JP6453023B2 - Organoaluminum material - Google Patents

Organoaluminum material Download PDF

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JP6453023B2
JP6453023B2 JP2014206830A JP2014206830A JP6453023B2 JP 6453023 B2 JP6453023 B2 JP 6453023B2 JP 2014206830 A JP2014206830 A JP 2014206830A JP 2014206830 A JP2014206830 A JP 2014206830A JP 6453023 B2 JP6453023 B2 JP 6453023B2
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aluminum oxide
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ダヤン・ワン
ピーター・トレフォナス・ザ・サード
キャサリン・エム.オコンネル
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ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC
ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC
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Description

  The present invention relates generally to the field of solution-based organometallic compounds, and more specifically to the field of manufacturing coated substrates using the solution-based organometallic compounds.

There is a need for specific layers with etch selectivity in lithography and for specific semiconductor manufacturing, for example organic light emitting diode (OLED) manufacturing or layers for blocking both oxygen and moisture in photovoltaic devices. It has resulted in the use of membranes containing oxymetal domains in manufacturing. The oxymetal layer is generally characterized as a film containing a majority amount of inorganic domains (oxymetal domains) with (-M-O-) n- linkage, where M is a metal and n> 1. The oxymetal layer may be composed of less than half the amount of other elements, such as carbon. Layers composed of mixed domains that include both oxymetal and metal nitride domains can be used.

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 oxymetal domain-containing films varies in part depending on the specific metal used and the amount of (-MO-) n domains present in the film, such domains As the amount of increases, it provides greater etch resistance. Barrier films used for OLED applications conventionally include Al or Si, ie, (—Al—O—) n or (—Si—O—) n domains (where n> 1). Includes 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 defect in such a barrier film, such as a pinhole, or any other defect that causes incomplete coverage of the underlying film provides 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, International Publication No. WO 2012/103390 describes an aluminum oxide or silicon oxide layer next to a reactive inorganic layer on a flexible (plastic) substrate to reduce gas or vapor transport through the laminate. A laminate having one or more oxide-containing barrier layers is disclosed. According to this patent application, this reactive inorganic layer functions to react with any gas or vapor that penetrates the barrier layer. This patent application does not suggest a suitable material for forming such a barrier layer, but focuses on conventional film deposition techniques such as evaporation techniques.

Spin-on technology is widely used in electronic device manufacturing, and spin-on technology offers advantages over conventional vapor deposition methods of depositing films. For example, the spin-on technique can use existing equipment, can be completed within minutes, and can provide a uniform coating on the substrate. Conventional aluminum sources such as Al (Oi-Pr) 3 suffer from very poor solubility in solvents conventionally used in electronic device manufacturing, as well as high sensitivity to water / moisture. Such conventional aluminum sources typically form aluminum oxide particles upon exposure to moisture, such as residual moisture found in common solvents. Such aluminum oxide particles cause problems in liquid dispensing systems, and even if they can be dispensed, such particles cause defect problems during the manufacture of electronic devices.

International Publication No. WO2012 / 103390 Pamphlet

  Thus, there is a need for an aluminum source and method suitable for spin-on deposition of an aluminum oxide containing film for use as a barrier in an electronic device substrate. There is a further need for a method of depositing such an aluminum oxide-containing barrier directly on an electronic device substrate rather than on a separate flexible (plastic) substrate.

The present invention provides a step of providing a substrate, wherein a layer of a coating composition is disposed on the substrate, wherein the coating composition has the formula AlL 1 x L 2 y , wherein L 1 = (C 1 -C 6 ) alkoxy , L 2 = (C 5 -C 20 ) β-diketonate or OR 1 , R 1 = (C 4 -C 10 ) hydrocarbyl moiety, x is an integer from 0 to 2, and y is an integer from 1 to 3. And x + y = 3) and (ii) an organic solvent having the formula HOR 1 and curing the coating composition to form an aluminum oxide layer on the substrate. A method for forming an aluminum oxide layer is provided.

  As used throughout this specification, the following abbreviations shall have the following meanings unless the context clearly indicates otherwise: ca. G = gram; mmol = mmol; mL = milliliter; μL = microliter; μm = micrometer = micron; nm = nanometer; Å = angstrom; and rpm = number of revolutions per minute . Unless otherwise indicated, 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” mean linear, branched and cyclic alkyl and “alkoxy”, respectively. The term “cure” refers to any process that increases the molecular weight of a film or layer by polymerizing or otherwise, such as by condensation. The articles “a”, “an” and “the” mean singular and plural. All numerical ranges include boundary values and can be combined arbitrarily unless it is clear that such numerical ranges are constrained to add up to 100%.

