Anti-cracking polysiloxane dielectric planarization compositions, methods, and films

Abstract

The invention relates to anti-cracking polysiloxane dielectric planarization compositions, methods, and films. The present disclosure relates to a composition for planarizing a surface of a semiconductor device, the composition comprising a catalyst, at least one solvent, and at least one polysiloxane resin, the at least one polysiloxane resin comprising a polysilsesquioxane block and a polydisiloxane block. The polydisiloxane block includes at least one selected from the group consisting of an aryl group or an alkyl group having a substituted or unsubstituted carbon.

Description

[0001] This application is a divisional application of the invention patent application filed on December 18, 2018, with application number 201880087090.9 and entitled "Crack-resistant polysiloxane dielectric planarization composition, method and film". Technical Field

[0002] This invention relates to planarization materials, and more particularly, to planarization dielectric materials for semiconductor and display manufacturing. Background Technology

[0003] In advanced semiconductor manufacturing, such as microprocessors, memory devices, and displays using light-emitting diodes, dielectric materials are required. These dielectric materials can be spin-coated onto the surface of the device to fill deep spaces or gaps between device structures, thereby providing a relatively flat surface suitable for subsequent device layer processing.

[0004] Improvements are needed in planarizing dielectric materials to provide planarization for advanced semiconductor devices with trenches six micrometers deep or deeper. Advantageously, such dielectric materials are crack-resistant at these thicknesses, even when exposed to temperatures exceeding 400°C. High light transmittance is also important for optoelectronic applications. The dielectric material should also be thermally stable when exposed to temperatures exceeding 400°C. Summary of the Invention

[0005] This disclosure relates to a composition for planarizing the surface of a semiconductor device, the composition comprising a catalyst, at least one solvent, and at least one polysiloxane resin, said at least one polysilsesquioxane resin comprising polysilsesquioxane blocks and polydisquioxane blocks. The polydisquioxane blocks conform to the following general formula: , R1 and R2 are each independently selected from aryl groups or alkyl groups having substituted or unsubstituted carbon atoms.

[0006] Various embodiments relate to compositions for planarizing semiconductor devices. The composition comprises a catalyst, at least one solvent, and at least one polysiloxane resin, said at least one polysilsesquioxane resin comprising polysilsesquioxane blocks and polydisquioxane blocks. The polydisquioxane blocks conform to the following general formula: , R1 and R2 are each independently selected from aryl or alkyl groups having substituted or unsubstituted carbon atoms. In some embodiments, the polydisiloxane block comprises at least one of the following: poly(diphenylsiloxane) block, poly(phenylmethylsiloxane) block, and poly(dimethylsiloxane) block. In some specific embodiments, the polydisiloxane block consists of poly(diphenylsiloxane) block and poly(phenylmethylsiloxane) block. In some other embodiments, the polydisiloxane block consists of poly(dimethylsiloxane) block. In some embodiments, the polysilsesquioxane block comprises at least one of the following: poly(methylsilsesquioxane) block and poly(phenylsilsesquioxane) block. In some embodiments, the concentration of the polydisiloxane block is from 0.1 mol% to 50 mol% of the polysiloxane resin. In some embodiments, the weight-average molecular weight of the polydisiloxane block in the composition is from 100 Da to 5,000 Da. In some embodiments, the at least one solvent comprises at least one of the following: ethyl lactate, propylene glycol propyl ether, propylene glycol monomethyl ether acetate, ethanol, isopropanol, and n-butyl acetate. In some embodiments, the catalyst comprises at least one of the following: tetramethylammonium acetate, tetramethylammonium hydroxide, tetrabutylammonium acetate, hexadecyltrimethylammonium acetate, and tetramethylammonium nitrate. In some embodiments, the composition further comprises a surfactant. In some embodiments, the composition further comprises a crosslinking agent. In some embodiments, the at least one polysiloxane resin comprises a first polysiloxane resin and a second polysiloxane resin. In some embodiments, the at least one polysiloxane resin is a first polysiloxane resin and further comprises a second polysiloxane resin composed of a poly(silsesquioxane) resin.

