WO2004078814A2 - Fluorinated polymers, methods of production and uses in ferroelectric devices thereof - Google Patents

Abstract

Fluorinated polymers having ferroelectric properties are described herein that include: a) at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof; and b) at least one adhesion promoter. Fluorinated polymer coating compositions having ferroelectric properties are also described herein that include: a) at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof; b) at least one adhesion promoter; and c) at least one solvent. Methods of producing a fluorinated polymer having ferroelectric properties are described herein that include: a) providing at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof; b) providing at least one adhesion promoter; c) polymerizing the at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof to produce the fluorinated polymer; and d) incorporating the at least one adhesion promoter with the fluorinated polymer. Methods of producing a fluorinated polymer coating composition having ferroelectric properties are also described herein that include: a) providing at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof; b) providing at least one adhesion promoter; c) providing at least one solvent; d) polymerizing the at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof to produce the fluorinated polymer; and e) incorporating the at least one adhesion promoter and the solvent with the fluorinated polymer.

Description

FLUORINATED POLYMERS, METHODS OF PRODUCTION AND USES IN FERROELECTRIC DEVICES THEREOF

This application claims priority to US Provisional Application Serial No.: 60/452129 filed on March 4, 2003, which is commonly-owned and incorporated herein in its entirety by reference.

BACKGROUND

Thin film ferroelectrics and ferroelectric devices have applications in semiconductors, microwave circuits and optical systems. Conventional thin film ferroelectrics and ferroelectric devices consist of materials, such as bismuth titanate, platinum, strontium, lanthanum, yttrium, lead, silicon and combinations thereof.

Ferroelectric memory devices, such as ferroelectric random access memory (FRAM), are useful devices because they combine real-time memory with the ability to retain data after the power source is turned off. FRAM also has a lower power requirement, can achieve a much higher data density and is faster than non-volatile memories, such as flash memory and MRAM (magnetic random access memory). Flash memory is the current industry standard and will run into limitations in the near future with respect to scaling the memory down. MRAM uses a magnetic charge to store infonnation, as opposed to the electric charge of existing memory devices, and is a relatively new technology. The challenge for MRAM, like flash memory, is to be able to scale the product down, such that it can be cheaper and faster than conventional memory.

FRAM can also be compared with polymer ferroelectric random access memory (PFRAM). FRAM is using inorganic materials, needs higher process temperature, and is already being used in the industry. PFRAM materials should be processed at lower temperatures than those currently used in chip manufacturing, including FRAM processing temperatures. This low temperature processing enables the use of new, cheaper processing technologies. Most of the efforts in the field of thin film ferroelectrics and ferroelectric devices is directed to developing new materials and compositions and/or improving on known materials and compositions that may have been unsuitable for such applications in the past, so that scaling the product down and utilizing faster and cheaper processing steps can be realized. US Patent 6,617,018 issued to Tamai et al. teaches films that contain "functional microparticles". As described in Tamai, the functional microparticles, such as iron oxide base magnetic powders, ferromagnetic alloy powders and other ferroelectric materials are formed into a layer, compressed and bound together through the use of a resin material. Tamai uses fluorinated polymers as one of the contemplated resin materials, because it has a higher density, i.e. a large weight of the resin used has a smaller volume, but as Tamai mentions, the liquid in which the functional microparticles are dispersed is not critical.

Monomer and polymer-based materials have been used for thin film layers in a number of electronic and semiconductor applications and devices. However, it would be ideal • to utilize monomer and/or polymer-based materials that have few or no additives, in order to control quality, manufacturing costs and replication from application to application, hi order to produce thin film fenOelectric devices, the polymers being utilized in the device must be substantially perfect with relation to polymer formation and film production. Furthermore, polymer properties, such as crystallinity, chain order, co-monomer type and content, monomer connectivity, morphology and thermal changes to packing order should be understood and investigated when trying to produce a robust thin film with high ferroelectric properties, given that ferroelectric properties are greatly influenced by such previously- mentioned polymer properties.

Fluorinated polymers, such as polyvinylidene fluoride (PVDF) and PVDF-based copolymers and polymers, copolymers and terpolymers comprising trifluoroethylene and chlorotrifluoroethylene, have been studied for years in a variety of applications. Fluorinated polymers, however, are currently not being used as coatings in integrated circuits (IC) fabrication, layered component production or in memory-type device production primarily because of several technical challenges, including polydispersity, adhesion and incompatibility with conventional process temperatures. A fluorinated polymer that is useful in the kinds of applications previously mentioned should be able to be deposited to a surface and should have high ferroelectric properties, a narrow molecular weight distribution (MWD) and a relatively high adhesion for memory devices and layered components. In addition, the fluorinated polymer should have a molecular weight range of 35-55 kg/mole in some applications. Furthermore, monomer order, stereochemistry and chain structure must be controlled. The resulting thin film should also contain high crystallinity in tl e correct domain structure and orientation. In order to meet these goals, along with others, fluorinated monomer precursors and fluorinated polymers, copolymers and terpolymers have been developed that can be used to produce stable, robust thin films with improved ferroelectric properties and relatively low polarization fatigue for use in IC production, layered components and memory devices.

Therefore, fluorinated polymers should be developed that have a) high ferroelectric

, properties, b) a narrow molecular weight distribution (MWD) and c) high adhesion for memory devices and layered components. As mentioned, monomer order, stereochemistry and chain structure must be controlled. Thin films produced using these fluorinated polymers should also contain high crystallinity in the correct domain structure and orientation, hi order to meet these goals, along with others, fluorinated monomer precursors and fluorinated polymers, copolymers and terpolymers should be developed that can be used to produce stable, robust thin films with improved fenOelectric properties and relatively low polarization fatigue for use in IC production, layered components and memory devices.

SUMMARY OF THE SUBJECT MATTER

Fluorinated polymers having ferroelectric properties are described herein that comprise: a) at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof; and b) at least one adhesion promoter. Fluorinated polymer coating formulations having ferroelectric properties are also described herein that comprise: a) at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof; b) at least one adhesion promoter; and c) at least one solvent.

Methods of producing a fluorinated polymer having ferroelectric properties are described herein that comprise: a) providing at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof; b) providing at least one adhesion promoter; c) polymerizing the at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof to produce the fluorinated polymer; and d) incorporating the at least one adhesion promoter with the fluorinated polymer. Methods of producing a fluorinated polymer composition having ferroelectric properties are also described herein that comprise: a) providing at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof; b) providing at least one adhesion promoter; c) providing at least one solvent; d) polymerizing the at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof to produce the fluorinated polymer; and e) incorporating the at least one adhesion promoter and the solvent with the fluorinated polymer.

DETAILED DESCRIPTION

Fluorinated polymers have now been developed that have a) high ferroelectric properties, b) a narrow molecular weight distribution (MWD) and thus, a low polydispersity, and c) high adhesion for memory devices and layered components. In some embodiments, the fluorinated polymers may have a number average molecular weight range of 35 to 55 kg/mole, however, it should be understood that contemplated materials will have ferroelectric properties even if the molecular weight is outside of this range. Monomer order, stereochemistry and chain structure are controlled. Thin films produced using these fluorinated polymers also contain high crystallinity in the correct domain structure and orientation. Fluorinated monomer precursors and fluorinated polymers, copolymers and terpolymers as described herein can be used to produce stable, robust thin films with unproved ferroelectric properties and relatively low polarization fatigue for use in IC production, layered components and memory devices.

