid such as formic acid or aqueous hydrochloric acid in step 120 to partially convert the carboxylate to its acid form. In step 130, the ROMA copolymer of step 120 is washed with a suitable mixture of aqueous and organic solvents to remove any remaining inorganics, leaving the copolymer and any aqueous insoluble residual monomers in the organic phase. The residual monomers are then extracted in step 140 with another aqueous and organic solvent mixture leaving a substantially pure solution of the ROMA copolymer. In step 150, the ROMA copolymer of step 140 is heated in the presence of an excess of alcohol to take advantage of the equilibrium shown below to reduce the concentration of the carboxylic acid moiety of the ROMA copolymer to reduce the solubility of the copolymer and thereby reduce it in an aqueous alkali solution. The dissolution rate (DR), thus forming the above (DRM) ROMA copolymer. In step 160, the (DRM) ROMA copolymer is purified and typically transferred to a suitable casting solvent by solvent exchange. In step 170, an additive such as a suitable PAC and a suitable crosslinking compound is added to form a useful (DRM) ROMA copolymer composition.

Moreover, the examples illustrate specific examples of forming copolymer compositions of the present invention and discuss various evaluations of such specific examples of properties for the copolymers, copolymer compositions, and film embodiments of the present invention.

For the property test, the molecular weights (Mw and Mn) were determined by gel permeation chromatography (GPC) using polystyrene standards. Among them, gas chromatography is used.

COMA copolymer embodiment

Examples A1 through A5 illustrate exemplary methods of forming copolymers from norbornene-type monomers and maleic anhydride monomers.

Example A1: Synthesis of MA/NB polymer

Maleic anhydride (MA, 7.4 g, 75.0 mmol), 2-norbornene (NB, 7.1 g, 75.0 mmol) and AIBN (1.2 g, 7.5 mmol) were dissolved in THF (20.4 g) and charged appropriately Size in the reaction vessel. The solution was aerated with nitrogen for 10 minutes to remove oxygen and then heated to 70 °C. The mixture was stirred at 70 ° C for 5.0 hours, after which time the solution was cooled to room temperature. The reaction mixture was then diluted with EtOAc (20 mL) and EtOAc (EtOAc)EtOAc. About 13.0 g (90%) of MA/NB polymer (GPC Mw = 4,100, Mn = 1,800) was isolated.

Example A2: Synthesis of MA/BuNB Polymer

Maleic anhydride (MA, 9.8 g, 100 mmol), 5-butyl-2-norbornene (BuNB, 15.0 g, 100 mmol) and AIBN (1.64 g, 10.0 mmol) were dissolved in THF (37.2 g) and placed in a reaction vessel of appropriate size. The solution was aerated with nitrogen for 10 minutes to remove oxygen and then heated to 70 °C. The mixture was stirred at 70 ° C for 16 hours, after which time the solution was cooled to room temperature. The reaction mixture was then added to hexane (2 L) to afford a white powder, which was filtered and dried in a vacuum oven at <RTIgt; About 19.3 g (78%) of MA/BuNB polymer (GPC Mw = 3,200, Mn = 1,900) was isolated.

Example A3: Synthesis of MA/NB/BuNB Polymer

Maleic anhydride (MA, 7.4 g, 75.0 mmol), 2-norbornene (NB, 3.5 g, 37.5 mmol), 5-butyl-2-norbornene (BuNB, 5.6 g, 37.5 mmol) and AIBN (1.2 g, 7.5 mmol) was dissolved in THF (23.6 g) and placed in a suitably sized reaction vessel. The solution was aerated with nitrogen for 10 minutes to remove oxygen and then heated to 70 °C. The mixture was stirred at 70 ° C for 20.5 hours, after which time the solution was cooled to room temperature. The reaction mixture was diluted with 20 g of THF and added to hexane (1L) to afford white powder, which was filtered and dried in a vacuum oven at 80 ° C for 16 hours. About 14.5 g (88%) of MA/NB/BuNB polymer (GPC Mw = 3,500, Mn = 1,700) was isolated.

Example A4: Synthetic MA/HxNB/NBC ₄ F ₉ polymer

Maleic anhydride (MA, 7.4 g, 75.0 mmol), 5-hexyl-2-norbornene (HxNB, 10.7 g, 60.0 mmol), 5-perfluorobutyl-2-norbornene (NBC ₄ F) ₉ , 4.7 g, 15.0 mmol) and AIBN (1.23 g, 7.5 mmol) were dissolved in THF (30.4 g) and placed in a reaction vessel of appropriate size. The solution was aerated with nitrogen for 10 minutes to remove oxygen and then heated to 70 °C. The mixture was stirred at 70 ° C for 20.5 hours, after which time the solution was cooled to room temperature. The reaction mixture was added to hexane (1 L) to give a white powder, which was filtered and dried in a vacuum oven at <RTIgt; About 14.3 g (66%) of MA/HxNB/NBC ₄ F ₉ polymer (GPC Mw = 3,200, Mn = 2,000) was isolated.

