High refractive index photoresist composition

Abstract

A composition comprising a photocurable resin, the photocurable resin having a weight average molecular weight of 3,000 to 50,000 Daltons, a glass transition temperature of at least 100 degrees Celsius, and containing the following siloxane units: 50 to 80 mole percent (HSiC>3 / 2), 10 to 30 mole percent (R * SiC>3 / 2), 10 to 40 mole percent (Ar * SiC>3 / 2), and a Si-OZ content of 20.0 mole percent or less, the mole percent values ​​being based on the moles of silicon atoms in the photocurable resin; R * is the photocurable group, and Ar in each occurrence * is selected from the group of halogen substituted aryl and polyaryl groups; Z in each occurrence is selected from hydrogen and an alkyl group; and subscript x and subscript y in each occurrence are independently either 1 or 2.

Description

[Technical field]

[0001] The present invention relates to photoresist resins, negative photoresist compositions containing the photoresist resins, and methods of using the negative photoresist compositions. [Background technology]

[0002] There are two approaches to making optical light emitting diode (OLED) displays. The first approach is to pattern a relatively low refractive index (RI) negative photoresist composition to create a lens patch over the diode pixels, and then fill the perimeter of the lens patch with a relatively high RI planarizing polymer. The second possible approach is to pattern a relatively high RI photoresist composition to create a lens patch over the RGB diode pixels, and then fill the perimeter of the lens patch with a lower RI planarizing polymer. Companies are requesting photoresist compositions to prepare OLED displays using this second approach, but the second approach has challenges.

[0003] The challenge of the second approach is to find a photoresist resin with a high enough RI to form a negative photoresist composition with a high enough RI suitable for making lens patches. The difference in RI between the relatively high RI negative photoresist composition for lens materials and the relatively low planarizing polymer should be at least 0.10. A typical planarizing polymer has an RI of 1.45 (RI values ​​herein are measured at 632 nm and 21-23° C.), therefore the negative photoresist composition must have an RI of at least 1.55. A suitable photoresist resin that can be formulated into an acceptable negative photoresist composition that can be spin-coated on a substrate must have a weight average molecular weight in the range of more than 3,000 to 100,000 daltons, preferably 5,000 to 20,000 daltons, so that a uniform coating can be formed. The photoresist resin must further have a glass transition temperature (Tg) at least 10 degrees Celsius (° C.) higher than the bake temperature of the photoresist so that the photoresist resin is not tacky and lacks the desired mechanical properties, meaning the glass transition temperature of the photoresist resin should be above 100° C. The photoresist resin must be photocurable, particularly photocurable in a pattern through a photomask, and soluble in a developer material, such as a tetramethylammonium hydroxide (TMAH) solution, to remove the uncured material and leave the patterned cured material.

[0004] It would be desirable to provide a photoresist resin that meets the requirements for use as a photoresist in making OLED displays according to the second approach. Summary of the Invention

[0005] The present invention provides photoresist resins suitable for preparing negative photoresist compositions that meet the requirements for use as photoresists in the fabrication of OLED displays, by first patterning the negative photoresist composition as lens patches over RGB diode pixels, and then planarizing with a lower RI planarizing polymer, and a process for making such OLED displays.

[0006] The present invention is the result of discovering a method for preparing a photoresist resin with a sufficiently high RI to be suitable as a photoresist resin in a negative photoresist composition having an RI of 1.55 or greater, the photoresist resin having a weight average molecular weight in the range of 3,000-50,000 Daltons, a Tg of at least 100° C., and exhibiting solubility in TMAH solution. Moreover, the photoresist resin (and negative photoresist composition) achieves these properties while containing a Si-OZ content of less than 20.0 mole percent (mol%) relative to the silicon atom content, and can achieve these properties even with a Si-OZ content of 1.0 mol% or less, where "Si-OZ" refers to hydroxyl and alkoxyl groups bonded to silicon atoms. Other photoresist resins contain higher amounts of Si-OH to achieve solubility in basic developer solutions. The present invention is the result of discovering the combination of functional groups necessary to prepare such photoresist resins, and in particular the concentration range of each functional group necessary to achieve these properties. In particular, it has been discovered that a SiH content is necessary to achieve solubility in basic developer solutions.

[0007] Furthermore, organic resins having small silane molecules (weight average molecular weight less than 500 Daltons) and / or pendant silyl groups on the organic polymer backbone can be avoided in the composition to prevent potential outgassing problems associated with such molecules from contaminating optical lenses. Small silane molecules can outgas upon exposure to light during baking or curing. Similarly, organic resins having pendant silyl groups can undergo cleavage of the silyl groups upon exposure to light during baking or curing, and the cleaved groups can outgas. Outgassing molecules are undesirable because they can contaminate other components in the process. Fortunately, the resins and compositions of the present invention do not have to include small silane molecules and / or organic resins having pendant silyl groups.

[0008] In a first aspect, the present invention provides a composition comprising a photocurable resin, the photocurable resin having a weight average molecular weight in the range of 3,000 to 50,000 Daltons, a glass transition temperature of at least 100 degrees Celsius, and containing 50 to 80 mole percent of the following siloxane units: (HSiO 3 / 2 ), 10 to 30 mole percent of (R * SiO 3 / 2 ), 10 to 40 mole percent of (Ar * SiO 3 / 2 ), and a Si-OZ content of less than 20.0 mole percent, the mole percent values ​​being based on the moles of silicon atoms in the photocurable resin; R * is the photocurable group, and Ar in each occurrence * is selected from the group of halogen substituted aryl and polyaryl groups, Z in each occurrence is selected from hydrogen and alkyl groups, and subscript x and subscript y in each occurrence are independently either 1 or 2. The composition may be a negative photoresist composition comprising 10 to 50 weight percent of the photoresist resin of any one of claims 1 to 4, a photoinitiator at a concentration of 1 to 3 weight percent, and 49 to 89 weight percent solvent, the weight percent being based on the weight of the photoresist composition. The photocurable resin may have a Si-OZ content of 1.0 mole percent or less.

[0009] In a second aspect, the present invention is a process for preparing an optical light emitting diode display using a negative photoresist composition version of the first aspect, the process comprising: (a) providing a substrate comprising a plurality of diodes; (b) coating the negative photoresist composition onto the substrate comprising a plurality of diode pixels; (c) exposing the negative photoresist composition present on the diode pixels to harden the photoresist resin in the negative photoresist composition to form lens patches over the diode pixels; (d) washing away the unexposed / uncured negative photoresist composition with an aqueous alkaline solution; (e) applying a planarizing polymer onto the substrate and the lens patches; and (f) curing the planarizing polymer, as shown below.