Fluorinated polymers having ferroelectric properties are described herein that comprise: a) at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof; and b) at least one adhesion promoter. Fluorinated polymer coating compositions having ferroelectric properties are also described herein that comprise: a) at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof; b) at least one adhesion promoter; and c) at least one solvent.

Methods of producing a fluorinated polymer having ferroelectric properties are described herein that comprise: a) providing at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof; b) providing at least one adhesion promoter; c) polymerizing the at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof to produce the fluorinated polymer; and d) incorporating the at least one adhesion promoter with the fluorinated polymer. Methods of producing a fluorinated polymer coating composition having ferroelectric properties are also described herein that comprise: a) providing at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof; b) providing at least one adhesion promoter; c) providing at least one solvent; d) polymerizing the at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof to produce the fluorinated polymer; and e) incorporating the at least one adhesion promoter and the solvent with the fluorinated polymer. In order to produce fluorinated polymers, co-polymers and te olymers that are necessary to deposit thin films with ferroelectric properties, a monomer system or combination of monomers can be selected based a number of desirable factors, such as reactivity and estimated degree of difficulty in obtaining the target polymer. As used herein, the term "ferroelectric" means that property of a particular material that determines that it will be polarized in one direction or the other, or reversed in direction, when a sufficiently large positive or negative electric field is applied remaining until so disturbed. Ferroelectric compositions and/or compounds, over certain temperature ranges, have a natural or inherent deformation (polarization) of the electrical fields or electrons associated with the atoms and groups in the crystal lattice. This deformation results in the development of positive and negative poles and consequent "direction" of polarization, which can be reversed when the crystal is exposed to an external field. Ferroelectric crystals are internally strained and, as a consequence, show unusual piezoelectric and elastic properties.

As used herein, the term "monomer" refers to any chemical compound that is capable of forming a covalent bond with itself or a chemically different compound in a repetitive manner. The repetitive bond formation between monomers may lead to a linear, branched, super-branched, or three-dimensional product. Furthermore, monomers may themselves comprise repetitive building blocks, and when polymerized the polymers formed from such monomers are then termed "blockpolymers". Monomers may belong to various chemical classes of molecules including organic, organometallic or inorganic molecules. The molecular weight of monomers may vary greatly between about 40 Dalton and 20000 Dalton. However, especially when monomers comprise repetitive building blocks, monomers may have even higher molecular weights. Monomers may also include additional groups, such as groups used for crosslinking. At least one of the monomers or monomer classes chosen to use in assembly of the fluorinated polymer will comprise fluorine. Contemplated monomers may also comprise other halogens, such as chlorine, in addition to fluorine. Other contemplated monomers may include non-fluorinated monomers; however, the choice to utilize those monomers will depend entirely on the desired properties of the target fluorinated polymer and the reactivity of those non-fluorinated monomers with the fluorinated monomers. Monomers for some contemplated embodiments comprise trifluoroethylene (also known as VF₃, wherein V = vinyl, or TrFE), vinylidene fluoride (also known as VF₂ or VDF), chlorotrifluoroethylene (also known as VF₃C1 or CTFE), VF₂C1 and VF₂C1₂. Other monomers that may be utilized include 1,1,1,3-tetrafluoropropene, 1,1,1,3,3-pentafluoropropene and hexafluoropropene. These monomers can all be used to form polymers, co-polymers or terpofymers, depending on the desired properties of the fluorinated polymer. One way to determine tlie proper combination of monomers for the particular application is to investigate the chain microstructural/stereochemical requirements found in the ferroelectric response. Also, it has been discovered that the chlorine in the chlorinated monomer can be removed from the polymer. The chloride may be reductively replaced by hydrogen, or replaced with other functional groups used for adhesion control. Depending upon the monomer, the chloride may also be eliminated to a double bond to provide further functionality for crystallization control.

Any suitable polymerization process can be used to produce the fluorinated polymers, such as free-radical emulsion and solution polymerization, oxidation/reduction polymerization, anionic, cationic, or transition metal-catalyzed polymerization. Variables that are important to the polymerization process include pressure, choice of and use of a catalyst, stoichiometry, solvent(s) choice, agitation, temperature, addition strategy, monomer reactivity and reactor free volume (head space). As used herein, the term "catalyst" means any substance that affects the rate of the chemical reaction without itself being consumed or undergoing a chemical change. Catalysts/initiators may be inorganic, organic, or a complex of organic groups and metal halides. Catalysts may also be liquids, solids, gases or a combination thereof. In some embodiments, a conventional catalyst may be used, and in other embodiments, the catalyst may be produced on-site and right before it is to be used in the reaction process, especially if thermal stability of the catalyst is a concern. In contemplated embodiments, the desired catalyst will allow access to lower process temperatures than what is normally considered "standard practice" in the industry, along with enabling a "clean polymerization process", which means not introducing metal or sulfur contamination into the polymerization reaction - a problem in most conventional and generally accepted processes. Contemplated catalysts include fluorinated alkyl or aryl peroxides and partially fluorinated alkyl or aryl peroxides, including perfluorobutyl peroxide and the like, and combinations thereof. Other contemplated catalysts include cumene hydroperoxide, benzoylperoxide, t- butylperoxide, t-butylhydroperoxide, adipoylperoxide, cumene hydroperoxide, cyclohexyl percarbonate. Perfluoroperoxides may also be used in conjunction with a fluorinated solvent to produce a clean polymer.

Polymers produced from the monomers and processes contemplated herein exhibit additional properties and characteristics not generally seen in conventional polymers, such as

VF₂ and VF₃ stoichiometry and location on the polymer chain, VF₂ and VF₃ stereochemistry, block type and block location, molecular weight, polydispersity and melting temperature (T_m).

Contemplated solvents for the polymerization steps include any suitable pure or mixture of organic or inorganic molecules that are volatilized at a desired temperature and/or easily solvates the chosen monomers. It should be understood that the polymer will come out of solution after formation, so the solvent should only solubilize the monomer and not the polymer. The solvent may also comprise any suitable pure or mixture of polar and non-polar compounds. In some embodiments, the solvent comprises perfluoroalkane, trichloroethylene, cyclohexanone, butryolactone, and anisole. As used herein, the term "pure" means is composed of a single molecule or compound. For example, pure water is composed solely of H₂O. As used herein, the term "mixture" means that component that is not pure, including salt water. As used herein, the term "polar" means that characteristic of a molecule or compound that creates an unequal charge, partial charge or spontaneous charge distribution at one point of or along tlie molecule or compound. As used herein, the term "non-polar" means that characteristic of a molecule or compound that creates an equal charge, partial charge or spontaneous charge distribution at one point of or along the molecule or compound. Particularly preferred solvents include, but are not limited to 1,1,1,3,3-pentafluoropropane (HFC-245fa), perfluoromethylcyclohexane, perfluorodecalin, perfluoromethyldecalin, benzotrifluoride, carbon tetrachloride, perfluoroalkane and mixtures thereof.