Aluminum sources suitable for use in the present invention are those of formula AlL 1 x L 2 y , where L 1 = (C 1 -C 6 ) alkoxy, L 2 = (C 5 -C 20 ) β-diketonate or OR 1 , R 1 = (C 4 -C 10 ) hydrocarbyl moiety, x is an integer from 0 to 2, y is an integer from 1 to 3, and x + y = 3). Preferably, L 1 = (C 1 -C 4 ) alkoxy, and more preferably L 1 = (C 1 -C 3 ) alkoxy. x is preferably 0 or 1, more preferably x = 0. Preferably, L 2 = (C 5 -C 15 ) β-diketonate or OR 1 , and more preferably L 2 = OR 1 . As used herein, “(C 4 -C 10 ) hydrocarbyl” refers to any hydrocarbon moiety containing 4 to 10 carbon atoms. This (C 4 -C 10 ) hydrocarbyl moiety may be aromatic or aliphatic, preferably aliphatic. The (C 4 -C 10 ) hydrocarbyl moiety is optionally one or more substituents selected from the group consisting of hydroxyl, carboxylic acid, and (C 1 -C 6 ) alkylcarboxylate, preferably hydroxyl and ( One or more substituents selected from the group consisting of C 1 -C 6 ) alkylcarboxylates, more preferably one or more substituents selected from the group consisting of hydroxyl and (C 1 -C 4 ) alkylcarboxylates groups, even more preferably 1 or more substituents selected from hydroxyl and (C 2 -C 4) group consisting of alkyl carboxylates. More preferably, the (C 4 -C 10 ) hydrocarbyl moiety of R 1 is bonded to oxygen via a secondary carbon atom. y = 2 or 3 is preferred, more preferably y is 3. The most preferred organoaluminum compounds are of the formula AlL 2 3 where L 2 is as defined above. Those skilled in the art will recognize that organoaluminum compounds useful as aluminum sources in the present invention can form dimers or trimers in solution, especially when small amounts of water are present. Such dimers or trimers can be used successfully in the methods of the invention. Thus, in solution, the organoaluminum compound in the present invention has the formula Al m O m-1 L 1 x2 L 2 y2 where L 1 and L 2 are as defined above, m = 1-3 X2 = 0-4, y2 = 1-5, and x2 + y2 = m + 2). This dimer or trimer can be used successfully in the method of the invention.

Organoaluminum compounds in the present invention can be prepared by a variety of procedures known in the art, typically with a starting aluminum compound of formula Al ((C 1 -C 6 ) alkoxy) 3 and a suitable high Produced by a ligand exchange reaction with the next ligand, eg HL 2 or an alkali or alkaline earth salt thereof, eg K + -L 2 , where L 2 is as defined above. Is done. Preferably, the higher order ligand used in the ligand exchange reaction has the formula HL 2 and more preferably has the formula HOR 1 , where R 1 is as defined above. In a general procedure, the starting aluminum compound Al ((C 1 -C 6 ) alkoxy) 3 is combined with a higher order ligand and a suitable organic solvent in a flask. This mixture is then heated, typically at reflux, for a time that allows the desired ligand exchange to occur. After this procedure, one, two or all three of the (C 1 -C 6 ) alkoxy ligands on the starting aluminum compound can be exchanged with a corresponding number of higher order ligands. The number of (C 1 -C 6 ) alkoxy ligands replaced will depend on the steric hindrance of the specific (C 1 -C 6 ) alkoxy ligand, the steric hindrance of the specific higher order ligand used, and the mixture being heated. It will be appreciated by those skilled in the art that increasing the length of time will result in more ligand exchange. Suitable compounds useful as higher order ligands in the present invention include, but are not limited to, 2,4-octanedione, methyl glycolate, ethyl glycolate, ethyl lactate, 2-methyl-1-butanol, 4-methyl 2-pentanol, and diethyl tartrate. Preferred organic solvents are methyl glycolate, ethyl glycolate, ethyl lactate and diethyl tartrate.

Any suitable organic solvent can be used for such ligand exchange reactions, preferably the organic solvent has the formula HOR 1 , where R 1 is as defined above. Preferably higher order ligands are also used as organic solvents for the ligand exchange reaction. In this method, there is a large excess of higher order ligands and typically all three of the (C 1 -C 6 ) alkoxy ligands are replaced with higher order ligands as shown according to the following formula: .

If the organic solvent used in the ligand exchange reaction is not a solvent having the formula HOR 1 , an organoaluminum compound containing a higher order ligand, ie, Al (OR 1 ) 3 in the above formula is derived from such an organic solvent. Should be separated and then combined with a solvent having the formula HOR 1 .