[0007] Various embodiments relate to methods for preparing planarization compositions. The methods include dissolving at least one polysiloxane resin in one or more solvents to form a resin solution, and adding a catalyst to the resin solution. The at least one polysiloxane resin comprises polysilsesquioxane blocks and polydisiloxane blocks. The polydisiloxane blocks conform to the following general formula: , R1 and R2 are each independently selected from aryl or alkyl groups having substituted or unsubstituted carbon atoms. In some embodiments, the polydisiloxane block comprises at least one of the following: poly(diphenylsiloxane) block, poly(phenylmethylsiloxane) block, and poly(dimethylsiloxane) block. In some embodiments, the concentration of the polydisiloxane block is from 0.1 mol% to 50 mol% of the polysiloxane resin.

[0008] Various embodiments relate to planarization films for semiconductor devices. The planarization film comprises catalyst residues and a cured polysiloxane. The cured polysiloxane comprises polysilsesquioxane blocks and polydisiloxane blocks. The polydisiloxane blocks conform to the following general formula: , R1 and R2 are each independently selected from aryl or alkyl groups having substituted or unsubstituted carbon atoms. In some embodiments, the polydisiloxane block comprises at least one of the following: poly(diphenylsiloxane) block, poly(phenylmethylsiloxane) block, and poly(dimethylsiloxane) block. In some embodiments, the weight-average molecular weight of the polydisiloxane block is from 100 Da to 5,000 Da. In some embodiments, the concentration of the polydisiloxane block is from 0.1 mol% to 50 mol% of the polysiloxane resin.

[0009] The above and other features of the invention, and the ways in which they are obtained, will become more apparent and the invention itself will be better understood by referring to the following description of embodiments of the invention in conjunction with the accompanying drawings. Attached Figure Description

[0010] Figure 1 This is a schematic cross-sectional view of a portion of a semiconductor device, showing the surface topography to be planarized.

[0011] Figure 2 for Figure 1 A schematic cross-sectional view of a portion of a semiconductor device, illustrating surface topography planarization via a planarization film according to an embodiment of the present disclosure.

[0012] Figure 3 Related to Example 15 below, and showing the thermogravimetric analysis results of a planarized film according to an embodiment of the present disclosure. Detailed Implementation

[0013] Embodiments of this disclosure can employ the compositions described below for coating onto the surfaces of semiconductor devices (such as microprocessors, memory devices) and displays employing light-emitting diodes and other types of displays, thereby planarizing the semiconductor device surface. The compositions comprise a polysiloxane resin containing polysilsesquioxane blocks and polydisiloxane blocks. The coating can be applied, for example, by spin coating or trench coating. It has been found that planarization films formed by curing the compositions according to embodiments of this disclosure exhibit excellent crack resistance at thicknesses greater than 7 micrometers, even when subjected to temperatures exceeding 400°C. It has been found that planarization films formed by curing some embodiments of the compositions according to this disclosure exhibit excellent crack resistance at thicknesses greater than 10 micrometers, even when subjected to temperatures of 380°C. It has also been found that planarization films formed by curing the compositions according to embodiments of this disclosure exhibit high hardness and high light transmittance. It has also been found that planarization films formed by curing the compositions according to embodiments of this disclosure are thermally stable after exposure to a temperature of 360°C for 24 hours.

[0014] Figure 1 This is a schematic cross-sectional view of a portion of a semiconductor device, showing the surface topography to be planarized. Figure 1 A semiconductor device 10 is shown, which includes a substrate 12 and at least one surface feature 14. Depending on the requirements, the substrate 12 may comprise, for example, silicon, silicon dioxide, silicon nitride, aluminum, copper, or any other material in various layers of the semiconductor device 10 having various thicknesses and arrangements. In some embodiments, the surface feature 14 may be a trench formed in the substrate 12.