In some contemplated embodiments, the solvent or solvent mixture (comprising at least two solvents) comprises those solvents that are considered part of the hydrocarbon family of solvents. Hydrocarbon solvents are those solvents that comprise carbon and hydrogen. It should be understood that a majority of hydrocarbon solvents are non-polar; however, there are a few hydrocarbon solvents that could be considered polar. Hydrocarbon solvents are generally broken down into three classes: aliphatic, cyclic and aromatic. Aliphatic hydrocarbon solvents may comprise both straight-chain compounds and compounds that are branched and possibly crosslinked, however, aliphatic hydrocarbon solvents are not considered cyclic. Cyclic hydrocarbon solvents are those solvents that comprise at least three carbon atoms oriented in a ring structure with properties similar to aliphatic hydrocarbon solvents. Aromatic hydrocarbon solvents are those solvents that comprise generally three or more unsaturated bonds with a single ring or multiple rings attached by a common bond and/or multiple rings fused together. Contemplated hydrocarbon solvents include toluene, xylene, p-xylene, m-xylene, mesitylene, solvent naphtha H, solvent naphtha A, alkanes, such as pentane, hexane, isohexane, heptane, nonane, octane, dodecane, 2-methylbutane, hexadecane, tridecane, pentadecane, cyclopentane, 2,2,4-trimethylpentane, petroleum ethers, halogenated hydrocarbons, such as chlorinated hydrocarbons, nitrated hydrocarbons, benzene, 1,2-dimethylbenzene, 1,2,4-trimethylbenzene, mineral spirits, kerosine, isobutylbenzene, methylnaphthalene, ethyltoluene, ligroine. Particularly contemplated solvents include, but are not limited to, pentane, hexane, heptane, cyclohexane, benzene, toluene, xylene and mixtures or combinations thereof. In other contemplated embodiments, the solvent or solvent mixture may comprise those solvents that are not considered part of the hydrocarbon solvent family of compounds, such as ketones, such as acetone, diethyl ketone, methyl ethyl ketone and the like, alcohols, esters, ethers and amines. In yet other contemplated embodiments, the solvent or solvent mixture may comprise a combination of any of the solvents mentioned herein. Once the fluorinated polymers, copolymers or terpolymers are formed, the polymers are solvated to deposit a film. It should be understood that the solvents and solvent blends used in this step of the film formation may be different from those previously mentioned, since it was understood that those solvents previously mentioned should solvate only the monomers and not the polymers. Contemplated variables to consider when forming the polymer solution are choice of solvent (solvation of solvents, volatility of solvents), concentration of ingredients, the formulation technique, contamination control of metals or particulates (ion exchange, filtration), the polymer to be solvated, surfactants for controlling surface deformities and adhesion promotion strategies.* In addition contemplated variables to consider when forming the polymer solution are filtration strategies to reduce crystallinity and phase separation defects in the film, as the fluoropolymers are known to phase separate upon heating and RT equilibration. Variables include, concentration, filter pore size, temperature prior to filtration and temperature at filtration. Preferred variables include heating prior to filtration and hot filtration. Other preferred deposition process variable include in-line filtration.

During film production, as previously mentioned, the polymer solution may be applied to a surface, such as a wafer or substrate by any conventional method and/or apparatus, including being spun-cast onto a surface or substrate. In other embodiments, the polymer solution may be applied by dip coating, spray coating, roll coating, printing, inkjet printing, screen printing, contact planarization and combinations thereof. In order to produce a high quality film, according to the goals previously mentioned, it is important to monitor the solvent choice, the spin and bake step as well as the choice of substrate. Furthermore, as mentioned, it's important to take into account adhesion promotion strategies, which may include coupling an adhesion promoter to the polymer, the polymer solution and/or the substrate by a) incorporating an adhesion promoter into the polymer during polymerization, b) subsequent grafting of a promoter onto the polymer, c) formulation of adhesion promoters whose solubility characteristics in die film cause it to migrate to the interfaces or d) a combination thereof. The adhesion promoter is chosen based on it's solubility characteristics and parameters as compared to the polymer, as well as it's adhesive characteristics and ability to either physically or chemically react to the interface surfaces (polymer and substrate) and create a high adhesive bond. It should also be understood that it's important to choose an adhesive promoter that provides a suitable adhesive interface at the smallest possible loading in order that the ferroelectric properties of the final film won't be compromised. The phrase "adhesion promoter" as used herein means any component that when used with or coupled to the polymer and/or the substrate or surface, improves the adhesion thereof to substrates compared with the polymers alone. Preferably at least one adhesion promoter is utilized with the fluorinated polymer.

Adhesion promoters contemplated herein may comprise compounds having at least bifunctionality wherein the bifunctionality may be the same or different and at least one of the first functionality and the second functionality comprises Si-containing groups; N-containing groups; C bonded to O-containing groups; hydroxyl groups; and C double bonded to C- containing groups. The phrase "compound having at least bifunctionality" as used herein means any compound having at least two functional groups capable of interacting or reacting, or forming bonds as follows. The functional groups may react in numerous ways including addition reactions, nucleophilic and electrophilic substitutions or eliminations, radical reactions, etc. Further alternative reactions may also include the formation of non-covalent bonds, such as Van der Waals, electrostatic bonds, ionic bonds, and hydrogen bonds.

Examples of useful adhesion promoters are disclosed in commonly assigned pending US Application Serial Number 158513 filed May 30, 2002 incorporated herein in its entirety.

It is contemplated that the silicon-containing groups are selected from Si-H, Si-O, and Si-N; the N-containing groups are selected from such as C-NH₂ or other secondary and tertiary amines, imines, amides, and imides; the carbon atom bonded to O-containing groups are selected from =CO, carbonyl groups such as ketones and aldehydes, esters, -COOH, alkoxyls having 1 to 5 carbon atoms, ethers, glycidyl ethers; and epoxies; the hydroxyl group is phenol; and the C double bonded to C-containing groups are selected from allyl and vinyl groups. For semiconductor applications, the more preferred functional groups include the Si- containing groups; C bonded to O-containing groups; hydroxyl groups; and vinyl groups. Contemplated adhesion promoters may also comprise an organic resin-based material that further comprises phenolic-containing resins, novolac resins, such as CRJ-406 or HRJ- 11040 (both from Schenectady International, Inc.), organic acrylate and/or a styrene resins, epoxy and/or glycidylepoxy resins, and polyimide or polyamide-based resins. Other adhesion promoters may comprise polydimethylsiloxane materials, ethoxy or hydroxy-containing silane monomers, vinyl-containing silane monomers, acrylated silane monomers, or silyl hydrides, epoxy and/or glycidoxy propyl silane monomers or epoxy and or glycidyl epoxy monomers.

