KR20160049857A - Organometal materials and process - Google Patents

Abstract

A coating composition is used in depositing a film on an electronic device substrate. The film is treated under a condition in which an oxymetal precursor material layer is formed on a matrix precursor material layer. Then, the layers are hardened, so a hardened oxymetal layer is produced to be disposed on a hardened matrix layer. According to the present invention, multiple oxymetal films are directly provided to an electronic device substrate, so problematic mixing of films, which may occur when a conventional spin-on scheme for depositing an oxymetal film one by one is used, may be resolved.

Description

[0001] ORGANOMETAL MATERIALS AND PROCESS [0002]

The present invention relates generally to the field of solution-borne organometallic compounds, and more particularly to the field of manufacturing electronic devices using such solution-based organometallic compounds.

The need for a layer with etch selectivity in lithography and the need for a layer to block both oxygen and moisture in the manufacture of organic light emitting diodes (OLEDs) or in the manufacture of photovoltaic devices, such as photovoltaic devices, And the like. The oxymetal layer is typically characterized by a film that has multiple inorganic domains (oxy metal domains) with a (-MO-) _n bond (M is metal and n> 1) and can be composed in small amounts to other elements such as carbon do. The oxymetal layer may be composed of mixed domains such as containing both an oxymetal domain and a metal nitride domain.

Conventional oxymetal films may contain one or more metals such as Hf, Zr, Ti, W, Al, Ta and Mo depending on the particular application. Etching a film made of a metal oxy domain Castle, (MO-) _n Due to the increased levels provide a greater etch resistance level of the _n-domain (MO-) present in the film of the domain, as well as the particular metal In part. The barrier film used in OLED applications generally comprises Al or Si, i.e. (-Al-O-) _n or (-Si-O-) _n domains, respectively, where n> 1. While silicon oxide containing films are known to reduce the migration of water vapor, aluminum oxide containing films are known to reduce the migration of oxygen (O ₂ ). As with other drawbacks that lead to incomplete coverage of the pinhole or bottom film, certain defects in this barrier film can be a possible passage for gas or water vapor to pass through the bottom film.

Oxymetal films such as alumina and silica films can typically be applied on electronic device substrates by chemical vapor deposition (CVD). For example, International Patent Application No. WO 2012/103390 discloses an oxide-containing barrier such as an aluminum oxide or silicon oxide layer adjacent a reactive inorganic layer on a flexible (plastic) substrate for reduction of gas or vapor movement through the stack A stack having at least one layer is disclosed. According to this patent application, the reactive inorganic layer acts to react with any gas or water vapor passing through the barrier layer. This patent application does not suggest a material suitable for forming such a barrier layer and has focused on conventional film deposition techniques such as vapor deposition techniques.

Spin-on technology is widely used in electronic device manufacturing, including the deposition of oxymetal films, and offers advantages over conventional vapor deposition processes for deposition films. For example, spin-on technology can use conventional equipment, can be completed in a matter of minutes, and can provide a uniform coating on the substrate. Conventional spin-on technology deposits one oxymetal film at a time. When multiple oxymetal films are used, such as in a barrier stack, each oxymetal film must be applied separately and cured. Conventional spin-on techniques for oxymetal films deposit an oxymetal precursor on a substrate, then bake to remove the solvent and cure to form an oxymetal film. If such a film is not cured prior to deposition of the second film, the solvent used in the second oximetallic precursor solution can cause intermixing problems with the first uncured oxy metal film.

Therefore, a need exists for a method for providing multiple oxy-metal films directly from a single liquid deposition process onto an electronic device substrate.

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 surface energy of the matrix precursor material is higher than the surface energy of the oxymetal precursor material .

The invention also deposit a coating composition layer comprising a matrix precursor material, the oxy surface energy of 20 to 40 erg / cm ² metal precursor material and an organic solvent on a substrate and to an electronic device; Treating the layer of coating composition under conditions such that a layer of precursor material is formed on the layer of matrix precursor material; A method of forming an oxymetal layer on a matrix layer on an electronic device substrate, comprising curing a matrix precursor material layer and an oxymetal precursor material layer.

In the present specification, the following abbreviations shall have the following meanings, unless expressly referred to herein: ca. = About; C = Celsius temperature; g = gram; mg = milligram; mmol = mmol; L = liters; mL = milliliters; μL = microliter; nm = nanometer; Å = Angstrom; And rpm = revolutions per minute. Unless otherwise indicated, all amounts are in weight percent ("wt%") and all ratios are in molar ratio. The term "oligomer" refers to dimers, trimers, tetramers, and other materials having a relatively low molecular weight capable of further curing. "Alkyl" and "alkoxy" refer to linear, branched and cyclic alkyl and alkoxy, respectively. The term "cure" means any process that increases the molecular weight of a substance or layer by polymerization, or condensation, and the like. The terms "film" and "layer" are used interchangeably throughout this specification. Singular " refers to both singular and plural. All numerical ranges are inclusive and can be combined in any order, except that the numerical range is limited to 100% in total.

A coating composition useful in the present invention comprises 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 surface energy of the matrix precursor material is greater than the surface energy of the oxymetal precursor material high. Various matrix precursor materials, such as polymeric materials, silicon-containing materials, organometallic materials, or combinations thereof, may be suitably used, provided that such matrix precursor materials must be curable and that the oxymetal precursor material used Should have a surface energy higher than the surface energy, be soluble in the organic solvent used, be stable under the conditions used for the placement of the coating composition layer on the substrate, and withstand the curing temperature of the oxymetal precursor material upon curing It must have sufficient thermal stability. Depending on the particular oximetallic precursor material and the particular use of the invention, the curing temperature of the oxymetal precursor material can range from 250 to 400 DEG C for a maximum of 60 minutes or more. For certain applications, such as oxygen or moisture barrier films, the matrix precursor material should provide a cured matrix having relatively dense film form and relatively hydrophobic hydrophilic functionalities. Preferably, the matrix precursor material is selected from a polymer 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 surface energy higher than the surface energy of the oxymetal precursor material. Preferably, the matrix precursor material has a surface energy of at least 10 ergs / cm ² higher than the surface energy of the oxymetal precursor material used, more preferably at least 15 ergs / cm ² Higher.

Exemplary polymer matrix precursor materials useful in the present invention include, without limitation, polyarylene materials such as polyphenylene materials and arylcyclobutene-based materials available under the SiLK ^™ and CYCLOTENE ^™ brands, respectively, from the Dow Chemical Company . It will be appreciated by those skilled in the art that various other polymer matrix materials may be suitably employed as matrix precursor materials in the present invention. Such polymeric materials are commercially available or can be prepared by a variety of methods known in the art .