[0015] Surface feature 14 can be described as having a width W and a depth D. In some embodiments, the depth D of surface feature 14 can be as small as 0.01 μm, 0.1 μm, 0.5 μm, or 1 μm, or as large as 3 μm, 5 μm, 10 μm, or 100 μm. In some embodiments, the depth D of surface feature 14 can range from 0.01 μm to 100 μm, 0.1 μm to 10 μm, 0.5 μm to 5 μm, or 1 μm to 3 μm. In some embodiments, the width W of surface feature 14 can be as small as 0.01 μm, 0.1 μm, 1 μm, or 10 μm, or as large as 50 μm, 100 μm, 500 μm, or 1000 μm. In some embodiments, the width W of surface feature 14 can range from 0.01 μm to 1000 μm, 0.1 μm to 500 μm, 1 μm to 100 μm, or 10 μm to 50 μm.

[0016] Figure 2 for Figure 1 A schematic cross-sectional view of a portion of a semiconductor device 10, showing the planarization of surface feature 14 by a planarization film 16 according to an embodiment of the present disclosure. Figure 2 A semiconductor device 10 is shown after a planarization film 16 has been formed from a composition comprising a polysiloxane resin according to an embodiment of the present disclosure. The planarization film 16 may fill surface features 14 to provide a substantially flat surface 18 on which subsequent device layers (not shown) may be formed. In some embodiments, the planarization film 16 may have a thickness T greater than 6 micrometers on a portion of the semiconductor device 10. In some embodiments, the planarization film 16 may have a thickness T greater than 10 micrometers on a portion of the semiconductor device 10.

[0017] Figure 1 and Figure 2 An example is shown in which a planarization film 16 can be formed according to an embodiment of the present disclosure. It should be understood that the planarization film 16 according to an embodiment of the present disclosure can be formed on many other morphologies involving different arrangements of conductive, non-conductive, and semi-conductive materials. For ease of illustration, Figure 1 and Figure 2 Only one surface feature 14 is shown in the diagram. However, it should be understood that embodiments may include multiple surface features 14.

[0018] The planarization film 16 can be formed, for example, by spin coating or tank coating of a composition comprising at least one solvent, catalyst, and polysiloxane resin onto at least a portion of the semiconductor device 10, as described below. In some embodiments, the composition may also contain a surfactant. In some embodiments, the composition may also contain a crosslinking agent. In some embodiments, the composition is substantially composed of a composition comprising at least one solvent, catalyst, surfactant, and at least one polysiloxane resin, as described below. In some embodiments, the composition is substantially composed of a composition comprising at least one solvent, catalyst, surfactant, crosslinking agent, and at least one polysiloxane resin, as described below.

[0019] In some embodiments, the polysiloxane resin may comprise polysilsesquioxane blocks and polydisquioxane blocks. The polysilsesquioxane blocks may comprise any type having the formula [RSiO 3 / 2 ] n The polysilsesquioxane, wherein R is hydrogen, an alkyl group, an aryl group, or an alkoxy group. For example, in some embodiments, the polysilsesquioxane block may include a poly(methylsilsesquioxane) block, a poly(phenylsilsesquioxane) block, a poly(methylphenylsilsesquioxane), or any combination thereof.

[0020] Polydisiloxane blocks are defined according to the following formula: Formula I: , R1 and R2 are each independently selected from aryl groups or alkyl groups having substituted or unsubstituted carbon atoms.

[0021] For example, in some embodiments, the polydisiloxane block may include a poly(diphenylsiloxane) block, wherein R1 and R2 are each phenyl groups. In some embodiments, the polydisiloxane block may include a poly(dimethylsiloxane) block, wherein R1 and R2 are each methyl groups. In some embodiments, the polydisiloxane block may include a poly(phenylmethylsiloxane) block, wherein R1 is a phenyl group and R2 is a methyl group.