An example of a contemplated adhesion promoter having silicon-containing groups is silanes of the Formula I: (R₁₄) (Rι₅)ιSi(R₁₆)_m(R₁₇)_n wherein Rι , R₁₅, R₁₆, and R₁₇ each independently represents hydrogen, hydroxyl, unsaturated or saturated alkyl, substituted or unsubstituted alkyl where the substituent is amino or epoxy, saturated or unsaturated alkoxyl, unsaturated or saturated carboxylic acid radical, or aryl; at least two of R₁₄, R_15j R₁₆, and R₁₇ represent hydrogen, hydroxyl, saturated or unsaturated alkoxyl, unsaturated alkyl, or unsaturated carboxylic acid radical; and k+l+m+n<4. Examples include vinylsilanes such as H₂C=CHSi(CH₃)₂H and H₂C=CHSi(R_]8)₃ where R₁₈ is CH₃O, C₂H₅O, AcO, H₂C=CH, or H₂C=C(CH₃)O-, or vinylphenylmethylsilane; allylsilanes of the formula H₂C=CHCH₂- Si(OC₂H₅)₃ and H₂C=CHCH₂-Si(H)(OCH₃)_2; glycidoxypropylsilanes such as (3- glycidoxypropyl)methyldiethoxysilane and (3 -glycidoxypropyl)trimethoxysilane; methacryloxypropylsilanes of the formula H₂C=(CH₃)COO(CH₂)₃-Si(OR₁₉)₃ where R₁₉ is an alkyl, preferably methyl or ethyl; aminopropylsilane derivatives including H₂N(CH₂)₃Si(OCH₂CH₃)₃, H₂N(CH₂)₃Si(OH)₃ , or H₂N(CH₂)₃OC(CH₃)₂CH=CHSi(OCH₃)₃. The aforementioned silanes are commercially available from Gelest.

An example of a contemplated adhesion promoter having C bonded to O-containing groups is glycidyl ethers including but not limited to l,l,l-tris-(hydroxyphenyl)ethane tri- glycidyl ether which is commercially available from TriQuest. Another example of a contemplated adhesion promoter having carbon bonded to oxygen-containing groups is esters of unsaturated carboxylic acids containing at least one carboxylic acid group. Examples include itifunctional methacrylate ester, trifunctional acrylate ester, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and glycidyl methacrylate. The foregoing are all commercially available from Sartomer.

A contemplated adhesion promoter having vinyl groups is vinyl cyclic pyridine oligomers or polymers wherein the cyclic group is pyridine, aromatic, or heteroaromatic. Useful examples include but not limited to 2-vinylpyridine and 4-vinylpyridine, commercially available from Reilly; vinyl aromatics; and vinyl heteroaromatics including but not limited to vinyl quinoline, vinyl carbazole, vinyl imidazole, and vinyl oxazole.

Contemplated adhesion promoters having silicon-containing groups is the polycarbosilane disclosed in commonly assigned copending allowed US Patent Application Serial Number 09/471299 filed December 23, 1999 incorporated herein by reference in its entirety. The polycarbosilane is that shown' in Formula II:

in which R₂₀, R2₆, and R₂₉ each independently represents substituted or unsubstituted alkylene, cycloalkylene, vinylene, allylene, or arylene; R₂ι, R₂₂, R₂ , ₂4, R2₇, and R₂₈ each independently represents hydrogen atom or organo group comprising alkyl, alkylene, vinyl, cycloalkyl, allyl, or aryl and may be linear or branched; R₂₅ represents organosilicon, silanyl, siloxyl, or organo group; and p, q, r, and s satisfy the conditions of [4< p + q + r + s <100,000], and q and r and s may collectively or independently be zero. The organo groups may contain up to 18 carbon atoms but generally contain from about 1 to about 10 carbon atoms. Useful alkyl groups include -CH₂- and -(CH₂)_t- where t>l. Contemplated polycarbosilanes include dihydridopolycarbosilanes in which R₂₀ is a substituted or unsubstituted alkylene or phenyl, R ι group is a hydrogen atom and there are no appendent radicals in the polycarbosilane chain; that is, q, r, and s are all zero. Another preferred group of polycarbosilanes are those in which the R₂ι, R₂2, R23, R24, R2S, and R₂₈ groups of Formula II are substituted or unsubstituted alkenyl groups having from 2 to 10 carbon atoms. The alkenyl group may be ethenyl, propenyl, allyl, butenyl or any other unsaturated organic backbone radical having up to 10 carbon atoms. The alkenyl group may be dienyl in nature and includes unsaturated alkenyl radicals appended or substituted on an otherwise alkyl or unsaturated organic polymer backbone. Examples of these preferred polycarbosilanes include dihydrido or alkenyl substituted polycarbosilanes such as polydihydridocarbosilane, polyallylhydrididocarbosilane and random copolymers of polydihydridocarbosilane and polyallylhydridocarbosilane.

In yet other contemplated polycarbosilanes, the R₂ι group of Formula II is a hydrogen atom and R₂₁ is methylene and the appendent radicals q, r, and s are zero. Other contemplated polycarbosilane compounds of the invention are polycarbosilanes of Fonnula II in which R₂₁ and R₂₇ are hydrogen, R₂₀ and R₂ are methylene, and R₂₈ is an alkenyl, and appendent radicals q and r are zero. The polycarbosilanes may be prepared from well known prior art processes or provided by manufacturers of polycarbosilane compositions. Some polycarbosilanes, the R₂ι group of Formula II is a hydrogen atom; R₂₄ is -CH₂-; q, r, and s are zero and p is from 5 to 25, which can be obtained from Starfire Systems, Inc. Specific examples of these most prefened polycarbosilanes follow:

As can be observed in Formula II, the polycarbosilanes utilized may contain oxidized radicals in the form of siloxyl groups when r > 0. Accordingly, R₂₅ represents organosilicon, silanyl, siloxyl, or organo group when r > 0. It is to be appreciated that the oxidized versions of the polycarbosilanes (r > 0) operate very effectively in, and are well within the purview of the present invention. As is equally apparent, r can be zero independently of p, q, and s the only conditions being that the radicals p, q, r, and s of the Formula II polycarbosilanes must satisfy the conditions of [4< p + q + r + s< 100,000], and q and r can collectively or independently be zero.

Polycarbosilanes may be produced from starting materials that are presently commercially available from many manufacturers and by using conventional polymerization processes. As an example of synthesis of the polycarbosilanes, the starting materials may be produced from common organo silane compounds or from polysilane as a starting material by heating an admixture of polysilane with polyborosiloxane in an inert atmosphere to thereby produce the corresponding polymer or by heating an admixture of polysilane with a low molecular weight carbosilane in an inert atmosphere to thereby produce the corresponding polymer or by heating an admixture of polysilane with a low molecular carbosilane in an inert atmosphere and in the presence of a catalyst such as polyborodiphenylsiloxane to thereby produce the conesponding polymer. Polycarbosilanes may also be synthesized by Grignard Reaction reported in U.S. Patent 5,153,295 hereby incorporated by reference in its entirety.

An example of an adhesion promoter having hydroxyl groups is phenol-formaldehyde resins or oligomers of the Formula III: - [R₃₀C₆H₂(OH)(R₃₁)]_U- where R₃₀ is substituted or unsubstituted alkylene, cycloalkylene, vinyl, allyl, or aryl; R₃ι is alkyl, alkylene, vinylene, cycloalkylene, allylene, or aryl; and u=3-100. Examples of useful alkyl groups include - CH₂- and -(CH₂)_V- where v>l. A particularly useful phenol-formaldehyde resin oligomer has a molecular weight of 1500 and is commercially available from Schenectady International Inc.

