JP6647780B2 - Organometallic materials and methods - Google Patents

Description

  The present invention relates generally to the field of solution-borne organometallic compounds, and more specifically to the field of electronic device manufacturing using organometallic compounds derived from this solution.

The need for specific layers with etch selectivity in lithography and for certain semiconductor fabrications, such as organic light emitting diode (OLED) fabrication or layers for blocking both oxygen and moisture in photovoltaic devices, is increasing the need for electronic devices. Manufacturing has led to the use of membranes containing oxymetal domains. The oxymetal layer is generally characterized as a membrane containing a majority of inorganic domains (oxymetal domains) with (-MO-) _n linkages, where M is a metal and n>1; And the oxymetal layer may be composed of less than half of other elements, for example carbon. The oxymetal layer can be composed of mixed domains that include both oxymetal domains and metal nitride domains.

Conventional oxymetal films can include one or more metals, such as Hf, Zr, Ti, W, Al, Ta and Mo, depending on the specific application. The etch resistance of the oxymetal domain-containing film varies, in part, with the specific metal used and the amount of (-MO-) _n domains present in the film, and such domains Provides greater etch resistance as the amount of is increased. Barrier films used for OLED applications conventionally contain Al or Si, ie, (-Al-O-) _n or (-Si-O-) _n domains (where n> 1). Include each. Aluminum oxide-containing films are known to reduce oxygen (O ₂ ) transport, while silicon oxide-containing films are known to reduce water vapor transport. Any defects in such a barrier film, such as pinholes, or any other defects that cause incomplete coverage of the underlying film, will provide a path that allows gas or vapor to access the underlying film. .

  Oxymetal films, such as alumina and silica films, are conventionally applied by chemical vapor deposition (CVD) on electronic device substrates. For example, WO 2012/103390 describes a method for reducing the transport of gas or vapor through a laminate, such as an aluminum oxide or silicon oxide layer next to a reactive inorganic layer on a flexible (plastic) substrate. A barrier laminate having one or more oxide-containing barrier layers is disclosed. According to this patent application, the reactive inorganic layer functions to react with any gas or vapor that penetrates the barrier layer. This patent application does not suggest suitable materials for forming such a barrier layer and focuses on conventional film deposition techniques, for example, deposition techniques.

  Spin-on techniques are widely used in electronic device fabrication, for example, in the deposition of oxymetal films, and spin-on techniques offer advantages over conventional deposition methods of depositing films. For example, spin-on technology can use existing equipment, can be completed within minutes, and can provide a uniform coating on a substrate. Conventional spin-on techniques allow for the deposition of one oxymetal film at a time. When multiple oxymetal films are used, such as in barrier laminates, each oxymetal film must be separately applied and cured. Conventional spin-on techniques for oxymetal films deposit a solution of the oxymetal precursor on the substrate, followed by baking to remove the solvent, and then curing to form the oxymetal film. If such a film has not been cured prior to the deposition of the second film, the solvent used in the second oxymetal precursor solution is mixed with the uncured first oxymetal film. It can cause intermixing problems.

International Publication No. WO2012 / 103390 pamphlet

  There is a need in the art for a process for providing a plurality of oxymetal films directly on an electronic device substrate from a single liquid deposition process.

The present invention provides a composition comprising a matrix precursor material, an oxymetal precursor material having a surface energy of 20 to 40 erg / cm ² , and an organic solvent, wherein the matrix precursor material is an oxymetal precursor material. Provide a composition having a surface energy higher than the surface energy.

The present invention is a step of disposing a layer of a coating composition on an electronic device substrate, wherein the coating composition has a matrix precursor material, an oxymetal precursor material having a surface energy of 20 to 40 erg / cm ² , and Comprising an organic solvent, subjecting the coating composition layer to conditions such that the layer of oxymetal precursor material forms on the layer of matrix precursor material, and the layer of matrix precursor material and There is also provided a method of forming an oxymetal layer on a matrix layer on an electronic device substrate, comprising a step of curing a layer of an oxymetal precursor material.

  As used throughout this specification, the following abbreviations shall have the following meanings unless the context clearly indicates otherwise: ca. G = gram; mg = milligram; mmol = mmol; L = liter; mL = milliliter; μL = microliter; nm = nanometer; Å = angstrom; and rpm = rotation per minute. number. Unless indicated otherwise, all amounts are percent by weight (% by weight) and all ratios are molar ratios. The term "oligomer" refers to dimers, trimers, tetramers and other relatively low molecular weight materials that can be further cured. "Alkyl" and "alkoxy" refer to linear, branched and cyclic alkyl and alkoxy, respectively. The term "curing" refers to any process that increases the molecular weight of a material or layer by polymerizing or otherwise, such as, for example, by condensation. The terms “membrane” and “layer” are interchangeable throughout this specification. The articles "a", "an" and "the" mean the singular and the plural. All numerical ranges include boundary values and can be arbitrarily combined except where it is clear that such numerical ranges are constrained to add up to 100%.

Useful coating compositions matrix precursor material in the present invention, oxy-metal precursor material having a surface energy of 20~40erg / cm ^2, and comprises an organic solvent, wherein the matrix precursor material of said oxy-metal precursor material It has a higher surface energy than the surface energy. A variety of matrix precursor materials may be suitably used, including, but not limited to, polymer-based materials, silicon-containing materials, organometallic materials, or combinations thereof, provided that such matrix precursor materials are used. The body material can be cured, has a surface energy higher than the surface energy of the oxymetal precursor material used, is soluble in the organic solvent used, and has a coating composition on a substrate. Is stable under the conditions used to place the layers, and has sufficient thermal stability to withstand the curing temperature of the oxymetal precursor material when cured. Depending on the particular oxymetal precursor material, and the particular use of the present invention, the cure temperature of the oxymetal precursor material over a period of up to 60 minutes or longer can range from 250 to 400 ° C. Was. For certain applications, such as oxygen or moisture barrier films, the matrix precursor material has a relatively dense film morphology and provides a cured matrix with relatively low polarity and hydrophilic functionality. Should. Preferably, the matrix precursor material is selected from a polymer-based material and a silicon-containing material, more preferably the matrix precursor material is a silicon-containing material. The matrix precursor material used in the coating composition of the present invention has a higher surface energy than the surface energy of the oxymetal precursor material. Preferably, the matrix precursor material has a high surface energy 10erg / cm ² or more than the surface energy of the oxy-metal precursor materials used, and more preferably, has a high surface energy 15erg / cm ² or more.

Typical polymer matrix precursor materials useful in the present invention include, but are not limited to, polyarylene materials, such as polyphenylene materials, and arylcyclobutene-based materials, such as SiLK ⁽ available from The Dow Chemical Company ^{). R)} and CYCLOTENE ^(TM) under the brand those available respectively the like. Those skilled in the art will recognize that a variety of other polymeric matrix materials can be suitably used as the matrix precursor material in the present invention. Such polymer-based materials can be commercially available or can be manufactured by various known methods.

Typical silicon-containing matrix precursor materials include, but are not limited to, siloxane materials and silsesquioxane materials, preferably silsesquioxane. The siloxane material has the general formula (R ₂ SiO ₂ ) _n And the silsesquioxane material has the general formula (RSiO _3/2 ) _n Wherein R is typically OH, C _1-4 Alkoxyl, C _1-4 Alkyl and C _6-10 This R substituent on at least one Si is selected from _1-4 Alkyl and C _6-10 Selected from aryl. Suitable silsesquioxanes are typically prepared by a condensation reaction between one or more organotrialkoxysilanes, the organotrialkoxysilanes typically having the formula RSi (OR) ₃ (Wherein each R is independently C _1-4 Alkyl, and C _6-10 Selected from aryl). Such silicon-containing materials are generally commercially available, for example, from Dow Corning (Midland, Michigan), or various methods known in the art, for example, US Pat. No. 273 (You et al.). Such silicon-containing materials include silicon-metal hybrid materials, for example, silicon-titanium hybrid materials and silicon-zirconium hybrid materials.