Exemplary silicon-containing matrix precursor materials include, but are not limited to, siloxane materials and silsesquioxane materials, and 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 aryl, and the R substituent on at least one Si is selected from C _1-4 alkyl and C _6-10 aryl. Suitable silsesquioxanes are typically condensation reactions of one or more organic trialkoxysilanes, typically having the formula RSi (OR) ₃ , wherein each R is independently selected from C _1-4 alkyl and C _6-10 aryl. . Such silicon-containing materials are generally commercially available, for example, from Dow Corning (Md., USA) or may be prepared by a variety of methods known in the art, such as those described in US Pat. No. 6,271,273 (You et al. . Such silicon-containing materials include silicon-metal hybrid materials such as silicon-titanium hybrid materials and silicon-zirconium hybrid materials.

Various organometallic materials can be used as the matrix precursor material. Suitable organometallic materials form films and are typically polymeric (e.g., oligomeric), but may be non-polymeric, may contain a single metal, or may contain two or more different metals. That is, a single organometallic material, such as an oligomer, can have only one metal species, or can have two or more different metal species. On the other hand, a mixture of organometallic materials in which each material has a single metal species can be used for deposition of mixed metal films. It is preferred that the organometallic material contains one or more atoms of a single metal species other than the different metal species. Suitable metals useful for the organometallic materials of the present invention are any metals belonging to groups 3-14 of the periodic table. Preferably, the metal is selected from Groups 4, 5, 6 and 13, and more preferably Groups 4, 5, and 6. Preferred metals include titanium, zirconium, hafnium, tungsten, tantalum, molybdenum and aluminum, and more preferably titanium, zirconium, hafnium, tungsten, tantalum and molybdenum.

One class of organometallic materials suitable for use in the compositions of the present invention are metal-oxygen oligomers of formula (1)

In this formula,

Each X is independently selected from light attenuating moieties, diketones, C _2-20 polyols and C _1-20 alkoxides;

And M is a Group 3 to Group 14 metal.

Preferred X substituents are diketones and C _1-20 alkoxides, and more preferably diketones and C _1-10 alkoxides. In one embodiment at least one X is a diketone of the structure:

Wherein each R is independently selected from the group consisting of hydrogen; It is preferably selected from C _1-12 alkyl, C _6-20 aryl, C _1-12 alkoxy, and C _6-10 phenoxy, more preferably all X substituents are diketones. 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. Exemplary R groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenethyl, naphthyl; Phenoxy, methylphenoxy, dimethylphenoxy, ethylphenoxy and phenyloxymethyl. The preferred structure of the metal-oxygen oligomer has the formula (1a)

In this formula,

M, X and R are as described above.

Such metal-oxygen oligomers are described in U.S. Patent No. 7,364,832. Similar metal-oxygen oligomers useful in the present invention are also described in U.S. Patent Nos. 6,303,270; 6,740,469; And 7,457,507, and U.S. Patent Application Publication No. 2012/0223418.

Another suitable class of organometallic materials useful in the present invention are oligomers comprising at least one metal-containing pendant group. Preferably, the organo-metallic oligomer comprising at least one metal-containing pendant group comprises at least one (meth) acrylate monomer, and more preferably at least one metal-containing (meth) acrylate monomer as polymerized units. Even more preferably, the organo-metallic oligomer comprising at least one metal-containing pendant group comprises at least one monomer of formula (2) as polymerized units:

In this formula,

R ¹ is H or CH ₃ ;

M is a Group 3 to Group 14 metal;

L is a ligand;

n represents 1 to 4 as the number of ligands.

Preferably, M is a metal selected from Groups 4, 5, 6 and 13, and more preferably Groups 4, 5, and 6. M is preferably titanium, zirconium, hafnium, tungsten, tantalum, molybdenum and aluminum, and more preferably titanium, zirconium, hafnium, tungsten, tantalum and molybdenum, still more preferably zirconium, hafnium, tungsten and tantalum.

The ligand in formula (2), L may be any suitable ligand, but the ligand must be capable of being cleaved during the curing step to form a metal oxide containing the hard mask. Preferably, the ligand comprises an oxygen or ring atom that is bonded to, coordinated to, or otherwise interacts with the metal. Exemplary ligand classes include one or more of the following groups: alcohols, thiols, ketones, thiones and imines, and preferably alcohols, thiols, ketones, and thiones. Preferably, L is selected from the group _consisting of C _1-6 alkoxy, beta-diketonate, beta-hydroxyketonate, beta-ketoester, beta-diketonate, amidinate, guanidinate, ≪ / RTI > More preferably, L is selected from one or more of C _1-6 alkoxy, beta-diketonate, beta-hydroxy ketone, and beta-keto ester, and even more preferably L is selected from C _1-6 alkoxy . The number of ligands is represented by "n" in the formula (2) and is an integer of 1-4, preferably 2-4, and more preferably 3-4. Preferred monomers of formula (2) 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 methacrylate, 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 organo-metallic compound of formula (2) can be prepared in a variety of ways, for example by reacting a metal tetraalkoxide with acrylic or methacrylic acid in a suitable solvent such as acetone.

Organo-metallic oligomers comprising one or more metal-containing pendant groups may be composed of polymerized units of a single monomer (homopolymer) or polymerized units of two or more monomers (copolymer). Suitable copolymers can be prepared in conventional manner by polymerizing one or more monomers comprising a metal-containing pendant group with one or more other monomers and the other monomers can be prepared by reacting a metal - containing pendant groups. Suitable ethylenically unsaturated monomers include alkyl (meth) acrylate monomers, aryl (meth) acrylate monomers, hydroxyalkyl (meth) acrylate monomers, alkenyl Such as, without limitation, styrene and substituted styrene monomers. Preferably, the ethylenically unsaturated monomer is a C _1-12 alkyl (meth) acrylate monomer and a hydroxy (C _1-12 ) alkyl (meth) acrylate monomer, and more preferably a C _1-12 alkyl Acrylate monomers and hydroxy (C _2-6 ) alkyl (meth) acrylate monomers. The copolymers may be random, alternating or block copolymers. These organic-metal oligomers may be composed of 1, 2, 3, 4 or more ethylenically unsaturated monomers besides monomers containing metal-containing pendant groups as polymerized units, such as metal-containing (meth) acrylate monomers .

Another class of organometallic materials suitable for use as matrix precursor materials in the coating compositions of the present invention is compounds of formula (3)

In this formula,

R ² is C _1-6 alkyl;

M ¹ is a Group 3 to Group 14 metal;

R ³ is C _2-6 alkylene-X- or C _2-6 alkylidene-X-;

Each X is independently selected from O and S;

z is an integer from 1 to 5;

L < ¹ > is a ligand;

m is the number of ligands and is an integer from 1 to 4;

p is an integer from 2 to 25;

R ² is preferably 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 Groups 4, 5, and 6. It is preferable that M ¹ is titanium, zirconium, hafnium, tungsten, tantalum, molybdenum and aluminum, and more preferably titanium, zirconium, hafnium, tungsten, tantalum and molybdenum, still more preferably titanium, zirconium, hafnium, tungsten and tantalum Do. X is preferably O. R ³ is selected from C _2-4 alkylene-X- and C _2-4 alkylidene-X-, and more preferably C _2-4 alkylene-O- and C _2-4 alkylidene-O- . Preferably, p is 5-20, and more preferably 8-15. z is preferably from 1 to 4, and more preferably from 1 to 3.