Adhesion promoters can be added in small, effective amounts depending on the fluorinated polymer and/or the application. In contemplated embodiments, the at least one adhesion promoter is added in an amount less than about 30% based on the weight of the contemplated fluorinated polymer. In other contemplated embodiments, the at least one adhesion promoter is added in an amount less than about 20% based on the weight of the contemplated fluorinated polymer. In yet other embodiments, the at least one adhesion promoter is added in an amount less than about 15% based on the weight of the contemplated fluorinated polymer. In other embodiments, the at least one adhesion promoter is added in an amount less than about 7% based on the weight of the present fluorinated polymer. A layered component is also contemplated herein and comprises: a substrate; a fluorinated polymer coating material and/or film as described herein, wherein the film and/or material is coupled to the substrate; and at least one additional layer of material or film. Contemplated coating materials, coating solutions and films can be utilized are useful in the fabrication of a variety of electronic devices, micro-electronic devices, particularly semiconductor integrated circuits and various layered materials for electronic and semiconductor components, including hardmask layers, dielectric layers, etch stop layers and buried etch stop layers. These coating materials, coating solutions and films are quite compatible with other materials that might be used for layered materials and devices, such as adamantane-based compounds, diamantane-based compounds, silicon-core compounds, organic dielectrics, and nanoporous dielectrics. Compounds that are considerably compatible with the coating materials, coating solutions and films contemplated herein are disclosed in PCT Application PCT/US01/32569 filed October 17, 2001; PCT Application PCT/US01/50812 filed December 31, 2001; US Application Serial No. 09/538276; US Application Serial No. 09/544504; US Application ^' Serial No. 09/587851; US Patent 6,214,746; US Patent 6,171,687; US Patent 6,172,128; US Patent 6,156,812, US Application Serial No. 60/350187 filed January 15, 2002; and US 60/347195 filed January 8, 2002, which are all incorporated herein by reference in their entirety.

Surfaces contemplated herein may comprise any desirable substantially solid material, such as a substrate, wafer or other suitable surface. Particularly desirable substrate layers would comprise films, glass, ceramic, plastic, metal or coated metal, or composite material. Surface and/or substrate layers comprise at least one layer and in some instances comprise a plurality of layers. In prefened embodiments, the substrate comprises a silicon or germanium arsenide die or wafer surface, a packaging surface such as found in a copper, silver, nickel or gold plated leadframe, a copper surface such as found in a circuit board or package interconnect trace, a via-wall or stiffener interface ("copper" includes considerations of bare copper and its oxides), a polymer-based packaging or board interface such as found in a polyimide-based flex package, lead or other metal alloy solder ball surface, glass and polymers such as polyimide. In more prefened embodiments, the substrate comprises a material common in the integrated circuit industries as well as the packaging and circuit board industries such as silicon, copper, glass, and another polymer. Suitable surfaces contemplated herein may also include another previously formed layered stack, other layered component, or other component altogether. An example of this may be where a dielectric material and CVD baπier layer are first laid down as a layered stack - which is considered the "surface" for the subsequently spun-on layered component.

At least one layer is coupled to the surface or substrate. As used herein, the term "coupled" means that the surface and layer or two layers are physically attached to one another or there's a physical attraction between two parts of matter or components, including bond forces such as covalent and ionic bonding, and non-bond forces such as Van der Waals, electrostatic, coulombic, hydrogen bonding and/or magnetic attraction. Also, as used herein, the term coupled is meant to encompass a situation where the surface and layer or two layers are directly attached to one another, but the term is also meant to encompass the situation where the surface and the layer or plurality of layers are coupled to one another indirectly - such as the case where there's an adhesion promoter layer between the surface and layer or where there's another layer altogether between the surface and layer or plurality of layers.

Additional contemplated layers comprise inorganic-based compounds, such as silicon- based materials disclosed in commonly assigned US Patent 6,143,855 and pending US Serial No. 10/078919 filed February 19, 2002; (for example Honeywell NANOGLASS® and HOSP® products), gallium-based, germanium-based, arsenic-based, boron-based compounds or combinations thereof, and organic-based compounds, such as polyethers, polyarylene ethers disclosed in commonly assigned US Patent 6,124,421 (such as Honeywell FLARE™ product), polyimides, polyesters and adamantane-based or cage-based compounds disclosed in commonly assigned WO 01/78110 and WO 01/08308 (such as Honeywell GX-3™ product). These materials may be applied by spin coating the material on to the surface, rolling the material on to the surface, dripping the material on to the surface, and/or spreading the material on to the surface. PECVD oxide dielectric is deposited be plasma enhanced chemical vapor deposition (PECVD).

The layered component contemplated herein may also comprise a diffusion blocking material that is not on the component in the form of a layer, but is instead being used to "block" any individual pores/voids and not to cover the entire underlying layer. In some embodiments, the diffusion blocking material will react with the underlying low k dielectric material or layer and in other embodiments, the diffusion blocking material will not be reactive with the underlying low k dielectric material or layer. In other embodiments the diffusion blocking layered component contemplated may consist of a densified layer of the low k material or contain phase separated elements of the low k material densified in such a manner as to block diffusion of species. Diffusion blocking materials, such as those contemplated herein, can be found in commonly-owned US Provisional Application 60/385482 filed on June 3, 2002, which is incorporated herein in its entirety. Other materials may be utilized in additional layers of the layered component. Several of the contemplated materials are described in the following issued patents and pending applications, which are herein incorporated by reference in their entirety: (PCT/US00/15772 filed June 8, 2000; US Application Serial No. 09/330248 filed June 10, 1999; US Application Serial No. 09/491166 filed June 10, 1999; US 6,365,765 issued on April 2, 2002; US 6,268,457 issued on July 31, 2001; US Application Serial No. 10/001143 filed November 10, 2001; US Application Serial No. 09/491166 filed January 26, 2000; PCT/US00/00523 filed January 7, 1999; US 6,177,199 issued January 23, 2001; US 6,358,559 issued March 19, 2002; US 6,218,020 issued April 17, 2001; US 6,361,820 issued March 26, 2002; US 6,218,497 issued April 17, 2001; US 6,359,099 issued March 19, 2002; US 6,143,855 issued November 7, 2000; and US Application Serial No. 09/611528 filed March 20, 1998).

Solutions of organohydridosiloxane and organosiloxane resins can be utilized for forming caged siloxane polymer films that are useful in the fabrication of a variety of electronic devices, micro-electronic devices, particularly semiconductor integrated circuits and various layered materials for electronic and semiconductor components, including hardmask layers, dielectric layers, etch stop layers and buried etch stop layers. These organohydridosiloxane resin layers are quite compatible with other materials that might be used for layered materials and devices, such as adamantane-based compounds, diamantane- based compounds, silicon-core compounds, organic dielectrics, and nanoporous dielectrics. Compounds that are considerably compatible with the organohydridosiloxane resin layers contemplated herein are disclosed in PCT Application PCT/USOl/32569 filed October 17, 2001; PCT Application PCT/USO 1/50812 filed December 31, 2001; US Application Serial No. 09/538276; US Application Serial No. 09/544504; US Application Serial No. 09/587851; US Patent 6,214,746; US Patent 6,171,687; US Patent 6,172,128; US Patent 6,156,812, US Application Serial No. 60/350187 filed January 15, 2002; and US 60/347195 filed January 8, 2002, which are all incorporated herein by reference in their entirety.

