HK1077370A - Photosensitive compositions based on polycyclic polymers - Google Patents

Description

Photosensitive composition based on polycyclic polymer

Background

Technical Field

The present invention relates to polycyclic polymers, and in particular to lithographic polymer compositions containing polycyclic polymers.

Related art field

The rapid growth of the microelectronics industry has led to a great demand for photolithographic dielectric polymeric materials having improved electronic characteristics for each generation of microelectronic device packages. Industry development requires integrated circuits that are smaller, faster, and consume less energy. To meet these demands, the integrated circuit elements and the packaging of such circuitry must be of high density with submicron features. One way to increase the number of components per chip is to minimize the size of the components on the chip. Thus, the wires must be made thin and placed in close proximity to each other. The reduction of gaps between wires in circuitry and the reduction of packaging for such circuitry has resulted in increased circuit efficiency and speed, thereby allowing greater memory capacity, faster processing of information, and lower power requirements. However, the reduction in the spacing between the conductors can cause an increase in the capacitance of the coupled wires, resulting in greater crosstalk, loss of more capacitance and an increase in the rc time constant.

To limit this capacitive coupling and the increase in deleterious effects such as transmission delay, while switching noise, there is a growing interest in high performance polymers with low dielectric constants. In addition, there is also a growing interest in such low dielectric constant materials with suitable modulus for packaging integrated circuit components. However, currently known polymers are often difficult to pattern, e.g., such low dielectric constant polymers that are often used to pattern wiring patterns and photoresist compositions have very similar etch characteristics. Thus, efforts to selectively exclude portions of the polymer can be problematic. To overcome this selectivity problem, it is known to form an intervening material between the polymer and the resist composition, between which such intervening material can be selectively patterned to form a hard mask, which can then be used to pattern the underlying polymer material.

Other steps that require the formation of a hard mask may not be cost effective, and therefore alternative methods of patterning low dielectric constant polymer materials that do not require such steps may be advantageous. To this end, U.S. Pat. No. 6,121,340 discloses a negative-working photodefinable dielectric composition comprising a photoinitiator and a polycyclic addition polymer comprising repeating units having hydrolyzable pendant functional groups (e.g., silyl ethers). Upon exposure to a radiation source, the photoinitiator catalyzes the hydrolysis of the hydrolyzable groups to selectively effect crosslinking in the polymer backbone to form a pattern. The dielectric material of the' 340 patent is thus in a photolithographic environment or is itself lithographically printable. However, the dielectric composition disclosed in the' 340 patent does not require the presence of moisture as the hydrolysis reaction proceeds. It is known that the presence of such moisture in the dielectric layer can cause reliability problems in the completed device and device package.

Accordingly, it would be desirable to have low dielectric constant materials with suitable modulus for use in the microelectronics industry that are in a lithographic environment or that are themselves lithographically processable without the presence of moisture for performing the lithography. In addition, there is a desire for methods of application of such lithographic materials and for microelectronic devices that use such lithographic materials as dielectric materials.

Summary of The Invention

An exemplary embodiment of the present invention is a polymer composition comprising a copolymer having a backbone with repeating units of formula I:

wherein X is selected from O, -CH₂-and-CH₂-CH₂-; m is an integer from 0 to 5; and each occurrence of R¹，R²，，R³And R⁴Independently selected from the group consisting of:

(a)H，，C₁to C₂₅Of (2) isBranched and cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl and alkynyl groups;

(b) c containing one or more hetero atoms selected from O, N and Si₁To C₂₅Linear, branched and cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl and alkynyl groups of (a);

(c) an epoxy group comprising a group of formula II:

wherein A is selected from C₁To C₆A linear, branched and cycloalkylene linking group of (1), R²³And R²³Independently selected from H, methyl, and ethyl;

(d) an epoxy group comprising a group of the following formula III:

wherein p is an integer of 0 to 6, R²³And R²⁴As defined above, and each occurrence of R²¹And R²²Independently selected from H, methyl and ethyl;

(e)-(CH₂)_nC(O)OR⁵R⁵，-(CH₂)_nC(O)OR⁶，-(CH₂)_nOR⁶，-(CH₂)_nOC(O)R⁶，-(CH₂)_nC(O)R⁶and- (CH)₂)_nOC(O)OR⁶(ii) a And

(f) two R connected by a linking group¹，R²，R³And R⁴In any combination of (1), the linking group is selected from C₁To C₂₅Linear, branched and cyclic alkylene and alkylenearyl groups of (a); wherein n is an integer from 1 to 25, R⁵Is an acid-labile group, R⁶Is selected fromH，C₁To C₆Linear, branched, and cyclic alkyl groups of (a), containing epoxy groups of formula II above; and wherein a portion of the repeat units comprising structure I comprise at least one epoxy-functional pendant group.

Other examples of the invention are directed to photodefinable dielectric compositions comprising the polymer compositions described above and a material that photonically forms a catalyst.

Further exemplary embodiments of the invention are directed to methods of forming a photodefinable layer on a substrate and comprise providing a substrate, coating at least one side of the substrate with a composition comprising a copolymer composition and a photonically formed catalyst material as described above, exposing the layer on the coated substrate to radiation, and curing the radiation-exposed layer.

Other embodiments of the invention are directed to electrical or electronic devices comprising a layer comprising or derived from a photodefinable dielectric composition as described above, and devices made according to the methods of the invention.

Description of the exemplary embodiments

Unless otherwise indicated, all numbers, values and/or expressions referring to quantities of ingredients, reaction conditions and the like used herein are to be understood as modified in all instances by the term "about".

Various numerical ranges are disclosed in this patent application. Because these ranges are continuous, they include every value between the minimum and maximum values for each range. Unless otherwise indicated, the various numerical ranges specified in the specification and claims are approximations that reflect the uncertainty of the various measurements encountered in obtaining such values.

The term "polymer composition" as used herein is meant to encompass the synthesized copolymer, as well as residues from the starting materials, catalysts, and other ingredients that accompany the synthesis of the copolymer, wherein such residues are understood to be non-covalently incorporated therein. Such residues and other ingredients considered to be part of the polymer composition are typically mixed or blended with the copolymer such that they are accompanied by the copolymer when transferred between vessels or between solvent or dispersion media. The polymer composition also includes materials added after the synthesis of the copolymer that provide specific properties to the polymer composition.

The term "low K composition" as used herein generally refers to a material having a low dielectric constant, typically a material having a dielectric constant less than that of thermoformed silicon dioxide, and particularly a material having a dielectric constant less than about 3.9.

The term "modulus" as used herein refers to the ratio of stress to strain and, unless otherwise stated, refers to the Young's modulus or tensile modulus measured in the linear elastic region of the stress-strain curve. Modulus values were measured according to ASTM method D1708-95.

The terms "acid labile" and "acid labile group" as used herein refer to a portion of a molecule, i.e., a group that reacts in a catalytic manner in the presence of an acid.

The term "photodefinable dielectric composition" as used herein refers to a composition on a substrate in which or which is itself capable of forming a patterned layer. I.e., the layer does not require the use of another material layer, such as a photoresist layer, formed thereon to form the patterned layer. Further, such photodefinable dielectric compositions are understood to be useful as durable insulating materials and/or barriers or buffer layers in the preparation of a variety of electrical and electronic devices, as a non-limiting example as stress buffer layers in the packaging of semiconductor devices. The lithographic compositions used in the present invention can be formed into layers for patterning processes by a variety of electromagnetic radiations including, but not limited to: ultraviolet (UV) radiation, deep ultraviolet radiation (DUV), electron beam or X-ray radiation.

The term "photonically catalyst-forming material" as used herein refers to materials that will be destroyed, decomposed, or otherwise change their molecular composition upon exposure to a suitable form of energy, non-limiting examples of which are UV radiation, DUV radiation, electron beam, and X-ray radiation, to form a compound capable of catalyzing a crosslinking reaction in a photodefinable dielectric composition.

The term "cure" as used herein is intended to mean crosslinking of the components of the photodefinable dielectric composition to produce the desired physical and chemical properties of the film, non-limiting examples being low dielectric constant, low moisture absorption characteristics, low modulus and resistance to chemical attack. When processing the polymer composition, the composition may be partially cured in one process step and "fully" cured in a subsequent process step.

Exemplary embodiments of the present invention are directed to polymer compositions comprising a copolymer comprising a backbone having repeat units of formula I:

wherein X is selected from O, -CH₂-, and-CH₂--CH₂-; m is an integer from 0 to 5, sometimes 0 to 3, and in other cases 0 to 2. Each occurrence of R in formula I¹，R²，R³And R⁴Independently selected from the group consisting of:

(a)H，，C₁to C₂₅Linear, branched and cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl and alkynyl groups of (a);

(b)C₁to C₂₅Linear, branched and cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl and alkynyl groups of (a), containing one or more heteroatoms selected from O, N and Si;

(c) an epoxy group comprising a group of formula II:

wherein A is selected from C₁To C₆A linear, branched and cycloalkylene linking group of (1), R²³And R²³Independently selected from H, methyl, and ethyl;

(d) an epoxy group comprising a group of the following formula III:

wherein p is an integer of 0 to 6, R²³And R²⁴As described above, and each occurrence of R²¹And R²²Independently selected from H, methyl and ethyl;

(e)-(CH₂)_nC(O)OR⁵，-(CH₂)_nC(O)OR⁶，-(CH₂)_nOR⁶，-(CH₂)_nOC(O)R⁶，-(CH₂)_nC(O)R⁶and- (CH)₂)_nOC(O)OR⁶(ii) a And

(f) two R connected by a linking group¹，R²，R³And R⁴In any combination of (1), the linking group is selected from C₁To C₂₅Linear, branched and cyclic alkylene and alkylenearyl groups of (a); wherein n is an integer from 1 to 25, R⁵Is an acid-labile group, R⁶Is selected from H, C₁To C₆Linear, branched and cyclic alkyl groups containing the above defined groups of formula II. In the copolymers of the present invention, a portion of the repeat units having structure I contain at least one epoxy functional pendant group.

Such exemplary embodiments may include a first repeat unit comprising 65 to 75 mole% of structural formula I, wherein R¹，R²And R³Is H, R⁴Is a decyl group, and 25 to 35 mole% of a second repeat unit of formula I, wherein R¹，R²And R³Is H, R⁴Is an epoxy group containing a group of formula II wherein A is methylene and R is²³And R²⁴Is H.

In the structural formula I, any R¹，R²，R³And R⁴May have the formula- (CH)₂)_nC(O)OR⁵In which R is⁵Are acid-labile groups, i.e., react catalytically in the presence of an acid from a carboxylic acid group. R⁵May be any suitable acid-labile group and includes, but is not limited to, -C (CH)₃)₃，-Si(CH₃)₃，-CH(R⁷)CH₂CH₃，-CH(R⁷)C(CH₃)₃Dicyclopropylmethyl, dimethylcyclopropylmethyl, and compounds defined by one or more of formulas IV-X:

and

wherein R is⁷Selected from H and C₁To C₆Linear, branched and cyclic alkyl groups.

In another exemplary embodiment of the invention, the copolymer backbone further comprises one or more repeat units selected from repeat units having structural units XI XV:

and

wherein X is as defined above and y is 0, 1, or 2; r¹²Is selected from C₁To C₆Linear, branched and cyclic alkyl groups of (a); r¹⁵Selected from H and C₁To C₄Linear and branched alkyl groups.

Further, for the exemplary embodiments, when the copolymer includes one or more of repeat units XI XV, those repeat units are present in an amount of at least 1 mole%, in some cases at least 2 mole%, and in other cases at least 3 mole% of the copolymer. In addition, the copolymer includes one or more of repeat units XI XV up to 10 mole%, in some cases up to 9 mole%, in other cases up to 7 mole%, and in some cases up to 5 mole%. One or more of the repeat units XI XV may be present in the copolymer within any of the numerical ranges described above.