[0022] In some embodiments, the polysiloxane resin may comprise a single type of polydisiloxane block. For example, in some embodiments, the polydisiloxane block consists of poly(dimethylsiloxane) blocks, such as in SST-3PM2 dimethylsiloxane copolymer resin purchased from Gelest Inc., Morrisville, Pennsylvania. In other embodiments, the polysiloxane resin may comprise more than one type of polydisiloxane block. For example, in some embodiments, the polydisiloxane block may comprise any combination of poly(diphenylsiloxane) blocks, poly(dimethylsiloxane) blocks, or poly(phenylmethylsiloxane) blocks. In some embodiments, the polydisiloxane block may consist of poly(diphenylsiloxane) blocks and poly(phenylmethylsiloxane) blocks, such as in SST-3PM4 tetramer resin purchased from Gelest Inc., Morrisville, Pennsylvania. In some other embodiments, the polydisiloxane block may be composed of poly(diphenylsiloxane) blocks, poly(dimethylsiloxane) blocks, and poly(phenylmethylsiloxane) blocks.

[0023] The polydisiloxane blocks in the polysiloxane resin may have a weight-average molecular weight (Mw). In some embodiments, the weight-average molecular weight (Mw) of the polydisiloxane blocks in the composition is as low as 100 Da, 200 Da, 500 Da, 800 Da, 1,000 Da, or 1,200 Da, or as high as 1,600 Da, 2,100 Da, 2,600 Da, 3,400 Da, 4,300 Da, or 5,000 Da, or in any range defined by any two of the foregoing values. For example, in some embodiments, the Mw of the polydisiloxane blocks in the composition is in the range of 100 Da to 5,000 Da, 200 Da to 4,300 Da, 1,000 Da to 2,100 Da, 1,200 Da to 4,300 Da, or 1,200 Da to 1,600 Da. In some embodiments, the Mw of the polydisiloxane block in the composition is about 1,300 Da. As is known in the art, Mw can be measured by gel permeation chromatography.

[0024] In some embodiments, the concentration of the polydisiloxane block in the polysiloxane resin may be as low as 0.1 mol%, 1 mol%, 10 mol%, or 20 mol% of the polysiloxane resin, or as high as 25 mol%, 30 mol%, 35 mol%, 40 mol%, or 50 mol% of the polysiloxane resin, or within any range defined by any of the foregoing values. For example, in some embodiments, the concentration of the polydisiloxane block in the composition may be in the range of 0.1 mol% to 50 mol%, 1 mol% to 45 mol%, 10 mol% to 40 mol%, or 20 mol% to 30 mol% of the polysiloxane resin.

[0025] Without being bound by any theory, it is believed that the flexibility provided by the long polydisiloxane blocks in the polysiloxane resins described herein offers stress relief between the relatively rigid polysilsesquioxane blocks. Compared to, for example, polytrisiloxane or polytetrasiloxane blocks, the use of polydisiloxane blocks provides additional flexibility by limiting the crosslinking opportunities of the polymer resin. It is also believed that films without such stress relief are more likely to fracture due to the accumulation of high stress within the film. Therefore, even at thicknesses exceeding 7 micrometers and after exposure to temperatures exceeding 400°C, planarized films formed from compositions according to embodiments of this disclosure are crack-resistant.

[0026] In some embodiments, the at least one polysiloxane resin may be composed of any of the aforementioned polysiloxane resins. In other embodiments, the at least one polysiloxane resin may include a first polysiloxane resin and a second polysiloxane resin different from the first polysiloxane resin. In some embodiments, the first polysiloxane resin and the second polysiloxane resin are each one of the aforementioned polysiloxane resins. In other embodiments, the first polysiloxane resin may be one of the aforementioned polysiloxane resins, and the second polysiloxane resin may be a poly(silsesquioxane) resin that is not one of the aforementioned polysiloxane resins, for example, a poly(phenyl-methylsilsesquioxane) resin.

[0027] The at least one solvent may include a single solvent, such as ethylene glycol ether, ethylene glycol ether acetate, n-butyl acetate, ketone, or alcohol. Ethylene glycol ether may include, for example, propylene glycol propyl ether or propylene glycol methyl ether. Ethylene glycol ether acetate may include, for example, propylene glycol methyl ether acetate (PGMEA), 2-ethoxyethyl acetate, or 2-methoxyethyl acetate. Ketones may include, for example, acetone or diethyl ketone. Alcohols may include, for example, isopropanol, butanol, or ethanol. In other embodiments, the at least one solvent includes a mixture of two or more of the aforementioned solvents.