  Various organometallic materials can be used as the matrix precursor material. Suitable organometallic materials are film-forming and are typically polymeric (eg, oligomeric), but may be non-polymeric and include a single metal, Alternatively, two or more different metals may be included. That is, a single organometallic material, eg, an oligomer, may have only one metal species or may include two or more different metal species. Alternatively, a mixture of organometallic materials, each material having a single metal species, may be used to deposit the mixed metal film. It is also preferred that the organometallic material comprises one or more atoms of a single metal species that is not a different metal species. Suitable metals useful in the organometallic materials of the present invention are any metals from Groups 3-14 of the Periodic Table. Preferably, the metal is selected from Groups 4, 5, 6, and 13, and more preferably, from Groups 4, 5, and 6. Preferred metals include titanium, zirconium, hafnium, tungsten, tantalum, molybdenum and aluminum, more preferably titanium, zirconium, hafnium, tungsten, tantalum and molybdenum.

  One type of organometallic material suitable for use in the compositions of the present invention is a metal-oxygen oligomer of formula (1):

Wherein each X is independently selected from a light attenuating moiety, a diketone, a _C2-20 polyol, and a _C1-20 alkoxide, and M is a Group 3-14 metal. Preferred X substituents are diketones and _{C 1-20} alkoxide, more preferably a diketone and _{C 1-10} alkoxide. In certain embodiments, at least one X is preferably a diketone having the structure:

Wherein each R is independently selected from hydrogen, C _1-12 alkyl, C _6-20 aryl, C _1-12 alkoxy and C _6-10 phenoxy, and more preferably both X substituents are Diketone. More preferably, each R is independently selected from C _1-10 alkyl, C _6-20 aryl, C _1-10 alkoxy and C _6-10 phenoxy. Typical groups for R include methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenethyl, naphthyl, phenoxy, methylphenoxy, dimethylphenoxy, ethylphenoxy and phenyloxy-methyl. A preferred structure of the metal-oxygen oligomer has the following formula (1a):

Wherein M, X and R are as described above. This metal-oxygen oligomer is disclosed in U.S. Patent No. 7,364,832. Also similar metal-oxygen oligomers useful in the present invention are U.S. Patent Nos. 6,303,270, 6,740,469, and 7,457,507, and U.S. Patent Application Publication No. 2012/0223418. No.

  Another suitable type of organometallic material useful in the present invention is an oligomer containing one or more pendant metal-containing groups. Preferably, the organometallic oligomer comprising one or more metal-containing pendant groups comprises as polymerized units one or more (meth) acrylate monomers, and more preferably, one or more metal-containing (meth) acrylate monomers. Even more preferably, the organometallic oligomer comprising one or more metal-containing pendant groups comprises, as polymerized units, one or more monomers of the following formula (2):

Where R ¹ = H or CH ₃ , M = Group 3-14 metal, L is a ligand, and n represents the number of ligands and is an integer from 1 to 4. Preferably, M is a metal selected from Groups 4, 5, 6 and 13, more preferably a metal selected from Groups 4, 5, and 6. Preferably, M = titanium, zirconium, hafnium, tungsten, tantalum, molybdenum and aluminum, more preferably titanium, zirconium, hafnium, tungsten, tantalum and molybdenum, even more preferably zirconium, hafnium, tungsten and tantalum. is there.

The ligand L in formula (2) can be any suitable ligand, as long as it can be cleaved during the curing step to form a metal oxide-containing hardmask. Preferably, the ligand comprises an oxygen or sulfur atom bound to, coordinated with, or otherwise interacting with the metal. Typical types of ligands include one or more of the following groups: alcohols, thiols, ketones, thiones and imines, and preferably alcohols, thiols, ketones and thiones. Preferably, L, C _1-6 alkoxy, beta - diketonate, beta - hydroxy Kettner DOO, beta - ketoesters, beta - is selected from one or more hydroxy imine - Jikechiminato, amidinate, guanidinate and beta. L is, C _1-6 alkoxy, beta - diketonate, beta - hydroxy ketones and beta - more preferably selected from one or more keto ester, and even more preferably, L is selected from C _1-6 alkoxy Is done. The number of ligands is represented by "n" in formula (2), where n is an integer of 1-4, preferably 2-4, and more preferably 3-4. Preferred monomers of formula (2) include Zr (C _1-4 alkoxy) ₃ acrylate, Zr (C _1-4 alkoxy) ₃ methacrylate, Hf (C _1-4 alkoxy) ₃ acrylate, Hf (C _1-4 Alkoxy) ₃ methacrylate, Ti (C _1-4 alkoxy) ₃ acrylate, Ti (C _1-4 alkoxy) ₃ methacrylate, Ta (C _1-4 alkoxy) ₄ acrylate, Ta (C _1-4 alkoxy) ₄ methacryl Acrylate, Mo (C _1-4 alkoxy) ₄ acrylate, Mo (C _1-4 alkoxy) ₄ methacrylate, W (C _1-4 alkoxy) ₄ acrylate, and W (C _1-4 alkoxy) ₄ methacrylate . The organometallic compound of formula (2) can be prepared by various methods, such as by reacting a metal tetraalkoxide with acrylic acid or methacrylic acid in a suitable solvent (eg, acetone).

The organometallic oligomer containing one or more pendant metal-containing groups may be composed of polymerized units of a single monomer (homopolymer) or may be composed of polymerized units of a mixture of two or more monomers (copolymer). Suitable copolymers can be made by conventional methods, such as by polymerizing one or more monomers containing pendant metal-containing groups with one or more other monomers, and such other monomers may optionally be And pendant metal-containing groups as disclosed in U.S. Patent Application No. 13 / 624,946. Suitable ethylenically unsaturated monomers include, but are not limited to, alkyl (meth) acrylate monomers, aryl (meth) acrylate monomers, hydroxyalkyl (meth) acrylate monomers, alkenyl (meth) acrylate, (meth) acrylic acid, And vinyl aromatic monomers such as styrene and substituted styrene monomers. Preferably, the ethylenically unsaturated monomers are selected from _C1-12 alkyl (meth) acrylate monomers, and hydroxy ( _C1-12 ) alkyl (meth) acrylate monomers, and more preferably _C1-12 alkyl ( It is selected from meth) acrylate monomers and hydroxy ( _C2-6 ) alkyl (meth) acrylate monomers. Such a copolymer can be a random, alternating or block copolymer. These organometallic oligomers comprise as polymerized units monomers containing metal-containing pendant groups, such as metal-containing (meth) acrylate monomers, as well as from one, two, three, four or more types of ethylenically unsaturated monomers. It may be configured.

  A further class of organometallic materials suitable for use as matrix precursor materials in the coating compositions of the present invention are compounds of formula (3):

In the formula, R ² ＣC _1-6 alkyl, M ¹ is a Group 3 to Group 14 metal, and R ³ ＣC _2-6 alkylene-X— or C _2-6 alkylidene-X— X is independently selected from O and S; z is an integer from 1 to 5; L ¹ is a ligand; m represents the number of ligands and an integer from 1 to 4; It is an integer of 25. Preferably, R ² is C _2-6 alkyl, more preferably C _2-4 alkyl. Preferably, M ¹ is a metal selected from Groups 4, 5, 6, and 13, and more preferably a metal selected from Groups 4, 5, and 6. M ¹ = preferably titanium, zirconium, hafnium, tungsten, tantalum, molybdenum and aluminum, more preferably titanium, zirconium, hafnium, tungsten, tantalum and molybdenum, and even more preferably titanium, zirconium, hafnium , Tungsten and tantalum. X is preferably O. Is preferably R ³ is selected from _{C 2-4} alkylene -X- and _{C 2-4} alkylidene -X-, preferably from _{C 2-4} alkylene -O- and _{C 2-4} alkylidene -O- by arrangement Selected. Preferably, p = 5-20, more preferably 8-15. Preferably, z = 1 to 4, and more preferably, z = 1 to 3.