[0010] The photoresist resins and negative photoresist compositions of the present invention are useful in preparing OLED articles according to the process of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Test methods refer to the test method most recent to the priority date of this document unless a date is given with the test method number. Reference to a test method includes both a reference to the testing society and the test method number. The following test method abbreviations and identifiers apply herein: ASTM refers to ASTM International Methods, EN refers to European Norm, DIN refers to Deutsches Institut fur Normung, ISO refers to the International Organization for Standards, and UL refers to the Underwriters Laboratory.

[0012] Products identified by trade names refer to compositions available under those trade names as of the priority date of this document.

[0013] "Plurality" means two or more. "And / or" means "and, or alternatively." All ranges are inclusive of endpoints unless otherwise indicated. All weight percent (wt%) values ​​are by weight of the composition and all volume percent (vol%) values ​​are by volume of the composition unless otherwise indicated.

[0014] The siloxane units have the following terms in this application, each O 1 / 2 is shared with another siloxane unit, O 1 / 2 For example, the chemical structure (RSiO 1 / 2 The molecule with SiOSiR corresponds to RSiOSiR, with O in each siloxane unit. 1 / 2 corresponds to a single oxygen atom. The "Q" type siloxane unit has the chemical structure (SiO 4 / 4 ), which means that it is a silicon atom bonded to four other siloxane units through oxygen. A "T" type siloxane unit has the chemical structure (RSiO 3 / 4 ), where R is hydrogen, hydrocarbyl, or some other group bonded to a silicon atom that is bonded to three other siloxane units through oxygen atoms. A "D" type siloxane unit has the chemical structure (RR'SiO 3 / 4 ), where each of R and R' is hydrogen, hydrocarbyl, or some other group bonded to a silicon atom that is bonded to two other siloxane units through an oxygen atom. An "M" type siloxane unit has the chemical structure (RR'R"SiO 1 / 2 ), where each of R, R', and R'' is a hydrogen, hydrocarbyl, or other group bonded to a silicon atom that is bonded through an oxygen atom to another siloxane unit.

[0015] Nuclear magnetic resonance (NMR) spectroscopy is used to determine the resin structure. NMR spectra are recorded using a Varian XL-400 spectrometer. 1 H, 13 C and 29Chemical shifts for Si spectra are referenced to internal solvent resonances and reported relative to tetramethylsilane.

[0016] "Molecular weight" refers to weight average molecular weight unless otherwise specified herein. Weight average molecular weight and polydispersity were determined by gel permeation chromatography (GPC) using a Waters 600 pump, a Waters 717 autosampler, and a Waters 410 differential refractometer.

[0017] Determine the glass transition temperature (Tg) of the resin using a DSC-Q2000 instrument by loading 6-10 milligrams of dry resin (resin dried for 10 hours in a vacuum oven at 80 °C and 133 Pascals (1 millimeter of mercury) into a sample pan and measuring the temperature increase from 23 °C to 200 °C at a rate of 10 °C / min.

[0018] The composition of the present invention may include a photocurable resin, and may be made of a photocurable resin. The photocurable resin may include the following siloxane unit, (HSiO 3 / 2 ), (R * SiO 3 / 2 ), (Ar * SiO 3 / 2 ), and optionally, (ZO) x (R * )SiO (3-x) / 2 and / or (ZO) y (Ar * )SiO (3-y) / 2 It can comprise and consist of units, where R * is a photocurable group, preferably independently in each occurrence selected from the group consisting of an epoxy-containing group, an acrylate-containing group, an acryloxy group, a vinyl ether group, and a vinyl group. * The group is independently selected at each occurrence from the group consisting of an epoxycyclohexylethyl group ("CHEp" group), a glycidoxypropyl group ("Ep" group), and a methacryloxypropyl group ("MA" group). * The groups may be the same or different. Ar* is selected from the group consisting of halogen-substituted aryl groups and polyaryl groups. * The group, independently at each occurrence, is selected from the group consisting of those having the following chemical structures (i)-(v):

[0019] [ka] For convenience herein, the chemical structures are represented as Ar * The following abbreviations are used for groups: (i) "An", (ii) "Naph", (iii) "TBP", (iv) "PBP", and (v) "TPS". Z is independently selected in each occurrence from hydrogen and an alkyl group. Desirably, the alkyl group is an alkyl group having 1 or more carbon atoms, and may have 2 or more, 3 or more, 4 or more, 5 or more, or even 6 or more carbon atoms, while typically containing 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, or even 2 or less carbon atoms. Desirably, Z is independently selected in each occurrence from the group consisting of hydrogen, a methyl group, and an ethyl group. The subscript x and the subscript y are independently either 1 or 2 in each occurrence.

[0020] Photoresist resins of the invention desirably have the following average chemical structure (I): (HSiO 3 / 2 ) a (R * SiO 3 / 2 ) b (Ar * SiO 3 / 2 ) c [(ZO) x (R * )SiO (3-x) / 2 ] d [(ZO) y (Ar * )SiO (3-y) / 2 ] e (I) During the ceremony, R * , Ar* , Z and the subscripts x and y are as defined above. The subscript a represents the (HSiO 3 / 2 ) the average molar ratio of siloxane units, relative to the total moles of siloxane units in the resin, has a value of 0.50 or more, and can have a value of 0.60 or more, or even 0.70 or more, while typically having a value of 0.80 or less, and can have a value of 0.70 or less, or even 0.60 or less. The subscript b represents the (R * SiO 3 / 2 ) the average molar ratio of siloxane units, based on the total moles of siloxane units in the resin, has a value of 0.10 or more, and can have a value of 0.15 or more, 0.20 or more, or even 0.25 or more, while typically having a value of 0.30 or less, 0.25 or less, 0.20 or less, or even 0.15 or less. The subscript c represents the (Ar * SiO 3 / 2 ) the average molar ratio of siloxane units, based on the total moles of siloxane units in the resin, has a value of 0.10 or more, and can have a value of 0.20 or more, or even 0.30 or more, while typically having a value of 0.40 or less, 0.30 or less, or even 0.20 or less. The subscript d indicates the (ZO) x (R * )SiO (3-x / 2) The subscript e represents the average ratio of siloxane units (ZO) in the resin. y (Ar * )SiO (3-y / 2)The sum of subscript d and subscript e, which is the average molar ratio of siloxane units, has a value of 0 or greater, and can have a value greater than 0, 0.001 or greater, or even 0.005 or greater, while typically being sufficiently low so that the total Si-OZ content is 20 mol% or less, 18 mol% or less, 16 mol% or less, 14 mol% or less, 12 mol% or less, 10 mol% or less, 8 mol% or less, 6 mol% or less, 4 mol% or less, 2.0 mol% or less, desirably 1.0 mol% or less, or even 0.5 mol% or less, or even 0.1 mol% or less, based on the moles of Si atoms in the resin. Generally, the sum of subscript d and subscript e is 0.20 or less, 0.18 or less, 0.16 or less, 0.15 or less, 0.12 or less, 0.10 or less, 0.08 or less, 0.06 or less, 0.04 or less, 0.03 or less, 0.02 or less, and desirably 0.01 or less, 0.005 or less, or even 0.001 or less, based on the total number of moles of siloxane units in the resin. Subscript x and subscript y in each occurrence are independently either 1 or 2. The sum of the values ​​of subscript a, subscript b, subscript c, subscript d, and subscript e is 1.00 (ie, preferably a+b+c+d+e=1.00).