Embodiments of the copolymer include repeat units of formula I that contain an epoxy functional group. Preferably, when suitably catalyzed, the epoxy groups crosslink with adjacent epoxy groups to produce a crosslinked polymer that is resistant to attack by solvents. Such epoxy functional group-containing repeat units are included in the copolymer at a level of at least 20 mole%, in some cases at least 25 mole%, and in other cases at least 35 mole%. In addition, repeat units comprising epoxy functionality are included in the copolymer at levels up to 95 mole%, in some cases up to 75 mole%, in other cases up to 60 mole%, in some cases up to 50 mole%, and in other cases up to 35 mole%. The amount of epoxy functional groups in the copolymer is determined based on the desired physical properties of the copolymer and/or the photodefinable layer and cured layer comprising or derived from the copolymer. The amount of epoxy functional groups in the copolymer can vary between any of the values recited above.

Such copolymer embodiments have excellent physical properties, particularly useful in lithographic compositions for electrical or electronic devices. Such as low moisture adsorption (less than 2 weight percent), low dielectric constant (less than 3.9 low modulus (less than 3gigapascal (gpa)), low curing temperature (less than 200 c), and good solubility in many common organic solvents.

In exemplary embodiments of the invention, the polymer composition is a low K composition. As low K compositions, the polymer compositions, photodefinable dielectric compositions containing the polymer compositions, and/or cured layers and/or films derived from such photodefinable dielectric compositions have a dielectric constant of less than 3.9. The dielectric constant of the polymer composition, photodefinable dielectric compositions containing the polymer composition, and/or cured layers and/or films derived from such photodefinable dielectric compositions typically is at least 2.2, in some cases at least 2.3, and in other cases at least 2.5. Likewise, the dielectric constant of the polymer composition, photodefinable dielectric compositions containing the copolymer, the polymer composition, and/or cured layers and/or films derived from such photodefinable dielectric compositions can be as high as 3.3, in some cases as high as 2.9, and in other cases as high as 2.6. The dielectric constant is sufficiently low to reduce propagation delay and mitigate crosstalk between wires in electrical and/or electronic devices comprising the inventive polymer composition. The dielectric constant of the copolymer, the polymer composition, photodefinable dielectric compositions containing the polymer composition, and/or cured layers and/or films derived from such photodefinable dielectric compositions can vary between any of the values recited above.

In exemplary embodiments of the present invention, the modulus of the copolymer, the polymer composition, photodefinable dielectric compositions containing the copolymer, and/or cured layers and/or films derived from such photodefinable dielectric compositions is generally at least 0.1GPa, in some cases at least 0.2GPa, and in other cases at least 0.3 GPa. Also, the modulus of the copolymers, polymer compositions, photodefinable dielectric compositions containing the copolymers, and/or cured layers and/or films derived from such photodefinable dielectric compositions can be up to 3GPa, in some cases up to 1GPa, and in other cases up to 0.7 GPa. When the modulus is too low, the material has an elastic viscosity and may be difficult to control in production. When the modulus is too high, high stress may be induced, creating reliability problems. The modulus of the copolymers, polymer compositions, photodefinable dielectric compositions containing the copolymers, and/or cured layers and/or films derived from such photodefinable dielectric compositions can vary between any of the values recited above.

In other exemplary embodiments, the polymer composition is a photodefinable dielectric composition containing a polymer composition having a moisture content of less than 2 weight percent, sometimes less than 0.8 weight percent, and sometimes less than 0.3 weight percent, and/or a cured layer and/or film derived from such a photodefinable dielectric composition. It is clear that this embodiment provides improved moisture barrier adsorption characteristics compared to other previously known photolithographic polymeric materials.

As discussed above, the mole% of the epoxy functional groups in the backbone of the copolymer determines many of the physical properties of the copolymer and/or photodefinable and cured layers containing or derived from the copolymer. As a non-limiting example, when the copolymer includes from 15 mole% to 95 mole% of repeating units containing an epoxy group, the copolymer generally has a moisture absorption of less than 2 weight percent and a dielectric constant of less than 3.3. In other non-limiting embodiments, when the copolymer includes from 20 mole% to 60 mole% of repeating units containing epoxy groups, the copolymer has a moisture absorption of less than 0.8 weight percent and a dielectric constant of less than 2.9; and when the copolymer includes from 25 mole% to 35 mole% of repeating units containing an epoxy group, the copolymer has a moisture absorption of less than 0.3 weight percent and a dielectric constant of less than 2.6.

"moisture absorption" as used herein is determined by measuring weight gain according to ASTM D570-98.

The copolymers of the present invention have a glass transition temperature of at least 170 ℃, sometimes at least 200 ℃, and sometimes at least 220 ℃. Also, the copolymers of the invention have glass transition temperatures of up to 350 ℃, sometimes up to 325 ℃, in other cases up to 300 ℃, and in some cases up to 280 ℃. The copolymer has a glass transition temperature that allows processing of the polymer composition, a lithographic composition comprising the copolymer, and a cured layer comprising the copolymer. By way of non-limiting example, the glass transition temperature is sufficient to allow continuous reflow during microchip production. The glass transition temperature of the copolymer may vary between any of the values recited above. The glass transition temperature of the copolymers used according to the invention was determined by means of Dynamic Mechanical Analysis (DMA) on a Rheometric scientific dynamic Analyzer Model RDAII commercially available from TAInstants, New Castle, DE, according to ASTM D5026-95 (temperature: increasing from ambient temperature to 400 ℃ at a rate of 5 ℃ per minute).

The copolymers of the present invention have a weight average molecular weight (Mw) of at least 10,000, in some cases at least 30,000, in other cases at least 50,000, in some cases at least 70,000, and in other cases at least 90,000. Also, such copolymers have a Mw of up to 500,000, sometimes up to 400,000, in other cases up to 300,000, in some cases up to 250,000, and in other cases up to 140,000. Mw is determined by Gel Permeation Chromatography (GPC) using poly (norbornene) standards. The Mw of the copolymer is sufficient to provide the desired physical properties to the copolymer and/or photodefinable layers and cured layers comprising or derived from the copolymer. The Mw of the copolymer can vary between any of the values recited above.

In an exemplary embodiment. The polymer composition further comprises a solvent selected from the group consisting of active and inactive compounds. The solvent may be one or more of hydrocarbon solvents, aromatic solvents, cycloaliphatic cyclic ethers, acetates, esters, lactones, ketones, amides, aliphatic mono-and polyvinyl ethers, cycloaliphatic mono-and polyvinyl ethers, aromatic mono-and polyvinyl ethers, cyclic carbonates, and mixtures thereof. Non-limiting examples of specific solvents that may be used include cyclohexane, benzene, toluene, xylene, 1,3, 5-trimethylbenzene, tetrahydrofuran, anisole, terpenoids, cyclohexene oxide, alpha-pinene oxide, 2, 2' - [ methylenebis (4, 1-phenyleneoxymethylene)) dioxirane, 1, 4-cyclohexenedimethanol divinyl ether, bis (4-vinyloxyphenyl) methane, cyclohexanone, and decalin.

Exemplary embodiments of the present invention comprise polymer compositions of photon-catalyzed negative-working photopolymer compositions useful as protective coatings for substrates for printer board applications, including redistribution layers for assembling multilayer devices and high density interconnected microporous substrates. As described in this exemplary embodiment, the polymer composition may be a photolithographic polymer composition that may be applied as a dielectric layer and patterned to encapsulate an integrated circuit against environmental and mechanical stress. In addition, the photolithographic compositions can be used as redistribution layers, passivation layers, and stress buffering materials for conventional wafer metrology, as well as logic wafer level packaging, Application Specific Integrated Circuits (ASICs), discrete memory and passive devices. Thus, the photodefinable polymer compositions can be used to fabricate electronic devices that include the photodefinable polymer compositions as active (e.g., stress buffer materials) or passive (e.g., passivation layers) features.

The copolymers of the invention can be prepared by vinyl addition polymerization. Monomer compositions comprising polycycloolefin monomers as described by structure I, and optionally structures XI XV, are polymerized in solution in the presence of the desired catalyst. Ethylene addition catalysts useful in preparing the copolymers of the present invention include nickel and palladium compounds as disclosed in PCT WO97/33198 and PCT WO 00/20472.

Non-limiting examples of vinyl addition catalysts useful in making the copolymers used in the present invention are represented by the formula:

E_n’Ni(C₆F₅)₂

wherein n' is 1 or 2 and E represents a neutral 2 electron donor ligand. When n' is 1, E is preferably a pi-arene ligand, such as toluene, benzene, and 1,3, 5-trimethylbenzene. When n' is 2, E is preferably selected from diethyl ether, THF (tetrahydrofuran), ethyl acetate (EtOAc) and dioxane. In exemplary embodiments of the invention, the ratio of monomer to catalyst in the reaction medium may be from about 5000: 1 to about 50: 1, and in another exemplary embodiment the ratio is from about 2000: 1 to about 100: 1. The reaction may be carried out at a temperature ranging from about 0 ℃ to about 70 ℃ in a suitable solvent. In an exemplary embodiment, the temperature may range from about 10 ℃ to about 50 ℃, and in another exemplary embodiment the temperature ranges from about 20 ℃ to about 40 ℃. Catalysts of the above formula that may be used to make the copolymers of the present invention include, but are not limited to, (toluene) bis (perfluorophenyl) nickel, (1, 3, 5-trimethylbenzene) bis (perfluorophenyl) nickel, (benzene) bis (perfluorophenyl) nickel, bis (tetrahydrofuran) bis (perfluorophenyl) nickel, bis (ethyl acetate) bis (perfluorophenyl) nickel, and bis (dioxane) bis (perfluorophenyl) nickel.

Suitable polymerization solvents for free radical and vinyl addition polymerization reactions include, but are not limited to, hydrocarbons and aromatic solvents. Hydrocarbon solvents useful in the present invention include, but are not limited to, alkanes and cycloalkanes such as pentane, hexane, heptane and cyclohexane. Non-limiting examples of aromatic solvents include benzene, toluene, xylene, and 1,3, 5-trimethylbenzene. Other organic solvents such as diethyl ether, tetrahydrofuran, acetates, e.g. ethyl acetate, esters, lactones, ketones and amides may also be used. Mixtures of one or more of the above solvents may be used as polymerization solvents.

When using the vinyl-addition nickel catalysts disclosed above, the molecular weight of the polymer can be controlled by using molecular weight modifiers such as those disclosed in U.S. Pat. No. 6,136,499, the disclosure of which is incorporated herein by reference in its entirety. In one aspect of the invention, alpha-olefins (e.g., ethylene, propylene, 1-hexene, and 1-decene, and 4-methyl-1-pentene))) are suitable for molecular weight control.

As indicated above, exemplary embodiments of the present invention also refer to photodefinable dielectric compositions that include the copolymers of the present invention and materials that can photonically form catalysts.

Any suitable material that can photonically form a catalyst can be used in the present invention. Non-limiting examples of suitable materials from which the catalyst may be photonically formed include photoacid generators and photobase generators.

When the photoacid generator is used as a material for forming a catalyst via photons, the photoacid generator may include one or more compounds selected from onium salts, halogen-containing compounds, and sulfonate salts. In an exemplary embodiment of the present invention, the photoacid generator comprises one or more compounds selected from the group consisting of: 4, 4' -tris (tert-butylphenyl) trifluoromethanesulfonate sulfonium salt; diphenyliodotetrakis (pentafluorinated phenyl) sulfonium borate; triaryl-sulfonium tetrakis (pentafluorophenyl) borate; triphenylsulfonium tetrakis (pentafluorophenyl) -borate sulfonium salt; 4, 4' -di-tert-butylphenyl tetrakis (pentafluorophenyl) borate; sulfonium tris (tert-butylphenyl) tetrakis (pentafluorophenyl) borate, and iodonium (4-methylphenyl-4- (1-methylethyl) phenyltetrakis (pentafluorophenyl) borate.

Such photoacid generators are present at levels sufficient to promote vulcanization and crosslinking. Thus, when such photoacid generators are used in the photodefinable dielectric composition, they are present in an amount of at least 0.5 weight percent, in some cases at least 0.75 weight percent, and in other cases at least 1 weight percent of the photodefinable dielectric composition. In some embodiments, the photo-acidity is present in an amount of up to 10 weight percent, in some cases up to 7.5 weight percent, and in other cases up to 5 weight percent of the photodefinable dielectric composition. The amount of photoacid generator in the photodefinable dielectric can vary between any of the values recited above.