Ligand L ¹ in the formula (3) it is, as long as can be cleaved to form a metal oxide-containing hard mask during the curing process, the ligand may be any suitable ligand. Preferably, the ligand comprises an oxygen or sulfur atom bound to, coordinated with, or otherwise interacting with the metal. Typical types of ligands include one or more of the following groups: alcohols, thiols, ketones, thiones and imines, and preferably alcohols, thiols, ketones and thiones. Preferably, L ¹ is selected from one or more of C _1-6 alkoxy, beta-diketonate, beta-hydroxyketonate, beta-ketoester, beta-diketiminate, amidinate, guanidinate and beta-hydroxyimine. L ¹ is, C _{1-6 -} alkoxy, beta - diketonate, beta - hydroxy Kettner DOO and beta - it is more preferable to be selected from one or more keto ester, and even more preferably L ¹ is beta diketonate, It is selected from beta-hydroxyketonates and beta-ketoesters. The number of ligands is represented by “m” in formula (3), where m can be 1 to 4, and preferably 2 to 4. Preferred ligands for L ¹ include benzoylacetonate, pentane-2,4-dionate (acetoacetate), hexafluoroacetoacetate, 2,2,6,6-tetramethylheptane-3,5-dionate, and Ethyl-3-oxobutanoate (ethyl acetoacetate). Oligomers of formula (3) can be prepared by conventional means known in the art, such as, for example, those disclosed in US patent application Ser. No. 13 / 624,946.

  A variety of non-polymeric organometallic materials can be used as the matrix precursor material in the coating compositions of the present invention, provided that such compounds are capable of forming a film under the conditions used. Suitable non-polymeric organometallic materials may be homoleptic or heteroleptic (ie, include different ligands) and include, but are not limited to, metal ketonates, metal ketiminates, metal amidinates, and the like. Typical non-polymeric organometallic compounds include, but are not limited to, hafnium 2,4-pentanedionate, hafnium di-n-butoxide (bis-2,4-pentanedionate), hafnium tetramethylheptanedion Nato, hafnium trifluoropentanedionate, titanium allyl acetoacetonate tris-iso-propoxide, titanium di-n-butoxide (bis-2,4-pentanedionate), titanium di-iso-propoxide (bis-2,4) -Pentanedionate), titanium di-iso-propoxide (bis-tetramethylheptanedionate), tantalum (V) tetraethoxide 2,4-pentanedionate, zirconium di-n-butoxide (bis-2,4- Pentanedionate), zirconium di-isopropoxy (Bis-2,4-pentanedionate), zirconium dimethacrylate di-n-butoxide, zirconium tetramethacrylate, zirconium hexafluoropentanedionate, zirconium tetra-2,4-pentanedionate, zirconium 2,2 6,6-tetramethyl-3,5-heptanedionate, and zirconium trifluoropentanedionate. Such non-polymeric organometallic materials are generally commercially available or can be made by various known methods.

  It will be appreciated by those skilled in the art that more than one organometallic material can be used as the matrix precursor material in the coating composition of the present invention. If a combination of organometallic materials is used, these materials may be in various amounts, for example, from 90: 1 to 1:99 (weight ratio), preferably from 90:10 to 10:90 (weight). Ratio) can be used in varying amounts. Preferably, no combination of organometallic materials is used.

Various oxymetal precursor materials can be suitably used in the coating compositions of the present invention, provided that such oxymetal precursor materials can form films, can be cured, It has a (static) surface energy of 40 erg / cm ² and is soluble in the organic solvents used. Preferably, oxymetal precursor material 20~35erg / cm ^2, and more preferably it has a (static) surface energy in the range of 20~30erg / cm ^2. The oxymetal precursor material of the present invention is different from the matrix precursor material.

Suitable oxymetal precursor materials include metals selected from Groups 3-14 and have at least one low surface energy ligand, ie, a ligand that is relatively more hydrophobic. Preferably, the oxymetal precursor material comprises a metal selected from titanium, zirconium, hafnium, tungsten, tantalum, molybdenum and aluminum. Low surface energy ligands have more fatty (ie, hydrocarbyl) properties as compared to other ligands used in oxymetal precursor materials or as compared to matrix precursor materials. Branched or cyclic alkyl moieties are considered to be relatively more hydrophobic than the corresponding linear alkyl moieties, and increasing the branched or cyclic nature of such moieties is dependent on the ligand and its It is believed to help lower the surface energy of the resulting oxymetal precursor material. Similarly, increasing carbon chain length of the alkyl and aryl moieties also lowers the surface energy of the ligand. The low surface energy ligand contains one or more _C4-20 hydrocarbyl moieties. Suitable hydrocarbyl moieties include aliphatic and aromatic hydrocarbyl moieties. The hydrocarbyl moiety may be optionally substituted with fluorine, in which case one or more of the hydrogens in the hydrocarbyl moiety is replaced with a corresponding number of fluorine. Preferred hydrocarbyl moieties are C _4-20 alkyl and C _6-20 aryl, each of which is optionally substituted with fluorine. Such C _4-20 hydrocarbyl moieties may be linear, branched or cyclic. C _6-20 aryl moieties include C _6-20 aralkyl moieties and C _6-20 alkaryl moieties such as benzyl, phenethyl, tolyl, xylyl, ethylphenyl, styryl and the like. If the low surface energy ligand contains a _C4-6 alkyl moiety, the alkyl moiety is preferably branched or cyclic. Preferably, the low surface energy ligand is one or more _C6-20 hydrocarbyl moieties, more preferably one or more _C6-16 hydrocarbyl moieties, even more preferably one or more _C8-16 hydrocarbyl moieties, and even more preferably. _Contains one or more _C10-16 hydrocarbyl moieties. Preferred compounds useful for forming low surface energy ligands in the oxymetal precursor materials of the present invention are alcohols having a _C4-20 hydrocarbyl moiety, and carboxylic acids having a _C4-20 hydrocarbyl moiety. When a carboxylic acid containing compound is used to form a low surface energy ligand, it is preferred that the carboxylic acid containing compound has one carboxylic acid functional group. Compounds having multiple carboxylic acid functionalities tend to form gels, which are not suitable for the coating compositions of the present invention.

  Oxymetal precursor materials useful in the coating compositions of the present invention may be monomeric or oligomeric, and are preferably oligomeric. Preferred oxymetal precursor materials are those of the following general formula (4):

Wherein M is a Group 3-14 metal, and L ¹ is selected from (C ₁ -C ₆ ) alkoxy, (C ₁ -C ₃ ) carboxyalkyl, and (C ₅ -C ₂₀ ) β-diketonate. _Where L ² is a low surface energy ligand containing a C _4-20 hydrocarbyl moiety, m is the valency of M, z is an integer from 1 to 50, and x 2 is 0 to (m (z) −2). Y2 is an integer from 1 to (m (z) -2 (z-1)), and x2 + y2 = m (z) -2 (z-1). is there. Preferably, m = 3 or 4. Preferably, z = 1-30, more preferably 1-25, even more preferably 1-20, even more preferably 3-25, and even more preferably 3-15. . Preferably, L ² _ＯO —C _4-20 hydrocarbyl or OC (O) —C _4-20 hydrocarbyl, and more preferably L ² _ＯO —C _6-20 hydrocarbyl or OC (O) —C _{6. -20} hydrocarbyl, and even more preferably ^L 2 _{= OC 6-16} hydrocarbyl or OC _{(O) -C 6-16} hydrocarbyl. Optionally, _(C 4 _{-C 20)} hydrocarbyl moiety ^{L 2} is hydroxyl, carboxylic _acid, 1 or more substituents selected from the group consisting of _(C 1 -C ₆₎ alkyl carboxylate and fluoro, preferably One or more substituents selected from the group consisting of (C ₁ -C ₆ ) alkyl carboxylate and fluoro, and more preferably one or more selected from the group consisting of (C ₁ -C ₄ ) alkyl carboxylate and fluoro Including a substituent of Suitable low surface energy ligands (L ² ) include, but are not limited to, hexanoate, heptanoate, octanoate, nonanoart, decanoate, dodecanoate, cyclohexanoate, benzoate, methylbenzoate, naphthanoate, phenoxy, benzyloxy, benzyloxy, t -Butoxy and cyclohexyloxy. For certain applications, in order to provide oxy-metal precursor material having a sufficiently low surface energy, L ¹ all ligands need not be replaced by L ² ligand. In some embodiments, the amount of ^{L 2} ligands, based on the total number of ligands, 25% to 100%, more preferably 25-95%, even more preferably 30-95%, and even more preferably 35 to 90 %. This percentage of ^{L 2} ligands according to the equation y2 / (x2 + y2) × 100 ( respectively, wherein the x2 and y2 represents the number of ^{L 1} ligand and ^{L 2} ligand), can be calculated.