[0021] The photoresist resin, and the composition as a whole, may be free of unsaturated carbon-carbon bonds (ie, carbon-carbon double and triple bonds).

[0022] Desirably, the composition is a negative photoresist composition comprising or consisting of a photoresist, a photoinitiator, a solvent, and optionally up to 2% by weight of additional additives.

[0023] A negative photoresist composition typically contains 10% or more, 20% or more, 30% or more, or even 40% or more by weight of a photoresist resin, and typically contains 50% or less, 40% or less, 30% or less, or even 20% or less by weight of a photoresist resin, based on the weight of the negative photoresist composition.

[0024] A negative photoresist composition typically contains a photoinitiator in a concentration of 1 wt % or more, or 2 wt % or more, based on the weight of the negative photoresist composition, while typically the concentration is 3 wt % or less, and can be 2 wt % or less.

[0025] Photocurable group R *is an epoxy-containing group or a vinyl ether group, the photoinitiator is a cationic photoinitiator (also called a photoacid generator or PAG). A cationic photoinitiator is a chemical that undergoes actinic decomposition upon exposure to light. This decomposition produces active cationic and anionic species. In other words, the cationic photoinitiator comprises an active cationic species and an anionic species. In some embodiments, the cationic species comprises an onium salt. The onium salt can include diaryliodonium salts, triarylsulfonium salts, tetraarylphosphonium salts, and the like. In some embodiments, the anionic species is selected from the group of BF4-, PF6-, AsF6-, SbF6-, and (C6F5)4B-. Examples of PAGs include bis(4-dodecylphenyl)iodonium hexafluoroantimonate, (p-dodecylphenyl)(p-methylphenyl)iodonium hexafluoroantimonate, (p-isopropylphenyl)(p-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium nitrate, diphenyliodonium hexafluorophosphate, (4-fluorophenyl)diphenylsulfonium triflate, N-hydroxynaphthalimide triflate, (4-iodo ...

[0046] Examples of the sulfonium hexafluorophosphate include (4-phenyl)diphenylsulfonium triflate, (4-methoxyphenyl)diphenylsulfonium triflate, (4-phenoxyphenyl)diphenylsulfonium triflate, triarylsulfonium hexafluorophosphate, triphenylsulfonium perfluoro-1-butanesulfanate, triphenylsulfonium triflate, tris(4-tert-buityphenyl)sulfonium perflurro-1-butanesulfonate, bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate, and bis(4-tert-butylphenyl)iodonium p-toluenesulfonate.

[0026] Photocurable group R *is an acrylate-containing group, an acryloxy group, or a vinyl group. The photoinitiator is a free radical photoinitiator. A free radical photoinitiator is a chemical that undergoes actinic decomposition upon exposure to light. This decomposition produces active free radicals that induce polymerization of the acrylate-containing group, the acryloxy group, or the vinyl group. The free radical photoinitiator is not limited and may be selected from any known free radical type photoinitiator effective in promoting the crosslinking reaction. Examples of photoinitiators (b) include diethoxyacetophenone (DEAP), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, diethoxyxanthone, chloro-thioxanthone, azo-bisisobutyronitrile, N-methyldiethanolamine benzophenone, 4,4'-bis(dimethylamino)benzophenone, diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1-phenylpropan-1-one, and the like. -[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and combinations thereof.

[0027] The negative photoresist composition includes a solvent, which is typically present in a concentration of 49% or more by weight, and may be present in a concentration of 50% or more, 60% or more, 70% or more, or even 80% or more by weight, based on the weight of the negative photoresist composition, and is typically present in a concentration of 89% or less by weight, or even 80% or less, 70% or less, 60% or less, or even 50% or less by weight. Examples of suitable solvents include methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), 2-heptanone, methyl pentyl ketone (MAK), cyclopentanone, cyclohexanone, lactate alkyl esters such as ethyl lactate, 1,2-propylene glycol monomethyl ether monoacetate (PGMEA), alkylene glycol monoalkyl esters, butyl acetate, 2-ethoxyethanol, and ethyl 3-ethoxypropionate.

[0028] The negative photoresist composition may include additional additives such as any combination of any one or more of additives selected from sensitizers, surfactants, and quenchers. Sensitizers are useful for increasing the activity of the photoinitiator by absorbing radiation at a first wavelength and emitting radiation at a second wavelength and transferring the emitted radiation to the photoinitiator. Surfactants are useful for improving the uniformity of the coating of the composition on the substrate or an underlying layer on the substrate. Quenchers include basic materials such as organic amines. Suitable quenchers include the compounds listed in paragraphs 306-315 of US Patent Application Publication No. 2003 / 0017415, the organic base additives described in US Patent No. 8,148,043, and the oxamines found in US Patent No. 1,099,0012. Specific examples include tertiary arylamines such as 2-(2-aminophenyl)-isoindole-1,3-dione, 1-(2-((1H-1,2,3-benzotriazol-1-ylmethyl)amino)phenyl)ethanone, 1-((2,3-dimethyl-phenylamino)-methyl)-pyrrolidine-2,5-dione, 1-(2-methyl-4-phenylamino-3,4-dihydro-2H-quinolin-1-yl)-heptan-1-one, 2-((3-fluoro-4-methyl-phenylamino)-methyl)-phenol, N,N-diethylaniline, tri(1-methyl-ethanol-2-yl)-amine, tri(2-(3'-methylbutyloxy)ethyl)-amine, tri(2-(hexyloxy)ethyl)-amine, and tri(2-(methoxymethoxy)ethyl-1)-amine. The total concentration of the additional additives can be 0% or more, or even 1% or more, by weight, based on the weight of the negative photoresist composition, while typically is 2% or less, or even 1% or less.