Preferred organic solvents for the ligand exchange reaction are those having the formula HOR 1 , where R 1 is a (C 4 -C 10 ) hydrocarbyl moiety, which is preferably aliphatic. This (C 4 -C 10 ) hydrocarbyl moiety is optionally hydroxyl, carboxylic acid and (C 1 -C 6 ) alkylcarboxylate, preferably hydroxyl and (C 1 -C 6 ) alkylcarboxylate, more preferably May comprise one or more substituents selected from the group consisting of hydroxyl and (C 1 -C 4 ) alkylcarboxylates, even more preferably hydroxyl and (C 2 -C 4 ) alkylcarboxylates. A preferred organic solvent is an α-hydroxy ester. It is also preferred that the (C 4 -C 10 ) hydrocarbyl moiety of R 1 is bonded to oxygen via a secondary carbon atom. Suitable organic solvents include, but are not limited to, methyl glycolate, ethyl glycolate, ethyl lactate, 2-methyl-1-butanol, 4-methyl-2-pentanol and diethyl tartrate. Preferred organic solvents are methyl glycolate, ethyl glycolate, ethyl lactate and diethyl tartrate.

A coating composition useful in the method of the present invention comprises an organoaluminum compound of formula AlL 1 x L 2 y as described above and an organic solvent of formula HOR 1 as described above. If a higher order ligand is also used as the organic solvent for the ligand exchange reaction, the reaction product can be used in that solvent without separation. Preferably, the coating composition is filtered prior to use to remove any insoluble material that forms during the ligand exchange reaction.

  The coating composition of the present invention can optionally include one or more surface leveling agents (or surfactants) or binder polymers. Any suitable surfactant can be used, but such surfactants are typically nonionic. The amount of such surfactants useful in the compositions of the present invention is well known to those skilled in the art and is typically in the range of 0-2% by weight. A variety of binder polymers can be used, for example, to provide improved coating quality or leveling on the substrate. Suitable binder polymers are disclosed in US patent application Ser. No. 13 / 776,496.

  In some cases, the coating composition of the present invention can further comprise one or more curing agents to assist in curing the deposited organoaluminum film. Exemplary curing agents include thermal acid generators (TAG) and photoacid generators (PAG). A preferred curing agent is a thermal acid generator. The amount of such hardener is within the ability of one skilled in the art. Any suitable curing agent can be used in the coating composition of the present invention.

  The coating compositions of the present invention are useful for forming an aluminum oxide layer on a variety of substrates, such as electronic device substrates, packaging substrates, separation substrates, or any other substrate on which a gas barrier can be used. Various electronic device substrates, for example, packaging substrates such as multichip modules, flat panel display substrates including flexible display substrates, integrated circuit substrates, photovoltaic device substrates, light emitting diodes (LEDs, organic light emitting diodes, ie Substrates for OLEDs, etc.), semiconductor wafers, polycrystalline silicon substrates, etc. 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, and gold. It is comprised from 1 or more types of. 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. It is intended to encompass multi-chip wafers, packages for various levels, or other assemblies requiring solder connections. Substrates that are particularly suitable for the hard mask layer are patterned wafers, such as patterned silicon wafers, patterned sapphire wafers, and patterned gallium arsenide wafers. Such a wafer can be of any suitable size. Preferred wafer diameters are 200 mm to 300 mm, but wafers with smaller and larger diameters can be suitably used according to the present invention. As used herein, the term “semiconductor substrate” includes any substrate having a structure or semiconductor layer containing one or more active or operable portions of a semiconductor device. The term “semiconductor substrate” refers to any construct that includes a semiconductor material, such as, but not limited to, a bulk semiconductor material, such as a semiconductor wafer, alone or in an assembly that includes other materials thereon, and alone. Of semiconductor material in an assembly comprising or other materials. A semiconductor device refers to a semiconductor substrate on which at least one microelectronic device is fabricated on a substrate or fabricated in batch. 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 layer of the coating composition of the present invention may be applied onto a substrate such as an electronic device substrate by any suitable means such as spin coating, spray coating, slot die coating, doctor blading, curtain coating, roller coating, dip coating, etc. Can be arranged. Spin coating, spray coating and slot die coating are preferred. In a typical spin coating method, the coating composition of the present invention is applied to an electronic device substrate rotating at a speed of 500 to 4000 rpm over a period of 15 to 90 seconds to provide a desired organoaluminum compound on the substrate. Get a layer of. It will be appreciated by those skilled in the art that the height of the organoaluminum compound layer can be adjusted by varying the rotational speed as well as the percentage solids in the coating composition.