The ligand L < ¹ > of formula (3) may be any ligand as long as it is a ligand that can be cleaved during the curing step to form a metal oxide containing a hard mask. Preferably, the ligand comprises an oxygen or sulfur atom that is bonded, coordinated, or otherwise interacts with the metal. Typical classes of ligands are those comprising one or more of the following groups: alcohols, thiols, ketones, thiones and imines, preferably alcohols, thiols, ketones and thiones. Preferably L ¹ is selected from the group _consisting of one or more of C _1-6 alkoxy, beta-diketonate, beta-hydroxyketonate, beta-keto ester, beta-diketinimide, amidinate, guanidinate and beta -hydro Lt; / RTI > L ¹ is one or more C _1-6 alkoxy, beta-diketonates, beta-hydroxy-beta-keto carbonate and - more preferably selected from the keto ester, L ¹ is the beta-diketonates, beta-hydroxy-keto Nate and beta-keto esters are more preferred. The number of ligands may be represented by "m" in formula (3) and may be 1-4, preferably 2-4. Preferred ligands as L < ¹ > include: benzoyl acetonates; Pentane-2,4-dionate (acetoacetate); Hexafluoroacetoacetate; 2,2,6,6-tetramethylheptane-3,5-dionate; And ethyl-3-oxobutanoate (ethylacetoacetate). The oligomer of formula (3) can be prepared by conventional methods known in the art, as described in U.S. Patent Application 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, and such compounds can form films under the conditions used. Suitable non-polymeric organometallic materials can be homoleptic or heteroleptic (i.e., contain other ligands) and include, without limitation, metal ketonates, metal ketiminates, metal amidinates, and the like. can do. Exemplary non-polymeric organo-metallic compounds include, but are not limited to, hafnium 2,4-pentanedionate; Hafnium di-n-butoxide (bis-2,4-pentanedionate); Hafnium tetramethyl heptanedionate; 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-iso-propoxide (bis-2,4-pentanedionate); zirconium dimethacrylate di-n-butoxide; Zirconium hexafluoropentanedionate, zirconium tetra-2,4-pentanedionate, zirconium 2,2,6,6-tetramethyl-3,5-heptanedionate, and zirconium trifluoro These non-polymeric organometallic materials are generally commercially available or can be prepared by a variety of known methods.

It will be apparent to one of ordinary skill in the art that one or more organometallic materials can be used as the matrix precursor material in the coating compositions of the present invention. When combinations of organometallic materials are used, such materials can be used in various amounts, such as a weight ratio of 99: 1 to 1:99, preferably 90:10 to 10:90. Preferably, a combination of organometallic materials is not used.

Various oxy-metal precursor material may be suitably used in the coating compositions of the present invention, such oxy-metal precursor material may form a film, and may be cured for 20 to 40 (static) in erg / cm ² surface Energy, and can be dissolved in the organic solvent used. Preferably, the oxymetal precursor material has a (static) surface energy in the range of 20 to 35 erg / cm ² , more preferably 20 to 30 erg / 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 Group 3 to Group 14 and have at least one low surface energy ligand, i. E., A relatively hydrophobic ligand. Preferably, the oxymetal precursor material comprises a metal selected from titanium, zirconium, hafnium, tungsten, tantalum, molybdenum and aluminum. Low surface energy ligands are more fatty (or hydrocarbyl) than other ligand or matrix precursor materials used in oxymetal precursor materials. The branched or cyclic alkyl moieties are relatively more hydrophobic relative to their corresponding linear alkyl moieties, and increasing the natural or branched portion of the cyclic or lower alkyl moiety will lower the surface energy of the ligand and consequently the oxymetal precursor material To reduce the surface energy of the substrate. Similarly, the alkyl and aryl moieties of increasing carbon chain lengths also lower the surface energy of the ligand. The low surface energy ligands of the present invention comprise at least one C _4-20 hydrocarbyl moiety. Suitable hydrocarbyl moieties include aliphatic hydrocarbyl moieties and aromatic hydrocarbyl moieties. The hydrocarbyl moiety may be optionally substituted with fluorine, wherein one or more hydrogens in the hydrocarbyl moiety are replaced with the corresponding number of fluorine. Preferred hydrocarbyl moieties are C _4-20 alkyl and C _6-20 aryl, each optionally substituted with fluorine. The C _4-20 hydrocarbyl moiety may be linear, branched or cyclic. The C _6-20 aryl portion comprises a C _6-20 aralkyl and C _6-20 alkaryl partial section, such as benzyl, phenethyl, tolyl, xylyl, ethylphenyl, styryl. When the low surface energy ligand comprises a C _4-6 alkyl moiety, such alkyl moiety is preferably branched or cyclic. Preferably, the low surface energy ligand comprises at least one C _6-20 hydrocarbyl moiety, more preferably at least one C 6 _-16 hydrocarbyl moiety, even more preferably at least one C _8-16 Hydrocarbyl moiety, and even more preferably at least one C _10-16 hydrocarbyl moiety. Preferred compounds for use in forming a low surface energy in the ligand oxy metal precursor materials of the present invention is a carboxylic acid with an alcohol and a C _4-20 hydrocarbyl moiety having a C _4-20 hydrocarbyl parts. When the carboxylic acid-containing-compound is used to form a low surface energy ligand, it is preferred that the carboxylic acid-containing compound has a single carboxylic acid functionality. Compounds having multiple carboxylic acid functionality tend to form gels that are not suitable for the coating compositions of the present invention.

The oxymetal precursor material used in the coating compositions of the present invention may be monomeric or oligomeric, preferably oligomeric. A preferred oxymetal precursor material is the material of formula (4).