[0029] The process of the present invention is a process for preparing an optical light emitting diode display, the process comprising: (a) providing a substrate, such as a silicon wafer, comprising a plurality of diode pixels; (b) coating a negative photoresist composition as described herein onto the substrate, the substrate comprising a plurality of diode pixels; (c) exposing the negative photoresist composition present on the diode pixels to harden a photoresist resin in the negative photoresist composition to form a lens patch on the diode pixel; (d) rinsing off the unexposed / uncured negative photoresist composition with an aqueous alkaline solution; (e) applying a planarizing polymer onto the substrate and the lens patch; and (f) curing the planarizing polymer, as shown below.

[0030] Step (b) desirably comprises spin-coating the negative photoresist composition of the present invention onto the substrate. Suitable alternative methods for applying the negative photoresist composition onto the substrate include spray coating, dip coating, slit coating and gravity coating.

[0031] Step (c) desirably includes exposing the negative photoresist composition through a mask to selectively expose certain portions of the negative photoresist composition and cause hardening of the photoresist in the exposed negative photoresist composition. Preferably, the mask allows exposure only of portions of the negative photoresist composition present over the diode pixels, such that the photoresist hardens into lens patches over the diode pixels.

[0032] Step (d) is performed after step (c) and includes washing the uncured negative photoresist composition from the substrate, thereby leaving only the cured portion. Washing with an alkaline aqueous solution. Desirably, the alkaline aqueous solution includes an aqueous solution of tetramethylammonium hydroxide (2.35 to 2.62 wt % concentration). Other examples of the alkaline aqueous solution are choline, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, propylamine, diethylamine, dipropylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, pyrrole, piperidine, l,8-diazabicyclo[5.4.0]-7-undecene, and l,5-diazabicyclo[4.3.0]-5-nonene.

[0033] The planarizing polymer is a curable polymer that is applied over the hardened photoresist on the substrate and fills the spaces between the hardened photoresist portions to form a planar surface on the substrate. The planarizing polymer can be applied by spin coating, spray coating, dip coating, slit coating, or gravity coating. After the planarizing polymer is applied, it is cured to form a hardened polymer coating on the substrate.

[0034] The cured planarizing polymer desirably has a RI at least 0.1 lower than the RI of the negative photoresist composition. The cured or uncured negative photoresist composition and photoresist resin have a RI of 1.55 or greater, and may be 1.60 or greater, or 1.65 or greater. The RI is determined by ellipsometry using 632 nanometer light at 21-23°C. EXAMPLES

[0035] Table 1 lists the materials used in preparing the following examples.

[0036] [Table 1] IRGANOX is a trademark of BASF SE Company. DOWSIL is a trademark of The Dow Chemical Company.

[0037] Synthesis of hydrosilsesquioxane (HSQ) resin The HSQ resin is prepared by controlled hydrolysis of trichlorosilane in the presence of concentrated sulfuric acid in toluene (following the teachings of Frye, CL; Collins, WT; J. Am. Chem. Soc. 92(19); 1970, 5586-5588). The HSQ resin has a weight average molecular weight of 2,200 and a polydispersity index of 2.78. The moles of hydroxy and alkoxy relative to the moles of silicon are less than 0.1% by weight.

[0038] 9-Allyloxyanthracene Synthesis 9-Allyloxyanthracene (CAS#125340-11-6) is prepared by reacting 208.3 g of 9-(hydroxymethyl)anthracene (Sigma-Aldrich), 121.0 g of 2-bromopropene (Signa-Aldrich) and 1.5 g of sodium hydroxide in 500 g of toluene at 70° C. for 6 hours. After 6 hours, the mixture is cooled to 25° C., neutralized with acetic acid, and then filtered. Volatiles are removed by rotovap at 40° C. Recrystallization in ethanol yielded a yellow crystalline powder. 1 H-NMR (CDCl3): d 8.42(m,3H), 8.02(d,2H), 7.50(m,4H), 6.10(m,1H), 5.41(S,2H), 5.38(d,1H), 5.25(d,1H), 4.20(d,2H).

[0039] (3-(anthracen-9-ylmethoxy)propyl)triethoxysilane synthesis (3-(anthracen-9-ylmethoxy)propyl)triethoxysilane was prepared by reacting 9-allyloxyanthracene (22.2 g) with triethoxysilane (16.5 g) in the presence of Karstedt's platinum catalyst (0.02 g) in toluene (100 g) at 60° C. for 3 hours. After the reaction was complete, 0.5 g of activated carbon was added and stirred for 30 minutes. The mixture was cooled to 25° C. and filtered through a 0.4 micrometer membrane filter. The volatiles were removed by rotovap (40° C. / 100 Pascal) to give a clear, pale yellow-brown liquid. 1 H-NMR (CDCl3): d.8.61(S,2H), 8.45(d,2H), 8.20(d,2H), 7.70(m,4H), 5.68(S,2H), 4.62(m,8H), 4.05(2H), 1.42(2H), 1.28(9H), 0.56(2H).

[0040] Example 1: Example 1 has an average chemical structure of the following form of structure (I): (HSiO 3 / 2 ) 0.56 (EpSiO 3 / 2 ) 0.17 (AnSiO 3 / 2 ) 0.27 [(ZO) x (Ep)SiO (3-x) / 2 ] d [(ZO) y (An * )SiO (3-y) / 2 ] e wherein the material has a weight average molecular weight of 4,920 as determined by GPC, a polydispersity (PDI) of 3.05, and a Si-OZ content of less than 1 mol %.

[0041] Example 1 is prepared in the following manner: 1,000 grams (g) of HSQ resin solution (weight % based on HSQ resin solution weight) consisting of 75 weight % HSQ resin in 25 weight % toluene is added to a 3 liter flask. 107.8 g of allyl glycidyl ether, 331.6 g of 9-(hydroxymethyl)anthracene, and 0.080 g of Karstedt's platinum catalyst are added. The mixture is stirred at 80° C.1 The reaction is monitored by H nuclear magnetic resonance (NMR) spectroscopy. After stirring at 80° C. for 6 hours, 10 g of activated carbon is added to the solution and stirred at 80° C. for an additional hour, then cooled to 25° C. The solution is filtered through a 0.45 micrometer polytetrafluoroethylene (PTFE) filter and solvent exchanged into PGMEA using a rotovap (40° C. / 133 Pascals). The resulting PGMEA solution is diluted to 30% solids by weight (non-volatile content "NVC" at 120° C. for 30 minutes) and then filtered through a 0.2 micrometer PTFE filter to obtain the final product. Store in a high density polyethylene bottle. The solution is primarily Example 1, but contains small amounts of the following free isomerized monomers ( 1 It also contains 0.6% by weight of A and 1.5% by weight of B) as determined by 1 H NMR.