  During or after deposition of a layer of the coating composition of the present invention on a substrate, optionally to form a layer of organoaluminum compound, excluding any remaining solvent and other relatively volatile components This layer is baked at a relatively low temperature. Typically, the substrate is baked at a temperature of 125 ° C or lower, preferably 60-125 ° C, and more preferably 90-115 ° C. The baking time is typically 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, and more preferably 6 to 180 seconds. When the substrate is a wafer, this baking step can be performed by heating the wafer on a hot plate.

After some baking step to remove the solvent, the organoaluminum compound layer is cured, for example in an oxygen-containing atmosphere, for example in air. This curing step is preferably performed on a hot plate type apparatus, but oven curing can be used to obtain comparable results. Typically, such curing is performed by heating the organoaluminum compound layer at a curing temperature of 150 ° C or higher, preferably 150-450 ° C, and more preferably 200-400 ° C. The final cure temperature selection depends primarily on the desired cure rate, with higher cure temperatures requiring shorter cure times. Typically, the cure time can be from 10 seconds to 120 minutes. Shorter cure times are preferred and can typically be 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes. One skilled in the art will recognize that longer cure times may be used. This curing step is performed to thermally decompose at least a portion of the organoaluminum compound, preferably all of the organoaluminum compound, so that (-MO-) n (where n> 1, preferably n > 2, more preferably n> 5, even more preferably n> 10, and even more preferably n> 25) resulting in a hard mask layer comprising oxyaluminum domains (aluminum oxide) having linkages. Typically, the amount of aluminum in the cured oxyaluminum domain-containing film can be 95 mol% or less (or higher), and preferably 50-95 mol%. The aluminum oxide layer formed from the composition of the present invention includes oxyaluminum domains and can include other domains, such as aluminum nitride domains, and optionally carbon, such as 5 mol% carbon or less. Can be included in quantity.

  If the composition of the present invention includes an optional TAG, the organoaluminum compound layer should be heated to a temperature sufficient to activate the TAG and generate an acid. Typically, the temperature used to cure the organoaluminum compound layer to form the aluminum oxide-containing layer is sufficient to activate the TAG. Alternatively, when a PAG is used in the composition of the present invention, the organoaluminum compound layer can be exposed to light of a suitable wavelength or to an electron beam to generate the corresponding acid. This exposure step can occur before, during, or before and during the step of curing the organoaluminum compound layer to form the aluminum oxide-containing film.

  When the organoaluminum layer of the present invention is cured at a temperature of 200 ° C. or higher, the resulting aluminum oxide-containing film is stripped (removed) with a solvent conventionally used in anti-reflective coating and photoresist applications. It is resistant to it. The organoaluminum oligomer layer of the present invention is cured at a temperature of 350 ° C. or higher, and the resulting aluminum oxide-containing film is peeled off by an alkali or solvent developer conventionally used in the development of imaged photoresist layers. It is also resistant to.

  If the final curing step is performed in such a way that rapid development of solvent and curable by-products does not destroy the film quality, the first baking step may not be essential. For example, ramped bake begins at a relatively low temperature and then gradually rises to the 250-400 ° C. range can produce acceptable results. In some cases it may be preferred to have a two-stage curing process in which the first stage is a low bake temperature below 250 ° C and the second stage is a higher bake temperature, preferably 250-400 ° C. The two-stage curing process promotes uniform film formation and planarization of preexisting substrate surface topologies.

  While not wishing to be bound by theory, the conversion of organoaluminum to aluminum oxide is dependent on the moisture contained in the coating and / or the water adsorbed from the atmosphere during the deposition and curing process. It is thought to involve decomposition. Thus, this curing process is preferably performed in air or in an atmosphere where moisture is present to facilitate complete conversion to aluminum oxide. This curing process can also be aided by exposure of the coating to ultraviolet radiation, preferably ultraviolet radiation in the wavelength range of about 200-400 nm. This exposure process can be applied separately from or in conjunction with the thermosetting process.

  The cured aluminum oxide-containing layer (or film) can be suitably used as a hard mask, dielectric layer, barrier layer, or for some other suitable application in the manufacture of various devices. The cured aluminum oxide-containing layer of the present invention is used as a barrier layer such as an oxygen barrier, in the manufacture of LEDs, and preferably in the manufacture of OLEDs, or in packaging applications or as a low diffusion gas barrier in isolation applications. Especially suitable.

  Depending on the specific application, the aluminum oxide-containing layer of the present invention can be subjected to further processing steps such as patterning. Such further 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 aluminum oxide-containing layer. The oxymetal-containing 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 hard mask layer and the subsequently applied organic layer. In the case of subsequently applied photoresist layers, this surface energy mismatch results in severe pattern collapse. In order to make the surface of the aluminum oxide-containing film of the present invention more compatible with the subsequently applied organic layer, this surface can optionally be treated with a suitable surface treatment agent.