Embodiments of the copolymers of the present invention are present in the photodefinable dielectric composition in an amount sufficient to provide the desired physical properties of the resulting composition, as well as the coated and cured layers formed from the dielectric composition described above. In some exemplary embodiments of the invention, the copolymer is present in the photodefinable dielectric composition in an amount of at least 5 weight percent, in some cases at least 15 weight percent, and in other cases at least 25 weight percent of the photodefinable dielectric composition. Also, the copolymer can be present in the photodefinable dielectric composition in an amount of up to 65 weight percent, in some cases up to 60 weight percent, and in other cases up to 55 weight percent. The copolymer content in the photodefinable dielectric can vary between any of the values recited above.

It is understood that exemplary embodiments of the present invention can include other suitable components and/or materials such as are required to make and utilize photodefinable dielectric compositions in accordance with the present invention. Such other suitable components and/or materials include one or more components selected from the group consisting of: sensitizer component, solvent, catalyst scavenger, tackifier, antioxidant, flame retardant, stabilizer, reactive diluent and plasticizer.

Where appropriate, the photodefinable dielectric compositions of the invention can contain any suitable sensitizer component. Such suitable sensitizer components include, but are not limited to, anthracenes, phenanthrenes, chrysenes, benzpyrenes, fluoranthenes, rubrenes, pyrenes, xanthones, indanthrenes, thioxanthen-9-ones, and mixtures thereof. In some exemplary embodiments, suitable sensitizer components include 2-isopropyl-9H-thioxanthen-9-one, 4-isopropyl-9H-thioxanthen-9-one, 1-chloro-4-propoxythioxanthone, phenothiazine, and mixtures thereof.

In exemplary embodiments of the present invention having a photonically formable catalyst material and a sensitizer component, the latter is present in the photodefinable dielectric composition in an amount of at least 0.1 percent by weight, in some cases at least 0.5 percent by weight, and in other cases at least 1 percent by weight of the photodefinable dielectric composition. Likewise, the sensitizer component can be present in the photodefinable dielectric composition in an amount of up to 10 weight percent, in some cases up to 7.5 weight percent, and in other cases up to 5 weight percent of the photodefinable dielectric composition. The amount of sensitizer component present in the photodefinable dielectric in this exemplary embodiment can vary between any of the values recited above.

When a catalyst scavenger is used in embodiments of the photodefinable dielectric composition, it can include an acid scavenger and/or a base scavenger. A non-limiting example of a suitable base scavenger useful in the present invention is trifluoromethyl sulfonamide. Non-limiting examples of acid scavengers useful in the present invention include secondary and/or tertiary amines such as pyridine, phenothiazine, tri (n-propylamine), triethylamine and lutidine in its isomeric form.

In exemplary embodiments of the present invention having a photonically formable catalyst species and a catalyst scavenger, the latter is present in the photodefinable dielectric composition in an amount of at least 0.1 percent by weight, in some cases at least 0.25 percent by weight, and in other cases at least 0.5 percent by weight of the photodefinable dielectric composition. Also, the catalyst scavenger is present in the photodefinable dielectric composition in an amount of up to 5 weight percent, in some cases up to 4 weight percent, and in other cases up to 3.5 weight percent of the photodefinable dielectric composition. The amount of catalyst scavenger present in the photodefinable dielectric composition in this exemplary embodiment can vary between any of the values recited above.

In exemplary embodiments of the invention, the solvent comprises a suitable active and/or inactive compound. Suitable solvent compounds include, but are not limited to, hydrocarbon solvents, aromatic solvents, cycloaliphatic cyclic ethers, acetates, esters, lactones, ketones, amides, cycloaliphatic vinyl ethers, aromatic vinyl ethers, cyclic carbonates, and mixtures thereof. In this exemplary embodiment, suitable solvent compounds include one or more compounds selected from the group consisting of: cyclohexane, benzene, toluene, xylene, 1,3, 5-trimethylbenzene, tetrahydrofuran, anisole, cyclohexene oxide, alpha-pinene oxide, 2, 2' - [ methylenebis (4, 1-phenylenemethylene oxide))) bis-ethylene oxide, 1, 4-cyclohexanedimethanol divinyl ether, bis (4-vinyloxyphenyl) methane, cyclohexanone and decalin.

In exemplary embodiments of the present invention, the solvent is present in the photodefinable dielectric composition in an amount of at least 20 percent by weight, in some cases at least 30 percent by weight, and in other cases at least 40 percent by weight, in some cases at least 45 percent by weight, and in other cases at least 50 percent by weight of the photodefinable dielectric composition. The solvent is present in an amount sufficient to provide the desired rheological properties, a non-limiting example being viscosity, to the photodefinable dielectric composition. Likewise, the solvent can be present in the photodefinable dielectric composition in an amount of up to 95 weight percent, in some cases up to 80 weight percent, and in other cases up to 70 weight percent, in some cases up to 60 weight percent of the photodefinable dielectric composition. The amount of solvent present in the photodefinable dielectric composition in this exemplary embodiment can vary between any of the values recited above.

Any suitable tackifier may be used in the present invention. Suitable adhesion promoters increase the adhesion strength between a layer of the photodefinable dielectric composition and a substrate coated thereon. In an exemplary embodiment of the invention, the adhesion promoter includes one or more compounds selected from the group consisting of 3-aminopropyltriethoxysilane and compounds described by structural formula XVI:

wherein z is 0, 1 or 2; r⁸Is selected from C₁To C₂₀Linear, branched and cyclic alkylene groups of (a) containing alkylene oxide and poly (alkylene oxide) linking groups of from 2 to 6 carbon atoms, wherein the alkylene portion of the repeating group contains 2 to 6 carbon atoms and the poly (alkylene oxide) has a molecular weight of from 50 to 1,000; each occurrence of R⁹Independently selected from C₁To C₄Linear and branched alkyl groups of (a); and each occurrence of R¹⁸Selected from H and C₁To C₄Linear and branched alkyl groups.

Any suitable reactive diluent may be used in the present invention. Suitable reactive diluents improve one or more physical properties of the photodefinable dielectric composition and/or a coating formed from the photodefinable dielectric composition. In some exemplary embodiments, the reactive diluent comprises one or more compounds selected from epoxides and compounds described by structural units XVII and XVIH:

CH₂＝CH-O-R¹⁰-O-CH＝CH₂ (XVII).

CH₂＝CH-O-R¹¹ (XVIII)

wherein R is¹⁰Is selected from C₁To C₂₀Linear, branched and cyclic alkylene, arylene and alkarylene radicals, alkylene oxides containing from 2 to 6 carbon atoms, poly (alkylene oxide) linking radicals in which the alkylene part of the repeating group contains from 2 to 6 carbon atoms and the poly (alkylene oxide) has a molecular weight of from 50 to 1,000, [ - - -R¹³--N--C(O)O-]_m--R¹³Wherein each occurrence of R¹³Independently selected from C₁To C₂₀Linear, branched and cyclic alkylene, aryleneAlkyl and alkylene aryl, and m is an integer from 1 to 20; and R¹¹Is selected from C₁To C₂₀Linear and branched alkyl and alcohol alkyl groups of (a).

In still further exemplary embodiments, the reactive diluent comprises one or more reactive diluents selected from the group consisting of 1, 4-butanediol vinyl ether, 1, 6-hexanediol vinyl ether, 1, 8-octanediol vinyl ether, 1, 4-dimethanol cyclohexane vinyl ether, 1, 2-ethylene glycol vinyl ether, 1, 3-propylene glycol vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 1, 4-butanediol vinyl ether, 1, 6-hexanediol vinyl ether, and 1, 8-octanediol vinyl ether.

In exemplary embodiments of the present invention, the reactive diluent is present in the photodefinable dielectric composition in an amount of at least 0.5 percent by weight, in some cases at least 1 percent by weight, and in other cases at least 2.5 percent by weight, in some cases at least 5 percent by weight, and in other cases at least 7.5 percent by weight of the photodefinable dielectric composition. The reactive diluent is present in an amount sufficient to provide the photodefinable dielectric composition and a coating formed from the photodefinable dielectric composition with the desired physical properties. Likewise, the reactive diluent is present in the photodefinable dielectric composition in an amount of up to 95 weight percent, in some cases up to 60 weight percent, and in other cases up to 30 weight percent, in some cases only 1 weight percent of the photodefinable dielectric composition. The amount of reactive diluent present in the photodefinable dielectric composition in this exemplary embodiment can vary between any of the values recited above.

When the photodefinable dielectric composition includes a solvent and/or a reactive diluent, the photodefinable dielectric composition is in the form of a fluid liquid solution.

In exemplary embodiments of the invention, the solution viscosity of the photodefinable dielectric composition is at least 10 Centipoise (CPS), in some cases at least 100CPS, and in other cases at least 500 CPS. Also, the solution viscosity of the photodefinable dielectric composition is up to 25,000cps, in some cases up to 20,000cps, in other cases up to 15,000cps, in some cases up to 10,000cps, in other cases up to 5,000cps, and in some cases up to 3,000 cps. The solution viscosity was measured at 25 ℃ on a Brookfield DV-E viscometer, available from Brookfield Engineering Laboratories, Middleboro, Mass., using a suitable spindle. The viscosity of the photodefinable dielectric composition present in this exemplary embodiment can vary between any of the values recited above.

One exemplary embodiment of the present invention is directed to a method of forming a photolithographic layer on a substrate. The method comprises providing a substrate, coating at least one side of the substrate with the photodefinable dielectric composition described above, exposing the coated layer to radiation, and curing the radiation-exposed layer.

Any suitable coating method can be used to coat the substrate with the photodefinable dielectric composition. In exemplary embodiments, suitable coating methods include, but are not limited to, spin coating, dip coating, brush coating, roll coating, spray coating, solution casting, fluidized bed deposition, extrusion coating, curtain coating, meniscus coating, mask or stencil printing, and the like. In an exemplary embodiment of the present invention, spin coating as well as curtain coating is utilized because the method has simple and highly consistent characteristics. Cast films from the photodefinable dielectric compositions have properties such as toughness, high resistance to solvents, unusual pinhole defects, excellent planarity, and adhesion, among other properties.

The coating layer may be exposed using any suitable energy source for exposure. Suitable energy sources include radiation. Non-limiting examples of radiation sources include, but are not limited to, photon irradiation and/or electron beams. Non-limiting examples of photon irradiation are ultraviolet irradiation at wavelengths from 200nm to 700nm, sometimes 300nm to 500nm, sometimes 360nm to 440 nm. In a further non-limiting example, the radiation dose is from 50mJ/cm²To 2,000mJ/cm²。

In an exemplary embodiment, a method of forming a photodefinable layer on a substrate includes the step of forming a pattern in a cured layer. By way of non-limiting example, the pattern may be formed by reverse developing the exposed layer. In exemplary embodiments, when the layer is exposed imagewise, it is typically imaged by photon irradiation of a light-shielding film, non-limiting examples of which include electron beam, X-ray, ultraviolet or visible radiation. Suitable radiation sources include mercury, mercury/xenon, xenon lamps, KrF lasers, X-rays or electron beams. Reverse development exposure of the photodefinable dielectric composition of the invention can be achieved at many different wavelengths as described above. In areas where the photon radiation attacks the lithographic coating, the sensitizer or photoacid generator can be effective to induce the formation of free acid. The free acid catalyzes the crosslinking of pendant epoxy groups on the polymer backbone, which in turn converts the photonic image region of the polymer from a solvent soluble state to a solvent insoluble state. The soluble regions (non-photonically patterned regions of the polymer) are readily removed with a suitable solvent developer.

In an exemplary embodiment, a method of forming a photolithographic layer on a substrate includes the step of developing the layer. Any suitable solvent-based developer may be used in the present invention. Suitable developers are those that can remove soluble portions from a cured layer formed from the photodefinable dielectric composition. Suitable developers include, but are not limited to, toluene, 1,3, 5-trimethylbenzene, xylene, decalin, limonene and BioAct EC-7R (terpene diene-based solvent component formulated with a surfactant) available from Petroferm corporation, Fernandina Beach, FL.

Any suitable solvent development process may be used in the present invention. In exemplary embodiments, suitable solvent development methods include, but are not limited to, spraying, stirring, and/or immersion methods. Spray development includes the step of spraying the patterned polymer coated substrate with an atomized continuous stream or a dispersed stream of developer for a period of time sufficient to remove the non-crosslinked polymer from the substrate. The polymer coated substrate may be subjected to a final wash with a suitable solvent such as alcohol. Agitation and immersion techniques include agitating a developing solvent throughout the patterned coating or immersing the patterned coating substrate in a developing solvent to dissolve the non-crosslinked polymer, and then rinsing the developed substrate with a developing solvent or other suitable solvent (e.g., alcohol). In all of the above development techniques, the developed coating matrix can be spin coated at high speed to remove residual solvents and solutes.