[0042] [ka]

[0043] Example 2: Example 2 has an average chemical structure of the form of structure (I) below: (HSiO 3 / 2 ) 0.59 (EpSiO 3 / 2 ) 0.17 (AnSiO 3 / 2 ) 0.24 [(ZO) x (Ep)SiO (3-x) / 2 ] d [(ZO) y (An)SiO (3-y) / 2 ] e wherein the material has a weight average molecular weight of 4,857 as determined by GPC, a PDI of 3.03, and a Si-OZ content of less than 1 mol %.

[0044] Prepare Example 2 in a manner similar to Example 1, except use 100 grams (g) of HSQ resin solution (25 wt % in toluene), 10.78 g of allyl glycidyl ether, 33.16 g of 9-(hydroxymethyl)anthracene, 0.024 g of Karstedt's platinum catalyst, and 2.0 g of activated carbon.

[0045] Store in a high density polyethylene bottle. The solution is mainly that of Example 2, 1 It also contains small amounts of free isomerized monomers A (0.5 wt%) and B (1.3 wt%) as determined by H NMR.

[0046] Example 3: Example 3 has an average chemical structure of the form of structure (I) below: (HSiO 3 / 2 ) 0.68 (EpSiO 3 / 2 ) 0.17 (AnSiO 3 / 2 ) 0.15 [(ZO) x (Ep)SiO (3-x) / 2 ] d [(ZO) y (An)SiO (3-y) / 2 ] e wherein the material has a weight average molecular weight of 5,554 as determined by GPC, a PDI of 3.12, and a Si-OZ content of less than 1 mol %.

[0047] Prepare Example 3 in a manner similar to Example 1, except use a 500 milliliter flask containing 100 grams (g) of HSQ resin solution (25 wt % in toluene), 10.78 g of allyl glycidyl ether, 19.91 g of 9-(hydroxymethyl)anthracene, 0.024 g of Karstedt's platinum catalyst, and 2.0 g of activated carbon.

[0048] Store in a high density polyethylene bottle. The solution is mainly that of Example 2, 1 It also contains small amounts of free isomerized monomers A (0.5 wt %) and B (1.0 wt %) as determined by 1 H NMR.

[0049] Example 4: Example 4 has an average chemical structure of the form of structure (I) below: (HSiO 3 / 2 ) 0.53 (CHEpSiO 3 / 2 ) 0.20 (AnSiO 3 / 2 ) 0.27 [(ZO) x (CHEp)SiO (3-x) / 2 ] d [(ZO) y (An)SiO (3-y) / 2 ] e wherein the material has a weight average molecular weight of 7,821 as determined by GPC, a PDI of 4.50, and a Si-OZ content of less than 1 mol %.

[0050] Prepare Example 4 in a manner similar to Example 1, except use a 500 milliliter flask containing 100 grams (g) of HSQ resin solution (25 wt % in toluene), 10.78 g of 4-vinyl-1-cyclohexene 1,2-epoxide (instead of allyl glycidyl ether), 33.16 g of 9-(hydroxymethyl)anthracene, 0.024 g of Karstedt platinum catalyst, and 2.0 g of activated carbon.

[0051] Store in a high density polyethylene bottle. The solution is mainly that of Example 2, 1 It also contains a small amount of free isomerized monomer B (1.7 wt %) as determined by 1 H NMR.

[0052] Example 5: Example 5 has an average chemical structure of the form of structure (I) below: (HSiO 3 / 2 ) 0.63 (CHEpSiO 3 / 2 ) 0.20 (AnSiO 3 / 2 ) 0.17 [(ZO) x (CHEp)SiO (3-x) / 2 ] d [(ZO) y (An)SiO(3-y) / 2 ] e wherein the material has a weight average molecular weight of 33,966 as determined by GPC, a PDI of 18.65, and a Si-OZ content of less than 1 mol %.

[0053] Prepare Example 5 in a manner similar to Example 1, except use a 500 milliliter flask containing 100 grams (g) of HSQ resin solution (25 wt % in toluene), 10.78 g of 4-vinyl-1-cyclohexene 1,2-epoxide (instead of allyl glycidyl ether), 22.12 g of 9-(hydroxymethyl)anthracene, 0.024 g of Karstedt platinum catalyst, and 2.0 g of activated carbon.

[0054] Store in a high density polyethylene bottle. The solution is mainly that of Example 2, 1 It also contains a small amount of free isomerized monomer B (1.0 wt %) as determined by 1 H NMR.

[0055] Example 6: Example 6 has an average chemical structure of the form of structure (I) below. (HSiO 3 / 2 ) 0.55 (CHEpSiO 3 / 2 ) 0.15 (NaphSiO 3 / 2 ) 0.30 [(ZO) x (CHEp)SiO (3-x) / 2 ] d [(ZO) y (Naph)SiO (3-y) / 2 ] e wherein the material has a weight average molecular weight of 9,538 as determined by GPC, a PDI of 3.31, and a Si-OZ content of less than 1 mol %.

[0056] Prepare Example 6 in a manner similar to Example 1, except use a 250 milliliter flask containing 100 grams (g) of HSQ resin solution (25 wt % in toluene), 8.79 g of 4-vinyl-1-cyclohexene 1,2-epoxide (instead of allyl glycidyl ether), 21.84 g of vinylnaphthalene (instead of 9-(hydroxymethyl)anthracene), 0.024 g of Karstedt's platinum catalyst, and 2.0 g of activated carbon in a high density polyethylene bottle.

[0057] Example 7: Example 7 has an average chemical structure of the form of structure (I) below: (HSiO 3 / 2 ) 0.50 (CHEpSiO 3 / 2 ) 0.20 (TPSSiO 3 / 2 ) 0.30 [(ZO) x (CHEp)SiO (3-x) / 2 ] d [(ZO) y (TPS)SiO (3-y) / 2 ] e wherein the material has a weight average molecular weight of 9,264 as determined by GPC, a PDI of 9.00, and a Si-OZ content of less than 1 mol %.

[0058] Prepare Example 7 in a manner similar to Example 1, except use a 250 milliliter flask containing 50.00 grams (g) of HSQ resin solution (25% by weight in toluene), 8.84 g of 4-vinyl-1-cyclohexene 1,2-epoxide (instead of allyl glycidyl ether), 25.51 g of 1,1-dimethyl-3,3,3-triphenyl-1-vinyldisiloxane (instead of 9-(hydroxymethyl)anthracene), 0.024 g of Karstedt's platinum catalyst, and 2.0 g of activated carbon in a high density polyethylene bottle.