Example A5: Synthesis of MA/PENB polymer

Maleic anhydride (MA, 7.4 g, 75.0 mmol), phenylethylnorbornene (PENB, 14.9 g, 75.0 mmol) and AIBN (1.2 g, 7.5 mmol) were dissolved in THF (32.1 g) and loaded. Into a suitably sized reaction vessel. The solution was aerated with nitrogen for 10 minutes to remove oxygen and then heated to 70 °C. The mixture was stirred at 70 ° C for 17.5 hours, after which time the solution was cooled to room temperature. The reaction mixture was diluted with 30 g of THF and added to hexane (1L) to afford white powder, which was filtered and dried in a vacuum oven at 80 ° C for 16 hours. About 16.7 g (75%) of MA/PENB polymer (GPC Mw = 3,400, Mn = 1,500) was isolated.

ROMA copolymer synthesis

Examples B1 to B5 respectively illustrate the method of ring-opening the maleic anhydride repeating unit in the COMA copolymers of Examples A1 to A5 with BuOH. Examples B6 and B7 illustrate the formation of a COMA copolymer of MA and PENB and a method of unblocking the maleic anhydride repeating unit in the COMA copolymer with BuOH. Examples B8 through B12 illustrate the method of ring opening the COMA copolymer of Example A1 with a different alcohol. Examples B13 and B14 illustrate the formation of a COMA copolymer of MA and PENB and a method of ring opening a maleic anhydride repeating unit in a COMA copolymer with MeOH. Example B15 illustrates a method in which a COMA copolymer is first formed, the copolymer is opened to form a ROMA copolymer, and then the dissolution rate of the ROMA copolymer is improved. Embodiment 15 is consistent with the process depicted in FIG.

Example B1: ROMA copolymer of MA/NB and BuOH

NaOH (2.3 g, 57.3 mmol), BuOH (19.3 g, 260 mmol) and THF (20.0 g) were placed in a reaction vessel of the appropriate size. The mixture was stirred at 70 ° C for 1 hour and then 20 g of THF containing the polymer obtained in Example 1 (10.0 g) was added. Reaction at 70 ° C 3 After the hour, the mixture was cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. The organic phase was separated and then concentrated in vacuo, redissolved in THF to afford about 20 wt% of the copolymer solution and then the copolymer was precipitated by adding THF solution to hexane (20-fold excess). The copolymer was isolated by filtration and dried in a vacuum oven at 80 ° C for 16 hours. About 10.1 g (73%) of ROMA polymer of MA/NB and BuOH (GPC Mw = 4,400, Mn = 2,400) was isolated.

Example B2: ROMA copolymer of MA/BuNB and BuOH

NaOH (0.9 g, 22.3 mmol), BuOH (7.5 g, 100.6 mmol) and THF (15.0 g) were placed in a reaction vessel of the appropriate size. The mixture was stirred at 70 ° C for 1 hour and then 7.5 g of THF containing the polymer obtained in Example 2 (5.0 g) was added. After reacting at 70 ° C for 3 hours, the mixture was cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. The organic phase was separated and then concentrated in vacuo, redissolved in THF to afford about 20 wt% of the copolymer solution and then the copolymer was precipitated by adding THF solution to hexane (20-fold excess). The copolymer was isolated by filtration and dried in a vacuum oven at 80 ° C for 16 hours. Approximately 4.7 g (72%) of a ring-opening polymer of MA/BuNB and BuOH (GPC Mw = 3,800, Mn = 2,300) was isolated.

Example B3: ROMA copolymer of MA/NB/BuNB and BuOH

NaOH (2.00 g, 50.0 mmol), BuOH (16.82 g, 227 mmol) and THF (15.0 g) were placed in a reaction vessel of the appropriate size. The mixture was stirred at 70 ° C for 1 hour and then 15.0 g of THF containing the polymer obtained in Example 3 (10.0 g) was added. After reacting at 70 ° C for 3 hours, the mixture was cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. Separating the organic phase and then in a vacuum It was concentrated, redissolved in THF to form about 20 wt% of a copolymer solution and then the copolymer was precipitated by adding a THF solution to hexane (20-fold excess). The copolymer was isolated by filtration and dried in a vacuum oven at 80 ° C for 16 hours. About 10.2 g (76%) of a ring-opening polymer of MA/NB/BuNB and BuOH (GPC Mw = 3,800, Mn = 2,200) was isolated.

Example B4: MA/HxNB/NBC ₄ F ₉ ROMA copolymer with BuOH

NaOH (1.45 g, 36.3 mmol), BuOH (12.22 g, 165 mmol) and THF (20.0 g) were placed in a reaction vessel of the appropriate size. The mixture was stirred at 70 ° C for 1 hour and then 15.0 g of THF containing the polymer obtained in Example 4 (10.00 g) was added. After reacting at 70 ° C for 3 hours, the mixture was cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. The organic phase was separated and then concentrated in vacuo, redissolved in THF to afford about 20 wt% of the copolymer solution and then the copolymer was precipitated by adding THF solution to hexane (20-fold excess). The copolymer was isolated by filtration and dried in a vacuum oven at 80 ° C for 16 hours. Approximately 7.2 g (58%) of a ring-opening polymer of MA/HxNB/NBC ₄ F ₉ and BuOH (GPC Mw = 3,700, Mn = 2,400) was isolated.