[0028] Catalysts may include, for example, tetramethylammonium acetate (TMAA), tetramethylammonium hydroxide (TMAH), tetrabutylammonium acetate (TBAA), hexadecyltrimethylammonium acetate (CTAA), tetramethylammonium nitrate (TMAN), triphenylamine, trioctylamine, tri-dodecylamine, triethanolamine, tetramethylphosphonium acetate, tetramethylphosphonium hydroxide, triphenylphosphine, trimethylphosphine, trioctylphosphine, aminopropyltriethoxysilane, aminopropyltriethoxysilane trifluoromethanesulfonate, and any combination thereof. Such catalysts can be activated by heating after the composition is applied to the semiconductor device 10 to induce polymerization and crosslinking of the composition, thereby forming a planarization film 16.

[0029] In some embodiments, the composition may also contain a surfactant. Surfactants have been found to reduce streaking, which can be particularly useful when spin-coating the composition onto large-diameter semiconductor device wafers or display substrates. In some embodiments, the surfactant may be a polyether-modified polydimethylsiloxane surfactant, such as BYK-Chemie, Wesel, Germany. ® -306 or BYK ® -307.

[0030] In some embodiments, the concentration of the surfactant in the composition may be as low as 0.01 wt%, 0.1 wt%, 0.4 wt%, 0.6 wt%, or 0.8 wt% of the total weight of the composition, or as high as 1 wt%, 5 wt%, 10 wt%, 15 wt%, or 20 wt% of the total weight of the composition, or within any range defined by any of the foregoing values. For example, in some embodiments, the concentration of the surfactant in the composition may be in the range of 0.01 wt% to 20 wt%, 0.1 wt% to 15 wt%, 0.4 wt% to 10 wt%, 0.6 wt% to 5 wt%, or 0.8 wt% to 1 wt% of the total weight of the composition.

[0031] In some embodiments, the composition may further comprise an organic acid that can volatilize or decompose at high temperatures to help stabilize the composition. In some embodiments, the organic acid may include trifluoroacetic acid, p-toluenesulfonic acid, citric acid, formic acid, or acetic acid, or any combination thereof. In some embodiments, the concentration of the organic acid may include as little as 0.01 wt%, 0.1 wt%, 0.2 wt%, or 0.4 wt% of the total weight of the composition, or as much as 0.5 wt%, 0.6 wt%, 0.8 wt%, or 1 wt% of the total weight of the composition, or within any range defined by any of the foregoing values. For example, in some embodiments, the concentration of the organic acid in the composition may be in the range of 0.01 wt% to 1 wt%, 0.1 wt% to 0.8 wt%, 0.3 wt% to 0.6 wt%, or 0.4 wt% to 0.5 wt% of the total weight of the composition.

[0032] In some embodiments, the composition may further comprise a crosslinking agent. The crosslinking agent forms bonds in the polysiloxane resin. Without being bound by any theory, it is believed that the bonds provided by the crosslinking agent provide additional structure and strength to the planarized film 16, thereby providing additional crack resistance. In some embodiments, the crosslinking agent may comprise bis-(trimethoxysilylpropyl)amine, 1,3-bis(triethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene, 2,6-bis(triethoxysilyl)naphthalene, 9,10-bis(triethoxysilyl)anthracene, 1,6-bis(trimethoxysilyl)pyrene, bis(triethoxysilyl)methane, 1,2-bis(triethoxysilyl)ethane, or 1-(triethoxysilyl)-2-(diethoxymethylsilyl)ethane, or any combination thereof.