M ^{+ m} _z O _z-1 L ¹ _x ² L ² _y2 (4)

Wherein M is a metal of group 3 to 14; L ¹ is selected from (C ₁ -C ₆ ) alkoxy, (C ₁ -C ₃ ) carboxyalkyl and (C ₅ -C ₂₀ ) β-diketonate; L ² is a low surface energy ligand comprising a C _4-20 hydrocarbyl moiety; m is the valence of M; z is an integer from 1 to 50; x2 is an integer of 0 to (m (z) -2 (z-1) -1); y2 is an integer of 1 to (m (z) -2 (z-1)); x2 + y2 = m (z) -2 (z-1). Preferably, m = 3 or 4. Preferably z = 1 to 30, more preferably 1 to 25, still more preferably 1 to 20, even more preferably 3 to 25, still more preferably 3 to 15. More preferably L ² = OC _6-20 hydrocarbyl or OC (O) -C ₆ -C ₂₀ hydrocarbyl, more preferably L ² = OC _4-20 hydrocarbyl or OC (O) ₂₀ hydrocarbyl, even more preferably L ² = OC _6-16 hydrocarbyl or OC (O) -C _6-16 hydrocarbyl. The (C ₄ -C ₂₀ ) hydrocarbyl portion of L ² is optionally substituted with a hydroxyl group, a carboxylic acid, a (C ₁ -C ₆ ) alkylcarboxylate and a fluoro, preferably a (C ₁ -C ₆ ) fluoro, more preferably (C ₁ -C ₄₎ comprises one or more substituents selected from the group consisting of alkyl carboxylate and fluoro. Suitable low surface energy ligands (L ² ) include, without limitation: hexanoate, heptanoate, octanoate, nonanoate, decanoate, dodecanoate, cyclohexanoate, benzoate, methyl Benzoate, naphthanoate, phenoxy, benzyloxy, t-butoxy and cyclohexyloxy. In certain applications, not all L < ^{1 >} ligands need be replaced with L < ^{2 & gt;} ligands in order to provide an oxymetal precursor material with a sufficiently low surface energy. In certain embodiments, the amount of L ² ligand is preferably 25-100% relative to the total number of ligands, more preferably 25-95%, even more preferably 30-95%, even more preferably 35 To 90%. The percentage of L ² ligand can be calculated by the formula y 2 / (x 2 + y 2) x 100, where x 2 and y ² refer to the number of L ¹ and L ² ligands, respectively.

The oxymetal precursor materials of the present invention may be prepared by various procedures in the art and generally can be prepared by a ligand exchange reaction between the starting metal compounds of the formula M ^{+ m} X _m wherein X is (C ₁ -C ₆ ) alkoxy or (C ₅ -C ₂₀ ) β-diketonate; And HL ^2, or an alkaline or K ^{+ -} inde suitable low surface energy such as a ligand, such as an alkali toyeom L2, wherein L ² is as defined above. Preferably, the low surface energy ligand used in the ligand exchange reaction has the formula HL ² . In a general procedure, the starting metal compound is combined with a low surface energy ligand in a flask and a suitable organic solvent. The mixture is then heated, usually at room temperature to 80 DEG C or higher, for a period of time during which the desired ligand exchange can take place. According to this procedure, one, two, or all three (C ₁ -C ₆ ) alkoxy or (C ₅ -C ₂₀ ) β-diketonate ligands on the starting metal compound have a corresponding number of low surface energy ligands Can be exchanged. The number of (C ₁ -C ₆₎ alkoxy or (C ₅ -C ₂₀₎ β- diketonates ligand is exchanged, along with increasing the time available for more ligand exchange, a particular (C ₁ -C ₆ ) alkoxy or (C ₅ -C ₂₀₎ β- diketonates being dependent on the steric hindrance, steric hindrance, and the mixture is heated for a specific time the low surface energy of the ligand ligand used be apparent to one of ordinary skill in the art will be.

The coating compositions of the present invention also include one or more organic solvents. Various organic solvents may be suitably used, and the matrix precursor material and the oxymetal precursor material are dissolved in a selected solvent or mixture of solvents. The solvent includes, but is not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, lactones, esters, glycols, glycol ethers, and mixtures thereof. Exemplary organic solvents include but are not limited to toluene, xylene, mesitylene, alkylnaphthalene, 2-methyl-1-butanol, Acid methyl ester, propylene glycol methyl ether acetate, and propylene glycol methyl ether. In a preferred embodiment, a solvent system comprising a plurality of first solvents and a minority of second solvents is used. More preferably, the first solvent has a relatively low surface energy, the second solvent has a relatively high boiling point as compared to the first solvent, and the second solvent has a higher surface energy than the surface energy of the oxymetal precursor material ). Exemplary second solvents include, but are not limited to, gamma-butyrolactone, gamma-valerolactone, dipropylene glycol methyl ether, benzyl benzoate, and the like. Generally, when a solvent mixture is used, the amount of the second solvent is from 0.1 to 10 wt% based on the total weight of the solvent system and the remaining weight is for the first solvent. Preferably, the organic solvent comprises <10,000 ppm water, more preferably <5000 ppm water, even more preferably ≤ 500 ppm water. The organic solvent preferably does not have a free carboxylic acid group or a sulfonic acid group.

The coating composition of the present invention may optionally comprise one or more additives such as a curing catalyst, an antioxidant, a dye, a contrast promoter, a binder polymer, and the like. Depending on the application, it may be desirable to add one or more curing catalysts to the composition of the present invention to assist in curing the matrix precursor material and / or oxymetal precursor material. Exemplary curing catalysts include a thermal acid generator (TAG) and a photoacid generator (PAG). TAGs and their use are well known in the art. Examples of TAGs include those sold under the names NACURE ^TM , CDX ^TM and K-PURE ^TM by King Industries, Norwalk, Connecticut in the United States. Photoacid generators (PAGs) and their uses are well known in the art, and they are activated by exposure to light or e-beams of the appropriate wavelength to generate acids. Suitable PAGs are available from a variety of sources, such as brands such as Iragacure ^TM from BASF (Ludwigshafen, Germany). A wide variety of binder polymers may be used to provide improved coating quality or leveling on the substrate, particularly where the matrix precursor material is an organometallic material. Suitable binder polymers are disclosed in U.S. Patent Application No. 13 / 776,496.

The coating compositions of the present invention may be prepared by sequentially combining a matrix precursor material, an oxymetal precursor material, an organic solvent, and any optional additives. It will be apparent to one of ordinary skill in the art that the concentration of the components of the compositions herein can vary within wide limits. Preferably, the matrix precursor material is present in the composition in an amount of from 2 to 20 wt%, preferably from 4 to 15 wt%, more preferably from 6 to 10 wt%, based on the total weight of the coating composition. Preferably, the oxymetal precursor material is present in the composition in an amount of 3 to 15 wt%, more preferably 5 to 10 wt%, and even more preferably 5 to 8 wt%, relative to the solids content of the matrix precursor material exist. It will be apparent to one of ordinary skill in the art that the components may be used in greater or lesser amounts in the coating compositions of the present invention.