Example B5: ROMA copolymer of MA/PENB and BuOH

NaOH (0.7 g, 18.5 mmol), BuOH (3.7 g, 50.7 mmol) and THF (20.0 g) were placed in a reaction vessel of the appropriate size. The mixture was stirred at 70 ° C for 1 hour and then 20.0 g of THF containing the polymer obtained in Example 5 (5.0 g) was added. After reacting at 70 ° C for 3 hours, the mixture was cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. The organic phase was separated and then concentrated in vacuo, redissolved in THF to afford about 20 wt% of the copolymer solution and then the copolymer was precipitated by adding THF solution to hexane (20-fold excess). Separating the copolymer by filtration and in a vacuum oven Dry at 80 ° C for 16 hours. Approximately 4.7 g (75%) of a ring-opening polymer of MA/PENB and BuOH (GPC Mw = 3,500, Mn = 2,200) was isolated.

Example B6: ROMA copolymer of MA/PENB and BuOH

Maleic anhydride (MA, 19.6 g, 200.0 mmol), phenylethylnorbornene (PENB, 39.6 g, 200.0 mmol) and AIBN (3.3 g, 20.0 mmol) were dissolved in THF (36.2 g) and loaded Into a suitably sized reaction vessel. The solution was aerated with nitrogen for 10 minutes to remove oxygen and then heated to 60 °C. The mixture was stirred at 60 ° C for 23 hours, after which time the solution was diluted to 20 wt% with 181.3 g of THF. The obtained solution was added to a suspension of NaOH (8.8 g, 220 mmol), BuOH (74.0 g, 1 mol) and THF (80.0 g), and the mixture was mixed at 70 ° C for 1 hour. The mixture was stirred at 70 ° C for 2 hours and then cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. The organic phase was separated and then concentrated in vacuo, redissolved in THF to afford about 20 wt% of the copolymer solution and then the copolymer was precipitated by adding THF solution to hexane (20-fold excess). The copolymer was isolated by filtration and dried in a vacuum oven at 80 ° C for 16 hours. Approximately 44.4 g (75%) of a ROMA copolymer of MA/PENB and BuOH (GPC Mw = 7,700, Mn = 4,000) was isolated.

Example B7: ROMA copolymer of MA/PENB and BuOH

Maleic anhydride (MA, 19.6 g, 200.0 mmol), phenylethylnorbornene (PENB, 39.6 g, 200.0 mmol) and AIBN (3.3 g, 20.0 mmol) were dissolved in EtOAc (36.2 g) Into a suitably sized reaction vessel. The solution was aerated with nitrogen for 10 minutes to remove oxygen and then heated to 60 °C. The mixture was stirred at 60 ° C for 20 hours. The reaction mixture was concentrated in vacuo and redissolved in THF (20 wt%). The resulting solution was added to a suspension of NaOH (8.80 g, 220 mmol), BuOH (74.12 g, 1 mol) and THF (74.12 g) at 70 ° C Mix for 1 hour. The mixture was stirred at 70 ° C for 2 hours and then cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. The organic phase was separated and then concentrated in vacuo, redissolved in THF to afford about 20 wt% of the copolymer solution and then the copolymer was precipitated by adding THF solution to hexane (20-fold excess). The copolymer was isolated by filtration and dried in a vacuum oven at 80 ° C for 16 hours. Approximately 37.5 g (51%) of a ROMA copolymer of MA/PENB and BuOH (GPC Mw = 9,900, Mn = 5,400) was isolated.

Example B8: ROMA copolymer of MA/NB and third butanol

NaOH (1.1 g, 28.5 mmol), t-BuOH (5.8 g, 77.8 mmol) and THF (20.0 g) were placed in a reaction vessel of the appropriate size. The mixture was stirred at 70 ° C for 3 hours and then 20.0 g of THF containing the polymer (5.0 g) obtained by the same method as in Example 1 was added. After reacting at 70 ° C for 16 hours, the mixture was cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. The organic phase was separated and then concentrated in vacuo, redissolved in THF to afford about 20 wt% of the copolymer solution and then the copolymer was precipitated by adding THF solution to hexane (20-fold excess). The copolymer was isolated by filtration and dried in a vacuum oven at 80 ° C for 16 hours. About 4.5 g (65%) of a ring-opening polymer of MA/NB and t-BuOH (GPC Mw = 3,000, Mn = 1,500) was isolated.

Example B9: ROMA copolymer of MA/NB and 2-methyl-2-adamantanol

NaOH (1.1 g, 28.5 mmol), 2-methyl-2-adamantanol (8.7 g, 52.0 mmol) and THF (40.0 g) were placed in a reaction vessel of appropriate size. The mixture was stirred at 70 ° C for 3 hours and then 20.0 g of THF containing the polymer obtained in Example 1 (5.0 g) was added. After reacting at 70 ° C for 16 hours, the mixture was cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. Separating the organic phase and then in the true It was concentrated in the air, redissolved in THF to form about 20 wt% of the copolymer solution and then the copolymer was precipitated by adding THF solution to hexane (20-fold excess). The copolymer was isolated by filtration and dried in a vacuum oven at 80 ° C for 16 hours. A ring-opening polymer (GPC Mw = 3,000, Mn = 1,500) of about 5.31 g (57%) of MA/NB and 2-methyl-2-adamantanol was isolated.