[0033] A method for preparing a planarization composition according to embodiments of the present disclosure may include providing at least one polysiloxane resin as described above, and dissolving the polysiloxane resin in one or more solvents to form a resin solution. The dissolution of the polysiloxane resin may be promoted by mixing the polysiloxane resin into one or more solvents for one to four hours. A catalyst as described above may be added to the resin solution. In some embodiments, a surfactant as described above may also be added to the resin solution. The resin solution may be stirred for an additional several hours, such as three hours, to form the composition. The composition may then be filtered through a 0.1-micron filter.

[0034] In use, the planarization composition according to embodiments of this disclosure can be applied to the semiconductor device 10, for example, by spin coating. Figure 1The coated semiconductor device 10 can then be baked at a temperature in the range of about 160°C to about 180°C to remove substantially all of the at least one solvent and form an uncured film. In some embodiments, once substantially all of the at least one solvent has been removed, a second coating of the planarization composition can be applied to the uncured film, and the coated semiconductor device 10 can be baked again at a temperature in the range of about 160°C to about 180°C to remove substantially all of the at least one solvent and form a second layer of the uncured film. The coating and backing processes can be completed until the desired thickness of the uncured film is achieved, after which the catalyst can be activated by heating to cure the film by polymerization and crosslinking of the polysiloxane resin to form the planarization film 16. The catalyst residues may be retained after curing.

[0035] In some embodiments, the planarization film 16 can be cured at temperatures as low as 250°C, 260°C, 280°C, 300°C, or 350°C, or as high as 400°C, 410°C, 420°C, 430°C, 440°C, or 450°C, or at any temperature between any two of the aforementioned temperatures. For example, in some embodiments, the planarization film 16 can be cured at temperatures in the range of 250°C to 450°C, 260°C to 440°C, 280°C to 430°C, 300°C to 420°C, or 350°C to 410°C.

[0036] In some embodiments, according to any of the above embodiments, the planarization film 16 may further include surfactant residues, including polyether-modified polydimethylsiloxane surfactants such as BYK. ® -307 residues.

[0037] Although the invention has been described with respect to exemplary designs, further modifications may be made to the invention within the spirit and scope of this disclosure. Furthermore, this application is intended to cover any deviations from this disclosure that are known or customary in the field to which this invention pertains. Example

[0038] Example 1 - Comparative Example - GR150F Poly(Silsesquioxane) Resin In a 200ml flask, 10g of BYK obtained from BK-Chemie was... ®-307 surfactant was added to 90 g of ethanol and stirred at room temperature for 1 hour to prepare a 10 wt% surfactant solution. In a 100 ml flask, 0.5 g of tetramethylammonium nitrate (TMAN) catalyst was added to 24.5 g of deionized water and stirred at room temperature for 1 hour to prepare a 2 wt% TMAN catalyst solution. In another 200 ml flask, 45.0 g of GR150F resin obtained from Techneglas, Perrysburg, Ohio was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form a GR150F resin solution. GR150 is a poly(silsesquioxane) resin containing equimolar amounts of poly(methylsilsesquioxane) blocks and poly(phenylsilsesquioxane) blocks with approximately 0.3 mol% of poly(dimethylsiloxane) blocks. In another 200 ml flask, 1.25 g of a 10 wt% surfactant solution and 0.8 g of a TMAN catalyst solution were added to 100 g of GR150F solution, and the mixture was stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was then filtered through a 0.1 micron filter.

[0039] A filtered planarization composition was spin-coated onto a four-inch silicon wafer at 1,500 rpm. The wafer with the cast film was then baked for 60 seconds each in air on two separate hot plates in a series of two hot plates, one with a surface temperature of 160°C and the other with a surface temperature of 180°C, to evaporate the solvent. The wafer with the baked coating was then cured at 350°C for 1 hour in a nitrogen atmosphere. Cracks in the cured coating were examined using an optical microscope and a scanning electron microscope. Severe cracks were observed in the cured coating.