  A surface treatment composition useful for treating the aluminum oxide-containing film surface of the present invention is that disclosed in US patent application Ser. No. 13 / 445,752, comprising an organic solvent and a surface treatment agent. 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 thermal acid generators, photoacid generators, antioxidants, dyes, contrast agents, 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-hydroxyisobutylene. Rick 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 behind the surface treatment agent. It is preferred that the organic solvent does not have a free carboxylic acid group or sulfonic acid group. Various surface treatment agents can be used in the surface treatment composition, and the surface treatment agent can be a polymer or non-polymer, and the surface treatment agent comprises one or more surface treatment moieties. be able to. Typical surface treatment moieties include hydroxyl (—OH), thiol (—SH), carboxyl (—CO 2 H), beta diketo (—C (O) —CH 2 —C (O) —), protected Carboxyl and protected hydroxyl groups are mentioned. Although amino groups will function, the surface treatment agent preferably does not contain amino groups, and preferably does not contain nitrogen, because such groups may be subsequently applied to coatings such as chemically amplified photoresists. This is because it can adversely affect the function of the device. 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. This protected carboxyl group and protected hydroxyl group are well known in the art. When the surface treatment agent contains one or more protected hydroxyl groups, it is preferred that TAG or PAG is used in the surface treatment composition.

Alternatively, rather than treating the formed aluminum oxide-containing layer separately with a surface treatment agent, the organoaluminum compound coating composition of the present invention has a surface energy of 20-40 erg / cm 2 and is hydroxyl, protected Further comprising a surface treatment agent comprising a surface treatment moiety selected from hydroxyl, protected carboxyl and mixtures thereof, such as those disclosed in co-genus US patent application Ser. No. 13 / 745,753 be able to. A minimum of one surface treatment portion is required per surface treatment agent molecule. As long as the surface energy of the surface treatment agent has a (static) surface energy in the range of 20 to 40 erg / cm 2 , there is no specific limitation on the number of surface treatment parts per surface treatment agent molecule. It will be appreciated by those skilled in the art that increasing the amount of surface treatment moiety in a surface treatment agent molecule typically increases the surface energy of that molecule. When added to the organoaluminum coating composition, the surface treatment agent is substantially free of protected carboxylic acid groups (ie, the surface treatment agent is protected to less than 0.5 mole percent, ie, “free” Of carboxylic acid groups). In addition to the surface treatment moiety, the surface treatment agent also includes one or more relatively hydrophobic moieties such as C 3-20 alkyl groups and C 6-20 aryl groups. Branched or cyclic alkyl groups are relatively more hydrophobic than the corresponding linear alkyl groups, and the increased branching or cyclic properties of such groups lower the surface energy of the surface treatment agent. It is thought to help. Similarly, increasing the carbon chain length of the alkyl and aryl groups also reduces the surface energy of the surface treatment agent. When this surface treatment agent is added to the organoaluminum coating composition of the present invention, the solvent system is a majority of the first solvent having a relatively low surface energy and relative to the first solvent. A second solvent having a higher boiling point is included in less than half, and this second solvent has a surface energy (tension) higher than the surface energy of the surface treatment agent.

  Without wishing to be bound by theory, if a surface treatment agent is present in the organoaluminum coating composition, the surface may be deposited during deposition of the coating composition and / or during any subsequent solvent removal step. It is conceivable that the treatment agent moves toward the surface of the film being formed. It is further contemplated that the relatively lower surface energy of the surface treatment agent helps drive the surface treatment agent toward the air interface. It will be appreciated by those skilled in the art that such movement of the surface treatment agent should substantially occur before the aluminum oxide-containing film is completely cured. Formation of the cured aluminum oxide-containing film substantially inhibits the transfer of the surface treatment agent. Since the surface treatment agent is present on the surface of the organoaluminum compound layer, the temperature used to cure the organoaluminum compound layer should be selected so that the surface treatment agent does not substantially decompose. If higher cure temperatures are required, more heat stable surface treatments such as vinyl aryl polymers such as hydroxystyrene polymers and polyhedral oligosilsesquioxane polymers can be used.

  Since surface energy is often difficult to measure, surrogate measurements such as water contact angles are typically used. The determination of the water contact angle is well known and the preferred method uses the Kruss drop shape analyzer model 100, using deionized (DI) water and a droplet size of 2.5 μL. An oxymetal-containing layer, such as an aluminum oxide-containing layer, typically has a water contact angle of 50 ° or less, such as 35 to 45 °. After treatment with the surface treatment composition, the aluminum oxide-containing film surface typically has a water contact angle of 55 ° or more, such as 55 to 70 °. After the treatment with the surface treatment agent, the aluminum oxide-containing film surface has a surface energy substantially compatible with the surface energy of the subsequently applied organic layer, i.e. the surface energy of the treated aluminum oxide-containing layer. Should be within 20% of the surface energy of the subsequently applied organic layer. Organic layers applied on aluminum oxide containing layers with subsequent processing steps will have fewer defects compared to aluminum oxide containing films without such surface treatment.