A method of forming a photodefinable layer on a substrate includes a curing step. In an exemplary embodiment of the present invention, the curing step is followed by a reverse development exposure step. The curing step may include a burn-in cycle. The bake cycle can increase the reaction rate of the epoxy crosslinking reaction. The acid of the photoacid generator has an increased mobility during curing, allowing the acid to find and react with the non-crosslinked epoxy functional groups, thereby further etching the pattern. In an exemplary embodiment of the invention, the curing step is carried out in an oven under an inert gas (e.g., nitrogen, argon or helium) at a temperature ranging from about 50 ℃ to 200 ℃ for a period of between 5 minutes and 60 minutes; or from about 100 ℃ to about 150 ℃ for a period of between 10 minutes and 40 minutes; or from about 110 ℃ to about 130 ℃ for a period of time between 15 minutes and 30 minutes; or from about 90 c to about 200 c for a period of from 1 minute to 60 minutes.

When the photodefinable layer is exposed to radiation and cured, the layer is in the form of a film that covers at least a portion of the surface of the substrate. The film can be of any suitable film thickness, typically defining the number, orientation and configuration of the conductive lines that provide the lithographic product. In exemplary embodiments, the thin film formed as described above has a thickness of at least 0.1 microns, in some cases at least 0.2 microns and in other cases at least 0.5 microns. Also, the films formed by the present invention have a thickness of up to 500 microns, sometimes up to 400 microns, in other cases up to 300 microns, sometimes up to 250 microns, sometimes up to 200 microns, in some cases up to 100 microns, sometimes up to 50 microns. In an exemplary embodiment, the film thickness is a function of solution concentration, spin speed, and spin time. In this exemplary embodiment, the film thickness in the radiation exposed and cured photodefinable layer can vary between any of the values recited above.

An exemplary embodiment of a method of forming a photolithographic layer on a substrate includes a soft bake cycle. In this exemplary embodiment, a soft-bake cycle is used to remove the remaining solvent. The soft bake cycle also relaxes the stresses generated from the flow of the photoresist film, increases the adhesion of the film to the substrate, and hardens the film for easier handling during processing. The soft-bake cycle is conducted under any suitable conditions. Suitable conditions include those sufficient to remove residual solvent, but avoid oxidation or thermal curing of the resin or undesirable reaction of formulation additives, and to render the resin sufficiently fluid to promote planarization. The conditions may vary depending in part on the composition of the polymer comprising the formulation. Suitable soft-bake conditions include, but are not limited to, temperatures of at least 90 ℃, sometimes at least 100 ℃, and in other cases at least 110 ℃ and up to 140 ℃, sometimes up to 130 ℃, and in other cases up to 120 ℃ for at least 1 minute, sometimes at least 2 minutes, in other cases at least 5 minutes and up to 30 minutes, sometimes up to 20 minutes, and in other cases up to 10 minutes. The soft-firing can be carried out in a convection oven, a belt oven or on a hot plate. Suitable sintering gases include vacuum, solvent vapors, air, and inert gases such as nitrogen, argon, and helium.

In an exemplary embodiment of a method of forming a photolithographic layer on a substrate, the method includes a final bake step. In this step, the solvent-developed coated substrate is subjected to a final bake in an oven at a temperature ranging from about 50 ℃ to about 200 ℃ in an inert gas atmosphere (e.g., nitrogen, argon, or helium), and sometimes at a temperature ranging from 100 ℃ to 200 ℃ and any remaining developing and/or rinsing solvent is removed. In some embodiments, it has been found that blanket exposure of the coating layer as part of the final bake step is effective in achieving the final bake. Typically this exposure is complementary to the thermal post-bake and has an energy ranging from about 200mJ to about 500 mJ.

The crosslinking reaction is completed as the thermal curing epoxy polymer continues to react through a variety of curing steps and through the cumulative effect of the various curing steps. In an exemplary embodiment of the invention, the glass transition temperature of the crosslinked polymer film has been increased from 180 ℃ to greater than 250 ℃ after the final firing step. As is known to those skilled in the art, the final glass transition temperature of a thermoset polymer is generally equivalent to the vulcanization temperature used for final cure. This is due to the limitation of molecular mobility when the cured polymer transitions from an elastic solid to a glassy solid at the Tg temperature. An important advantage of the lithographic composition of the present invention is that the final cure temperature is lower than the Tg of the non-crosslinked polymer solid, however, after the crosslinking reaction is complete, an increase in Tg to 70 ℃ is observed via Dynamic Mechanical Analysis (DMA).

In exemplary embodiments of the present invention and in place of the photo development and subsequent pattern development, the desired features may be fabricated by known etching techniques on the crosslinked film deposited from the polymer composition of the present invention. In this exemplary embodiment, the polymer composition layer is formed by the steps comprising: providing a substrate, fixing the film to the substrate by applying a solution of a substance comprising a photo-forming catalyst and a polymer composition of the invention, and thermally curing the solution.

In other exemplary embodiments, the method may include a soft-burn step as described above. In this exemplary embodiment, rather than photocrosslinking the coating or film to deposit the desired areas, the entire film is thermally crosslinked. Selected features are then etched into the crosslinked film to form a pattern by a suitable etching technique, such as, for example, reactive ion etching (r.i.e.) or laser ablation of selected wavelengths. The thermal crosslinking reaction is initiated via the thermal curing agent, and an acid is generated upon thermal activation. The thermally generated acid in turn catalyzes the crosslinking reaction of the epoxy functionality. The thermal curing agent or thermal acid generator includes many of the photoacid generators described above. In addition to photoactivation, photoacid generators are known to be activated at high temperatures. Typically, the activation temperature ranges from about 25 ℃ to about 250 ℃. Suitable thermal acid generators include onium salts, halogen-containing compounds, and sulfonates as exemplified above. It will be apparent to those skilled in the art that any thermally activated initiator may be used so long as it is capable of initiating a crosslinking reaction of the epoxy functional groups on the polymer backbone. Examples of such thermal curing agents or thermal acid generators include, but are not limited to, imidazoles, primary, secondary, and tertiary amines, quaternary ammonium salts, anhydrides, polysulfides, polythiols, carbolic acids, carboxylic acids, polyamides, quaternary phosphonium salts, and combinations thereof.

The coated, patterned, developed and cured films of the present invention have superior properties such as low dielectric constant, low moisture absorption, toughness, high resistance to solvents, and adhesion among other properties. Polymer films having at least some properties are useful in the fabrication of microelectronic devices having high density packaging, interconnections, and fine features such as microvoids as desired.

The layers formed from the photodefinable dielectric compositions of the invention and the cured and patterned layers and films produced using the methods described herein, along with their associated substrates, can be used as or as components of electrical and/or electronic devices. In an exemplary embodiment of the invention, the electrical and/or electronic device is a semiconductor device. In another exemplary embodiment, the electrical or electronic device is selected from the group consisting of a logic wafer, a passive device, a memory wafer, a micro-electromechanical system (MEMS) wafer, a micro-optical-electromechanical system (MOEMS) wafer, and an Application Specific Integrated Circuit (ASIC) wafer.

The following examples are for illustrative purposes and are not intended to limit the invention in any way. The proportion of repeating units incorporated into the polymer backbone is expressed in mole weight percent.

Examples

Example 1

(Synthesis of Polymer)

This example describes the synthesis of 50/50 copolymer polymerized from decyl norbornene/glycidyl methyl ether norbornene. All glassware was dried under a vacuum of 0.1 mm Hg at 60 deg.C for 18 hours. The glassware was then transferred to an oven and the reaction vessel was loaded into the oven. To the reaction vessel were added ethyl acetate (917g), cyclohexane (917g), decyl groupNorbornene (137G, 0.585mol) and glycidyl methyl ether norbornene (105G, 0.585 mol). The reaction vessel was then removed from the oven and connected to a dry nitrogen line. The reaction medium was then degassed by passing a stream of nitrogen through the solution for 30 minutes. Inside the oven, 9.36g (19.5mmol) of the nickel catalyst, i.e., bis (toluene) bis (perfluorophenyl) nickel, was dissolved in 15mL of toluene, taken up in a 25mL syringe, removed from the oven and injected into the reactor. The reaction was stirred at 20 ℃ for 5 hours. At this point a solution of peracetic acid (50 moles based on 975mmol of nickel catalyst) diluted with approximately 250ml of deionized water glacial acetic acid and 33g of 30 wt% hydrogen peroxide diluted with approximately 250ml of deionized water was added and the solution was stirred for 18 hours. The stirring was stopped and the water and solvent layers were allowed to separate. The aqueous layer was removed and 1 liter of distilled water was added. The solution was stirred for 20 minutes. The aqueous layer was separated and removed. The washing was performed 3 times in total with 1 liter of distilled water. The polymer was then deposited by addition to methanol. The solid polymer was recovered by filtration and dried in a vacuum oven at 60 ℃. After drying, 222g of dry polymer (94% conversion) were collected. The molecular weight of the polymer measured by GPC was 114,000 Mn 47,000, and the degree of Polymerization Distribution (PDI) was 2.42. The Tg of the polymer was DMA ═ 180 ℃.¹The polymer composition by H NMR was 48 mole% decyl norbornene: 52 mole% of epoxynorbornene.

Example 2

(Synthesis of Polymer)

This example describes the synthesis of 70/30 copolymer polymerized from decyl norbornene/glycidyl methyl ether norbornene. All glassware was dried under a 0.1 mm Hg vacuum at 60℃ for 18 hours. The glassware was then transferred to an oven and the reaction vessel was placed into the oven. Ethyl acetate (917g), cyclohexane (917g), decyl norbornene (192g, 0.82mol) and glycidyl methyl ether norbornene (62g, 0.35mol) were added to the reaction vessel. The reaction vessel was then removed from the oven and connected to dry nitrogen. The reaction medium was then degassed by passing a stream of nitrogen through the solution for 30 minutes. In an oven, 9.36g (19.5mmol) of a nickel catalyst, i.e., bis (toluene) bis (perfluorophenyl)) The nickel was dissolved in 15mL toluene, sucked into a 25mL syringe, removed from the oven and injected into the reactor. The reaction was stirred at 20 ℃ for 5 hours. At this point a solution of peracetic acid (50 moles based on 975mmol of nickel catalyst) diluted with approximately 250ml of deionized water glacial acetic acid and 33g of 30 wt% hydrogen peroxide diluted with approximately 250ml of deionized water was added and the solution was stirred for 18 hours. The stirring was stopped and the water and solvent layers were allowed to separate. The aqueous layer was removed and 1 liter of distilled water was added. The solution was stirred for 20 minutes. The aqueous layer was separated and removed. The washing was performed 3 times in total with 1 liter of distilled water. The polymer was then deposited by addition to methanol. The solid polymer was recovered by filtration and dried in a vacuum oven at 60 ℃. After drying, 243g of dry polymer (96% conversion) were collected. The molecular weight of the polymer measured by GPC was 115,366 Mn 47,424, and the degree of Polymerization Distribution (PDI) was 2.43. By passing¹The composition of the polymer for the H NNM assay was: 70 mole% of decyl norbornene; 30 mole% of glycidyl methyl ether norbornene.

Example 3

(Polymer Synthesis)

Synthesis of 40/60 copolymer from decyl norbornene/glycidyl methyl ether norbornene was prepared in the following manner. All glassware was dried at 160 ℃ for 18 hours. The dried glassware was transferred to an oven and the reaction vessel was placed into the oven. Toluene (670g), decyl norbornene (29.43g, 0.144mol), glycidyl methyl ether norbornene (16.6g, 0.212mol) were added to a 1L reaction vessel. The reaction vessel was then removed from the oven and connected to dry nitrogen. The reaction medium was then degassed by passing a stream of nitrogen through the solution for 30 minutes. Inside the oven, 1.59g (3.63mmol) of bis (toluene) bis (perfluorophenyl) nickel catalyst was dissolved in 7ml of toluene, taken up in a 10ml syringe, removed from the oven and injected into the reactor. The reaction was stirred at 20 ℃ for 1 hour. At this point Amberlite * IRC-718 ion exchange resin was added to the reaction vessel and the reaction stirred at ambient temperature for 5 hours. The solution was filtered to remove the resin and the polymer was then precipitated by addition to 3L of methanol. The solid polymer was recovered by filtration and dried overnight in a vacuum oven at 60 ℃. After drying74.0g of dry polymer (92.5% conversion) was collected. Mw is 164,941 Mn 59,454, PDI is 2.77,¹the polymer composition by H NMR was: 41 mole% decyl norbornene, 59 mole% glycidyl methyl ether norbornene.