The oxymetal precursor materials of the present invention can be made by various procedures known in the art, and typically have the formula M ^{+ m} X _m , where X is the ligand to be exchanged A starting metal compound, for example (C ₁ -C ₆ ) alkoxy or (C ₅ -C ₂₀ ) β-diketonate, and a suitable low surface energy ligand such as HL ² , or an alkali or alkaline earth salt thereof. , For example, K ⁺ -L ^{2 wherein} L ² is as defined above. Preferably, the low surface energy ligands used in the ligand exchange reaction has the formula HL ^2. In a general procedure, a starting metal compound is combined with a low surface energy ligand and a suitable organic solvent in a flask. The mixture is then heated to a temperature, typically from room temperature to 80 ° C. or higher, for a time to allow the desired ligand exchange to occur. After this procedure, one, two or all three of the (C ₁ -C ₆ ) alkoxy or (C ₅ -C ₂₀ ) β-diketonate ligands on the starting metal compound have a corresponding number of low Can be exchanged for surface energy ligands. The number of (C ₁ -C ₆ ) alkoxy or (C ₅ -C ₂₀ ) β-diketonate ligands to be replaced depends on the specific (C ₁ -C ₆ ) alkoxy or (C ₅ -C ₂₀ ) β-di. The steric hindrance of the ketonate ligand, the steric hindrance of the particular low surface energy ligand used, and the length of time that the mixture is heated will vary, with longer times being more. It will be recognized by those skilled in the art that this will result in a ligand exchange of

  The coating composition of the present invention also includes one or more organic solvents. A variety of organic solvents can be used as appropriate, provided that the matrix precursor material and the oxymetal precursor material are soluble in the selected solvent or mixture of solvents. Such solvents include, but are not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, lactones, esters, glycols, glycol ethers and mixtures thereof. Typically, organic solvents include, but are not limited to, toluene, xylene, mesitylene, alkylnaphthalene, 2-methyl-1-butanol, 4-methyl-2-pentanol, gamma-butyrolactone, ethyl lactate, Examples include hydroxyisobutylic acid methyl ester, propylene glycol methyl ether acetate, and propylene glycol methyl ether. In a preferred embodiment, a solvent system comprising a majority of the first solvent and less than half of the second solvent is used. More preferably, the first solvent has a relatively low surface energy, and the second solvent has a relatively higher boiling point than the first solvent, and the second solvent is an oxymetal It has a higher surface energy (tension) than the surface energy of the precursor material. Exemplary second solvents include, but are not limited to, gamma-butyrolactone, gamma-valerolactone, dipropylene glycol methyl ether, benzyl benzoate, and the like. Typically, when a solvent mixture is used, the amount of the second solvent is present in an amount of 0.1 to 10% by weight, based on the total weight of the solvent system, with the balance being the first. Is the weight of the solvent. Preferably, the organic solvent contains less than 10,000 ppm water, more preferably less than 5000 ppm water, and even more preferably less than 500 ppm water. It is preferable that the organic solvent does not contain a carboxylic acid group and a sulfonic acid group.

The coating composition of the present invention may optionally include one or more additives, such as a curing catalyst, antioxidants, dyes, contrast agents, binder polymers, and the like. Depending on the application, it may be desirable to add one or more curing catalysts to the compositions of the present invention to assist in curing the matrix and / or oxymetal precursor materials. Typical curing catalysts include thermal acid generators (TAGs) and photoacid generators (PAGs). TAG and its use are well known in the art. Examples of TAGs include those sold by King Industries, Norwalk, Connecticut, USA under the NACURE ^™ , CDX ^™, and K-PURE ^™ names. Photoacid generators (PAGs) and their use are well known in the art, and photoacid generators are activated by exposure to light of a suitable wavelength or by exposure to a beam of electrons (e-beam). To generate acid. Suitable PAGs are available from various sources, for example, under the IRGACURE ^™ brand from BASF ⁽ Ludwigshafen, Germany). Various binder polymers can be used to provide improved coating quality or leveling on the substrate, especially when the matrix precursor material is an organometallic material. Suitable binder polymers are disclosed in U.S. Patent Application No. 13 / 776,496.

  The coating composition of the present invention can be prepared by combining the matrix precursor material, the oxymetal precursor material, the organic solvent, and any optional additives in any order. One skilled in the art will recognize that the concentrations of the components in the compositions of the present invention can be varied over a wide range. Preferably, the matrix precursor material is present in the composition in an amount of 2-20%, preferably 4-15%, and more preferably 6-10% by weight, based on the total weight of the coating composition. I do. Preferably, the oxymetal precursor material is present in the composition in an amount of 3 to 15%, more preferably 5 to 10%, and even more preferably 5 to 8% by weight, based on the solids content of the matrix precursor material. Present in the amount. One skilled in the art will recognize that higher or lower amounts of such components may be used in the coating compositions of the present invention.

  In use, the coating composition of the present invention is disposed on an electronic device substrate. Various electronic element substrates, such as packaging substrates such as multi-chip modules, flat panel display substrates, integrated circuit substrates, substrates for light emitting diodes (LEDs), such as organic light emitting diodes (OLEDs), semiconductor wafers, Polycrystalline silicon substrates and the like can be used in the present invention. Such substrates are typically silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, gold, It is composed of at least one of glass, organic or inorganic coated glass. Suitable substrates can be in the form of wafers such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, integrated optical circuits and LEDs. As used herein, the term "semiconductor wafer" refers to "electronic device substrate," "semiconductor substrate," "semiconductor device," and various packages for various levels of interconnection, such as single chip wafers , Multi-chip wafers, packages for various levels, or other assemblies that require solder connections. Particularly suitable substrates include LEDs, for example, OLEDs. Such a substrate can be of any suitable size. The preferred wafer substrate diameter is between 200 mm and 300 mm, but wafers having smaller and larger diameters may be suitably used in accordance with the present invention. As used herein, the term "semiconductor substrate" includes any structure having an active or drivable portion of a semiconductor device or any substrate having one or more semiconductor layers. The term "semiconductor substrate" refers to, but is not limited to, bulk semiconductor materials, such as semiconductor wafers alone or in assemblies containing other materials, as well as assemblies alone or containing other materials. Are defined to mean any construct that includes a semiconductor material, including a layer of semiconductor material. A semiconductor device refers to a semiconductor substrate on which at least one microelectronic element has been fabricated or has been batch fabricated. Preferred substrates are substrates for LEDs, more preferably substrates for OLEDs. Also preferred are flexible display substrates and photovoltaic element substrates, more preferred are flexible display substrates for LEDs and more preferably for OLEDs.