Example 1: In a 250 mL round bottom flask fitted with a heating mantle and connected to a condenser, 4.0 g of aluminum tri-isopropoxide (Al (Oi-Pr) 3 ) 50.0 g of ethyl lactate Mixed with. The ethyl lactate was not anhydrous and contained residual amounts of water. With proper stirring (with a magnetic stir bar), the mixture was heated to 88 ° C. (controlled by a thermocouple) and maintained at this temperature for 2 hours. It was then subjected to reflux and held at reflux for 1.5 hours. Heating was then stopped and the mixture was allowed to cool to room temperature with spontaneous stirring. The solution was then filtered through a 1.0 μm perfluoropolyethylene (PFPE) syringe filter to remove insoluble material and then filtered through a 0.2 μm PFPE filter. Using the following weight loss method, this filtered solution was found to contain about 13.2% solids. This ligand exchange reaction in excess ethyl lactate provided tris ((1-ethoxy-1-oxopropan-2-yl) oxy) aluminum.

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

Example 2: In a 250 mL round bottom flask fitted with a heating mantle and connected to a condenser, 4.0 g Al (Oi-Pr) 3 was 50.0 g ethyl lactate and 0.1 g (0.28) Equivalents) of deionized (DI) water. The ethyl lactate was not anhydrous and contained residual amounts of water. With proper stirring (with a magnetic stir bar), the mixture was heated to 88 ° C. (controlled by a thermocouple) and maintained at this temperature for 2 hours. It was then brought to reflux temperature and held at reflux for 1.5 hours. Heating was then stopped and the mixture was allowed to cool to room temperature with spontaneous stirring. The solution was then filtered through a 1.0 μm PFPE filter to remove insoluble material and then filtered through a 0.2 μm PFPE filter. Using the weight reduction method described in Example 1, this filtered solution was found to contain about 8.8% solids.

  Example 3: Example 2 was repeated except that 0.2 g (0.57 equivalents) of DI water was used. After filtration, using the weight loss method described in Example 1, this solution was found to contain about 7.8% solids.

  Example 4: The procedure of Example 2 was repeated except that 0.5 g (1.42 equivalents) of DI water was used. After filtration, using the weight loss method of Example 1, this solution was found to contain about 6.7% solids.

Example 5: In a 250 mL round bottom flask fitted with a heating mantle and connected to a condenser, 4.0 g Al (Oi-Pr) 3 was mixed with 55.2 g ethyl lactate. This ethyl lactate was not anhydrous. The mixture was heated to reflux temperature and maintained at reflux for 2 hours, properly stirring with a magnetic stir bar method. Heating was then stopped and the mixture was allowed to cool to room temperature with spontaneous stirring. Then 0.20 g (0.57 equivalents) of DI water and 15.0 g of ethyl lactate were mixed and the mixture was fed to the reaction flask with stirring for about 6.5 minutes. The reaction mixture was then heated again to reflux temperature and held at reflux for 2 hours, after which the heating was stopped and the reaction mixture was allowed to cool naturally to room temperature. The reaction mixture solution was then filtered through a 1.0 μm PFPE filter to remove insoluble material and then filtered through a 0.2 μm PFPE filter. After filtration, using the weight loss method of Example 1, this solution was found to contain about 7.9% solids.

  Example 6: 50 g of ethyl lactate was first used to prepare a mixture of 0.30 g (0.85 eq) DI water and 20.0 g of ethyl lactate, this mixture being for a period of about 8.0 minutes The procedure of Example 5 was repeated except that the reaction flask was fed with stirring. After filtration, using the weight loss method of Example 1, this solution was found to contain about 8.1% solids.

Example 7: In a round bottom flask equipped with a heating mantle and a condenser, 4.0 g Al (Oi-Pr) 3 was added to 50 g 2-methyl-1-butanol. This mixture was then heated to reflux temperature and held at that temperature for 5 hours. After removing insoluble material by filtration through a PFPE syringe filter, using the weight loss method of Example 1, the solution was found to contain 2-3% solids.

  Example 8 The procedure of Example 7 was repeated except that 50 g of propylene glycol monomethyl ether was used instead of 2-methyl-1-butanol. After removing insoluble material by filtration through a PFPE syringe filter, using the weight loss method of Example 1, the solution was found to contain 2-3% solids.