Example B10: ROMA copolymer of MA/NB and 2,2,3,3,4,4,4-heptafluoro-1-butanol

NaOH (1.1 g, 28.5 mmol), 2,2,3,3,4,4,4-heptafluoro-1-butanol (7.8 g, 39.0 mmol) and THF (20.0 g) were charged to the appropriate size. In the container. The mixture was stirred at 70 ° C for 3 hours and then 20.0 g of THF containing the polymer obtained in Example 1 (5.0 g) was added. After reacting at 70 ° C for 16 hours, the mixture was cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. The organic phase was separated and then concentrated in vacuo, redissolved in THF to afford about 20 wt% of the copolymer solution and then the copolymer was precipitated by adding THF solution to hexane (20-fold excess). The copolymer was isolated by filtration and dried in a vacuum oven at 80 ° C for 16 hours. About 5.1 g (50%) of a ring-opening polymer of MA/NB and BuOH (GPC Mw = 3,600, Mn = 1,900) was isolated.

Example B11: ROMA copolymer of MA/NB and 4-tert-butylcyclohexanol

NaOH (1.1 g, 28.5 mmol), 4-t-butylcyclohexanol (12.2 g, 78.1 mmol) and THF (20.0 g) were placed in a reaction vessel of appropriate size. The mixture was stirred at 70 ° C for 3 hours and then 20.0 g of THF containing the polymer obtained in Example 1 (5.0 g) was added. After reacting at 70 ° C for 16 hours, the mixture was cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. The organic phase was separated and then concentrated in vacuo, redissolved in THF to afford about 20 wt% of the copolymer solution and then the copolymer was precipitated by adding THF solution to hexane (20-fold excess). Separation of the copolymer by filtration It was dried in a vacuum oven at 80 ° C for 16 hours. Approximately 5.2 g (58%) of a ring-opening polymer of MA/NB and 4-tert-butylcyclohexanol (GPC Mw = 3,300, Mn = 1,600) was isolated.

Example B12: ROMA copolymer of MA/NB and 4-tert-butylphenol

NaOH (1.1 g, 28.5 mmol), 4-tert-butylphenol (7.8 g, 52.0 mmol) and THF (15.0 g) were placed in a reaction vessel of appropriate size. The mixture was stirred at 70 ° C for 3 hours and then 7.5 g of THF containing the polymer obtained in Example 1 (5.0 g) was added. After reacting at 70 ° C for 16 hours, the mixture was cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. The organic phase was separated and then concentrated in vacuo, redissolved in THF to afford a &lt;RTI ID=0.0&gt;&gt; The copolymer was isolated by filtration and dried in a vacuum oven at 80 ° C for 16 hours. Approximately 5.4 g (61%) of a ring-opening polymer of MA/NB and 4-tert-butylphenol (GPC Mw = 3,400, Mn = 1,800) was isolated.

Example B13: ROMA copolymer of MA/PENB and MeOH

Maleic anhydride (MA, 14.7 g, 150 mmol), phenylethylnorbornene (PENB, 29.7 g, 150 mmol) and AIBN (2.5 g, 15.0 mmol) were dissolved in THF (27.1 g) and charged. In the container. The solution was aerated with nitrogen for 10 minutes to remove oxygen and then heated to 60 °C. The mixture was stirred at 60 ° C for 24 hours, after which time the solution was diluted with 148.04 g of THF to 20 wt%. The resulting solution was added to a suspension of NaOH (6.6 g, 165 mmol), MeOH (24.0 g, 750 mmol) and THF (24.0 g), and the mixture was stirred at 70 ° C for 1 hour. The mixture was stirred at 70 ° C for 3 hours and then cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. The organic phase is separated and then concentrated in vacuo, redissolved in THF to form about 20 wt% copolymer solution and then added to the THF solution The copolymer was precipitated in an alkane (20-fold excess). The copolymer was isolated by filtration and dried in a vacuum oven at 80 ° C for 16 hours. Approximately 28.7 g (58%) of a ring-opening polymer of MA/PENB and MeOH (GPC Mw = 6,400, Mn = 3,500) was isolated.

Example B14: ROMA copolymer of MA/PENB and MeOH

Maleic anhydride (MA, 14.7 g, 150 mmol), phenylethylnorbornene (PENB, 29.7 g, 150 mmol) and AIBN (2.5 g, 15.0 mmol) were dissolved in EtOAc (27.1 g) and charged. In the container. The solution was aerated with nitrogen for 10 minutes to remove oxygen and then heated to 60 °C. The mixture was stirred at 60 ° C for 24 hours. The reaction mixture was concentrated in vacuo and redissolved in THF (20 wt%). The resulting solution was added to a suspension of NaOH (6.6 g, 165 mmol), MeOH (24.0 g, 750 mmol) and THF (24.0 g), and the mixture was stirred at 70 ° C for 1 hour. The mixture was stirred at 70 ° C for 3 hours and then cooled to room temperature. The reaction mixture was treated with concentrated aqueous hydrochloric acid to carry out protonation, and then washed 3 times to remove residual salts and acids. The organic phase was separated and then concentrated in vacuo, redissolved in THF to afford about 20 wt% of the copolymer solution and then the copolymer was precipitated by adding THF solution to hexane (20-fold excess). The copolymer was isolated by filtration and dried in a vacuum oven at 80 ° C for 16 hours. Approximately 30.4 g (61%) of a ring-opening polymer of MA/PENB and MeOH (GPC Mw = 9,700, Mn = 5,300) was isolated.