[0059] Example 8: Example 8 has an average chemical structure of the form of structure (I) below: (HSiO 3 / 2 )0.60 (CHEpSiO 3 / 2 ) 0.20 (TPSSiO 3 / 2 ) 0.20 [(ZO) x (CHEp)SiO (3-x) / 2 ] d [(ZO) y (TPS)SiO (3-y) / 2 ] e wherein the material has a weight average molecular weight of 13,538 as determined by GPC, a PDI of 5.98, and a Si-OZ content of less than 1 mol %.

[0060] Prepare Example 8 in a manner similar to Example 1, except use a 250 milliliter flask containing 50.00 grams (g) of HSQ resin solution, 5.84 g of 4-vinyl-1-cyclohexene 1,2-epoxide (instead of allyl glycidyl ether), 17.02 g of 1,1-dimethyl-3,3,3-triphenyl-1-vinyldisiloxane (instead of 9-(hydroxymethyl)anthracene), 0.024 g of Karstedt's platinum catalyst, and 2.0 g of activated carbon. Store in a high density polyethylene bottle.

[0061] Example 9: Example 9 has an average chemical structure of the form of structure (I) below: (HSiO 3 / 2 ) 0.45 (CHEpSiO 3 / 2 ) 0.20 (TPSSiO 3 / 2 ) 0.35 [(ZO) x (CHEp)SiO (3-x) / 2 ] d [(ZO) y (TPS)SiO (3-y) / 2 ] e .

[0062] Example 9 is prepared in the same manner as Example 8, except that 29.80 g of 1,1-dimethyl-3,3,3-triphenyl-1-vinyldisiloxane and 2.0 g of activated carbon are used. Example 9 has a weight average molecular weight of 9,562, a polydispersity of 4.32, and a Si-OZ content of less than 1.0 mole % relative to the silicon atom concentration.

[0063] Example 10: (HSiO 3 / 2 ) 0.40 (CHEpSiO 3 / 2 ) 0.20 (TPSSiO 3 / 2 ) 0.40 [(ZO) x (CHEp)SiO (3-x) / 2 ] d [(ZO) y (TPS)SiO (3-y) / 2 ] e .

[0064] Example 10 is prepared in the same manner as Example 8, except that 34.04 g of 1,1-dimethyl-3,3,3-triphenyl-1-vinyldisiloxane and 2.0 g of activated carbon are used. Example 9 has a weight average molecular weight of 9,728, a polydispersity of 4.56, and a Si-OZ content of less than 1.0 mole % relative to the silicon atom concentration.

[0065] Example 11: Example 11 has an average chemical structure of the form of structure (I) below: (HSiO 3 / 2 ) 0.55 (CHEpSiO 3 / 2 ) 0.15 (TBPSiO 3 / 2 ) 0.30 [(ZO) x (CHEp)SiO (3-x) / 2 ] d [(ZO) y (TBP)SiO (3-y) / 2 ] e wherein the material has a weight average molecular weight of 8,350 as determined by GPC, a PDI of 3.12, and a Si-OZ content of less than 1 mol %.

[0066] Prepare Example 11 in a manner similar to Example 1, except use a 250 milliliter flask containing 100.00 grams (g) of HSQ resin solution (25% by weight in toluene), 8.79 g of 4-vinyl-1-cyclohexene 1,2-epoxide (instead of allyl glycidyl ether), 54.40 g of 2,4,6-tribromophenyl allyl ether (instead of 9-(hydroxymethyl)anthracene), 0.024 g of Karstedt's platinum catalyst, and 2.0 g of activated carbon in a high density polyethylene bottle.

[0067] Example 12: Example 12 has an average chemical structure of the form of structure (I) below: (HSiO 3 / 2 ) 0.55 (CHEpSiO 3 / 2 ) 0.15 (PBPSiO 3 / 2 ) 0.30 [(ZO) x (CHEp)SiO (3-x) / 2 ] d [(ZO) y (PBP)SiO (3-y) / 2 ] e wherein the material has a weight average molecular weight of 8,215 as determined by GPC, a PDI of 3.08, and a Si-OZ content of less than 1 mol %.

[0068] Prepare Example 12 in a manner similar to Example 1, except use a 250 milliliter flask containing 100.00 grams (g) of HSQ resin solution (25% by weight in toluene), 8.79 g of 4-vinyl-1-cyclohexene 1,2-epoxide (instead of allyl glycidyl ether), 74.85 g of pentabromophenyl allyl ether (instead of 9-(hydroxymethyl)anthracene), 0.024 g of Karstedt's platinum catalyst, and 2.0 g of activated carbon in a high density polyethylene bottle.

[0069] Example 13: Example 13 has an average chemical structure of the form of structure (I) below: (HSiO 3 / 2 ) 0.55 (MASiO 3 / 2 ) 0.15 (AnSiO 3 / 2 ) 0.30 [(ZO) x (MA)SiO (3-x) / 2 ] d [(ZO) y (An)SiO (3-y) / 2 ] e where the SiOZ content is 12.5 mol %, and the material has a weight average molecular weight of 17,027 and a PDI of 5.89 as determined by GPC.

[0070] Example 13 is prepared by mixing 50 g PGMEA, 20.0 g 3-(anthracen-9-ylmethoxy)propyl)triethoxysilane, 12.4 g trichlorosilane, and 6.21 g methacryloxypropyltrimethoxysilane in a 500 milliliter flask. A solution of 200 grams PGMEA and 6.61 g water is added to the mixture with stirring over 1 hour at 20° C. After the addition is complete, stirring is continued for 2 hours at 20° C. The resulting resin solution is transferred to a 1-liter separatory funnel and washed with 100 milliliters of deionized water. The phase separated water is discarded. The remaining cloudy solution is transferred to a 1-liter pear flask and about 20 g of ethanol is added. The solution is stripped using a rotovap at 40° C. and 500 Pascal pressure, diluted to 30% solids by weight with PGMEA, and then filtered through a 0.20 micrometer PTFE filter to provide Example 13. Store in HDPE bottles.

[0071] Example 14: Example 14 has an average chemical structure of the form of structure (I) below: (HSiO 3 / 2 ) 0.55 (MASiO 3 / 2 ) 0.15 (NapSiO 3 / 2 ) 0.30 [(ZO) x (MA)SiO (3-x) / 2 ] d [(ZO)y (Nap)SiO (3-y) / 2 ] e where the Si-OZ content is 10.9 mol % and the material has a weight average molecular weight of 11,884 and a PDI of 6.53 as determined by GPC.