Example 4

(Polymer Synthesis)

This example describes the synthesis of a copolymer polymerized from decyl norbornene/glycidyl ether norbornene (70/30) having different molecular weights. The synthesis was carried out under an inert gas atmosphere of nitrogen. Glassware was washed with Alconox * detergent and rinsed three times with distilled water. All glassware was dried overnight in a pressurized air oven at 120 ℃. The solvent and monomers were degassed by passing a stream of dry nitrogen through the liquid for at least 1 hour prior to use. Solutions of the catalyst and cocatalyst were prepared in a dry box. The catalyst was prepared by dissolving 0.00189g (allyl) palladium (tricyclohexylphosphine) trifluoroacetate (756g/mol) in 0.4mL of dichloromethane to produce a 0.00625 molar solution. 457X 10 are produced by dissolving 0.011g of lithium tetrakis (pentafluorophenyl) borate (875g/mol) in 25g of toluene^-9The cocatalyst is prepared from the mol/mL solution of (A). 1-hexene was added as a chain transfer agent in the portion described in the table below to control the molecular weight. To a dry snap-on cap vial was added solvent, monomer, catalyst and cocatalyst in the following order:

TABLE I

Reagent	Quality (g)	MW(g/mol)	Molar mass (mol)
				1. Toluene	50
2. Monomer
				AGE-NB	2.05g	234	8.75mmol
decyl-NB	0.68g	162	3.75mmol
				3.1-hexene	0.42-0.84g	84.16	40-80mol％
4.LiFABA	0.0109	875g/mol	0.0125mmol
				Pd catalyst	0.00189g	756g/mol	0.0025mmol

GE-NB ═ glycidyl methyl ether norbornene

decyl-NB ═ decyl norbornene

LifABA ═ lithium tetrakis (pentafluorophenyl) borate

Palladium catalyst (allyl) palladium (tricyclohexylphosphine) trifluoroacetate salt

The addition of the individual components is accompanied by continuous stirring. The sample vial was snap-capped under nitrogen and placed in a fume hood where it was immersed in a 30 ℃ silicon oil bath with stirring for 4.5 hours. The sample was then opened and the deposition was carried out by dropping the viscous solution into methanol. The resulting solid was filtered through a glass fritted funnel of size M. To ensure that all traces of residual monomer are eliminated, the deposited polymer is dissolved in toluene and deposited in methanol. The deposited polymer was recovered by filtration and dried under vacuum at 70 ℃ for 18 hours and weighed.

Reaction of	Mol% of 1-hexene	Conversion rate%	Molecular weight (Mw/Mn)	PDI
					1	40	85	192/71	2.70
2	60	89	93/36	2.58
					3	80	59	56/28	2.00

Example 5

(Polymer Synthesis)

50/50 copolymer was prepared by polymerization of hexyl norbornene and 5-norbornene-2-methyl-2, 3-epoxypropyl carboxylate according to the following procedure. A25 ml Wheaton serum bottle and magnetic stir bar were placed in an oven and dried for 18 hours at 160 ℃. The dry bottle was transferred to an oven under nitrogen atmosphere. The vial was charged with hexyl norbornene (1.78g, 0.01mol), 5-norbornene-2-methyl-2, 3-epoxypropylcarboxylate (2.08g, 0.01mol) and 12.0g of toluene. The bottle was sealed with a snap-on cap of Teflon * and transferred to a fume hood. The reaction medium was then degassed by bubbling dry nitrogen through the solution for 10 minutes. Inside the oven, bis (toluene) bis (perfluorophenyl) nickel catalyst (0.0973g, 0.20mmol) was dissolved in 3.3ml of toluene, taken up in a 10ml syringe, removed from the oven and injected into the reaction vial. The reaction mixture was stirred at room temperature for 48 hours. To the reaction flask was added 0.56g of Amberlite * IRC-718 ion exchange resin available from Rohm and Haas and the solution was further mixed for 5 hours. The resin was removed by filtration. The polymer was precipitated into 100mL of methanol and recovered by filtration. The deposited polymer was washed with 25mL of methanol and dried in a vacuum oven at 60 ℃ for 18 hours. 1.80g (47% yield) of dry polymer was recovered.

Example 6

(Polymer Synthesis)

Synthesis of 65/25/10 copolymer from decyl norbornene/glycidyl methyl ether norbornene/t-butyl ester norbornene was prepared in the following manner. All glassware was dried at 160 ℃ for 18 hours. The dried glassware was transferred to an oven and the reaction vessel was placed into the oven. Toluene (750g), decyl norbornene (56.2g, 0.24mol), glycidyl methyl ether norbornene (16.6, 0.091mol) and tert-butyl ester norbornene (7.17g, 0.088mol) were added to a 1L reaction vessel. The reaction vessel was then removed from the oven and connected to dry nitrogen. The reaction medium was then degassed by passing a stream of nitrogen through the solution for 30 minutes. Inside the oven, 1.80g (4.1mmol) of bis (toluene) bis (perfluorophenyl) nickel catalyst was dissolved in 8ml of toluene, taken up in a 10ml syringe, removed from the oven and injected into the reactor. The reaction was stirred at 20 ℃ for 1 hour. At this time 180g of Amberlite * IRC- -718 ion exchange resin was added to the reaction vessel and the reaction was stirred at room temperature for 5 hours. The solution was filtered to remove the resin and the polymer was then precipitated by addition to 3L of methanol. The solid polymer was recovered by filtration and dried in a vacuum oven at 60 ℃ overnight. 74.0g of dry polymer (92.5% conversion) was collected after drying. Mw is 122,208 Mn 50,743 and PDI is 2.41.

Example 7

(Polymer Synthesis)

A synthetic 65/25/10 copolymer was prepared from hexyl norbornene/glycidyl methyl ether norbornene/t-butyl ester norbornene in the following manner. All glassware was dried at 160 ℃ for 18 hours. The dried glassware was transferred to an oven and the reaction vessel was placed into the oven. Toluene (750g), hexyl norbornene (51.39g, 0.288mol), glycidyl methyl ether norbornene (19.98g, 0.11mol) and tert-butyl ester norbornene (8.62g, 0.044mol) were added to a 1L reaction vessel. The reaction vessel was then removed from the oven and connected to dry nitrogen. The reaction solution was then degassed by passing a stream of nitrogen through the solution for 30 minutes. Inside the oven, 2.16g (4.9mmol) of bis (toluene) bis (perfluorophenyl) nickel catalyst was dissolved in 8ml of toluene, taken up in a 10ml syringe, removed from the oven and injected into the reactor. The reaction was stirred at 20 ℃ for 1 hour. At this time 180g of Amberlite * IRC-718 ion exchange resin was added to the reaction vessel and the reaction was stirred at room temperature for 5 hours. The solution was filtered to remove the resin and the polymer was then precipitated by addition to 3L of methanol. The solid polymer was recovered by filtration and dried overnight in a vacuum oven at 60 ℃. After drying 69.8g of dry polymer (87.2% conversion) was collected. Mw is 127,866 Mn 51,433 and PDI is 2.48.

Example 8

(Polymer Synthesis)

This example describes the preparation of 40/55/5 copolymer from decyl norbornene/glycidyl methyl ether norbornene/triethoxysilyl norbornene. All glassware was dried at 160 ℃ for 18 hours. The dried glassware was transferred to an oven and the reaction vessel was placed into the oven. To the reaction vessel were added ethyl acetate (280g), cyclohexane (280g), decyl norbornene (34.7g, 0.16mol), glycidyl methyl ether norbornene (39.6, 0.22mol) and triethoxysilyl norbornene (2.56g, 0.01 mol). The reaction vessel was then removed from the oven and connected to dry nitrogen. The reaction solution was then degassed by passing a stream of nitrogen through the solution for 30 minutes. Inside the oven, 1.92g (4.0mmol) of bis (toluene) bis (perfluorophenyl) nickel catalyst was dissolved in 15ml of toluene, taken up in a 25ml syringe, removed from the oven and injected into the reactor. The reaction was stirred at 20 ℃ for 5 hours. At this time, 1.93g of 8-hydroxyquinoline (8-HQ) was added to the reaction vessel and the reaction was stirred at room temperature for 18 hours. The 8-HQ/nickel chelate was removed with methanol (5X 200 mL). To the reaction vessel was added 50g of Amberlite * IRC-718 ion exchange resin and the solution was stirred at room temperature overnight. The resin particles were removed by filtration and the polymer was precipitated by addition to methanol. The solid polymer was recovered by filtration and dried in a vacuum oven at 60 ℃ overnight. After drying 55.0g of dry polymer (76% conversion) was collected. The Mw of the polymer was 174,000 and Mn was 60,000 daltons. The polydispersity index is 2.9.

Example 9

(preparation of a PhotolithogrAN _ SNhic composition)

A polymer solution was prepared using 256.5g of the polymer obtained in example 2. The polymer was added to a 1-liter wide-mouth glass bottle and 313.5g of electronic grade 1,3, 5-trimethylbenzene were added. The bottles were sealed with a Teflon * polyethylene cap and the polymer was uniformly dispersed by spin coating the bottles at 50rpm for 18 hours. The polymer solution was filtered through a 0.45micron Teflon * filter to remove any particulate matter. This operation was performed in a laminar flow hood of a class 1000 clean room. The filtered polymer solution was collected in a class 1000 clean room bottle. The final concentration of the polymer was determined gravimetrically to be 45.0wt. % of the total weight of the composition. 20.0g of the polymer solution was weighed into a 50-ml amber clean bottle. All additives were weighed separately into 10-mL beakers and then dissolved in 5.0g of anisole. The additive package included Rhodorsil * PI 2074 (4-methylphenyl-4- (1 methylethyl) phenyl tetrakis (pentafluorophenyl) borate iodine salt) obtained from Rhodia. (0.2757g, 2.71X 10^-4mol), SpeedCure * CPTX 1-chloro-4-propoxy-9H-thioxanthone (0.826g, 0.271mmol) obtained from Lambson group, phenothiazine (Aldrich chemical) (0.054g, 0.271mmol), and Irganox * 1076 antioxidant (3, 5-di-tert-butyl-4-hydroxycinnamate) obtained from Ciba refining chemicals. (0.1378g, 2.60X 10^-4mol). The material was dissolved in 5.0g of anisole and the solution was filtered through a 0.22 micron syringe filter as it was added to the polymer solution. The solution was spun at 50rpm for 18 hours to disperse the additives in the polymer solution.

Example 10

(preparation of a PhotolithogrAN _ SNhic composition)

256.5g of the polymer obtained in example 2 were used to prepare a 45% by weight solution of the polymer in 1,3, 5-trimethylbenzene as described in example 9. 20.0g of polymer solution (45.0 wt.% solids) was weighed into a 50-ml amber clean bottle. Adding the preparation into the preparationWeighed into a 10-mL beaker and then dissolved in 5.0g of anisole. The additives were Rhodorsil * 2074 (4-methylphenyl-4- - (1 methylethyl) iodobenzene tetrakis (pentafluorophenyl) borate) (0.184g, 0.181mmol), isopropyl-9H-thioxanthen-9-one (First Cure ITX Albemarle 0.046g, 0.181mmol), phenothiazine (Aldrich Chemical Co.0.036g, 0.181mmol) and Irganox * 1076 antioxidant (CIBA refining Chemical) (0.1378g, 2.60X 10 antioxidant)^-4mol). The material was dissolved in 5.0g of anisole and the solution was filtered through a 0.22 micron syringe filter as it was added to the polymer solution. The solution was spun at 50rpm for 18 hours to disperse the additives in the polymer solution.