Example B15: (DRM) ROMA copolymer of MA/NB and BuOH

Maleic anhydride (MA, 98.1 g, 1.0 mol), 2-norbornene (NB, 94.2 g, 1.0 mol) and AIBN (3.3 g, 20.0 mmol) were dissolved in THF (31.2 g) and toluene (93.6 g). And loaded into a reaction vessel of appropriate size. The solution was aerated with nitrogen for 10 minutes to remove oxygen and then heated to 60 ° C with stirring. After 3 hours, THF (64.1 g) was added and AIBN (3.3 g, 20.0 mmol) and THF (39.4 g) were added at 8 hours and the mixture was stirred at 60 ° C 16 hours. The reaction mixture was then diluted with THF to 20 wt% and the resulting solution was added to a suspension of NaOH (44.1 g, 1.1 mol), BuOH (370.9 g, 5.0 mol) and mixed at 65 ° C for 3 hours. The mixture was then cooled to 40 ° C, treated with concentrated aqueous hydrochloric acid (126.2 g, 1.2 mol) for protonation, followed by successive use of toluene (384 g) and water (961 g) (1X) and THF (192 g) and water (961 g) (3X) Wash to remove inorganic residues. The organic phase was then separated and washed sequentially with a mixture of MeOH / water / hexane (1X) and MeOH / toluene / hexane (2X) to extract any residual monomer. After extraction, BuOH (74.18 g, 1.0 mol) and PGMEA (611 g) were added to the reaction mixture and evaporated until residual MeOH was less than 1%. The reaction mixture was then heated to 130 ° C for dissolution rate improvement. Samples were taken to monitor the dissolution rate of the copolymer. The reaction mixture was cooled and the solvent was exchanged for PGMEA when the desired dissolution rate was obtained. A 20 wt% solution of 651.4 g of polymer (GPC Mw = 13,600, Mn = 6,800) was obtained.

Although the above procedure includes a dissolution rate improving step, it should be understood that the process can be carried out in the absence of alcohol and addition of alcohol. To achieve this, the 20 wt% polymer solution of ROMA NB/MA-BuOH in PGMEA was heated at 125 ° C for 3 hours, and the infrared spectrum of the initial sample and the sample after heating for 3 hours was obtained with a Nicolet Avatar 320 FT-IR spectrometer and partially Infrared spectra are provided in Figures 2a and 2b, respectively. In addition, another 20 wt% polymer solution of different ROMA NB/MA-BuOH in PGMEA was heated at 125 ° C for 3 hours in the presence of BuOH. The infrared spectrum of the initial sample and the sample after heating for 3 hours was obtained with a Nicolet Avatar 320 FT-IR spectrometer and partial infrared spectra were provided in Figures 2c and 2d, respectively.

Referring first to Figures 2a and 2b, it can be seen that there is a significant increase in the two peaks "A" between the spectrum of the initial sample (Figure 2a) and the spectrum of the sample after heating for 3 hours (Figure 2b) indicating the frequency of carbonyl stretching of the MA ring structure. In addition, it was found that the carbonyl extension of the butyl ester carbonyl group between the two spectra was found. The intensity of the peak "B" and the shoulder "C" of the exhibition frequency is reduced. Therefore, the spectra indicate that heating a copolymer having a repeating unit of BuOH ring-opening maleic anhydride type without any added alcohol can cause some partial ring closure of the repeating units and the reduction in ring closure can be used for The amount of carboxylic acid providing the solubility of the polymer in an aqueous base solution.

Referring now to Figures 2c and 2d, it can be seen that the two peaks "A" representing the carbonyl stretching frequency of the MA ring structure are only slightly increased between the spectrum of the initial sample (Fig. 2c) and the spectrum of the sample after heating for 3 hours (Fig. 2d). . Further, it was found that the peak "B" indicating the frequency of stretching of the carbonyl group of the butyl ester carbonyl group between the two spectra was substantially kept constant and the strength of the shoulder "C" was lowered. Therefore, the spectrum indicates that heating a copolymer having a repeating unit of a BuOH ring-opening maleic anhydride type in the presence of an added alcohol may cause some partial ring closure of the repeating units and other portions of the repeating units Become a diester. Since both the ring closure and the diester formation reduce the amount of carboxylic acid available to provide the solubility of the polymer in the aqueous base solution, the dissolution rate of the initial copolymer is reduced.

Referring now to Figure 3, there is shown a dissolution rate modification step which causes a decrease in the dissolution rate of the initial ROMA copolymer with or without the addition of an alcohol moiety such as benzyl alcohol. Thus, the results presented in Figure 3 further indicate that this step must reduce the availability of the carboxylic acid moiety, which has been indicated by ring closure or diesterification or both.

Alkali dissolution rate

The polymer from each of Examples B1 to B12 and B15 was dissolved in PGMEA to form a 25 wt% polymer solution. Each solution was spin-coated on a 3 Å wafer and soft baked at 110 ° C for 100 seconds to obtain a polymer film having a thickness of about 3 μm. Development was carried out by immersing the wafer in a 0.4% TMAH developer solution. The dissolution rate of each film was determined by measuring the time required for the polymer film to become visually transparent (shown below).

Copolymer transparency

A solution of polymers B1 to B15 was applied to a glass wafer as described above to obtain a layer having a thickness of 3 μm. The transparency at 400 nm was measured before and after heat treatment at 250 ° C / 30 min in air. The transparency of each film was at least 98% prior to treatment, and the transparency of the polymers of Examples B2, B3 and B4, all of the polymers having alkyl NB repeating units was significantly reduced after heat treatment. B2 and B4 were reduced to 37% and 40%, respectively, and B3 was reduced to 78%. For the other examples, only Examples B13 and B14 exhibited a % reduction in transparency of up to 10%.