[0040] Example 2 – Comparative Example – Poly(silsesquioxane) Resin SST-3PM1 In a 200 ml flask, 45.0 g of SST-3PM1 resin, obtained from Gelest Inc., Morrisville, Pennsylvania, was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM1 resin solution. SST-3PM1 is a polysilsesquioxane resin containing 90 mol% poly(phenylsilsesquioxane) blocks and 10 mol% poly(methylsilsesquioxane) blocks. In another 200 ml flask, 1.25 g of a 10 wt% surfactant solution prepared as described above and 0.8 g of a TMAN catalyst solution prepared as described above were added to 100 g of the SST-3PM1 resin solution and stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was filtered through a 0.1 micron filter.

[0041] A filtered planarization composition was spin-coated onto a four-inch silicon wafer at 1,500 RPM. The wafer with the cast film was then baked for 60 seconds each in air on two separate hot plates at a surface temperature of 160°C and 180°C, respectively, to evaporate the solvent. The thickness of the baked coating was measured and found to be 28,439 Å. The wafer with the baked coating was then cured at 350°C for 1 hour in a nitrogen atmosphere. The cured coating was examined for cracks using optical and scanning electron microscopy. No cracks were observed in the cured coating.

[0042] Example 3 – Dimethylsiloxane copolymer resin SST-3PM2 In a 200 ml flask, 45.0 g of SST-3PM2 resin, obtained from Gelest Inc., Morrisville, Pennsylvania, was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM2 resin solution. SST-3PM2 is a dimethylsiloxane copolymer resin containing 70 mol% poly(phenylsilsesquioxane) blocks and 30 mol% poly(dimethylsiloxane) copolymer blocks. In another 200 ml flask, 1.25 g of the 10 wt% surfactant solution prepared as described above and 0.8 g of the TMAN catalyst solution prepared as described above were added to 100 g of the SST-3PM2 resin solution and stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was filtered through a 0.1 micron filter.

[0043] A filtered planarization composition was spin-coated onto a four-inch silicon wafer at 1,500 RPM. The wafer with the cast film was then baked for 60 seconds each in air on two separate hot plates in a series of two hot plates, one with a surface temperature of 160°C and the other with a surface temperature of 180°C, to evaporate the solvent. The wafer with the baked coating was then cured at 350°C for 1 hour in a nitrogen atmosphere. The cured coating was examined for cracks using optical microscopy and scanning electron microscopy. No cracks were observed in the cured coating.

[0044] Example 4 – Dimethylsiloxane copolymer resin SST-3PM4 In a 200 ml flask, 45.0 g of SST-3PM4 resin, obtained from Gelest Inc., Morrisville, Pennsylvania, was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM4 resin solution. SST-3PM4 is a dimethylsiloxane copolymer resin comprising 45 mol% poly(methylsilsesquioxane) blocks, 40 mol% poly(phenylsilsesquioxane) blocks, 15 mol% poly(phenylmethylsiloxane) blocks, and 10 mol% poly(diphenylsiloxane) blocks. In another 200 ml flask, 1.25 g of a 10 wt% surfactant solution prepared as described above and 0.8 g of a TMAN catalyst solution prepared as described above were added to 100 g of the SST-3PM4 resin solution and stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was filtered through a 0.1 micron filter.

[0045] A filtered planarization composition was spin-coated onto a four-inch silicon wafer at 1,500 RPM. The wafer with the cast film was then baked for 60 seconds each in air on two separate hot plates at a surface temperature of 160°C and 180°C, respectively, to evaporate the solvent. The thickness of the baked coating was measured and found to be 32,556 Å. The wafer with the baked coating was then cured at 350°C for 1 hour in a nitrogen atmosphere. The cured coating was examined for cracks using optical microscopy and scanning electron microscopy. No cracks were observed in the cured coating.

[0046] Example 5 – Poly(silsesquioxane) resin GR150F and dimethylsiloxane copolymer resin SST-3PM2 In a 200 ml flask, 45.0 g of GR150F resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form a GR150F resin solution. In another 200 ml flask, 45.0 g of SST-3PM2 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM2 resin solution. In yet another 200 ml flask, 1.25 g of the 10% by weight surfactant solution prepared as described above and 0.8 g of the TMAN catalyst solution prepared as described above were added to 95 g of the GR150F resin solution and 5 g of the SST-3PM2 resin solution, and stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was filtered through a 0.1 micron filter.