Example 11

(preparation of a PhotolithogrAN _ SNhic composition)

A polymer solution was prepared using 228.0g of the polymer obtained in example 2. The polymer was added to a 1-liter wide-mouth glass bottle and 342.0g of decalin was added. The bottle was sealed with a Teflon * polyethylene cap and the polymer was uniformly dispersed by spin coating the bottle at 50rpm for 18 hours. The polymer solution was filtered through a 0.45micron Teflon * filter to remove any particulate matter. This operation was performed in a laminar flow hood of a class 1000 clean room. The filtered polymer solution was collected in a clean (0 particles larger than 0.5 micron-Eagle Pitcher Co.) glass bottle. The final concentration of the polymer was determined gravimetrically to be 40.0 wt%. 20.0g of the polymer solution was weighed into a 50-ml amber clean bottle. All additives were weighed into 10-mL beakers and then dissolved in 5.0g of anisole. The additive package included Rhodorsil * 2074 (4-methylphenyl-4- (1 methylethyl) phenyl tetrakis (pentafluorophenyl) borate iodide obtained from Rhodia (0.2757g, 2.71X 10)^-4mol), isopropyl-9H-thioxanthen-9-one (First Cure ITXAlbemarle 0.046g, 0.181mmol), phenothiazine (Aldrich Chemical Co.) (0.054g, 0.271mmol) and Irganox * 1076 antioxidant (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) (CIBA finishing chemicals) (0.1378g, 2.60X 10)^-4mol). The material was dissolved in 5.0g of anisole and the solution was filtered through a 0.22 micron syringe filter as it was added to the polymer solutionA device. The solution was spun at 50rpm for 72 hours to disperse the additives in the polymer solution.

Example 12

(preparation of a PhotolithogrAN _ SNhic composition)

A polymer solution was prepared as described in example 9. 20.0g of the polymer solution (45.0 wt.% solids) containing the polymer synthesized in example 1 was weighed into a 50-ml amber clean bottle. The formulation additives were weighed into 10-mL beakers and then dissolved in 5.0g of anisole. The additives were Rhodorsil * PI 2074 (4-methylphenyl-4- (1 methylethyl) phenyltetrakis (pentafluorophenyl) borate (0.184g, 0.181mmol), isopropyl-9H-thioxanthen-9-one (firstCure ITX 0.046g, 0.181mmol), phenothiazine (Aldrich Chemical Co.0.036g, 0.181mmol) and Irganox * 1076 antioxidant (CIBA finishing Chemical) (0.1378g, 2.60X 10. sup. th.^-4mol). The material was dissolved in 5.0g of anisole and the solution was filtered through a 0.22 micron syringe filter as it was added to the polymer solution. The solution was spun at 50rpm for 18 hours to disperse the additives in the polymer solution.

Example 13

(preparation of a PhotolithogrAN _ SNhic composition)

A polymer solution was prepared as described in example 11. 20.0g of the polymer solution (40.0 wt.% solids) containing the polymer synthesized in example 2 was weighed into a 50-ml amber clean bottle. The formulation additives were weighed into 10-mL beakers and then dissolved in 5.0g of anisole. Additives are Rhodorsil * PI 2074 (4-methylphenyl-4- (1 methylethyl) phenyltetrakis (pentafluorophenyl) borate) (0.184g, 0.181mmol), isopropyl-9H-thioxanthen-9-one (FirstCure 0.046g, 0.181mmol), phenothiazine (Aldrich Chemical Co.0.036g, 0.181mmol), Irganox * 1076 antioxidant (CIBA finishing Chemical) (0.1378g, 0.26mmol) and 3-glycidoxypropyltrimethoxysilane (Sigma- -Aldrich) (0.4595g, 1.94 mmol). The material was dissolved in 5.0g of anisole and the solution was filtered through a 0.22 micron syringe filter as it was added to the polymer solution. The solution was spun at 50rpm for 18 hours to disperse the additives in the polymer solution.

Example 14

(preparation of a PhotolithogrAN _ SNhic composition)

A polymer solution was prepared as described in example 9. 20.0g of the polymer solution (45.0 wt.% solids) containing the polymer synthesized in example 1 was weighed into a 50-ml amber clean bottle. The formulation additives were weighed into 10-ml beakers and then dissolved in 5.0g of anisole. The additive was DTBPI-TF bis (4-tert-butylphenyl) trifluoromethanesulfonate iodide (PAG) (0.2757g, 5.08X 10^-4mol) (Toyo Gosei Kogyo Tokyo), 9-methoxyanthracene (sensitizer) (0.1378g, 6.62X 10^-4mol) and Irganox * 1076 antioxidant (0.1378g, 2. times.10)^-4mol) (CIBA refined chemicals). The material was dissolved in 5.0g of 1,3, 5-trimethylbenzene and the solution was filtered through a 0.22 micron syringe filter as it was added to the polymer solution. The solution was spun at 50rpm for 18 hours to disperse the additives in the polymer solution.

Example 15

(preparation of Polymer composition)

A polymer solution was prepared as described in example 9. 72.81g of a polymer solution (45.0 wt% solution) containing the polymer synthesized in example 2 was weighed into a 100ml amber clean bottle. The formulation additives were weighed into 10-mL beakers and then dissolved in 5.0g of anisole. The additives were Rhodorsil * PI 2074 (4-methylphenyl-4- - (1 methylethyl) phenyltetrakis (pentafluorophenyl) borate (1.6251g, 1.587mmol), 1-chloro-4-propoxy 9H-thioxanthone (speedCure CPTX 0.4837g, 1.587mmol) and Irganox * 1076 antioxidant (CIBA finishing Chemicals) (0.1378g, 2.60X 10 mol). The material was dissolved in 5.0g of anisole and the solution was filtered through a 0.22 micron syringe filter as it was added to the polymer solution. To this solution was added 1, 4-cyclohexanedimethanol divinyl ether (3.205g, 0.166mol) as a reaction solvent. The solution was spun at 50rpm for 18 hours to disperse the additives in the polymer solution.

Example 16

(mapping of the photolithographic composition)

A 2.5g aliquot of the composition described in example 9 was taken up in an Eppendorf pipette and applied to a 4 inch silicon wafer. The silicon wafer was spin coated at 500rpm for 10 seconds and then at 1000rpm for 60 seconds using a CEE 1000CB wafer spin coating apparatus. The wafer was placed on a hot plate at 100c and heated for 10 minutes to flash off the remaining solvent. Wafer inverse map (imagewise) exposure to 500mJ/cm²Through a patterned chrome-plated glass mask on an AB M mask aligner. The wafer was heated in a Despatch nitrogen oven at 100 ℃ for 20 minutes to allow a crosslinking reaction to occur in the exposed areas of the polymer film. The pattern was developed by stirring the wafer in 20mL of a terpene diene-based solvent for 60 seconds, spinning the wafer at 3000rpm for 60 seconds to remove the solvent slurry and then spraying the wafer with isopropanol for 10 seconds to fix the pattern. The wafer was then placed in a DespatchLND nitrogen oven and fired at 200 ℃ to allow complete crosslinking reaction.

Example 17

(mapping of the photolithographic composition)

A 2.5g aliquot of the composition described in example 11 was taken up in an Eppendorf pipette and applied to a 4 inch silicon wafer. The silicon wafer was spin coated at 500rpm for 10 seconds and then at 1000rpm for 40 seconds using a CEE 1000CB wafer spin coating apparatus. The wafer was placed on a hot plate at 120 ℃ to flash off the remaining solvent. Reverse mapping exposure of wafer to 500mJ/cm²Through a patterned chrome-plated glass mask on an AB M mask aligner. The wafer was heated in a Despatch nitrogen oven at 115 deg.c for 15 minutes to allow a crosslinking reaction to occur in the exposed areas of the polymer film. The pattern was developed by stirring the wafer in 20mL of a terpene diene-based solvent for 60 seconds, spinning the wafer at 3000rpm for 60 seconds to remove the solvent slurry and then spraying the wafer with isopropanol for 10 seconds to fix the pattern. The wafer was then placed in a Despatch nitrogen oven and baked at 160 ℃ for 60 minutes to allow complete crosslinking reaction.

Example 18

(mapping of the photolithographic composition)

A 2.5g aliquot of the composition described in example 14 was taken up in an Eppendorf pipette and applied to a 4 inch silicon wafer. The silicon wafer was spin coated at 500rpm for 10 seconds and then at 1000rpm for 60 seconds using a CEE 1000CB wafer spin coating apparatus. The wafer was placed on a hot plate at 100 ℃ and heated for 10 minutes to flash off the remaining solvent. Reverse mapping exposure of wafer to 500mJ/cm²Through a patterned chrome-plated glass mask on an AB M mask aligner. The wafer was heated in a Despatch nitrogen oven at 100 ℃ for 20 minutes to allow a crosslinking reaction to occur in the exposed areas of the polymer film. The pattern was developed by stirring the wafer in 20mL of a terpene diene-based solvent for 60 seconds, spinning the wafer at 3000rpm for 60 seconds to remove the solvent slurry and then spraying the wafer with isopropanol for 10 seconds to fix the pattern. The wafer was then placed in a Despatch nitrogen oven and baked at 200 ℃ to effect complete crosslinking.

Example 19

(mapping of the photolithographic composition)

A 4 inch silicon oxynitride coated silicon wafer was plasma treated on a March CS-1701 reactive ion etch unit using an 50/50 argon/oxygen gas mixture at 300mtorr pressure and 300W power for 30 seconds. The cleaned wafer was placed on the turntable of a CEE 1000CB wafer spin station and covered with a 10ml aliquot of adhesion promoter solution (3-aminopropyltriethoxysilane) (5 wt% ethanol in deionized water 95/5). The wafer was held stationary (0rpm) for 60 seconds and spun at 3500rpm for 60 seconds to remove excess solution. The wafer was fired on a hot plate at 130 ℃ for 30 minutes, the hot plate was removed, washed with ethanol for 15 seconds and then dried at 100 ℃ for 10 minutes. A 2.5g aliquot of the resist composition described in example 9 was taken up in an Eppendorf pipette and applied to a 4 inch silicon wafer. The silicon wafer was spin coated at 500rpm for 10 seconds and then at 1000rpm for 60 seconds using a CEE 1000CB wafer spin coating apparatus. The wafer was placed on a hot plate at 100 ℃ and heated for 10 minutes to flash off the remaining solvent. Reverse mapping exposure of wafer to 500mJ/cm²Through a patterned chrome-plated glass mask on an AB M mask aligner. Desp of wafers at 100 deg.CThe atch nitrogen oven was heated for 20 minutes to allow a crosslinking reaction to occur in the exposed areas of the polymer film. The pattern was developed by stirring the wafer in 20mL of a terpene diene-based solvent for 60 seconds, spinning the wafer at 3000rpm for 60 seconds to remove the solvent slurry and then spraying the wafer with isopropanol for 10 seconds to fix the pattern. The wafer was then placed in a Despatch nitrogen oven and baked at 200 ℃ to effect complete crosslinking.

Example 20

(mapping of the photolithographic composition)

A 2.5g aliquot of the composition described in example 13 was taken up in an Eppendorf pipette and applied to a 4 inch silicon wafer. The silicon wafer was spin coated at 500rpm for 10 seconds and then at 1000rpm for 40 seconds using a CEE 1000CB wafer spin coating apparatus. The wafer was placed on a hot plate at 120 ℃ and heated for 5 minutes to flash off the remaining solvent. Reverse mapping exposure of wafer to 500mJ/cm²Through a patterned chrome-plated glass mask on an AB M mask aligner. The wafer was heated in a Despatch nitrogen oven at 115 deg.c for 15 minutes to allow a crosslinking reaction to occur in the exposed areas of the polymer film. The pattern was developed by stirring the wafer in 20mL of a terpene diene-based solvent for 60 seconds, spinning the wafer at 3000rpm for 60 seconds to remove the solvent slurry and then spraying the wafer with isopropanol for 10 seconds to fix the pattern. The wafer was then placed in a Despatch nitrogen oven and baked at 160 ℃ for 60 minutes to allow complete crosslinking reaction.

Example 21

(spray development)

In this example, a resist composition was formulated and mapped using the same procedures, ingredients and amounts described in example 19. The pattern was developed by spraying the wafer with a limonene based developer for 60 seconds and then with isopropanol for 10 seconds. The samples were cured at 200 ℃ as described above.