  The coating composition of the present invention may be disposed on the electronic device substrate by any suitable means, for example, spin coating, slot die coating, doctor blading, curtain coating, roller coating, spray coating, dip coating, and the like. Spin coating and slot die coating are preferred. In a typical spin coating method, the composition of the present invention is applied to a substrate rotating at a speed of 500-4000 rpm for a period of 15-90 seconds to form a matrix precursor material and an oxymetal precursor material. Obtain the desired layer. Those skilled in the art will recognize that the overall height of the layer can be adjusted by varying the spin rate, as well as the percentage of solids in the composition.

  Without wishing to be bound by theory, the oxymetal precursor material migrates toward the surface of the forming film during deposition of the composition of the present invention and during any subsequent solvent removal steps. It is thought that. It is believed that the relatively low surface energy of the oxymetal precursor material helps the oxymetal precursor material to move to the air interface. The result is a multilayer structure in which a layer of oxymetal precursor material is disposed over a layer of matrix precursor material. Although there may be some intermixing of these layers, the top of the structure will be composed of a majority of the oxymetal precursor material, while the bottom will be composed of a majority of the matrix precursor material. Will be composed. One skilled in the art will recognize that such migration of the oxymetal precursor material should occur substantially prior to complete curing of the matrix precursor material. The formation of a cured matrix material film substantially inhibits migration of the oxymetal precursor material.

  During or after depositing the coating composition of the present invention on an electronic device substrate to form a multilayer structure (oxymetal precursor material layer over matrix precursor material layer), the structure is optionally relatively low. Baking at temperature removes any residual solvent and other relatively volatile components. Typically, the substrate is baked at a temperature of no more than 125C, preferably 60-125C, and more preferably 90-115C. The bake time is typically between 10 seconds and 10 minutes, preferably between 30 seconds and 5 minutes, and more preferably between 6 and 180 seconds. If the substrate is a wafer, this baking step can be performed by heating the wafer on a hot plate.

After an optional baking step to remove the solvent, the multilayered layer is cured, for example, in an oxygen-containing atmosphere, for example in air, or in an inert environment, for example in nitrogen. The curing step is preferably performed on a hot plate type apparatus, but oven curing may be used to achieve equivalent results. Typically, this curing is performed by heating the multilayer structure at a curing temperature of 150C or higher, preferably 150-400C. More preferably, the curing temperature is from 200 ° C to 400 ° C, even more preferably from 250 ° C to 400 ° C, and even more preferably from 250 ° C to 400 ° C. The choice of final cure temperature will vary primarily depending on the desired cure rate, with higher cure temperatures requiring shorter cure times. When the oxymetal precursor material layer of the present invention is cured at a temperature of 200 ° C. or more, the resulting oxymetal domain-containing film may be stripped with a solvent conventionally used in the application of antireflective coatings and photoresists ( (Removed). When the oxymetal precursor material of the present invention is cured at a temperature of 350 ° C. or higher, the resulting oxymetal domain-containing film may be developed using an alkali or solvent developer conventionally used in developing a photoresist layer to be imaged. Resistant to peeling by agents. Typically, the cure time can be from 10 seconds to 30 minutes, preferably 30 seconds to 30 minutes, more preferably 45 seconds to 30 minutes. During the curing step, at least a portion of the matrix precursor material forms a cured matrix material, and at least a portion of the oxymetal precursor material cures to form (-MO-) _n , where n> 100. A layer including an oxymetal domain having a connection is formed. Typically, the amount of metal in the cured oxymetal domain containing film can be up to 95 mol% (or higher), and preferably 50-95 mol%. The cured oxymetallic material layer may include, in addition to the oxymetallic domains, other domains, such as metal nitride domains, and in some cases, carbon in an amount of, for example, 5 mol% or less. Will be recognized by those skilled in the art.

  An initial baking step is not required if the final curing step is performed in such a way that the rapid development of solvents and curable by-products does not destroy film quality. For example, a ramped bake starting at a relatively low temperature and then gradually increasing to a range of 250-400 ° C. may produce acceptable results. In some cases, it may be preferable to have a two-stage curing process where the first stage is a low bake temperature below 250C and the second stage is a higher bake temperature, preferably 250-400C. The two-step curing process promotes uniform film formation and planarization of pre-existing substrate surface topology.

While not wishing to be bound by theory, the conversion of the oxymetal precursor material to the oxymetal domain containing film may be caused by the moisture contained in the coating and / or the atmospheric pressure during the deposition (casting) and during the curing process. It is thought to be accompanied by hydrolysis by the moisture adsorbed from. Thus, the curing process is preferably performed in air or an atmosphere in the presence of moisture to promote complete conversion of the oxymetal precursor material to the oxymetal domain containing film. However, when the polymeric matrix precursor material is used, in order to reduce the likelihood of degradation of the polymeric material, under an inert atmosphere, for example, it is preferable to cure the matrix precursor material under N ₂ . This curing process can also be assisted by exposure of the coating to ultraviolet radiation, preferably in the wavelength range of about 200-400 nm. This exposure process can be applied separately from or in conjunction with the thermosetting process.

  In some cases, a second layer of the coating composition of the present invention can be disposed on the cured oxymetallic material layer and can be treated as described above. This results in a cured structure having an alternating layer structure of cured matrix material-oxymetal material-matrix material-oxymetal material. This process can be repeated any number of times, and a stack of such alternating layers can be constructed.

  Depending on the specific application, the cured oxymetallic material layer of the present invention can be subjected to further processing steps, such as patterning. Such additional processing steps may require the application of one or more organic materials, such as a photoresist and an anti-reflective coating, to the surface of the oxymetal material layer. The cured oxymetallic material layer typically has a surface energy that is very different from the surface energy of the subsequently applied organic layer. This surface energy mismatch causes poor adhesion between the oxymetal material layer and the subsequently applied organic layer. In the case of a subsequently applied photoresist layer, this surface energy mismatch results in severe pattern collapse. In order to make the surface of the oxymetallic material film of the present invention more compatible with the subsequently applied organic layer, this surface may optionally be treated with a suitable surface treatment.

A surface treatment composition useful for treating the surface of a cured oxymetal material film is disclosed in U.S. Patent Application No. 13 / 745,752, which comprises an organic solvent and a surface treatment agent, wherein the surface treatment composition comprises The treatment agent includes one or more surface treatment portions. In some cases, the surface treatment composition can further include one or more additives, such as a thermal acid generator, a photoacid generator, an antioxidant, a dye, a contrast agent, and the like. Various organic solvents, such as, but not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, lactones, esters, glycols, glycol ethers and mixtures thereof may be suitably used. Typical organic solvents include, but are not limited to, toluene, xylene, mesitylene, alkylnaphthalene, 2-methyl-1-butanol, 4-methyl-2-pentanol, gamma-butyrolactone, ethyl lactate, 2-hydroxyisobutyrate Ric acid methyl ester, propylene glycol methyl ether acetate, and propylene glycol methyl ether. Suitable solvents have a relatively higher vapor pressure than the surface treatment agent, so that the solvent can be removed from the surface of the membrane, leaving the surface treatment agent behind. It is preferred that the organic solvent has no free carboxylic or sulfonic acid groups. Various surface treatments can be used in the surface treatment composition, and the surface treatment can be polymeric or non-polymeric, and the surface treatment comprises one or more surface treatment moieties. Can be included. Exemplary surface treated portion, hydroxyl (-OH), thiol (-SH), carboxyl _(-CO 2 H), Betajiketo _{(-C (O) -CH 2 -C} (O) -), protected Carboxyl and protected hydroxyl groups. Although the amino groups will function, the surface treatment agent preferably does not contain amino groups, and preferably does not contain nitrogen, because such groups are applied to a subsequently applied coating, such as a chemically amplified photo This is because the function of the resist may be adversely affected. A protected carboxyl group and a protected hydroxyl group are any groups that are cleavable under certain conditions and give rise to a carboxyl group or a hydroxyl group, respectively. The protected carboxyl and protected hydroxyl groups are well known in the art. If the surface treatment agent contains one or more protected hydroxyl groups, it is preferred that a thermal acid generator (TAG) or a photoacid generator (PAG) be used in the surface treatment composition.