Nanoporous silica dielectric films with dielectric constants ranging from 1.5 to about 3.8 can be also as at least one of the layers. Nanoporous silica compounds contemplated herein are those compounds found in US Issued Patents: 6,022,812; 6,037,275; 6,042,994; 6,048,804; 6,090,448; 6,126,733; 6,140,254; 6,204,202; 6,208,041; 6,318,124 and 6,319,855. These types of films are laid down as a silicon-based precursor, aged or condensed in the presence of water and heated sufficiently to remove substantially all of the porogen and to form voids in the film. The silicon-based precursor composition comprises monomers or prepolymers that have the formula: R_x-Si-L_y, wherein R is independently selected from alkyl groups, aryl groups, hydrogen and combinations thereof, L is an electronegative moiety, such as alkoxy, carboxy, amino, amido, halide, isocyanato and combinations thereof, x is an integer ranging from 0 to about 2, and y is an integer ranging from about 2 to about 4. Other nanoporous compounds and methods can be found in US Issued Patents 6,156,812; 6,171,687; 6,172,128; 6,214,746; 6,313,185; 6,380,347; and 6,380,270, which are incorporated herein in their entirety. Cage molecules, cage compounds and variations of these molecules and compounds are described in detail in PCT/USOl/32569 filed on October 18, 2001, which is herein incorporated by reference in its entirety.

As mentioned earlier, some additional layers may comprise a plurality of voids and/or pores in one or all of the layers. This plurality of voids can also be expressed by using the phrase "nanoporous layer". As used herein, the term "nanoporous layer" refers to any suitable low dielectric material (i.e. < 3.0) that is composed of a plurality of voids and a nonvolatile component. As used herein, the term "substantially" means a desired component is present in a layer at a weight percent amount greater than 51%. As used herein, the word "void" and/or "pore" means a volume in which mass is replaced with a gas. Appropriate gases include relatively pure gases and mixtures thereof, including air. It is contemplated that any one of the layers may comprise a plurality of voids. Voids/pores may have any suitable shape. Voids may be spherical, tubular, lamellar, discoidal, or other shapes. It is also contemplated that voids may have any appropriate diameter. It is further contemplated that voids have some connections with adjacent voids to create a structure with a significant amount of connected or "open" porosity. In prefened embodiments, voids have a mean diameter of less than 100 nanometers. In more prefened embodiments, voids have a mean diameter of less than 10 nanometers. And in still more prefened embodiments, voids have a mean diameter of less than one nanometer. It is further contemplated that voids may be uniformly or randomly dispersed within any one of the spin-on layers.

Additional layers of material may be coupled to the layered component in order to continue building a layered component or printed circuit board. It is contemplated that the additional layers will comprise materials similar to those already described herein, including metals, metal alloys, composite materials, polymers, monomers, organic compounds, inorganic compounds, organometallic compounds, resins, adhesives and optical wave-guide materials.

As used herein, the term "metal" means those elements that are in the d-block and f- block of the Periodic Chart of the Elements, along with those elements that have metal-like properties, such as silicon and germanium. As used herein, the phrase "d-block" means those elements that have electrons filling the 3d, 4d, 5d, and 6d orbitals surrounding the nucleus of the element. As used herein, the phrase "f-block" means those elements that have electrons filling the 4f and 5f orbitals surrounding the nucleus of the element, including the lanthanides and the actinides. Prefened metals include titanium, tantalum, tungsten, indium, silver, copper, aluminum, tin, bismuth, gallium and alloys thereof, silver coated copper, and silver coated aluminum. The term "metal" also includes alloys, metal/metal composites, metal ceramic composites, metal polymer composites, as well as other metal composites. As used herein, the term "compound" means a substance with constant composition that can be broken down into elements by chemical processes.

A layer of laminating material or cladding material can be coupled to the layered interface materials depending on the specifications required by the component. Laminates are generally considered fiber-reinforced resin dielectric materials. Cladding materials are a subset of laminates that are produced when metals and other materials, such as copper, are incorporated into the laminates. (Harper, Charles A., Electronic Packaging and Interconnection Handbook, Second Edition, McGraw-Hill (New York), 1997.)

Spin-on layers and materials may also be added to the layered interface materials or subsequent layers. Spin-on stacked films are taught by Michael E. Thomas, "Spin-On Stacked Films for Low ks_f Dielectrics", Solid State Technology (July 2001), incorporated herein in its entirety by reference.

Examples of other additional layers of materials comprise metals (such as those which might be used to form via fills or printed circuits and also those included in US Patent No. 5,780,755; 6,113,781; 6,348,139 and 6,332,233 all of which are incorporated herein in their entirety), metal diffusion layers, mask layers, anti-reflective coatings layers, adhesion promoter layers and the like.

The compounds, coatings, films, materials and the like described herein may be used to become a part of, form part of or form an electronic component and/or semiconductor component. As used herein, the term "electronic component" also means any device or part that can be used in a circuit to obtain some desired electrical action. Electronic components contemplated herein may be classified in many different ways, including classification into active components and passive components. Active components are electronic components capable of some dynamic function, such as amplification, oscillation, or signal control, which usually requires a power source for its operation. Examples are bipolar transistors, field- effect transistors, and integrated circuits. Passive components are electronic components that are static in operation, i.e., are ordinarily incapable of amplification or oscillation, and usually require no power for their characteristic operation. Examples are conventional resistors, capacitors, inductors, diodes, rectifiers and fuses. Electronic components contemplated herein may also be classified as conductors, semiconductors, or insulators. Here, conductors are components that allow charge carriers (such as electrons) to move with ease among atoms as in an electric current. Examples of conductor components are circuit traces and vias comprising metals. Insulators are components where the function is substantially related to the ability of a material to be extremely resistant to conduction of current, such as a material employed to electrically separate other components, while semiconductors are components having a function that is substantially related to the ability of a material to conduct current with a natural resistivity between conductors and insulators. Examples of semiconductor components are transistors, diodes, some lasers, rectifiers, thyristors and photosensors. Electronic components contemplated herein may also be classified as power sources or power consumers. Power source components are typically used to power other components, and include batteries, capacitors, coils, and fuel cells. Power consuming components include resistors, transistors, integrated circuits (ICs), sensors, and the like. Still further, electronic components contemplated herein may also be classified as discreet or integrated. Discreet components are devices that offer one particular electrical property concentrated at one place in a circuit. Examples are resistors, capacitors, diodes, and transistors. Integrated components are combinations of components that that can provide multiple electrical properties at one place in a circuit. Examples are integrated circuits in which multiple components and connecting traces are combined to perform multiple or complex functions such as logic.

EXAMPLES

TECHNICAL ISSUES:

Crystallinity Control: Ideally, crystallinity is controlled by having a polydispersity that is as close to 1 as possible and a low molecular weight. In contemplated embodiments, the polydispersity will be less than about 5. In other contemplated embodiments, the polydispersity will be less than about 3. In yet other embodiments, the polydispersity will be less than about 2. In other embodiments, the polydispersity will be less than about 1.5.

Crystallinity is also controlled by optimization of the polymerization to control polymerization microstructure. Of particular interest is the head-to-tail anangement of the monomers but of equal interest is the stereospecificity. These parameters are of interest in order to obtain the highest molecular structural regularity which encourages crystallization.