Tg

The Tg of the polymer was measured by adjusted DSC. The measurement conditions were 10 ° C / min under N ₂ flow. The copolymers of Examples B1 to B6, B11 and B12 each had a Tg of 150 ° C +/- 10 ° C, while the Tg of Examples B8 to B 10 were 183 ° C, 186 ° C and 177 ° C, respectively.

Copolymer composition example

a: dielectric constant

The dielectric constant of the film prepared from the copolymer composition of each of the copolymers B1 to B15 was measured at 1 kHz, 10 kHz, 100 kHz, and 1 MHz according to the technique of JIS-k6911 (Japanese Industrial Standard). A method of preparing each composition is provided in Examples C1a to C15a. The film thickness of each film (required for calculating the dielectric constant) was measured using a Lambda ace VM-1020 from Dainippon Screen MFG Co., Ltd.

Example C1a: The polymer from Example B1 was dissolved in PGMEA/EL (4/3) together with TrisP 3M6C-2-201 (25% on polymer from Toyo Gosei) and TMPTGE (20% on polymer). , 16wt%). The formulation was spin-coated on an aluminum plate (200 μm thickness, 100 mm×100 mm) at 300 rpm for 23 seconds, and soft baked at 110 ° C for 100 seconds to obtain a polymer film of about 3 μm, followed by using a broadband Hg vapor source (g The mask aligners of the h, i and i bands were exposed at 500 mJ/cm ² . After the exposure, the wafer was exposed to light at 220 ° C for 60 minutes under a nitrogen atmosphere to obtain a cured film.

Example C2a: The procedure for repeating C1a except that the polymer from Example B2 was dissolved in PGMEA (25 wt%) together with TrisP 3M6C-2-201 (25% on polymer) and TMPTGE (20% on polymer) The spin coating conditions were at 300 rpm for 3 seconds followed by 400 rpm for 20 seconds.

Example C3a: The process of repeating C1a except that the polymer from Example B3 was dissolved in PGMEA (25 wt%) together with TrisP 3M6C-2-201 (25% on polymer) and TMPTGE (20 wt% on polymer) The spin coating conditions were at 300 rpm for 3 seconds followed by 900 rpm for 20 seconds.

Example C4a: The process of repeating C1a except that the polymer from Example B4 was dissolved in PGMEA (25 wt%) together with TrisP 3M6C-2-201 (25% on polymer) and TMPTGE (20 wt% on polymer) The spin coating conditions were at 300 rpm for 3 seconds followed by 700 rpm for 20 seconds.

Example C5a: The process of repeating C1a except that the polymer from Example B5 was dissolved in PGMEA (25 wt%) together with TrisP 3M6C-2-201 (25% on polymer) and VG3101L (20 wt% on polymer) The spin coating conditions were at 300 rpm for 3 seconds followed by 800 rpm for 20 seconds.

Example C6a: The procedure for repeating C1a except that the polymer from Example B6 was dissolved in PGMEA (25 wt%) together with TrisP 3M6C-2-201 (25% on polymer) and VG3101L (20 wt% on polymer) The spin coating conditions were at 300 rpm for 3 seconds and at 1300 rpm for 20 seconds.

Example C7a: The process of repeating C1a except that the polymer from Example B7 was dissolved in PGMEA (25 wt%) together with TrisP 3M6C-2-201 (25% on polymer) and VG3101L (20 wt% on polymer) The spin coating conditions were continued at 300 rpm for 3 seconds, followed by 1370 rpm for 20 seconds.

Example C8a: The process of repeating C1a except that the polymer from Example B8 was dissolved in PGMEA (25 wt%) together with Tris-P PAC (25% on polymer) and TMPTGE (20% on polymer) And the spin coating conditions were continued at 300 rpm for 3 seconds, followed by 2000 rpm for 20 seconds.

Example C9a: The procedure for repeating C1a except that the polymer from Example B9 was dissolved in PGMEA/MAK with TrisP 3M6C-2-201 (25% on polymer) and TMPTGE (20% on polymer). The 3/1 (20 wt%) and spin coating conditions were at 300 rpm for 3 seconds, followed by 1500 rpm for 20 seconds.

Example C10a: The process of repeating C1a except that the polymer from Example B10 was dissolved in PGMEA (25 wt%) together with TrisP 3M6C-2-201 (25% on polymer) and TMPTGE (20% on polymer) The spin coating conditions were at 300 rpm for 3 seconds followed by 1000 rpm for 20 seconds.

Example C11a: The process of repeating C1a except that the polymer from Example B10 was dissolved in PGMEA (25 wt%) together with TrisP 3M6C-2-201 (25% on polymer) and TMPTGE (20% on polymer) The spin coating conditions were at 300 rpm for 3 seconds and then at 1500 rpm for 20 seconds.

Example C12a: The process of repeating C1a except that the polymer from Example B10 was dissolved in PGMEA (25 wt%) together with TrisP 3M6C-2-201 (25% on polymer) and TMPTGE (20% on polymer) The spin coating conditions were at 300 rpm for 3 seconds followed by 930 rpm for 20 seconds.