[0072] Prepare Example 14 by mixing 50 g PGMEA, 5.0 g 1-naphyltrimethoxysilane, 9.93 g trichlorosilane, and 10.0 g methacryloxypropyltrimethoxysilane in a 500 milliliter flask. Add a solution of 200 grams PGMEA and 5.27 g water to the mixture with stirring over 1 hour at 20° C. After addition is complete, continue stirring at 20° C. for 2 hours. Transfer the resulting resin solution to a 1-liter separatory funnel and wash with 100 milliliters of deionized water. Discard the phase separated water. Transfer the remaining cloudy solution to a 1-liter pear flask and add about 20 g ethanol. Strip the solution using a rotovap at 40° C. and 500 Pascal pressure, dilute with PGMEA to 30% solids by weight, then filter through a 0.20 micrometer PTFE filter to obtain Example 14. Store in an HDPE bottle.

[0073] Example 15: Example 15 has an average chemical structure of the form of structure (I) below: (HSiO 3 / 2 ) 0.55 (VESiO 3 / 2 ) 0.15 (AnSiO 3 / 2 ) 0.30 [(ZO) x (VE)SiO (3-x) / 2 ] d [(ZO) y (An)SiO (3-y) / 2 ] e where "VE" corresponds to CH2=CH-O(CH2)4-O-, the Si-OZ content is 7.8 mol%, and the material has a weight average molecular weight of 5,946 and a PDI of 3.34 as determined by GPC.

[0074] Prepare Example 15 by combining 100 g of HSQ resin (25 wt % in toluene), 33.16 g of 9-allyloxyanthracene, and 0.016 g of Karstedt's platinum catalyst in a 500 milliliter flask. Stir the mixture at 80° C. for 4 hours, then cool to 23° C. Filter the solution, then add 8.22 g of 1,4-butanediol vinyl ether and 0.5 g of DBTDL. Stir at 60° C. for 3 hours, then add 2.0 g of activated carbon. Stir for an additional hour, then cool to 25° C. Filter the solution and vacuum strip. Add PGMEA to form a 30 wt % solution of solids in PGMEA. Filter the solution through a 0.2 micrometer PTFE filter to obtain Example 15. Store in an HDPE bottle.

[0075] Comparative Example A: Comparative Example (Comparative) A has an average chemical structure in the form of structure (I) below. (HSiO 3 / 2 ) 0.75 (EpSiO 3 / 2 ) 0.25 [(ZO) x (Ep)SiO (3-x) / 2 ] d where the subscript d is less than 0.01 for all values ​​of x, and the material has a weight average molecular weight of 7,034 and a PDI of 3.21 as determined by GPC.

[0076] Comparative Example A is prepared by adding 200 g of HSQ resin solution (25 wt % in toluene), 32.3 g of allyl glycidyl ether, and 0.24 g of Karstedt's platinum catalyst to a 1-liter flask. The mixture is stirred at 80° C. for 2 hours. 5 wt % activated carbon is added to the solution and mixing is continued at 23° C. for 1 hour. The solution is filtered and subjected to vacuum stripping and solvent exchange with PGMEA to form a 30 wt % resin solution. The resin solution is filtered through a 0.2 micrometer PTFE filter and stored in a high density polyethylene bottle.

[0077] Comparative Example B: Comparative Example B has an average chemical structure in the form of structure (I) below. (HSiO 3 / 2 ) 0.75 (CHEpSiO 3 / 2 ) 0.25 [(ZO) x (CHEp)SiO (3-x) / 2 ] d where the subscript d is less than 0.01 for all values ​​of x, and the material has a weight average molecular weight of 10,520 and a PDI of 4.76 as determined by GPC.

[0078] Prepare Comparative Example B in a manner similar to Comparative Example A, except using a 500 milliliter flask, 100 g of HSQ resin solution (25 wt % in toluene), 14.6 g of 4-vinyl-1-cyclohexene 1,2-epoxide (instead of allyl glycidyl ether), and 0.12 g of Karstedt's platinum catalyst.

[0079] Comparative Example C: Comparative Example C has an average chemical structure in the form of structure (I) below. (HSiO 3 / 2 ) 0.60 (STSiO 3 / 2 ) 0.20 (CHEpSiO 3 / 2 ) 0.20 [(ZO) x (CHEp)SiO (3-x) / 2 ] d where "ST" is -CH2CH2Ph, where Ph is phenyl, the subscript d is less than 0.01 for all values ​​of x, and the material has a weight average molecular weight of 7,520 and a PDI of 4.76 as determined by GPC.

[0080] Prepare Comparative Example C in a manner similar to Comparative Example A, except using a 500 milliliter flask, 100 g of HSQ resin (25 wt % in toluene), 11.7 g of 4-vinyl-1-cyclohexene 1,2-epoxide (instead of allyl glycidyl ether), 9.82 g of styrene, and 0.12 g of Karstedt's platinum catalyst.

[0081] Comparative Example D: Comparative Example D has an average chemical structure in the form of structure (I) below. (HSiO 3 / 2 ) 0.50 (PhSiO 3 / 2 ) 0.38 [(HO) x (Ph)SiO (3-x) / 2 ] 0.12 where "Ph" refers to a phenyl group, and Comparative Example D has a weight average molecular weight of 21,800 and a PDI of 3.16 as determined by GPC, with a Si-OZ content of 12.0 mol %.

[0082] Comparative Example D is prepared by hydrolysis of chlorosilanes according to the teachings of US Pat. No. 7,756,384.

[0083] Comparative Example E: Comparative Example E has an average chemical structure in the form of structure (I) below. (MeSiO 3 / 2 ) 0.38 (PhSiO 3 / 2 ) 0.34 [(HO) x (Me)SiO (3-x) / 2 ] 0.12 [(HO) x (Ph)SiO (3-x) / 2 ] 0.16 where "Ph" refers to a phenyl group, and Comparative Example E has a weight average molecular weight of 2,430 and a PDI of 1.55 as determined by GPC, with a SiOZ content of 28.0 mol%.

[0084] Comparative Example E is prepared by hydrolysis of 18.69 g of methyltrichlorosilane and 26.44 g of phenyltrichlorosilane according to the teachings of US Pat. No. 7,756,384.

[0085] Comparative Example F: Comparative Example F is a blend of Comparative Example D and (3-glycidyloxypropyl)trimethoxysilane. Prepared by combining 8 g of Comparative Example D as a 30 wt % solution in PGMEA with 2 g of (3-glycidyloxypropyl)trimethoxysilane and mixing at 25° C. to form a homogenous mixture.

[0086] Example 16: Example 16 is prepared by blending 40 g of Example 1 and 10 g of Comparative Example 1 in a 100 milliliter high density polyethylene bottle to form a homogenous mixture.