In use, the coating composition of the present invention is located on an electronic device substrate. In the present invention, a wide variety of electronic device substrates may be used, such as: a packaging substrate such as a multi-chip module; Flat panel display substrate; An integrated circuit substrate; A substrate for a light emitting diode (LED) comprising an organic light emitting diode (OLED); A semiconductor wafer; Polycrystalline silicon substrate and the like. Such substrates are typically formed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, tungsten, nickel, Glass, glass coated with organic or inorganic materials. Suitable substrates may 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" is intended to encompass all types of semiconductor devices, including "electronic device substrates "," semiconductor substrates ", "semiconductor devices ", and single chip wafers, And packages for various levels of interconnection. A particularly suitable substrate is one comprising an LED comprising an OLED. Such a substrate may have an appropriate size. Despite the fact that smaller and larger diameters may be suitably employed in accordance with the present invention, the preferred wafer substrate diameter is 200 mm to 300 mm. As used herein, the term "semiconductor substrate" includes a substrate having at least one semiconductor layer or structure comprising an activated or operable portion of a semiconductor device. "Semiconductor substrate" is defined to mean any configuration comprising a semiconductor material, wherein a bulk semiconductor material, such as a semiconductor wafer, is included alone or in a combination comprising other materials, and the semiconductor material layer comprises a single material or other material But are not limited thereto. Semiconductor devices refer to at least one microelectronic device on a semiconductor substrate, or to be assembled and assembled. A preferred substrate is a substrate for an LED, more preferably a substrate for an OLED. Flexible display substrates and photovoltaic devices substrates are also preferred, and flexible display substrates for LEDs, more preferably OLEDs, are preferred.

The coating compositions of the present invention may be provided by any suitable means. For example, by 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 process, the compositions of the present invention are applied for 15 to 90 seconds on a substrate rotating at a speed of 500-4000 rpm to obtain a desired layer of matrix precursor material and oxymetal precursor material. It will be appreciated by those of ordinary skill in the art that the total height of the layers can be controlled by varying the spin rate as well as the percent solids in the composition.

Without being bound by theory, it is believed to migrate the surface of the film on which the oxymetal precursor material is formed during deposition of the composition of the present invention and during any subsequent solvent removal step. It is believed that the relatively low surface energy of the oxymetal precursor material helps to drive the oxymetal precursor material to the air interface. As a result, a multi-layer structure is obtained in which a layer of the oxymetal precursor material is disposed on the layer of the matrix precursor material. Although there may be some degree of intermixing between the layers, the top portion of the structure will mainly comprise the oxymetal precursor material, while the bottom portion will mainly comprise the matrix precursor material . It will be appreciated by those of ordinary skill in the art that the migration of such oxymetal precursor materials should occur substantially prior to curing of the matrix precursor material. Formation of the cured matrix material film substantially impedes migration of the oxymetal precursor material.

During or after deposition of the coating composition of the present invention on an electronic device substrate to form a multi-layer structure (a layer of the oxymetal precursor material on the matrix precursor material layer), the structure is optionally baked at a relatively low temperature to form a residual solvent and Eliminates other relatively volatile components. Typically, the substrate is baked at a temperature below 125 占 폚, preferably between 60 and 125 占 폚, more preferably between 90 and 115 占 폚. The baking time is typically 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, and more preferably 6 to 180 seconds. If the substrate is a wafer, this baking step may be performed by heating the wafer on a hot plate.

Following the optional baking step for solvent removal, the multilayer structure is cured in an oxygen-containing atmosphere (e.g., air) or an inert environment (e.g., in nitrogen). The curing step is preferably performed on hot plate-style equipment, but oven curing may be used to obtain equivalent results. Typically, such curing is carried out by heating the multilayer structure at a curing temperature of 150 ° C or higher, preferably 150 to 400 ° C. More preferably, the curing temperature is from 200 ° C to 400 ° C, more preferably from 250 ° C to 400 ° C, even more preferably from 250 ° C to 400 ° C. The choice of the final cure temperature depends primarily on the desired cure rate and a shorter cure time requires a higher cure temperature. When the oxymetal precursor material layer of the present invention is cured at a temperature of 200 ° C or higher, the resulting oxymetal domain-containing film is resistant to stripping (removal) by solvents commonly used in antireflective coatings and photoresist applications . When the oxymetal precursor material of the present invention is cured at a temperature of 350 DEG C or higher, the resulting oxymetal domain-containing film is also resistant to stripping by alkaline or solvent developers commonly used in the development of imaged photoresist layers Respectively. Typically, the curing time may be 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 oximetallic precursor material is cured to form oxymetal with a (-MO-) _n linkage (where n > 100) To form a layer containing the domain. Typically, the metal content in the cured oxymetal-containing film may be up to 95 mole percent (or more), and preferably 50 to 95 mole percent. It will be appreciated by those of skill in the art that the cured oxymetal material layer may contain other domains besides the oxy-metal domain, such as a metal nitride domain, and may optionally also contain carbon in an amount up to, for example, 5 mole% I will understand.

An initial baking step may not be necessary if the final curing step is performed in such a way that rapid evolution of the solvent and curing of the by-products are not allowed to interfere with the quality of the film. For example, a ramped bake starting at a relatively low temperature and gradually increasing to a range of 250 to 400 ° C may give acceptable results. In some cases it may be desirable to have a two stage curing process with a first stage of a lower baking temperature of less than 250 ° C and a second stage of a higher baking temperature of preferably between 250 and 400 ° C. The two-step curing process promotes the uniform filling and planarization of pre-existing substrate surface topography.

Without being bound by theory, it is believed that the conversion of the oxymetal precursor material to an oxymetal-containing film involves hydrolysis by moisture adsorbed from the ambient atmosphere contained within the coating and / or during deposition (casting) and curing processes . Thus, in order to facilitate the complete conversion of the oxymetal precursor material to the oxymetal-containing film, the curing process is preferably carried out in air or in an atmosphere in which moisture is present. However, when a polymeric matrix precursor material is used, it is desirable to cure the matrix precursor material under an inert atmosphere, such as N ₂ , to reduce the possibility of degradation of the polymeric material. Exposure of the coating to ultraviolet radiation, preferably radiation within a wavelength range of about 200 to 400 nm, may also aid the curing process. The exposure process may be applied separately or in combination with a thermal curing process.

Optionally, a second layer of the coating composition of the present invention may be disposed on the cured oxymetallic material layer and treated as described above. As a result, a cured structure having an alternating layer structure of a cured matrix material-oxymetal material-matrix material-oxymetal material is obtained. This process can be repeated any number of times to build up a stack of such alternating layers.

Depending on the particular application, the cured oxymetal material layer of the present invention may undergo additional processing steps such as patterning. This additional processing step may require the application of one or more organic materials such as photoresist and antireflective coatings to the surface of the oxymetal material layer. The cured oxymetal material layer typically has a very different surface energy than the subsequent applied organic layer. This mismatch of surface energy causes poor adhesion between the oxymetal material layer and the subsequent applied organic layer. In the case of a subsequently applied photoresist layer, this inconsistency in surface energy leads to severe pattern collapse. In order to make the surface of the oxymetal material film of the present invention more compatible with the subsequently applied organic layer, the surface may optionally be treated with a suitable surface treatment agent.