Also, i order to control and optimize crystallinity and dipole orientation, the dipole moment should be as high as possible. This optimal dipole moment is usually derived from an amorphous polymer through a combination of stress orientation and poling. However, since the polymer will likely be solution deposited and in some embodiments, formed by spin coating, the control of evaporation rate and solubility of the polymer will be keys to controlling crystallinity. Early blooming from low boiling solvents and high evaporation rates should be avoided to maximize crystallinity. A solvent blend will also likely be necessary, since the surface energies and solubilities will need to be controllable throughout the coating and baking processes.

Coating Process Considerations: hi addition, film defects may be controlled by a combination of filtration and heating which affect breakdown voltage and retention of polarization upon cycling. In particular higher polarization retention was found with samples that were filtered hot (Table 1) which indicates lower fatigue tendencies. Table 1: Electrical Test Results of Formulation Process Study

Epitaxial Pre-conditioning: Epitaxial Pre-conditioning is one method of increasing the likelihood of high chain orientation and therefore increasing the likelihood of high crystallinity. One of the most simple methods is to "roughen" on a molecular scale by wiping the substrate in a uniaxial direction. Pre-conditioning may also be done by depositing materials that are known to be highly crystalline, either by CVD or spin-cast.

Polymerization Methods: > Oxidation/reduction polymerization with a subsequent purification process, including ion exchange to remove metals and polymer fractionation by partial crystallization. Free radical emulsion polymerization followed by standard polymer fractionation with partial crystallization. Free radical solution polymerization with solvent or mixed solvent chosen to precipitate polymer at a desired molecular weight and molecular weight distribution. Anionic polymerization with stepwise addition of monomers to control monomer distribution and chain length. An example of an anionic initiator is butylithium. Polymer fractionation may still be needed to obtain monodispersity, and the Li (as an example of a metal cation used in the initiator) must be removed chemically. > TiCl₃/TiCl₄ with aluminum alkyl, followed by ion exchange metal removal and fractionation if required. This method is effective for low polymer molecular weight.

> Cationic polymerization at an interface using phase transfer catalysts with polymerization molecular weight and molecular weight distribution control by phase transfer layer.

> Any of the above with prep Liquid Chromatography or prep GPC to get the monodisperse molecular weight distribution needed.

> A combination of those shown above. For example, use anionic or BuLi polymerization with additional molecular weight distribution control by using mixed solvents or a specific solvent that allows polymer of the conect molecular weight to drop out of solution or to dissolve. Basically, it's a two fractionation process: get rid of short chains by dissolving them in a solvent or mixed solvent, then get rid of long chains by dissolving the chains you want in another solvent or at a different temperature.

Coating Solvent Considerations: HFC-245fa, trans 1,2 dichloroethylene, HCFC-141b, HCFC-123, HFC-236, HCFC-225ca/cb, blended with alcohols, ketones, chloiinated ethylenes, etc. can be used for coating. Blends can be azeotropic or azeotropic-like and may be nonflammable depending on the composition. Methods of deposition such as spin coating, aerosol spray and dip coating might be used.

Additives: Fluorocarbon additives to control thin film coating quality may also be applied. Fluorinated additives might be necessary to be compatible with the fluoropolymer. Contemplated additives are the same or similar to those produced by Honeywell International Inc. Other Co-polymers: Additional monomers include CF₃CH=CHF,

and CF CH=CFC1. These materials are derived from CF₃CH₂CF2H. Other monomers which may replace vinylidine fluoride include CHC1=CF₂, CC12=CF2 and analogues using bromide or iodide instead of chloride. Other monomers which may replace trifluoroethylene include CC1F=CF₂ and analogues using bromide or iodide instead of chloride. Chloride, bromide and iodide can subsequently be replaced by hydrogen through reduction.

EXAMPLE 1 Preparation of co-polymer using water as solvent.

1,1 Difluoroethylene (120g, 1.875mol) and 1,1,2-trifluoroethylene (51.2g,0.624mol) are charged into an autoclave followed by 500mL of water and perfluorobutylperoxide (1.199g, 2.8xl0-3mol, 0.7%wt with respect to olefins). The reactor is heated to 40-45°C and maintained for 12h. The reactor is then cooled to 20°C and the product isolated by filtration. After drying at 50°C/100mm for 4h, a yield of 34.2g (20%) is obtained. The product has a molecular weight of 205205, a polydispersity of 6.1 with a conesponding T_m of 127°C.

EXAMPLE 2 Preparation of co-polymer using water as solvent. This experiment is identical to that described in Example 1, except that the concentration of the peroxide initiator was increase to 3%wt. Yield of co-polymer was 39.4g (23%). No measurable improvement in yield is observed. The molecular weight was 131210, polydispersity of 9.8 and a T_m of 124°C

EXAMPLE 3 Preparation of co-polymer using a water/perfluorohexane solvent mix.

This experiment is identical to that described in Example 1 except that 400 mL of water and lOOmL of perfluorohexane was used as a co-solvent. Yield of co-polymer was 94.2g (55%) having a molecular weight of 200548, a polydispersity of 4.3 and a T_m of 128°C. While the yield has increased, the polydispersity value is too high and the T_m value is too low to be useful in this application.

EXAMPLE 4 Preparation of co-polymer using perfluorohexane as solvent.

This experiment is performed as described in Example 1 except the solvent has been changed to perfluorohexane. Yield of the co-polymer was 61.5g (36%) having a molecular weight of 100667, a polydispersity of 2.5 and a T_m of 146 °C. The prerequisite properties for the polymer have been achieved. EXAMPLE 5: Process to form a polymer formulation:

In this experiment, 2.5% of a 75/25% VDF/TrFE copolymer was dissolved in diethyl carbonate. The solution was heated to 70-80°C for 1 hour and then hot filtered at 39°C using a 0.1 micron filter. The formulation was deposited via spin coating on a silicon wafer using lOOOφrn, 15sec and 1500φm 15sec. The film was tested under our standard electrical test using a Sawyer-Tower circuit under the following conditions: reference capacitor at lOnF; Adjustable resistor: 0.5MOhm (needed for phase shift compensation). The transformer is used to achieve voltages higher than 10V (maximum of function generator). The capacitor area is given by Hg contact size (~0.0071cm.2); Measurements at 100Hz and 1kHz.; Fatigue tests were performed using a 10kHz signal for ~100s.

1 : Function Generator

2: Transformer, 1 :7

3: Ferroelectric capacitor

4: Linear reference capacitor

5: Adjustable resistor

6: Measurement ground

V1 : Channel 1 signal (proportional to electric field

V2: Channel 2 signal (proportional to polarization Thus, specific embodiments, methods of formation and applications of fluorinated polymers and fenoelectric polymers have been disclosed. It should be apparent, however, to those skilled in the art that many more modifications besides those already described are possible without departing from the inventive concepts herein. The inventive subject matter, therefore, is not to be restricted except in the spirit of the disclosure herein. Moreover, in inteφreting the specification, all terms should be inteipreted in the broadest possible manner consistent with the context. In particular, the terms "comprises" and "comprising" should be inteφreted as refe ing to elements, components, or steps in a non-exclusive manner, indicating that the referenced elements, components, or steps may be present, or utilized, or combined with other elements, components, or steps that are not expressly referenced.

Claims

CLAIMSWe claim:

1. A fluorinated polymer having fenoelectric properties, comprising:

at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof; and

at least one adhesion promoter.