  Since surface energy is often difficult to measure, a surrogate measurement, such as the water contact angle, is typically used. The determination of the water contact angle is well known and the preferred method uses a Kruss drop shape analyzer model 100, using deionized (DI) water and a droplet size of 2.5 μL. The cured oxymetal material layer typically has a water contact angle of 50 ° or less, for example, 35-45 °. After treatment with the surface treatment composition, the oxymetal material film surface typically has a water contact angle of 55 ° or more, for example 55-70 °. After treatment with the surface treatment agent, the oxymetal material film surface has a surface energy that substantially matches the surface energy of the subsequently applied organic layer, i.e., the surface energy of the treated hard mask layer is It should be within 20% of the surface energy of the subsequently applied organic layer. An organic layer applied over the oxymetal material layer with subsequent processing steps will have fewer defects compared to the oxymetal material film without such surface treatment.

  The cured matrix and oxymetal materials of the present invention can function properly as hard mask layers, dielectric layers, barrier layers, and the like. A preferred barrier layer structure produced according to the present invention comprises a layer of silicon oxide matrix material having a layer of titanium oxide or aluminum oxide (oxymetal material layer) disposed on the surface of the silicon oxide layer. This barrier layer structure is particularly suitable for use as an oxygen barrier in the manufacture of LEDs and preferably in the manufacture of OLEDs.

Example 1 Alumoxane Material 12.0 g of aluminum tris-isopropoxide (i.e., Al (Oi-Pr) ₃ ) in a 250 mL round bottom flask equipped with a magnetic stir bar and connected to a condenser and thermocouple. Was mixed with 150.0 g of ethyl lactate. With proper stirring, the mixture in the flask was heated by means of a heating mantle controlled by a thermocouple. The mixture was heated to reflux temperature and maintained at reflux for 2 hours. The heating was then stopped and the mixture was allowed to cool to room temperature with stirring. Ligand exchange reaction in this excess ethyl lactate provided tris ((1-ethoxy-1-oxopropan-2-yl) oxy) aluminum. Then 0.90 g DI water and 60.0 g ethyl lactate were mixed and the aqueous solvent mixture was fed into the reactor with stirring over a period of about 13 minutes. The reaction mixture was then heated again to reflux and held at reflux for 2 hours after which time heating was stopped and the reaction mixture was allowed to cool to room temperature, resulting from ethyl lactate. An alumoxane trimer with five ligands was provided. The reaction mixture was then filtered through a 1.0 μm perfluoropolyethylene (PFPE) filter to remove insoluble materials and then filtered through a 0.2 μm PFPE filter. Using a weight loss method in a thermal oven, the filtered solution was found to contain 6.2% solids.

Weight loss method:
About 0.1 g of the organoaluminum compound in the solution was weighed into a tared aluminum dish. About 0.5 g of the solvent used to form the organoaluminum compound (ethyl lactate) was added to the aluminum dish to dilute the test solution so that the test solution covered the aluminum dish more evenly. The aluminum dish was heated in a hot oven at about 110 ° C. for 15 minutes. After the aluminum dish was cooled to room temperature, the weight of the aluminum dish with the dried solid film was determined and the percentage of solids content was calculated.

Example 2:
With stirring, 50.0 g of the alumoxane solution from Example 1 was weighed into a 100 mL round bottom flask. Octanoic acid (0.9696 g, approximately 3 eq. Molar amount based on the number of ligands) was added to the flask. With appropriate stirring provided by a magnetic stir bar, the reaction is carried out at 60 ° C. for 3 hours to produce an alumoxane trimer having two ligands from ethyl lactate and three ligands from octanoic acid. Provided as. The reaction mixture changed from clear to cloudy, but this clouding began as the new compound containing the octanoate ligand began to lose its solubility in ethyl lactate, which is a very polar solvent. Was shown.

Example 3
One part of the solution from Example 2 was mixed with 3 parts of toluene to provide a clear solution. The solution was then filtered once through a 1.0 μm PFPE filter and three times through a 0.2 μm PFPE filter before being processed. The process involved spin-coating the filtered solution onto a bare silicon wafer at 500 rpm, followed by baking the coated film at 100 ° C. for 60 seconds. The surface water contact angle of this film was then measured using a KRUSS drop shape analyzer (DSA) 100 using a 2.5 μm DI water droplet size. The contact angle of this alumoxane film was found to be 82.6 °, but the film made from the aluminum material from Example 1 had a water contact angle of 25.2 °.

Example 4 Titanium Material 4.365 g of oligomeric butyl titanate (4.95 mmol, estimated average chain length of 4 titanium atoms) in a 100 mL round bottom flask equipped with a magnetic stir bar (available under the TYZOR BTP brand from Dorf Ketal) ) And 30.0 g of propylene glycol methyl ether acetate (PGMEA) were weighed. The mixture was stirred to ensure a homogeneous solution, after which 7.260 g (50.3 mmol) octanoic acid was added to the flask. With continuous stirring, the temperature of the reaction mixture was brought to 80 ° C. and maintained at 80 ° C. for 2.5 hours. The heating was then stopped, and the reaction mixture was allowed to cool to room temperature and the solution was used as is. Following the weight loss procedure of Example 1, this solution was found to contain oligomer octanoyl titanate at 12.06% solids.

Example 5:
A sample of the solution from Example 4 (4.453 g) was diluted by mixing it with 2.420 g of PGMEA. The diluted solution was then filtered through a 0.2 μm PFPE filter four times and then processed. The filtered sample was spin coated on a bare silicon wafer at 1500 rpm. The spin-coated film was then baked at 100 ° C. for 60 seconds. Using a KRUSS droplet shape analyzer (DSA) 100, with a droplet size of 2.5 μL, the wafer contact angle of this film was found to be 97.9 °. The control wafer was spin coated with a film of oligomeric butyl titanate (TYZOR BTP in PGMEA, having a solids content similar to the solution in Example 4), and then the control film was coated under the same conditions as the film in this example. Prepared by treatment with The water contact angle of this control membrane was found to be 49 °.

Example 6:
Coating composition samples were prepared as follows. A stock solution of B-staged polyphenylene matrix precursor material (SiLK ^™ D resin, available from The Dow Chemical Company) was diluted with PGMEA to provide a 4% by weight solution. 5.0 g of this stock matrix precursor solution was added to each of Samples AD. As shown in Table 1, various amounts of the oxymetal precursor material from Example 4 were also added to each of Samples BD. Sample A without the oxymetal precursor material was used as a control. The relative amount of the oxymetal precursor material from Example 4 on a solids basis compared to the amount of the matrix precursor material is also reported in Table 1. A certain amount of co-solvent, gamma-butyrolactone (GBL) was also added to each of Samples AD, as shown in Table 1. Each sample was filtered through a 0.2 μm PFPE syringe filter four times, then spin-coated at 1500 rpm on a bare silicon wafer, and then baked at 100 ° C. for 60 seconds. The water contact angles of these coats were measured using a KRUSS droplet shape analyzer (DSA) 100 with a 2.5 μL DI water droplet size and are reported in Table 1.

  As can be seen from the data in Table 1, the cured matrix material (control sample) itself is hydrophobic (low surface energy) as indicated by its high water contact angle of 83 °. However, as the data in Table 1 shows, the oxymetal precursor material from Example 4 can still reach the top surface and increase the water contact angle value compared to the control.

  The wafer containing the film from Sample B was then cut into test specimens, one of which was cured in a belt furnace at 380 ° C. for 30 minutes under a nitrogen atmosphere. The cured specimen, together with the specimen containing the uncured film of Sample B, was then subjected to positive SIMS analysis to determine the elemental distribution over the film thickness. Both the cured and uncured films clearly showed that the high concentration of titanium at the surface dropped sharply to insignificant levels of titanium in the bulk of the film. This clearly indicates that the oxymetal precursor material has concentrated at the surface, resulting in a structure having a layer of oxymetal material over a layer of matrix material.