A surface treatment composition useful for treating the surface of a cured oxy metal material film is disclosed in U.S. Patent Application No. 13 / 745,752, which includes an organic solvent and a surface treatment agent, wherein the surface treatment agent comprises one or more surface treatment portions . Optionally, the surface treatment composition may further comprise at least one additive such as a thermal acid generator, photoacid generator, antioxidant, dye, 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 combinations thereof may suitably be used. Exemplary organic solvents include, but are not limited to, toluene, xylene, mesitylene, alkylnaphthalene, 2-methyl-1-butanol, 4-methyl-2-pentanol, gamma-butyrolactone, ethyl lactate, Isobutyrate methyl ester, propylene glycol methyl ether acetate, and propylene glycol methyl ether. A suitable solvent has a relatively higher vapor pressure than the surface treatment agent, so that the solvent can be removed from the surface of the film while leaving the surface treatment agent. It is preferable that the organic solvent does not have a free carboxylic acid group or a sulfonic acid group. A variety of surface treatment agents may be used in the surface treatment composition, which may be polymeric or non-polymeric, and include one or more surface treatment moieties. Exemplary surface treatment moieties include but are not limited to hydroxy (-OH), thiol (-SH), carboxyl (-CO ₂ H), betadiceto (-C (O) -CH ₂ -C (O) , And protected hydroxy groups. Although amino groups will also work, preferably the surface treatment agent does not contain an amino group, more preferably nitrogen, since such groups can adversely affect the function of the subsequently applied coating, such as chemically amplified photoresist to be. Protected carboxyl groups and protected hydroxy groups are any groups that can be cleaved under certain conditions to form carboxyl and hydroxy groups, respectively. Such protected carboxyl groups and protected hydroxy groups are well known in the art. When the surface treatment agent contains at least one protected hydroxy group, it is preferable that a thermal acid generator (TAG) or a photo acid generator (PAG) is used in the surface treatment composition.

Since surface energy is often difficult to measure, surrogate measurements such as water contact angle are typically used. Determination of the water contact angle is well known and a preferred method is to use a Kruss drop shape analyzer Model 100 using deionized water (DI water) and a 2.5 μL droplet size. The layer of cured oxymetal material typically has a water contact angle of 50 DEG or less, e.g. 35 to 45 DEG. After treatment with the surface treatment composition, the oxymetallic material film surface has a surface energy that substantially matches the subsequently applied organic layer. That is, the surface energy of the treated hard mask layer should be within 20% of the surface energy of the subsequently applied organic layer. Subsequent processing steps related to the organic layer applied over the oxymetal material layer will have fewer defects than the oximetal material film without this surface treatment.

The cured matrix material and oxymetal material of the present invention may function properly as a hard mask layer, a dielectric layer, a barrier layer, and the like. A preferred barrier layer structure made in accordance with the present invention comprises a layer of silicon oxide matrix material having a titanium oxide or aluminum oxide layer (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, preferably in the manufacture of OLEDs.

Example 1 Alumoxane Materials &lt; RTI ID = 0.0 &gt;

In a 250 mL round bottom flask equipped with a magnetic stir bar and connected with a condenser and a thermocouple, 12.0 g of aluminum tris-isopropoxide (or Al (Oi-Pr) ₃ ) were mixed with 150.0 g of ethyl acetate. With appropriate stirring, the mixture in the flask was heated using a heating mantle controlled through a thermocouple. The mixture was heated to reflux temperature and held under reflux for 2 hours. The heating was then stopped and the mixture allowed to cool naturally to room temperature with stirring. This ligand exchange reaction in excess of ethyl acetate provided tris ((1-ethoxy-1-oxopropan-2-yl) oxy) aluminum. Next, 0.90 g of DI water and 60.0 g of ethyl lactate were mixed and this aqueous solvent mixture was fed to the reactor over about 13 minutes with stirring. The reaction mixture was then heated to reflux and held under reflux for 2 hours after which the heating was stopped and the reaction mixture was allowed to cool naturally to room temperature to give an alumoxane trimer having five ligands derived from ethyl lactate alumoxane trimer). The reaction mixture was then filtered through a 1.0 mu m perfluoropolyethylene (PFPE) filter to remove any insoluble matter and then filtered through a 0.2 mu PFPE filter. As a result of using the weight loss method in a heat oven, the filtered solution was found to contain 6.2% solids.

Weight loss method

Approximately 0.1 g of the organoaluminum compound in solution state was weighed in a 0-point tared aluminum pan. About 0.5 g of the solvent (ethyl lactate) used to form the organoaluminum compound was added to the aluminum pan to dilute the test solution and cover the aluminum pan more flatly. The aluminum pan was heated in a heat oven at about 110 DEG C for 15 minutes. The aluminum pan was cooled to room temperature, the weight of the aluminum pan containing the dried solid film was determined, and the percent solids content was calculated.

Example 2

50.0 g of the alumoxane solution from Example 1 were weighed in a 100 mL round bottom flask with stirring. Octanoic acid (0.9696 g, about 3 molar equivalents based on the number of ligands) was added to the flask. The reaction was carried out at 60 DEG C for 3 hours under appropriate stirring provided by a magnetic stir bar to give the product an alumoxane trimer with two ligands derived from ethyl lactate and three ligands derived from octanoic acid . The reaction mixture turned from a transparent state to a cloudy state and this cloudiness began to lose its solubility in ethyl lactate, a solvent in which the new compound containing an octanoate ligand was an overly polar solvent .

Example 3

1 part of the solution from Example 2 was mixed with 3 parts of toluene to give a clear solution. Then, before treatment, the solution was filtered once through a 1.0 mu m PFPE filter and filtered three times through a 0.2 mu m PFPE filter. The treatment included spin coating the filtered solution on a bare silicon wafer at 500 rpm and then baking the coated film at 100 占 폚 for 60 seconds. Then, the surface water contact angle of the film was measured with a KRUSS drop shape analyzer (DSA) 100 at a size of 2.5 mu L DI water. The contact angle of the alumoxane film was 82.6 °, whereas 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 (assuming an average chain length of 4.95 mmoles, 4 titanium atoms) (available as Tyzor BTP trademark from Dorf Ketal) in a 100 mL round bottom flask equipped with a magnetic stir bar and 30.0 g Of propylene glycol methyl ether acetate (PGMEA) were weighed. The mixture was stirred to give a homogeneous solution, and then 7.260 g (50.3 mmoles) of octanoic acid was added to the flask. With continued stirring, the temperature of the reaction mixture was raised to 80 캜 and held at 80 캜 for 2.5 hours. Subsequently, heating was stopped and the reaction mixture was allowed to cool naturally to room temperature, and the solution was used as it was. As a result of the weight loss method of Example 1, it was found that the solution contained oligomeric octanoyl titanate having a solid content of 12.06%.