Example C13a: The process of repeating C1a except that the polymer from Example B13 was dissolved in PGMEA (25 wt%) together with Tris-P PAC (25% on polymer) and TMPTGE (20% on polymer) And the spin coating conditions were at 300 rpm for 3 seconds, followed by 1520 rpm for 20 seconds.

Example C14a: The process of repeating C1a except that the polymer from Example B14 was dissolved in PGMEA (25 wt%) together with Tris-P PAC (25% on polymer) and TMPTGE (20% on polymer) And the spin coating conditions were at 300 rpm for 3 seconds, followed by 1980 rpm for 20 seconds.

Example C15a: The procedure for repeating C1a except for the polymer solution from Example B15 and Tris-P PAC (25% on polymer) and VG3101L (20% on polymer) and the spin coating conditions were at 300 rpm It lasted for 3 seconds and then continued at 830 rpm for 20 seconds.

Except for the films of Examples C9a and C12a, the dielectric constants of all films were low at all frequencies, ranging from a low value range of 2.9 to 3.1 at 1 MHz and a low value range of 3.1 to 3.4 at 1 kHz. Although the results for C9a and C12a are higher, they also exhibit desirable low dielectric constant values in the range of 3.3 (1 MHz) to 3.7 (1 KHz).

b: transparency of cured film

A film having a thickness of about 3 μm was prepared on a glass plate using the copolymer compositions of each of the prepared Examples C1a, C3a, C4a, C6a and C13a to C15a. After soft baking at 110 ° C for 100 seconds, each film was exposed at 500 mJ/cm ² using a mask aligner having a broadband Hg vapor source (g, h and i bands). After the exposure, the wafer was exposed to light at 220 ° C for 60 minutes under a nitrogen atmosphere to obtain a cured film. The film-coated glass plate was heated in an oven at 250 ° C for 30 minutes in the air, and the transparency of the film at a wavelength of 400 nm was measured using an ultraviolet-visible spectroscope (Hitachi U-2000). The resulting heat-treated film was labeled as Examples C1b, C3b, C4b, C6b and C13b to C15b, and the % transparency of each film is provided below.

c: 5% weight loss temperature

A copolymer composition of each of the prepared Examples C1a to C4a, C6a, C7a, and C12a to C15a was used to prepare a film having a thickness of about 3 μm on a silicon oxide coated with a thermal oxide of 4 Å and exposed. . After each film was cured, a portion of the film was removed from the wafer and the 5% weight loss temperature was measured by TGDTA. The measurement conditions were 10 ° C / min under N ₂ flow. The resulting weight loss measurements are labeled as Examples C1c through C4c, C6c, C7c, and C12c through C15c and are provided below. As can be seen, the 5% weight loss temperature of each film exceeded 300 ° C and the heat stable temperature was considered to be up to and including 300 ° C.

d: lithography evaluation

A film having a thickness of about 3 μm was prepared on a glass plate using the copolymer composition of each of the prepared Examples C1a to C15a. After soft baking at 110 ° C for 100 seconds, the films were exposed at 500 mJ/cm ² through a glass mask chrome using a mask aligner with a broadband Hg vapor source (g, h and i bands). . After exposure, each wafer was subjected to immersion development using 0.4% TMAHaq for 10 seconds, washed with deionized water, followed by spin drying at 2000 rpm for 20 seconds. The final thickness of the remaining polymer of each wafer and the resolution of the line and space of 10 μm were measured. The results of these evaluations, as well as the initial film thickness of each wafer (labeled as Examples C1d to C15d) are provided below.

Referring now to Figures 4a and 4b, a photomicrograph of a portion of the image formed in Example C15d is shown. In Figure 4a, it is found that the 10 μm line and space are clearly resolved, while in Figure 4b In the middle, it was found that the 5 μm line and space were also well resolved.

Heat resistance

Example C5e: By cutting the patterned wafer in Example C5d into several pieces, heating the sheets in an oven under N ₂ to 220 ° C for 60 minutes and then observing the SEM cross section of the heated sheet The heat resistance was measured. After heat curing at 220 ° C, the pattern flow was observed.

Example C6e: By cutting the patterned wafer in Example C6d into several sheets, the sheets were heated to 220 ° C for 60 minutes in an N ₂ oven, and then the SEM cross sections of the heated sheets were observed. The heat resistance was measured. There was no pattern flow after thermal curing, thus indicating that the cured polymer film exhibited heat resistance and stability at least at 220 °C.

Example C7e: By cutting the patterned wafer in Example C7d into several sheets, the sheets were heated to 220 ° C for 60 minutes in an N ₂ oven, and then the SEM cross sections of the heated sheets were observed. The heat resistance was measured. There was no pattern flow after thermal curing, thus indicating that the cured polymer film exhibited heat resistance and stability at least at 220 °C.

Example C13e: Heat resistance was measured by cutting a film-coated wafer into a plurality of sheets, heating the sheets to 220 ° C for 60 minutes in an N ₂ oven, and then observing the SEM cross sections of the heated sheets. Sex. There was no pattern flow after thermal curing, thus indicating that the cured polymer film exhibited heat resistance and stability at least at 220 °C.