Example 7:
The procedure of Example 5 was repeated, except that the polyphenylene matrix precursor material was replaced with a silicon-containing matrix precursor material. A silsesquioxane oligomer of methyltrimethoxysilane / phenyltrimethoxysilane / tetraethylorthosilicate (25/50/25 molar ratio) having a weight average molecular weight of 4205 and a number average molecular weight of 2117 was prepared using known procedures. Was. This silsesquioxane oligomer material was first diluted with PGMEA to form a 4.0% solution. Five grams of this silsesquioxane matrix precursor material was added to each of Samples EH. Sample E served as a control and contained no oxymetal precursor material. As shown in Table 2, a fixed amount of the oxymetal precursor material from Example 4 was added to each of Samples FH. A co-solvent (GBL) was also added to each of these samples. Each of these samples was filtered, spun on a bare silicon wafer and baked, after which the determination of the water contact angle of these films was performed as described in Example 5. The results are reported in Table 2.

  The difference in water contact angle between Control Sample E and Samples FH clearly indicates that the oxymetal precursor material with low surface energy has migrated to the film surface during the coating process.

  The coat in this example was then subjected to curing at 380 ° C. for 30 minutes. The cured film was then measured for surface roughness using AFM (atomic force microscopy) at a 2 × 2 μm scan area and a 1.5 Hz scan rate. Lower surface roughness values indicate a smoother surface. As can be seen from the data reported in Table 3, samples F and H, which contained the oxymetal precursor material, provided a smoother film than control sample E, which contained no oxymetal precursor material.

Example 8:
Silsesquioxane oligomers of tetraethylorthosilicate / phenyltrimethoxysilane / vinyltrimethoxysilane / methyltrimethoxysilane (50/9/15/26 molar ratio) were prepared using known procedures. The silsesquioxane matrix precursor material was provided as a solution in a PGMEA / ethyl lactate (95/5 w / w) mixed solvent system having a 2.18% solids content. The coating composition was prepared by combining 5 g of this silsesquioxane matrix precursor material solution, 0.135 g of the oxymetal precursor material solution from Example 4, and 0.247 g of GBL. . The coating composition sample was then filtered through a 0.2 μm PFPE syringe filter four times, then spin coated on a bare silicon wafer at 1500 rpm, and the coated film was baked at 100 ° C. for 60 seconds. The coated wafer was then cut into test specimens, one of which was cured at 380 ° C. for 30 minutes. The cured specimen, along with a specimen having an uncured film deposited from the same coating composition, was then subjected to positive SIMS analysis using conventional equipment and process conditions to determine the metal (titanium) throughout the film thickness. ) Distribution was determined. SIMS data clearly showed that titanium was primarily distributed on the top surface of both the cured and uncured films.

Example 9:
Sample H from Example 7 was spin coated on a bare silicon wafer at 1500 rpm and the coated film was baked at 350 ° C. for 120 seconds to cure the film. The wafer was then re-coated with the same sample using the same processing conditions. The double coat laminate was then analyzed for its titanium distribution throughout its thickness in positive ion mode using SIMS. This SIMS analysis showed two local titanium maxima. One maxima was at the air-solid interface and the second maxima was at the interface between the two coating compositions, which was the top layer of the first coating composition deposition.

Example 10:
Except that 4.242 g of oligomeric butyl titanate (TYZOR BTP, estimated average chain length of 4 titanium atoms) and 15.01 g of PGMEA were weighed into a 100 mL round bottom flask equipped with a magnetic stir bar and condenser. The procedure of Example 4 was repeated. The stirred mixture was heated to 80 ° C., after which a solution of octanoic acid (6.339 g) in PGMEA (15.03 g) solution was fed to the stirred reaction mixture over 3.3 minutes. After the octanoic acid solution was fed to the flask, the reaction mixture was maintained at 80 ° C. for 2 hours, and then allowed to cool to room temperature. Based on stoichiometry, 91% of the butoxide ligand in the starting titanium material was replaced by the octanoic acid ligand. The reaction solution was used as is without further purification. According to the weight loss method of Example 1, this solution was found to have a solids content of 11.20%.

Example 11:
The procedure of Example 10 was repeated except that 4.301 g of oligomeric butyl titanate and 15.02 g of PGMEA were used. The octanoic acid / PGMEA solution was prepared by combining 6.115 g octanoic acid and 15.03 g PGMEA and fed to the stirred reaction mixture over 2.0 minutes. Based on stoichiometry, 85% of the butoxide ligand in the starting titanium material was replaced by the octanoic acid ligand. This reaction solution was used as is without further purification. According to the weight loss method of Example 1, this solution was found to have a solids content of 11.76%.

Example 12:
The two coating compositions, Sample I and Sample J, were 10 g of the silsesquioxane matrix precursor material from Example 7, the oxymetal precursor material of either Example 10 or Example 11, and GBL as co-solvent. Was produced in the amounts shown in Table 4. The relative amount, based on solids, of the oxymetal precursor material compared to the amount of the silsesquioxane matrix precursor material was 15% for each of Sample I and Sample J.

  Each of these samples was then filtered through a 0.2 μm PFPE syringe filter four times, then spin coated at 1500 rpm onto a bare silicon wafer, and then baked at 100 ° C. for 60 seconds. The water contact angle of these films was measured using a KRUSS droplet shape analyzer (DSA) 100 using a DI water droplet size of 2.5 μm and the results are reported in Table 4. The water contact angles of these films approximate the water contact angles obtained in Example 6, which means that the oxymetal precursor material has a sufficiently low surface energy to migrate to the top region of the coating. Indicate that not all of the ligands on the oxymetal precursor material need be low surface energy ligands.

Example 13: Hafnium material 10.0 g ethyl lactate and 5.289 g hafnium tetrabutoxide (available from TCI America) were weighed into a 100 mL round bottom flask equipped with a magnetic stir bar. Then a solution of 0.1219 g DI water and 5.1308 g ethyl lactate was added dropwise to the stirred mixture. The mixture was then heated to reflux and maintained at reflux with stirring for 2 hours, then allowed to cool to room temperature. A solution of 2.682 g of 2-naphthoic acid, 3.3748 g of octanoic acid and 8.047 g of ethyl lactate was then added to the mixture with stirring. The mixture was then heated to 60 ° C. with stirring and maintained at a temperature of 60 ° C. for 2 hours, then allowed to cool to room temperature. According to the weight loss method of Example 1, this solution was found to contain oligomeric octanoyl / naphthoyl hafnate at 17.5% solids.

Example 14: Preparation of Hf (OBu) acetyl-diethylene glycol copolymer.
A 500 mL three-necked flask was fitted with a reflux condenser, mechanical stirrer and addition funnel. The reactor was charged with 100 g (0.21 mol) of Hf (OBu) ₄ (available from Gelest Inc.). To this vigorously stirred material was added pentane-2,4-dione (42.5 g, 0.42 mol) very slowly over 6 hours. The reaction mixture was stirred overnight at room temperature. The n-butanol formed during the reaction was removed under vacuum, then 800 mL of ethyl acetate was added and the reaction flask was stirred vigorously at room temperature for 30 minutes. This solution was filtered through a fine frit to remove insoluble products. The residual solvent was removed under vacuum and a pale white solid was obtained (100.4 g, 90% yield). The product, Hf (OBu) ₂ (acac) _2, was used without further purification.