  Example 9: 6.5 g of the reaction mixture from Example 1 was weighed into a 20 mL glass vial and 6.5 g of ethyl lactate was also added. This diluted solution was then filtered through a 1.0 μm PFPE syringe filter once, then filtered through a 0.2 μm PFPE syringe filter multiple times, and the filtrate was placed in another 20 mL glass vial. The filtered sample was coated at 1500 rpm on multiple 200 mm (8 inch) silicon wafers. One wafer was then cured for 60 seconds at 200, 250, and 350 ° C, respectively. The thickness of this cured film is measured using a Therma-wave spectroscopic ellipsometer (model 7341) 673 nm wavelength and the film thickness is summarized in Table 1.

  Visual inspection of these wafers showed that all these films were of good quality. Each cured film was washed with ethyl lactate for 10 seconds and no film delamination was observed, indicating the formation of a crosslinked network.

Example 10: 7.51 g of the reaction mixture from Example 3 was weighed into a 20 mL glass vial and mixed with 7.69 g of ethyl lactate. This diluted solution was then filtered through a 1.0 μm PFPE syringe filter once, then filtered through a 0.2 μm PFPE syringe filter multiple times, and the filtrate was placed in another 20 mL glass vial. The filtered sample was coated on a 200 mm (8 inch) bare silicon wafer at 1500 rpm, after which the coating was baked at 100 ° C. for 60 seconds. The coated wafer was then cured in an oven in air at 400 ° C. for 30 minutes. In appearance, the cured film was silver (aluminum-like) in color and was of a satisfactory film quality. Before and after it was baked at 380 ° C. for 30 minutes under N 2 , the film thickness was measured using an ellipsometer with a refractive index input value of 1.77 (for alumina) to determine the thermal stability of the film. Were determined. Excellent thermal stability was observed for this cured film as evidenced by a constant film thickness before and after baking at 380 ° C.

  Example 11: Reaction mixture samples from Examples 5 and 6 were filtered once through a 1.0 μm PFPE filter to remove insoluble material in the solution. For this cure test, each of these two solutions was filtered through a 0.2 μm PFPE filter 3-4 times before processing. This process was spin-coated with this filtered solution onto a 200 mm bare silicon wafer at 1500 rpm, followed by soft baking at 100 ° C. for 60 seconds. Next, the film thickness was measured using a THERMA-WAVE spectroscopic ellipsometer (model 7341). This film thickness is reported in Table 2.

  A very good quality film was obtained with no apparent defects or haze in appearance. The coated wafer is then cut into 2 × 2 inch specimens that are then in air over 400 for various cure times of 30, 60, 90, and 120 minutes. It was subjected to a curing bake at 0C. The test results showed a constant film thickness up to 90 minutes curing time. A slight decrease in film thickness was observed after 120 minutes of curing time. This test result indicates that if the film is cured at 400 ° C. for 30 minutes, the film thickness will remain unchanged over the subsequent 60 minutes bake at the same temperature.

  Example 12: A multilayer barrier structure having an aluminum oxide barrier layer and a silicon oxide barrier layer was prepared as follows. The reaction mixture from Example 5 was filtered once through a 1.0 μm PFPE filter and then filtered through a 0.2 μm PFPE filter multiple times before processing.

  Silsesquioxane material is a 95/5 propylene glycol monomethyl ether acetate (PGMEA) / as an oligomer of 50/9/15/26 tetraethylorthosilicate / phenyl-trimethylsilane / vinyl-trimethylsilane / methyl-trimethylsilane. Prepared using known methods in an ethyl lactate solvent system. This formulation contained 2.18 wt% solids.

  On the silicon wafer, the reaction mixture from Example 5 was spin-coated at 1500 rpm, and then an aluminum oxide-containing film was formed by curing baking at 350 ° C. for 60 seconds. A film of the silsesquioxane material was spin-coated at 1500 rpm on the cured aluminum oxide-containing film, and then cured by baking at 350 ° C. for 60 seconds to form a silicon oxide-containing film. The total film thickness of this laminate was then measured using a THERMA-WAVE spectroscopic ellipsometer as described in Example 11 and found to be 1902 mm.

  Example 13: The procedure of Example 12 was repeated except that the reaction mixture from Example 6 was used as the organoaluminum compound coating composition. The total film thickness of this laminate was then measured using a THERMA-WAVE spectroscopic ellipsometer as described in Example 11 and found to be 1950 mm.