Example 22

This example illustrates that the polymer contained in the composition of the present invention can be cured at a temperature below the Tg of the polymer. The composition was formulated, mapped and developed as described in example 19. Final firing was carried out in a Despatch LND nitrogen oven at 160 ℃ for 1 hour. The polymer contained in the formulation had a Tg of 180 ℃ as determined by DMA. The polymer after firing exhibited a Tg of about 255 ℃.

Example 23

A resist composition is formulated, imaged and developed as shown in example 15. The entire polymer film was then exposed to 500MJ/cm in a non-reflective manner²To induce additional crosslinking of any unreacted epoxy groups. Final firing was carried out in a Despatch LND nitrogen oven at 120 ℃ for 2 hours. After curing, the polymer exhibited a Tg of about 257 ℃.

Example 24

(mapping of the photolithographic composition)

In this example, the composition was prepared as described in example 15. The photodefinable polymer composition was imaged and developed using the same procedure described in example 19. The pattern was developed by spraying the wafer with a limonene based developer for 60 seconds and then with isopropanol for 10 seconds. The mapped and developed polymer sample was then exposed to 500MJ cm²365nm UV radiation. The samples were cured in a Despatch LND nitrogen oven at 120 ℃ for 1 hour.

Example 25

In this example, the composition described in example 9 was applied to the following silicon wafer. The wafer was placed on a flat horizontal table and held in place with a tape of gummed paper. A blade with a very small notch of 12mils (300 microns) was placed adjacent the wafer. 15ml of the solution was applied to the edge of the wafer. A doctor blade is pulled across the wafer to spread the solution evenly across the wafer surface. The wafer was placed in a nitrogen oven set at 90 ℃ and dried for 45 minutes. The wafer was then reverse mapped to 500mJ/cm²The 365nm ultraviolet radiation passes through a chrome plated glass mask. The wafer was then returned to the nitrogen furnace and fired at 90 ℃ for 20 minutes to effect the crosslinking reaction. By spraying the wafer with a limonene based developer solventThe pattern was developed for 90 seconds. The film was rinsed with isopropanol for 15 seconds to fix the image. Circular micropores of 300 μm diameter were formed in the film.

Example 26

(mapping of the photolithographic composition)

In this example, the composition prepared in example 9 was applied to two silicon oxynitride coated silicon wafers and exposed to a back-mapped exposure to 500MJ/cm in the manner described in example 16²365nm radiation. The exposed wafer was then processed as follows:

chip number	Baking temperature	Time of baking
			1	90℃	20 minutes
2	120℃	15 minutes

The pattern was then fixed by spraying the wafer with a limonene based developer for 60 seconds and then rinsing with isopropanol for 10 seconds. The wafer was then baked in a nitrogen oven at 160 ℃ for 1 hour to complete the crosslinking reaction. Circular pores of 300 μm diameter were developed in the dielectric film. The wafer is broken for scanning electron microscopy. The inclination of the sidewalls of the 300 micron micropores was measured by SEM mapping and recorded as follows:

chip number	Side wall inclination
		1	78.4°
2	60.8°

In the application of the polymer composition as a dielectric layer, the pores must be opened to allow the power connections to be routed between the active integrated circuit die and the substrate to which the IC is attached. The best reliability performance of these interconnects is achieved when the occupation of the sloped sidewalls by the via openings results in a low mechanical stress build-up in the metal lines through the vias. In the compositions of the present invention, such sloped sidewalls are reduced products, which are about 40-50% of the resist composition during the bake phase. A unique feature of this resist composition is that sloped microporous sidewalls can be obtained even if a minimum shrinkage of about 10% is observed during firing.

Example 27

(mapping of the photolithographic composition)

5g of the polymer obtained in example 4 were dissolved in 5g of electronic grade 1,3, 5-trimethylbenzene. The solution was spun for 18 hours to dissolve the polymer. The polymer solution was filtered through a 0.45micron microporous filter to remove any particulates. To the solution were added 0.15g (0.148mmol) of Rhodorsil * 2074 photoinitiator and 0.75g (2.4mmol) of Speedcure * CTPX (Lambson group Co., Ltd.). The solution was spun for 18 hours to completely disperse the photosensitive compound. A 1 inch silicon oxynitride wafer was spin coated with 2.5g of the polymer solution. The resulting coating was soft baked by heating on a hot plate at 100 ℃ for 10 minutes. By imagewise exposing to 500MJ/cm²365nm (I line) radiation through a chrome plated glass maskA pattern is formed on the thin film. The resulting polymer film pattern was reinforced by heating in a nitrogen oven at 100 ℃ for 20 minutes. The pattern was developed by spraying the film with limonene for 60 seconds to dissolve the unexposed areas of the film. The wet film was then rinsed with isopropanol for 15 seconds. . The film was cured for 60 minutes at 200 ℃ under nitrogen.

Example 28

(mapping of the photolithographic composition)

In this example, the composition was formulated, imaged and developed using the same procedures, ingredients and amounts as in example 26, except that the polymer synthesized in example 4 was used as the photolithographic material.

Example 29

(mapping of the photolithographic composition)

In this example, the composition was formulated, imaged and developed using the same procedures, ingredients and amounts as in example 27, except that the polymer synthesized in example 7 was used as the photolithographic material.

Example 30

(mapping of the photolithographic composition)

The polymer film prepared and cast from the polymer obtained in example 9 was imaged on a 4 inch diameter silicon oxynitride wafer. The wafer was washed successively (30 seconds each) with chloroform, methanol, deionized water, and isopropanol. Each imbibition of solvent was released from a polyethylene wash bottle.

Example 31

(mapping of the photolithographic composition)

The polymer (25g) obtained in example 9 was dissolved in 30.5g of 1,3, 5-trimethylbenzene (Aldrich Chemical Co.) to obtain a solid concentration of 45% based on the total amount of the polymer and the solvent. 0.50g (0.92mmol) of the iodonium DtBPI-TF bis (tert-butylphenyl) trifluoromethanesulfonate PAG (Toyo Gosei Co. Ltd.) and 0.25g (1.2mmol) of 9-methoxyanthracene are weighed out and dissolved in 5ml of 1,3, 5-trimethylbenzene. The resulting solution was filtered through a 0.22 micropin cartridge filter. The solution containing the photoactive compound was spun for 18 hours to completely disperse the components.

The polymer solution was applied to a clean wafer by dispersing 2.5g of the solution on the wafer surface. The wafer was then spun at 500rpm for ten seconds and then at 1000rpm for an additional 60 seconds. The wafer was soft baked on a hot plate at 100c for 10 minutes to remove the remaining solvent. Reflective Exposure of the cast Polymer film to 500mJ/cm²The 365nm radiation passes through a glass mask of a chrome-plated metal plate. Curing was performed by heat-baking the wafer in a convection oven at 100 ℃ in a nitrogen atmosphere for 20 minutes. The pattern was then developed and the wafer was stirred with a limonene based developer solution for 60 seconds. The wafer was spun at 3000rpm to remove the solvent and partially dry the sample. The developed film was then immersed in isopropanol and heated on a hot plate at 100 ℃ for 60 seconds. Circular micropores of 300 micron diameter were opened through the membrane by this procedure. The resulting patterned film was then cured in a convection oven at 200 ℃ for 1 hour in a nitrogen atmosphere to effect curing of the epoxy crosslinking groups.

Example 32

(mapping of the photolithographic composition)

A polymer solution was prepared containing 45% solids similar to the 45% solids composition of example 30, except that 70/30 copolymer containing repeat units polymerized from decyl norbornene/glycidyl methyl ether norbornene was used. The solvent rinsed silicon oxynitride wafer was exposed to an oxygen/argon plasma (50/50) in a March CS-1701 r.i.e. e. plasma electroetcher driven by a Seren R600 of 13.56MHz for 60 seconds. The etched wafer was then mounted on the spin chuck of a Brewer science model 100CB spin coater. The adhesion promoter solution (applied to the wafer by dissolving a 10ml aliquot of 3-aminopropyltriethoxysilane in 200ml of ethanol/deionized water (95/5) solution and hardening at room temperature for 1 hour) was applied to the wafer by stirring 15ml of the solution over the wafer surface and holding the wafer still for 60 seconds. The wafer was then spun at 3500rpm for 60 seconds. The wafer surface was cleaned with 50ml of ethanol/water (95/5) solution during the first fifteen second spin cycle.The wafer was then dried on a hot plate at 100 ℃ for 60 seconds. The solution was applied to the treated wafer by dispensing 2g of the solution onto the surface of a stationary wafer. The wafer was then spun at 500rpm for 10 seconds and then at 1500rpm for an additional 40 seconds. The wafer was transferred to a hot plate to soft bake at 100 ℃ for 20 minutes to remove the remaining solvent. The resulting polymer film was measured by profilometry and yielded a thickness of 25 microns. By exposing the polymer film to 500mJ/cm²The 365nm ultraviolet radiation is patterned through a metallization mask. The pattern was formed by heat-baking the wafer in a convection oven at 100 ℃ for 20 minutes in a nitrogen atmosphere. The pattern was developed by spraying the film with a limonene based developer solvent for 60 seconds. The wet film was then rinsed with isopropanol and dried by heating on a hot plate at 100 ℃ for 60 seconds. The developed pattern produced a 50 to 300 μ M micropore opening that reduced the resolution to a 2: 1 micropore diameter to film thickness ratio. The patterned film was then cured in a convection oven at 200 ℃ for 1 hour under a nitrogen atmosphere to complete the curing of the epoxy crosslinking groups.

Example 33

(mapping of the photolithographically defined composition)

The same composition used in example 32 was used for silicon oxynitride wafers and mapped using the same procedure described in example 32, except that the wafers were treated with different adhesion promoters. A 2-micron thick layer of photosensitive polyimide (PI 2771 from HDMicrosystems) was applied to the wafer surface, patterned, developed and cured according to the polyimide material processing principles. The wafer was exposed to an oxygen/argon plasma (50/50 feed rate) for 60 seconds using a feed rate of 96 sccm/second. The patterned, developed and cured coating contains 50 to 300 μ M microvoid openings with resolution down to a microvoid diameter to film thickness ratio of 2: 1.

The invention has been described in terms of specific details of preferred embodiments thereof. Such detail should not be construed to limit the scope of the invention and should be covered to some extent by the appended claims.

Claims (56)

1. A copolymer composition comprising a copolymer having two or more repeat units of formula I:

wherein X is selected from O, -CH₂-, and-CH₂-CH₂-; m is an integer from 0 to 5; and each occurrence of R¹，R²，R³And R⁴Independently selected from one of the following groups:

(a)H，C₁to C₂₅Linear, branched and cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl and alkynyl groups of (a);

(b) c containing one or more hetero atoms selected from O, N and Si₁To C₂₅Linear, branched and cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl and alkynyl groups of (a);

(c) an epoxy group comprising a group of formula II:

wherein A is selected from C₁To C₆A linear, branched and cycloalkylene linking group of (1), and R²³And R²⁴Independently selected from H, methyl, and ethyl;

(d) an epoxy group comprising a group of the following formula III:

wherein p is an integer of 0 to 6, R²³And R²⁴As described above, and each occurrence of R²¹And R²²Independently selected from H, methyl and ethyl;

(e)-(CH₂)_nC(O)OR⁵，-(CH₂)_nC(O)OR⁶，-(CH₂)_nOR⁶，(CH₂)_nOC(O)R⁶，-(CH₂)_nC(O)R⁶and- (CH)₂)_nOC(O)OR⁶(ii) a And

(f) r linked by a linking group¹，R²，R³And R⁴In any combination of two, said linking group is selected from C₁To C₂₅Linear, branched and cyclic alkylene and alkylenearyl groups of (a); wherein n is an integer from 1 to 25, R⁵Is an acid-sensitive group, and R⁶Is selected from H, C₁To C₆Linear, branched and cyclic alkyl groups of (a), epoxy groups containing groups II as defined above; and is

Wherein a portion of the repeat units having structure I comprise at least one epoxy-functional pendant group.

2. A photodefinable dielectric composition comprising:

the copolymer composition of claim 1, and

a material that photonically forms a catalyst.