Example C14e: Heat resistance was measured by cutting a film-coated wafer into a plurality of sheets, heating the sheets to 220 ° C for 60 minutes in an N ₂ oven, and then observing the SEM cross sections of the heated sheets. Sex. There was no pattern flow after thermal curing, thus indicating that the cured polymer film exhibited heat resistance and stability at least at 220 °C.

g: NMP tolerance

Example C6g: The formulation of Example C6a was spin-coated on a 3 Å thermal oxide ruthenium wafer at 300 rpm for 3 seconds followed by 1300 rpm for 20 seconds, and soft baked at 110 ° C for 100 seconds to obtain about 2.3. The micron polymer film was then exposed at 500 mJ/cm ² using a mask aligner with a broadband Hg vapor source (g, h and i bands). After the exposure, the wafer was exposed to light at 220 ° C for 60 minutes under a nitrogen atmosphere to obtain a cured film. The wafer was immersed in NMP for 10 minutes at 40 ° C and then the film thickness was measured. The film thickness was maintained at 2.3 μm and no peeling was observed.

Example C15g: The formulation of Example C15a was spin-coated on a 3 Å thermal oxide ruthenium wafer at 300 rpm for 3 seconds and then at 1300 rpm for 20 seconds, and soft baked at 110 ° C for 100 seconds to obtain about 2.46. The micron polymer film was then exposed at 500 mJ/cm ² using a mask aligner with a broadband Hg vapor source (g, h and i bands). After the exposure, the wafer was exposed to light at 220 ° C for 60 minutes under a nitrogen atmosphere to obtain a cured film. The wafer was immersed in NMP for 60 minutes at 23 ° C and then the film thickness was measured. The film thickness was maintained at 2.56 μm (4% increase) and no cracking or peeling was observed.

It will be understood that the information provided above demonstrates that the specific examples of the copolymers of the present invention and the compositions comprising the copolymers are suitable for forming a self-imageable, thermally stable, highly transparent, low-k dielectric layer. More specifically, the copolymers and layers made therefrom are readily applied to substrates using well known microelectronic and/or optoelectronic treatments having a dielectric constant of 3.9 or less and exhibiting thermal stability at temperatures in excess of 300 °C. Sex.

In addition, it should be understood that although embodiments of the methods of making the specific examples of the copolymers of the present invention have been provided, such methods are not intended to be limiting. It is also possible to adjust and control the copolymer, the copolymer composition and the film obtained therefrom by using other reaction time, temperature, solvent and the like. The characteristics of a layer or structure. For example, when the polymerization examples reveal the use of AIBN as a polymerization initiator, other such initiators, such as the exemplary initiators listed above, may also be used and may be provided to have a different disclosure than disclosed in any particular embodiment. A copolymer of molecular weight. It should be understood that the modifications are within the scope of the specific examples of the invention. Similarly, other casting and polymerization solvents can be used and when such other solvents are used to make the copolymers, compositions, and films or layer embodiments described herein, such other solvents are also within the scope of the invention.

A‧‧‧峰

B‧‧‧Feng

C‧‧‧ shoulder

Claims (10)

A layer-forming polymer composition comprising: a self-imageable polymer consisting of a norbornene-type repeating unit and a maleic anhydride-type repeating unit, wherein: the norbornene-type repeating unit Ia indicates that it is derived from a norbornene-type monomer represented by Formula I: Wherein m is 0, 1 or 2, and each of R ¹ , R ² , R ³ and R ^{4 in} the repeating unit of the first type is independently hydrogen or a hydrocarbyl pendent group having high transparency in the visible spectrum. The maleic anhydride type repeating unit is represented by one or more of the formulae IIa, IIb and IIc derived from the maleic anhydride monomer represented by the formula II: Wherein R ⁵ and R ⁶ are each independently hydrogen, methyl, ethyl, fluorinated or perfluorinated methyl or ethyl, straight or branched C ₃ -C ₉ hydrocarbyl; straight or branched fluorinated or a perfluorinated C ₃ -C ₉ hydrocarbon group; one of a C ₆ -C ₁₈ substituted or unsubstituted cyclic or polycyclic hydrocarbon group; a photoactive compound (PAC); an epoxy resin comprising at least two Epoxy groups; and solvents. The polymer composition of the forming layer of claim 1 further comprising a maleic anhydride type repeating unit derived from the maleic anhydride type monomer represented by Formula III: Wherein R ⁷ and R ^{8 are the} same or different and are selected from the group consisting of hydrogen, methyl and ethyl. The polymer composition of claim 1, wherein R ⁵ is one of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group or a third butyl group. The polymer composition of claim 1, wherein the epoxy resin comprises three epoxy groups. The polymer composition of claim 1 or 2, wherein the PAC is Tris-P-2-201, 4NT-300 or TS-300. The polymer composition of claim 5, wherein the solvent is propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl n-amyl ketone (MAK) or a mixture thereof. The polymer composition of claim 5, wherein R ¹ to R ^{4 are} each hydrogen, R ⁵ is a butyl group and the epoxy resin is Techmore VG3101L, trimethylolpropane triglycidyl ether (TMPTGE) or Bisphenol A epoxy resin (LX-1). The polymer composition of claim 6, wherein the PAC is Tris-P 3M6C-2-201, the epoxy resin is Techmore VG3101L, and the solvent is propylene glycol monomethyl ether acetate (PGMEA). A polymer layer formed from the polymer composition of claim 1 which has a dielectric constant of 3.2 or less at 1 MHz. The polymer layer of claim 1, which has a transparency of greater than 85% at 400 nm after curing at 250 ° C for 30 minutes.