Example 5

A sample (4.453 g) of the solution obtained in Example 4 was mixed with 2.420 g of PGMEA and diluted. The diluted solution was then filtered four times with a 0.2 μm PFPE filter before processing. The filtered sample was spin coated onto a bare silicon wafer at 1500 rpm. The spin-coated film was baked at 100 DEG C for 60 seconds. The water contact angle of the film was found to be 97.9 ° with a 2.5 μL droplet size using a KRUSS liquid chromatograph (DSA) 100. The control wafer was prepared by spin-coating a film of oligomeric butyl titanate (TYZOR BTP / PGMEA, having a solids content similar to that of Example 4) and then processing the control film under the same conditions as the film of this example Respectively. The water contact angle of the control film was found to be 49 °.

Example 6

A coating composition sample was prepared as follows. The stock solution of B-stage polyphenylene matrix precursor material (SiLK (TM) D resin, available from The Dow Chemical Company) was diluted with PGMEA to obtain a 4 wt% solution. 5.0 g of the matrix precursor stock solution was added to each of the samples A-D. In addition, various amounts of the oxymetal precursor material of Example 4 were added to each of the samples B-D as shown in Table 1. Sample A containing no oxymetal precursor material was used as a control. The relative amounts of the oxymetal precursor materials of Example 4 compared to the amount of matrix precursor material, on a solid basis, Further, a co-solvent, gamma-butyrolactone, was added to each of the samples A-D as shown in Table 1. Each sample was filtered four times with a 0.2 μm PFPE syringe filter, spin-coated on a bare silicon wafer at 1500 rpm, and baked at 100 ° C. for 60 seconds. The water contact angle of such a coating film was measured using a KRUSS liquid-type analyzer (DSA) 100 at a size of 2.5 μL DI droplet, and is shown 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 a high water contact angle of 83 °. However, as shown by the data in Table 1, the oxymetal precursor material of Example 4 becomes the topmost surface and can increase the water contact angle value compared to the control.

The wafer containing the film of Sample B was cut into coupons, one of which cured at 380 占 폚 for 30 minutes under a nitrogen atmosphere in a furnace. The cured coupon was subjected to positive SIMS analysis along with the coupon containing the uncured film of sample B to determine the element distribution across the film thickness. Both cured and uncured films exhibited high concentrations of titanium on the surface, and dropped sharply to minute levels of titanium in the film bulk. This clearly indicates the formation of a structure in which the oxymetal precursor material is concentrated on the surface to have a layer of oxymetal material in the layer of the matrix material.

Example 7

The process 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 a known method Respectively. The silsesquioxane oligomer material was first diluted with PGMEA to prepare a 4.0% solution. A 5 grams of silsesquioxane matrix precursor material was added to each of the samples E-H. Sample E was used as control and did not contain oxymetal precursor material. The oxymetal precursor materials of Example 4 were added to each of the Samples F-H as shown in Table 2. A co-solvent (GBL) was also added to each sample. As described in Example 5, each sample was filtered, baked on spin-coating a bare silicon wafer, and then the water contact angle of the film was measured. The results are shown in Table 2.

The difference in water contact angle between control sample E and sample F-H clearly shows that the oxymetal precursor material with low surface energy moved to the film surface during the coating process.

Next, the coated film of this example was cured at 380 캜 for 30 minutes. The surface roughness of the cured film was measured using an atomic force microscope (AFM) at a scan speed of 1.5 Hz and a 2 x 2 μm scanning area. The lower the surface roughness value, the smoother the surface. As can be seen from the data in Table 3, samples F and H containing the oxymetal precursor material provided a smoother film than the control sample E without the oxymetal precursor material.

Example 8

Silsesquioxane oligomers of tetraethylorthosilicate / phenyltrimethoxysilane / vinyltrimethoxysilane / methyltrimethoxysilane (50/9/15/26 molar ratio) were prepared using known methods. The silsesquioxane matrix precursor material was prepared with a solvent in a mixed solvent system of PGMEA / ethyl lactate (95/5 w / w) with a solids content of 2.18%. A 5 g silsesquioxane matrix precursor material solution was prepared by combining 0.135 g of the oxymetal precursor material solution from Example 4 with 0.247 g GBL. The coating composition sample was filtered four times with a 0.2 μm PFPE syringe filter and spin-coated at 1500 rpm on a bare silicon wafer, and the coated film was baked at 100 ° C. for 60 seconds. The coated wafer was cut into coupons and one of them was cured at 380 ° C for 30 minutes. Positive SIMS analysis was performed using conventional apparatus and process conditions to measure the metal (titanium) distribution throughout the film thickness with the coupon having the uncured film deposited in the same coating composition. SIMS data clearly indicated that titanium was preferentially distributed on the topmost surface of both the cured film and the uncured film.

Example 9

Sample H of Example 7 was spin-coated on a bare silicon wafer at 1500 rpm and the coated film was baked at 350 DEG C for 120 seconds to cure the film. This wafer was again coated with the same sample using the same processing conditions. These two coating stacks were analyzed for titanium distribution over film thickness in positive ion mode using SIMS. The SIMS analysis showed two localized maximum values of titanium. The first maximum was at the air-solid interface and the second maximum was at the interface between the two coating compositions, which was the top layer of the first coating composition deposit.

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 stirring bar and a condenser. Was repeated. The stirred mixture was heated to 80 DEG C and then a solution of PGMEA (15.03 g) of octanoic acid (6.339 g) was added to the stirred reaction mixture for 3.3 minutes. After the octanoic acid solution was fed to the flask, the reaction mixture was maintained at 80 DEG C for 2 hours and cooled naturally to room temperature. Based on stoichiometry, 91% of the butoxide ligands in the starting titanium material were replaced by octanoic acid ligands. The reaction solution was used without further purification. According to the weight loss method of Example 1, it was confirmed that this solution had a solid 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 of octanoic acid with 15.03 g of PGMEA and fed to the stirred reaction mixture for 2.0 minutes. Based on the stoichiometry, 85% of the butoxide ligands in the starting titanium material were replaced by octanoic acid ligands. The reaction solution was used without further purification. According to the weight loss method of Example 1, it was confirmed that this solution had a solid content of 11.76%.

Example 12

Two coating compositions, Samples I and J, were prepared by mixing 10 grams of the silsesquioxane matrix precursor material from Example 7, the oxymetal precursor material of Example 10 or Example 11, and the GBL as co-solvent, &Lt; / RTI &gt; The relative amount of oxymetal precursor material compared to the amount of silsesquioxane matrix precursor material on a solids basis for each of Samples I and J was 15%.