3. The photodefinable dielectric composition of claim 2 for use in forming a photodefinable layer on a substrate by the steps of:

providing a substrate;

coating at least one side of a substrate with a composition comprising a photodefinable dielectric composition to form a coated layer;

exposing the coating layer to radiation; and

curing the radiation exposed layer.

4. The photodefinable dielectric composition of claim 2 for use in forming a photodefinable layer on a substrate by the steps of:

providing a substrate;

fixing the film by depositing a solution comprising a photodefinable dielectric composition on at least one side of the substrate to form a film;

a heat curing solution.

5. A low K composition comprising the composition of any one of claims 1-4.

6. The low K composition of claim 5 wherein the composition has a dielectric constant of less than 3.3.

7. The composition of any of claims 1-6, wherein the acid labile group R⁵Selected from: -C (CH)₃)₃，-Si(CH₃)₃，-CH(R⁷)CH₂CH₃，-CH(R⁷)C(CH₃)₃Bicyclopropylmethyl, dimethylcyclopropylmethyl, anda compound described by one or more of the structural formulae IV-X:

wherein R is⁷Selected from H and C₁To C₆Linear, branched, and cyclic alkyl groups.

8. The composition of any of claims 1-7, wherein the copolymer further comprises one or more repeat units having the following XI-XV structural units:

wherein X is as defined above and y is 0, 1 or 2; r¹²Is selected from C₁To C₆Linear, branched, and cyclic alkyl groups of (a); and R¹⁵Selected from H and C₁To C₄Linear as well as branched alkyl groups.

9. The composition of any of claims 1-8, wherein the repeat units having structure I comprising an epoxy functional group comprise from 15 mole% to 95 mole% of the copolymer.

10. The composition of claim 9 wherein the copolymer has a moisture absorption of less than 2 weight percent and a dielectric constant of less than 3.3.

11. The composition of any of claims 1-10, wherein the copolymer has a modulus of from 0.1Gpa to 3 Gpa.

12. The composition of any of claims 1-11, wherein the copolymer has a glass transition temperature of from 170 ℃ to 350 ℃.

13. The composition of any of claims 1-12, wherein the copolymer has a weighted average molecular weight of 10,000 to 500,000 as determined by gel permeation chromatography using a poly (norbornene) standard.

14. The composition of any of claims 1-13, further comprising a solvent selected from the group consisting of reactive and non-reactive compounds in a hydrocarbon solvent, an aromatic solvent, a cycloaliphatic cyclic ether, a cyclic ether, an acetate, an ester, a lactone, a ketone, an amide, an aliphatic monovinyl ether, an aliphatic polyvinyl ether, a cycloaliphatic monovinyl ether, a cycloaliphatic polyvinyl ether, an aromatic monovinyl ether, an aromatic polyvinyl ether, a cyclic carbonate, and mixtures thereof.

15. The composition of claim 14, wherein the solvent is selected from the group consisting of cyclohexane, benzene, toluene, xylene, 1,3, 5-trimethylbenzene, tetrahydrofuran, anisole, terpenoids, cyclohexene oxide, α -pinene oxide, 2, 2' - [ methylenebis (4, 1-phenylenemoxyethylene) ] bis-ethylene oxide, 1, 4-cyclohexanedimethanol divinyl ether, bis (4-vinyloxyphenyl) methane, cyclohexanone, and decalin.

16. The composition of any of claims 1-15, wherein the copolymer comprises 65 to 75 mole% of the first repeat unit of formula 1, wherein R¹，R²And R³Is H, and R⁴Is decyl, and 25-35 mole% of a second repeat unit of formula 1, wherein R¹，R²And R³Is H, R⁴Is an epoxy group containing a group of formula II, wherein A is methylene and R is²³And R²⁴Is H.

17. The composition of any one of claims 2-4, wherein the material that photonically forms the catalyst is a photoacid generator.

18. The composition of claim 17, wherein the photoacid generator comprises one or more compounds selected from the group consisting of: onium salts, halogen-containing compounds and sulfonates.

19. The composition of claim 18, wherein the photoacid generator comprises one or more compounds selected from the group consisting of: 4, 4' -di-tert-butylphenyl trifluoromethanesulfonate iodide salt; 4, 4' -tris (tert-butylphenyl) trifluoromethanesulfonate sulfonium salt; diphenyliodotetrakis (pentafluorinated phenyl) sulfonium borate; triaryl-sulfonium tetrakis (pentafluorophenyl) borate; triphenylsulfonium tetrakis (pentafluorophenyl) -borate sulfonium salt; 4, 4' -di-tert-butylphenyl tetrakis (pentafluorophenyl) borate; sulfonium tris (tert-butylphenyl) tetrakis (pentafluorophenyl) borate, and iodonium (4-methylphenyl-4- (1-methylethyl) phenyltetrakis (pentafluorophenyl) borate.

20. The composition of claim 18, wherein the photoacid generator is present in an amount of from 0.1 to 10 weight percent of the composition.

21. The composition of any one of claims 2-4, further comprising one or more components selected from the group consisting of: one or more sensitizer components, one or more solvents, one or more catalyst scavengers, one or more tackifiers, one or more antioxidants, one or more flame retardants, one or more stabilizers, one or more reactive diluents, and one or more plasticizers.

22. The composition of claim 21 wherein the sensitizer component comprises one or more components selected from the group consisting of: anthracene, phenanthrene, chrysene, benzpyrene, fluoranthene, rubrene, pyrene, xanthone, indanthrene and thioxanthen-9-one.

23. The composition of claim 22 wherein the sensitizer component comprises one or more components selected from the group consisting of: 2-isopropyl-9H-thioxanthen-9-one, 4-isopropyl-9H-thioxanthen-9-one, 1-chloro-4-propoxythioxanthone and phenothiazine.

24. The composition of claim 22, wherein the photonically formed catalyst material is a photoacid generator and the sensitizer component is present in an amount of 0.1 to 10 weight percent of the composition.

25. The composition of claim 21, wherein the catalyst scavenger is an acid scavenger.

26. The composition of claim 25 wherein the acid scavenger component is selected from one or more of a secondary amine and a tertiary amine.

27. The composition of claim 26 wherein the acid scavenger component comprises one or more components selected from the group consisting of: pyridine, phenothiazine, tri (n-propylamine), triethylamine and lutidine in its isomeric form.

28. The composition of claim 25, wherein the material that photonically forms the catalyst is a photoacid generator and the acid scavenger is present in an amount of 0.1 to 5 parts per part of photoacid generator.

29. The composition of claim 21 wherein the solvent comprises reactive and non-reactive compounds selected from the group consisting of hydrocarbon solvents, aromatic solvents, cycloaliphatic cyclic ethers, acetates, esters, lactones, ketones, amides, cycloaliphatic vinyl ethers, aromatic vinyl ethers, cyclic carbonates, and mixtures thereof.

30. The composition of claim 29, wherein the solvent comprises an active and an inactive compound selected from the group consisting of cyclohexane, benzene, toluene, xylene, 1,3, 5-trimethylbenzene, tetrahydrofuran, anisole, cyclohexene oxide, α -pinene oxide, 2, 2' - [ methylenebis (4, 1-phenylenemoxyethylene) ] bis-oxirane, 1, 4-cyclohexanedimethanol divinyl ether, bis (4-vinyloxyphenyl) methane, cyclohexanone, and decalin.

31. The composition of claim 21, wherein the adhesion promoter comprises one or more compounds described by structural unit XVI:

wherein z is 0, 1 or 2; r⁸Is a linking group selected from: c₁To C₂₀Linear, branched and cyclic alkylene groups of (a), alkylene oxides containing from 2 to 6 carbon atoms and poly (alkylene oxides), wherein the alkylene portion of the repeating group contains from 2 to 6 carbon atoms and the poly (alkylene oxides) have a molecular weight of from 50 to 1,000; each occurrence of R⁹Independently selected from C₁To C₄Linear and branched alkyl radicals of (a), and each occurrence of R¹⁸Selected from H and C₁Linear and branched alkyl groups to 4.

32. The composition of claim 21, wherein the reactive diluent comprises one or more compounds selected from epoxides and compounds described by structural units XVII and XVIII:

CH₂＝CH-O-R¹⁰-O-CH＝CH₂ (XVII)

CH₂＝CH-O-R¹¹ (XVIII)

wherein R is¹⁰Is a linking group selected from C₁To C₂₀Linear, branched and cyclic alkylene, arylene and alkarylene radicals, alkylene oxides containing from 2 to 6 carbon atoms, poly (alkylene oxides), where the alkylene part of the repeating group contains from 2 to 6 carbon atoms and the poly (alkylene oxides) have a molecular weight of from 50 to 1,000, - [ -R¹³-N-C(O)O-]_m-R¹³-, where R is present at each occurrence¹³Independently selected from C₁To C₂₀Linear, branched and cyclic alkylene, arylene ofAnd an alkarylene group, and m is an integer from 1 to 20; and R¹¹Is selected from C₁Linear and branched alkyl and alkanol groups of up to 20.

33. The composition of claim 21 wherein the one or more reactive diluents are selected from the group consisting of 1, 4-butanediol divinyl ether, 1, 6-hexanediol divinyl ether, 1, 8-octanediol divinyl ether, 1, 4-dimethanol cyclohexane divinyl ether, 1, 2-ethylene glycol divinyl ether, 1, 3-propylene glycol divinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 1, 4-butanediol vinyl ether, 1, 6-hexanediol vinyl ether, and 1, 8-octanediol vinyl ether.

34. The composition of claim 3, wherein the pattern is engraved in the cured layer.

35. The composition of claim 3, wherein the exposure radiation is provided by photonic radiation or electron beam.

36. The composition of claim 35, wherein the photonic radiation is ultraviolet radiation having a wavelength of from 300nm to 500 nm.

37. The composition of claim 3, wherein the exposure radiation dose is from 100mJ/cm²To 2,000mJ/cm²。

38. The composition of claim 3, wherein the layer is reverse developing exposed.

39. The composition of claim 3, wherein the layer is developed.

40. The composition of claim 3, wherein the curing step is carried out at a temperature of from 90 ℃ to 200 ℃ for a period of from 1 minute to 60 minutes.

41. The composition of claim 3, wherein the layer has a film thickness of from 0.1 to 250 microns.

42. The composition of claim 3, wherein a soft baking step is performed after application of the coating solution, wherein the soft baking step comprises exposing the coated substrate to a temperature of 90 ℃ to 140 ℃ for 1 minute to 30 minutes.

43. The composition of claim 3, wherein the coated substrate is exposed to radiation through the light-blocking film and the radiation is provided by one or more of X-ray, electron beam, ultraviolet radiation, and visible radiation.

44. The composition of claim 39, wherein the coated substrate is developed using a solvent development method selected from the group consisting of spray development, stir development, and immersion development.

45. The composition of claim 44, wherein the developer for development of the coated substrate comprises one or more compounds selected from the group consisting of: limonene, 1,3, 5-trimethylbenzene, decalin and toluene.

46. The composition of claim 3, which finally comprises a baking step whereby the coated substrate is heated to a temperature of from 100 ℃ to 200 ℃ for a period of from 30 minutes to 120 minutes.

47. The composition of claim 4, wherein the pattern is formed in a curing solution.

48. The composition of claim 47, wherein the pattern is formed using an etching technique.

49. The composition of claim 4, wherein the heat curing step is carried out at a temperature of 90 ℃ to 200 ℃.

50. The composition of claim 48, wherein the etching technique is selected from the group consisting of reactive ion etching and laser ablation.

51. An electrical or electronic device comprising a layer formed from the composition of any one of claims 2-4.

52. The electrical or electronic device of claim 51, wherein the device is a semiconductor device in a semiconductor device package.

53. The electrical or electronic device of claim 52, wherein the device is selected from the group consisting of a logic wafer, a passive device, a memory chip, a micro-electromechanical system (MEMS) wafer, a micro-optical-electromechanical system (MOEMS) wafer, and an Application Specific Integrated Circuit (ASIC) wafer.

54. An electrical or electronic device comprising a layer formed from the composition of any of claims 2-4 as a permanent insulation material.

55. An electrical or electronic device comprising a layer formed from the composition of any of claims 2-4 as a barrier layer.

56. An electrical or electronic device comprising a layer formed from the composition of any of claims 2-4 as a stress buffer layer in the packaging of semiconductor devices.