  Example 14: After the silsesquioxane film has been cured, a second layer of the organoaluminum compound coating composition from Example 6 is spin coated onto the surface of the cured silicon oxide-containing film, and The procedure of Example 13 was repeated except that it was cured under the same conditions to form a second aluminum oxide containing film. A second layer of silsesquioxane composition was then spin coated on the surface of the second aluminum oxide containing film and then cured to form a second silicon oxide containing film. This approach provided a multilayer (4-layer) barrier structure with alternating aluminum oxide-containing films and silicon oxide-containing films.

  Example 15: An organoaluminum compound reaction mixture from Example 6 was spin coated on a silicon wafer at 1500 rpm and then cured and baked at 350 ° C. for 2 minutes to form an aluminum oxide-containing film. On this cured aluminum oxide-containing film, a 10.8 wt% solution in 88.2 / 9.8 / 2 PGMEA / cyclopentane / gamma-butyrolactone was used as a polyphenylene resin (trade name of SiLK resin from Sadau Chemical Company). Film) was spin coated at 1500 rpm and then cured at 380 ° C. for 2 minutes. A second layer of aluminum oxide is then coated on the surface of the cured polyphenylene film by coating a layer of the composition from Example 6 on the surface of the cured polyphenylene film and then baking at 380 ° C. for 30 minutes. A containing film was formed. A second polyphenylene layer was spin coated on the second aluminum oxide containing film and cured under the same conditions as the first polyphenylene film. The resulting four-layer laminate had alternating layers of aluminum oxide-containing films and cured polyphenylene films.

  Example 16: The organoaluminum compound coating composition from Example 6 was spin coated onto a bare silicon wafer at 1500 rpm and then cured at 400 ° C. for 30 minutes to form an aluminum oxide containing film. On this cured aluminum oxide containing film, another layer of organoaluminum compound coating composition from Example 6 was spin coated and then cured under the same conditions. These coating and curing steps were performed twice more to provide a four layer aluminum oxide containing barrier laminate.

  Example 17: The ligand exchange procedure of Example 1 is repeated except that ethyl lactate is replaced with diethyl tartrate.

  Example 18: The ligand exchange procedure of Example 1 is repeated except that ethyl lactate is replaced with methyl glycolate.

  Example 19: The ligand exchange procedure of Example 1 is repeated except that ethyl lactate is replaced with ethyl glycolate.

  Example 20: The ligand exchange procedure of Example 1 is repeated except that ethyl lactate is replaced with 2-methyl-1-butanol.

  Example 21: The ligand exchange procedure of Example 1 is repeated except that ethyl lactate is replaced with 4-methyl-2-pentanol.

Claims (11)

  1. Providing a substrate, placing a layer of the coating composition on the substrate, wherein the coating composition has the formula AlL 1 x L 2 y , where L 1 = (C 1 -C 6 ) alkoxy, L 2 = OR 1 , R 1 = substituted (C 4 -C 10 ) hydrocarbyl moiety , wherein the substituted (C 4 -C 10 ) hydrocarbyl moiety is hydroxyl, carboxylic acid, and (C 1 -C 6 ) An organoaluminum compound comprising one or more substituents selected from the group consisting of alkylcarboxylates , wherein x is an integer from 0 to 2, y is an integer from 1 to 3, and x + y = 3) and curing the coating composition by heating the layer of the coating composition process, and at a temperature of 150 to 450 ° C. containing organic solvent having a (ii) formula HOR 1 Includes forming an aluminum oxide-containing layer on the substrate, a method of forming an aluminum oxide layer.
  2. R 1 Has been replaced (C 4 -C 10 ) Hydrocarbyl moiety, the substituted (C 4 -C 10 ) Hydrocarbyl moiety is a carboxylic acid and (C 1 -C 6 2. The method of claim 1 comprising one or more substituents selected from the group consisting of alkyl carboxylates).
  3. The method according to claim 1 or 2, wherein x = 0 or 1.
  4. The method according to claim 1 or 2, wherein x = 0.
  5. The method according to any one of claims 1 to 4, wherein L 1 = (C 1 -C 4 ) alkoxy.
  6. The method according to any one of claims 1 to 5, wherein the coating composition is disposed on the substrate by spin coating, spray coating or slot die coating.
  7. The method according to any one of claims 1 to 6, wherein the substrate is an electronic element substrate.
  8. The method according to claim 1, wherein the substrate is a flexible display substrate or a photovoltaic device substrate.
  9. The method of claim 8 , wherein the flexible display substrate comprises a light emitting diode.
  10. The method according to claim 1, further comprising disposing a layer of a second material on the aluminum oxide-containing layer and curing the layer of the second material.
  11. 11. The organic solvent of claim 1-10, wherein the organic solvent is selected from the group consisting of methyl glycolate, ethyl glycolate, ethyl lactate, 2-methyl-1-butanol, 4-methyl-2-pentanol, and diethyl tartrate. The method according to any one of the above.
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