[0087] Characterization of Examples and Comparative Examples Each of the examples and comparative examples in a negative photoresist composition is characterized.

[0088] Negative photoresist compositions for each of Examples 1-12 and 16 and each Comparative Example are prepared by combining a 20 g sample of each Example and Comparative Example with 0.06 g of (p-isopropylphenyl)(p-methylphenyl)iodonium tetrakis(pentafluorophenyl)borate (photoacid generator (PAG)). Mix until the PAG is dissolved. Filter the mixture through a 0.2 micrometer PTFE filter to obtain a negative photoresist composition containing 30 wt % resin and 1 wt % PAG in PGMEA solvent.

[0089] Negative photoresist compositions for Examples 13-15 are prepared by adding 3 wt% photoinitiator 1 to a 30 wt% solution of resin, mixing to form a homogenous solution, and then filtering through a 0.2 micrometer PTFE filter to obtain a negative photoresist composition comprising 30 wt% resin and 1 wt% photoinitiator 1 in PGMEA to form the composition.

[0090] Each negative photoresist composition is spin coated onto standard single-sided 4-inch polished low resistivity wafers or double-sided polished Fourier transform infrared (FTIR) wafers at a spin speed of 1,500 revolutions per minute, acceleration of 5,000, and time of 20 seconds unless otherwise noted. A Karl Suss CT62 spin coater is used. The wafers are pre-baked at 90° C. for 60 seconds, followed by broadband ultraviolet (UV) exposure (0.5 Joules / m 2 ) using a Fusion UV unit. The spin-coated wafers are post-baked at 90° C. for 60 seconds.

[0091] The negative photoresist composition coatings, both "as spun" before UV exposure and "cured" by UV exposure and post-bake, are characterized in the following manner. Glass transition temperature (Tg). Measure the Tg of the dried resin sample. Prepare a dried resin sample of the resin by drying the resin in a vacuum oven at 80 °C and 133 Pascal pressure for 10 hours. Measure the Tg of the dried resin using a DSC-Q2000 instrument with 6-10 milligrams of resin and increasing the temperature in the range of 23 °C to 200 °C at a rate of 10 °C / min. Coating quality: If the coating is uniform with no obvious defects, it is "good". If the coating has visible defects, is uneven and has a sticky surface, it is "poor". Coating Thickness. Coating thickness is determined by ellipsometry using an ellipsometer manufactured by J.A. Woollam Company using a light source with wavelengths ranging from 200 to 900 nanometers. Thickness is determined as the average of nine measurements on the coated wafer. Additionally, the standard deviation (SD) of the nine measurements is determined. Refractive Index. The refractive index (RI) is determined by ellipsometry while measuring the coating thickness. An ellipsometric procedure is used to measure the RI before and after curing, but the RI measured at a light wavelength of 632 nanometers is reported. Solvent and Developer Solubility. Determine the solubility of the coating in both PGMEA and TMAH. For PGMEA, rinse the coated wafer with approximately 20 milliliters of PGMEA while spinning (1,500 revolutions per minute, 5,000 acceleration, 20 seconds on a Karl Suss CT62 spin coater). Measure the coating thickness before and after rinsing, and report the solubility as the % coating thickness lost due to rinsing. For TMAH, immerse the coated wafer in an aqueous solution of TMAH (2.8 wt % TMAH) at 30° C. for 5 minutes. Measure the coating thickness before and after immersion, and report the solubility as the % coating thickness lost due to immersion. A loss of at least 98.0% indicates solubility in that solvent.

[0092] Table 2 shows the characteristics of the examples and Table 3 shows the characteristics of the comparative examples. "ND" means not determined.

[0093] [Table 2]

[0094] [Table 3]

Claims

1. 1. A composition comprising a photocurable resin, the photocurable resin having a weight average molecular weight in the range of 3,000 to 50,000 Daltons, a glass transition temperature of at least 100 degrees Celsius, and containing 50 to 80 mole percent of the following siloxane units: (HSiO ３／２ ), 10 to 30 mole percent of (R ＊ SiO ３／２ ), 10 to 40 mole percent (Ar ＊ SiO ３／２ ), and a Si-OZ content of 20.0 mole percent or less, the mole percent being based on the moles of silicon atoms in said photocurable resin; R ＊ is a photocurable group, and Ar in each occurrence ＊ is selected from the group of halogen-substituted aryl and polyaryl groups, and Z at each occurrence is selected from hydrogen and alkyl groups.

2. 10. The composition of claim 1, wherein the resin further comprises the photocurable group independently selected at each occurrence from the group consisting of an epoxy-containing group, an acrylate-containing group, an acryloxy group, a vinyl ether group, and a vinyl group.

3. The composition of claim 2 , wherein the photocurable groups are independently selected at each occurrence from epoxycyclohexylethyl groups, glycidoxypropyl groups, and methacryloxypropyl groups.

4. -Ar ＊ 3. The composition of claim 1 or claim 2, wherein the group is independently selected in each occurrence from the group consisting of those having the following chemical structures (i) to (iv): 【Chemical 1】

5. 10. The composition of claim 1, wherein the composition is a negative photoresist composition comprising 10 to 50 weight percent of the photoresist resin of claim 1, a photoinitiator at a concentration of 1 to 3 weight percent, and 49 to 89 weight percent solvent, the weight percents being based on the weight of the photoresist composition.

6. 10. A process for preparing an optical light emitting diode display using the negative photoresist composition of claim 5, said process comprising: (a) providing a substrate including a plurality of diodes; (b) coating the negative photoresist composition of claim 5 onto the substrate containing a plurality of diode pixels; (c) exposing the negative photoresist composition present on the diode pixels to harden the photoresist resin in the negative photoresist composition to form lens patches on the diode pixels; (d) washing away the unexposed / uncured negative photoresist composition with an aqueous alkaline solution; (e) applying a planarizing polymer over the substrate and lens patch; (f) curing the planarizing polymer.

7. 7. The process of claim 6, wherein step (b) comprises spin-coating the negative photoresist composition of claim 5 onto the substrate.

8. 8. The process of claim 6 or claim 7, wherein step (c) comprises exposing the negative photoresist composition through a mask to selectively expose certain portions of the negative photoresist composition and causing hardening of the photoresist in the exposed negative photoresist composition.

9. 8. The process of claim 6 or claim 7, wherein the aqueous alkaline solution comprises tetramethylammonium hydroxide.

10. 8. The process of claim 6 or claim 7, wherein the planarizing polymer is a curable polymer having a refractive index at least 0.1 lower than that of the hardened photoresist resin.

Images