Each sample was filtered four times with a 0.2 μm PFPE syringe filter, spin coated at 1500 rpm on a bare silicon wafer, and baked at 100 ° C. for 60 seconds. The water contact angles of the films were measured using a KRUSS liquid chromatograph (DSA) 100 at a size of 2.5 μL DI droplet size, and the results are shown in Table 4. The water contact angles of these films were similar to the water contact angles obtained in Example 6, indicating that all of the ligands on the oxymetal precursor material had low surface energy ligands &lt; RTI ID = 0.0 &gt; It is not necessary that

Example 13: Preparation of a hafnium material

10.0 g of ethyl lactate and 5.289 g of hafnium tetrabutoxide (available from TCI America) were weighed into a 100 mL round bottom flask equipped with a magnetic stir bar. To the stirred mixture was added dropwise a solution of 0.1219 g DI water and 5.1308 g ethyl lactate. The mixture was heated to reflux and maintained at reflux for 2 hours with stirring and then cooled to room temperature naturally. 2.682 g of 2-naphthoic acid, 3.3748 g of octanoic acid and 8.047 g of ethyl lactate was added dropwise to the mixture with stirring. The mixture was heated to 60 DEG C with stirring, held at 60 DEG C for 2 hours, and then cooled to room temperature naturally. According to the weight loss method of Example 1, it was confirmed that the solution contained oligomeric octanoyl / naphthoyl hafnate with 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 an addition funnel. 100 g (0.21 mol) of Hf (OBu) ₄ (available from Gelest Inc.) was added to the reactor. To this vigorously stirred material pentane-2,4-dione (42.5 g, 0.42 mol) was added very slowly over 6 hours. The reaction mixture was stirred overnight at room temperature. The n-butanol produced during the reaction was removed under vacuum, then 800 mL of ethyl acetate was added and the reaction flask was vigorously stirred at room temperature for 30 minutes. The solution was filtered through a fine frit to remove any insoluble product. The remaining solvent was removed in vacuo to give a pale solid (100.4 g, 90% yield). The product, Hf (OBu) ₂ (acac) _2, was used without further purification.

The above product (100.4 g, 0.19 mol) and ethyleneglycol (19.4 g, 0.18 mol) in ethyl acetate (500 mL) were added to a 1 L three-necked flask equipped with a reflux condenser, stir bar and calorimeter. The reaction mixture was refluxed at 80 &lt; 0 &gt; C for 24 hours. The reaction mixture was filtered through a fine frit and dried under vacuum. The white yellow solid was washed with heptane (3 x 1 L) and then dried under strong vacuum for 2 h to give the desired Hf (OBu) acetyl-diethylene glycol copolymer as a white powder (67 g).

Example 15 :

A coating composition was prepared using the Hf (OBu) acetyl-diethylene glycol copolymer of Example 14 as the organometallic matrix precursor material. A 2-methyl-1-butanol solution (6% solids) of Hf (OBu) acetyl-diethylene glycol copolymer was prepared. A substantial amount of the oxymetal (titanate) precursor solution of Example 11 was added to this solution. The relative amount of oxymetal (titanate) precursor material from Example 11 compared to the amount of organometallic matrix precursor material was 5% on a solid basis. A significant amount of GBL co-solvent (5 vol%) was also added to the composition. The composition was filtered four times through a 0.2 탆 PFPE syringe filter before spin coating the bare silicon wafer at 1500 rpm. The wafer was then baked at 100 DEG C for 60 seconds and then cured at 380 DEG C for 2 minutes to provide a layer of cured hafnium oxide matrix material and a layer of titanium oxide material over the hafnium oxide layer.

Example 16: Preparation of Zr (OBu) acetyl-diethylene glycol copolymer

25 wt% zirconium bis (acetylacetone) -bis (n-butoxide) (or Zr (acac) ₂ (OBu) ₂ ) in toluene / butanol was obtained 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 ethyl acetate. An equimolar amount of diethylene glycol was added to the mixture at room temperature, and the mixture was refluxed at 80 DEG C for 18 hours. The reaction mixture was then cooled and filtered to remove the white precipitate. The filtrate was concentrated to small volume using a rotary evaporator and the residue was taken up in heptane. The precipitate was then collected and dried in vacuo to give 20.8 g of the desired product, the structure of which was shown below.

Example 17 :

A coating composition was prepared using the Zr (OBu) acetyl-diethylene glycol copolymer of Example 16 as the organometallic matrix precursor material. A 2-methyl-1-butanol solution (6% solids) of Zr (OBu) acetyl-diethylene glycol copolymer was prepared. A substantial amount of the oxymetal (titanate) precursor solution of Example 11 was added to this solution. The relative amount of oxymetal (titanate) precursor material from Example 11 compared to the amount of organometallic matrix precursor material was 5% on a solid basis. A significant amount of GBL co-solvent (5 vol%) was also added to the composition. The composition was filtered four times through a 0.2 탆 PFPE syringe filter before spin coating the bare silicon wafer at 1500 rpm. The wafer was 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 (11)

Disposing a layer of a matrix precursor material, an oxymetal precursor material having a surface energy of 20 to 40 erg / cm &lt; 2 &gt; and an organic solvent on the electronic device substrate; Treating the coating composition layer with a condition that a layer of the oxymetal precursor material is formed on the layer of the matrix precursor material; A method of forming an oxymetal layer on a matrix layer on an electronic device substrate, comprising curing a layer of a matrix precursor material and a layer of an oxymetal precursor material. The method of claim 1, wherein the organic solvent comprises a first organic solvent and a second organic solvent. The method of claim 1, wherein the oxymetal precursor material is a metal selected from group 3 to 14. 4. The method of claim 3, wherein the metal is a metal selected from the group consisting of titanium, zirconium, hafnium, tungsten, tantalum, molybdenum and aluminum. The method of claim 1, wherein the matrix precursor material comprises a silicon-containing material. 2. The method of claim 1, wherein the matrix precursor material has a surface energy greater than the surface energy of the oximetallic precursor material. 7. The method of claim 6, wherein the matrix precursor material has a surface energy greater than or equal to 10 ergs / cm &lt; 2 &gt; than the surface energy of the oximetallic precursor material. The method of claim 1, wherein the matrix precursor material layer and the oxymetal precursor material layer are cured by heating. The method of claim 1, wherein the substrate is a substrate for a light emitting diode. 2. The method of claim 1, wherein a layer of a second coating composition is disposed on the surface of the cured oxymetal layer and the second composition layer is treated such that a layer of the second oxymetal precursor material is formed over the layer of the second matrix precursor material and; Further comprising curing a layer of a second matrix precursor material and a layer of a second oximetall precursor material. A matrix precursor material, an oxymetal precursor material having a surface energy of 20 to 40 erg / cm &lt; 2 &gt;, and an organic solvent, wherein the matrix precursor material has a higher surface energy than the surface energy of the oximetallic precursor material.