  In a 1 L three-necked flask equipped with a reflux condenser, a stir bar and a thermometer, a solution of the above product (100.4 g, 0.19 mol) and ethylenediglycol (19.4 g, 0.18 mol) in ethyl acetate (500 mL) Was put in. The reaction mixture was refluxed at 80 ° C. for 24 hours. The reaction mixture was filtered through a fine frit and then dried under reduced pressure. The white-brown solid was washed with heptane (3 × 1 L) and then dried under strong vacuum for 2 hours to give the desired Hf (OBu) acetyl-diethylene glycol copolymer as a white powder (67 g). The resulting product had the following structure.

Example 15:
A coating composition is prepared using the Hf (OBu) acetyl-diethylene glycol copolymer of Example 14 as an organometallic matrix precursor material. A solution of Hf (OBu) acetyl-diethylene glycol copolymer in 2-methyl-1-butanol (6% solids) is prepared. To this solution, a certain amount of the oxymetal (titanate) precursor solution of Example 11 is added. The relative amount of this oxymetal (titanate) precursor material from Example 11 to the amount of organometallic matrix precursor material is 5% on a solids basis. An amount of GBL co-solvent (5% by volume) is also added to the composition. The composition is filtered four times through a 0.2 μm PFPE syringe filter and then spin coated at 1500 rpm onto a bare silicon wafer. The wafer is then baked at 100 ° C. for 60 seconds and then cured at 380 ° C. for 2 minutes to provide a layer of cured hafnium oxide matrix material and a layer of titanium oxide material on the hafnium oxide layer.

Example 16: Preparation of Zr (OBu) acetyl-diethylene glycol copolymer.
25% by weight zirconium bis (acetylacetone) -bis (n-butoxide) in toluene / butanol (i.e., Zr (acac) ₂ (OBu) ₂ ) was purchased from Gelest Inc. And used without further purification. The solvent was removed from 200 g of Zr (acac) ₂ (OBu) ₂ and the residue was diluted with 250 mL of ethyl acetate. To this mixture, an equimolar amount of diethylene glycol was added at room temperature, and the mixture was refluxed at 80 ° C. for 18 hours. The reaction mixture was then cooled and filtered to remove a white precipitate. The filtrate was concentrated to a small volume using a rotary evaporator, and the residue was quenched with heptane. The precipitate was then collected and dried under reduced pressure to give 20.8 g of the desired product, the structure of which is shown below:

Example 17:
A coating composition is prepared using the Zr (OBu) acetyl-diethylene glycol copolymer of Example 16 as an organometallic matrix precursor material. A solution of Zr (OBu) acetyl-diethylene glycol copolymer in 2-methyl-1-butanol (6% solids) is prepared. To this solution, a certain amount of the oxymetal (titanate) precursor solution of Example 11 is added. The relative amount of this oxymetal (titanate) precursor material from Example 11 to the amount of organometallic matrix precursor material is 5% on a solids basis. An amount of GBL co-solvent (5% by volume) is also added to the composition. The composition is filtered four times through a 0.2 μm PFPE syringe filter and then spin coated at 1500 rpm onto a bare silicon wafer. The wafer is then baked at 100 ° C. for 60 seconds and then cured at 380 ° C. for 2 minutes to provide a layer of cured zirconium oxide matrix material and a layer of titanium oxide material over the zirconium oxide layer.

Claims (9)

Disposing a layer of a coating composition on an electronic device substrate, the coating composition comprising a matrix precursor material, an oxymetal precursor material having a surface energy of 20 to 40 erg / cm ² , and an organic solvent. Applying the coating composition layer to conditions such that the layer of oxymetal precursor material occurs on the layer of matrix precursor material; and the layer of matrix precursor material and the oxymetal precursor A method of forming an oxymetal layer on a matrix layer on an electronic device substrate, comprising the step of curing a layer of material , wherein the oxymetal precursor material is titanium, zirconium, hafnium, tungsten, tantalum, molybdenum and aluminum. A method comprising a metal selected from the group consisting of:   2. The method of claim 1, wherein said organic solvent comprises a first organic solvent and a second organic solvent.   The method of claim 1, wherein said matrix precursor material comprises a silicon-containing material.   The method of claim 1, wherein the matrix precursor material has a higher surface energy than a surface energy of the oxymetal precursor material. Wherein the matrix precursor material has a 10erg / cm ² or more higher surface energy than the surface energy of the oxy-metal precursor material, The method of claim 4.   The method of claim 1 wherein said matrix precursor material layer and said oxymetal precursor material layer are cured by heating.   The method of claim 1, wherein said substrate is a substrate for a light emitting diode.   Disposing a second layer of the coating composition on the surface of the cured oxymetal layer, and conditions such that a second layer of oxymetal precursor material results on the second layer of matrix precursor material. 2. The method of claim 1, further comprising: applying the second coating composition layer; and curing the second layer of the matrix precursor material and the second layer of the oxymetal precursor material. . A composition comprising a matrix precursor material, an oxymetal precursor material having a surface energy of 20 to 40 erg / cm ² , and an organic solvent, wherein the matrix precursor material has a surface energy greater than the surface energy of the oxymetal precursor material. have a high surface energy,
The matrix precursor material is a polyarylene material; an arylcyclobutene-based material; a general formula (R ₂ SiO ₂ ) _n , wherein R is OH, C _1-4 alkoxyl, C _1-4 alkyl and C _6- It is selected from ₁₀ aryl, and on at least one of Si, said R substituents are selected from _{C 1-4} alkyl and _{C 6-10} aryl) siloxane material having;. formula _{(RSiO 3/2) n} Wherein R is selected from OH, C _1-4 alkoxyl, C _1-4 alkyl and C _6-10 aryl, and on at least one Si, the R substituents are C _1-4 alkyl and C ₆ Selected from _-10 aryl); a metal-oxygen oligomer of formula (1),

(Wherein each X is independently selected from diketones, _C2-20 polyols and _C1-20 alkoxides, and M is a Group 3-14 metal); Formula (1a) metal-oxygen Oligomers,

(In formula (1a), R is independently selected from hydrogen, C _1-12 alkyl, C _6-20 aryl, C _1-12 alkoxy and C _6-10 phenoxy, and each X is independently a diketone, is selected from C _2-20 polyols and _{C 1-20} alkoxide, and M is a group 3 to group 14 metals);. an organometallic oligomers containing one or more monomers of formula (2) as polymerized units,

(In the formula (2), R ¹ = H or CH ₃ , M = Group 3 to Group 14 metal, L is C _1-6 alkoxy, beta-diketonate, beta-hydroxyketonate, beta-ketoester, beta- A ligand selected from one or more of diketiminate, amidinate, guanidinate and beta-hydroxyimine, and n represents the number of ligands and is an integer of 1 to 4); and a compound of formula (3):

(In the formula (3), R ² ＣC _1-6 alkyl, M ¹ is a Group 3 to Group 14 metal, and R ³ ＣC _2-6 alkylene-X- or C _2-6 alkylidene-X- Wherein each X is independently selected from O and S, z is an integer from 1 to 5, and L ¹ is C _1-6 alkoxy, beta-diketonate, beta-hydroxyketonate, beta-ketoester, beta A ligand selected from one or more of diketiminate, amidinate, guanidinate and beta-hydroxyimine, wherein m represents the number of ligands and is an integer from 1 to 4 and p is an integer from 2 to 25; ) Is selected from the group consisting of
And a composition, wherein the oxymetal precursor material is represented by the following general formula (4) :

( Wherein, M is a metal selected from the group consisting of titanium, zirconium, hafnium, tungsten, tantalum, molybdenum and aluminum , and L ¹ is (C ₁ -C ₆ ) alkoxy, (C ₁ -C ₃ ) carboxyalkyl, and _(C 5 _{-C 20)} is selected from β- diketonate, ^{L 2} is a low surface energy ligands containing _{C 4-20} hydrocarbyl moieties, m is the valence of M, z is 1 to 50 X2 is an integer from 0 to (m (z) -2 (z-1) -1), and y2 is an integer from 1 to (m (z) -2 (z-1)). , And x2 + y2 = m (z) -2 (z-1)).