2. The fluorinated polymer of claim 1 , where the polydispersity is less than about 5.

3. The fluorinated polymer of claim 2, wherein the polydispersity is less than about 3.

4. The fluorinated polymer of claim 3, wherein the polydispersity is less than about 1.5.

5. The fluorinated polymer of claim 1 , wherein the polymer is produced by using oxidation reduction polymerization, free radical emulsion polymerization, anionic polymerization, TiCl₃/TiCl with aluminum alkyl, cationic polymerization or a combination thereof.

6. The fluorinated polymer of claim 1 , wherein the at least one fluorine-based monomer precursor comprises trifluoroethylene, vinylidene fluoride, chlorotrifluoroethylene,

1,1,1,3-tetrafluoropropene, 1,1,1,3,3-pentafluoropropene, hexafluoropropene and combinations thereof.

7. The fluorinated polymer of claim 1 , wherein the at least one adhesion promoter is grafted onto the fluorinated polymer.

8. A film comprising the fluorinated polymer of claim 1 coupled to a substrate or surface.

9. An electronic component comprising the fluorinated polymer of claim 1.

10. An electronic component comprising the film of claim 8.

11. The film of claim 8, wherein the fluorinated polymer is deposited by spin-on coating, spray coating, dip coating, roll coating, printing, contact planarization, inkjet printing, screen printing or combinations thereof.

12. A fluorinated polymer composition having fenoelectric properties, comprising:

at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof;

at least one adhesion promoter; and

at least one solvent.

13. The fluorinated polymer of claim 12, where the polydispersity is less than about 5.

14. The fluorinated polymer of claim 13, wherein the polydispersity is less than about 3.

15. The fluorinated polymer of claim 14, wherein the polydispersity is less than about 1.5.

16. The fluorinated polymer of claim 12, wherein the polymer is produced by using oxidation/reduction polymerization, free radical emulsion polymerization, anionic polymerization, TiCl₃/TiCl₄ with aluminum alkyl, cationic polymerization or a combination thereof.

17. The fluorinated polymer of claim 12, wherein the at least one fluorine-based monomer precursor comprises trifluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, 1,1,1,3-tetrafluoropropene, 1,1,1,3,3-pentafluoropropene, hexafluoropropene and combinations thereof.

18. The fluorinated polymer of claim 12, wherein the at least one solvent comprises a fluorinated solvent.

19. The fluorinated polymer of claim 18, wherein the at least one solvent comprises 1,1,1 ,3 ,3 -pentafluoropropane, perfluoromethylcyclohexane, perfluorodecalin, perfluoromethyldecalin, benzotrifluoride, perfluoroalkane and mixtures thereof.

20. The fluorinated polymer of claim 12, wherein the at least one adhesion promoter is grafted onto the fluorinated polymer.

21. A film comprising the fluorinated polymer of claim 12 coupled to a substrate or surface.

22. An electronic component comprising the fluorinated polymer of claim 12.

23. An electronic component comprising the film of claim 21.

24. The film of claim 21 , wherein the fluorinated polymer is deposited by spin-on coating, spray coating, dip coating, roll coating, printing, contact planarization, inkjet printing, screen printing or combinations thereof.

25. A method of producing a fluorinated polymer having fenoelectric properties, comprising:

providing at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof;

providing at least one adhesion promoter;

polymerizing the at least one fluorine-based monomer precursor, at least one fluorine- based polymer or a combination thereof to produce the fluorinated polymer; and

incoφorating the at least one adhesion promoter with the fluorinated polymer.

26. The method of claim 25, further comprising providing a catalyst.

27. The method of claim 26, wherein polymerizing the at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof to produce the fluorinated polymer further includes incoφorating the catalyst.

28. The method of claim 27, wherein the catalyst comprises fluorinated alkyl or aryl peroxides, partially fluorinated alkyl or aryl peroxides or combinations thereof.

29. The method of claim 26, where the polydispersity of the fluorinated polymer is less than about 5.

30. The method of claim 29, where the polydispersity of the fluorinated polymer is less than about 3.

31. The method of claim 30, where the polydispersity of the fluorinated polymer is less than about 1.5.

32. The method of claim 26, wherein polymerization comprises oxidation/reduction polymerization, free radical emulsion polymerization, anionic polymerization, TiCl₃/TiCl with aluminum alkyl, cationic polymerization or a combination thereof.

33. The method of claim 26, wherein the at least one fluorine-based monomer precursor comprises trifluoroethylene, vinylidene fluoride, cl lorotrifluoroethylene, 1,1,1,3- tetrafluoropropene, 1,1,1,3,3-pentafluoropropene, hexafluoropropene and combinations thereof.

34. A film produced by the method of claim 26, wherein the film is coupled to a substrate.

35. An electronic component comprising the fluorinated polymer produced by the method of claim 26.

36. An electronic component comprising the film of claim 34.

37. The film of claim 34, wherein the fluorinated polymer is coupled to the substrate by depositing the fluorinated polymer by spin-on coating, spray coating, dip coating, roll coating, printing, contact planarization, inkjet printmg, screen printing or combinations thereof.

38. A method of producing a fluorinated polymer composition having fenoelectric properties, comprising: providing at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof;

providing at least one adhesion promoter;

providing at least one solvent;

polymerizing the at least one fluorine-based monomer precursor, at least one fluorine- based polymer or a combination thereof to produce the fluorinated polymer; and

incoφorating the at least one adhesion promoter and the solvent with the fluorinated polymer.

39. The method of claim 38 , further comprising providing a catalyst.

40. The method of claim 39, wherein polymerizing the at least one fluorine-based monomer precursor, at least one fluorine-based polymer or a combination thereof to produce the fluorinated polymer further includes incoφorating the catalyst.

41. The method of claim 39, wherein the catalyst comprises fluorinated alkyl or aryl peroxides, partially fluorinated alkyl or aryl peroxides or combinations thereof.

42. The method of claim 38, where the polydispersity of the fluorinated polymer is less than about 5.

43. The method of claim 42, where the polydispersity of the fluorinated polymer is less than about 3.

44. The method of claim 43 where the polydispersity of the fluorinated polymer is less than about 1.5.

45. The method of claim 38, wherein polymerization comprises oxidation/reduction polymerization, free radical emulsion polymerization, anionic polymerization, TiCl₃/TiCl₄ with aluminum alkyl, cationic polymerization or a combination thereof.

46. The method of claim 38, wherein the at least one fluorine-based monomer precursor comprises trifluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, 1,1,1,3- tetrafluoropropene, 1,1,1,3,3-pentafluoropropene, hexafluoropropene and combinations thereof.

47. The method of claim 38, wherein the at least one solvent comprises a fluorinated solvent.

48. The method of claim 47, wherein the at least one solvent comprises 1,1,1,3,3- pentafluoropropane, perfluoromethylcyclohexane, perfluorodecalin, perfluoromethyldecalin, benzotrifluori.de, perfluoroalkane and mixtures thereof.

49. A film produced by the method of claim 38, wherein the film is coupled to a substrate.

50. An electronic component comprismg the fluorinated polymer produced by the method of claim 38.

51. An electronic component comprising the film of claim 49.

52. The film of claim 49, wherein the fluorinated polymer is coupled to the substrate by depositing the fluorinated polymer by spin-on coating, spray coating, dip coating, roll coating, printing, contact planarization, inkjet printing, screen printing or combinations thereof.