[0047] A filtered planarization composition was spin-coated onto a four-inch silicon wafer at 1,500 RPM. The wafer with the cast film was baked in air for 60 seconds on each of two hot plates in a series of two hot plates, with a surface temperature of 160°C and 180°C, respectively, to evaporate the solvent. The thickness of the baked coating was measured and found to be 32,425 Å. The wafer with the baked coating was cured at 350°C for 1 hour in a nitrogen atmosphere. Cracks in the cured coating were examined using an optical microscope and a scanning electron microscope. Cracks were observed in the cured coating. The extent of the cracks was less than that observed in Comparative Example 1.

[0048] Example 6 – Poly(silsesquioxane) resin GR150F and dimethylsiloxane copolymer resin SST-3PM2 In a 200 ml flask, 45.0 g of GR150F resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form a GR150F resin solution. In another 200 ml flask, 45.0 g of SST-3PM2 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM2 resin solution. In yet another 200 ml flask, 1.25 g of the 10 wt% surfactant solution prepared as described above and 0.8 g of the TMAN catalyst solution prepared as described above were added to 75 g of the GR150F resin solution and 25 g of the SST-3PM2 resin solution, and stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was filtered through a 0.1 micron filter.

[0049] A filtered planarization composition was spin-coated onto a four-inch silicon wafer at 1,500 RPM. The wafer with the cast film was baked in air for 60 seconds on each of two hot plates in a series of two hot plates, with a surface temperature of 160°C and 180°C respectively, to evaporate the solvent. The thickness of the baked coating was measured and found to be 32,790 Å. The wafer with the baked coating was cured at 350°C for 1 hour in a nitrogen atmosphere. Cracks in the cured coating were examined using an optical microscope and a scanning electron microscope. Cracks were observed in the cured coating. The extent of the cracks was less than that observed in Comparative Example 1.

[0050] Example 7 – Poly(silsesquioxane) resin SST-3PM1 and dimethylsiloxane copolymer resin SST-3PM2 In a 200 ml flask, 30.0 g of SST-3PM1 resin was added to 70.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM1 resin solution. In another 200 ml flask, 30.0 g of SST-3PM2 resin was added to 70.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM2 resin solution. In yet another 200 ml flask, 1.25 g of the 10% by weight surfactant solution prepared as described above and 0.8 g of the TMAN catalyst solution prepared as described above were added to 100 g of the SST-3PM1 resin solution and 1 g of the SST-3PM2 resin solution, and stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was filtered through a 0.1 micron filter.

[0051] A filtered planarization composition was spin-coated onto a four-inch silicon wafer at 1,500 RPM. The wafer with the cast film was then baked for 60 seconds each on two separate hot plates in air to evaporate the solvent; the first hot plate had a surface temperature of 160°C and the second hot plate had a surface temperature of 180°C. The thickness of the baked coating was measured and found to be 12,942 Å. The wafer with the baked coating was then cured at 350°C for 1 hour in a nitrogen atmosphere. Cracks in the cured coating were examined using optical microscopy and scanning electron microscopy. No cracks were observed in the cured coating.

[0052] Example 8 – Poly(silsesquioxane) resin SST-3PM1 and dimethylsiloxane copolymer resin SST-3PM4 In a 200 ml flask, 45.0 g of SST-3PM1 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM1 resin solution. In another 200 ml flask, 45.0 g of SST-3PM4 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM4 resin solution. In yet another 200 ml flask, 0.5 g of the 10 wt% surfactant solution prepared as described above and 0.32 g of the TMAN catalyst solution prepared as described above were added to 10 g of the SST-3PM1 resin solution and 30 g of the SST-3PM4 resin solution, and stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was filtered through a 0.1 micron filter.

[0053] A filtered planarization composition was spin-coated onto two four-inch silicon wafers at 1,500 RPM. The wafers with the cast film were each baked for 60 seconds in air on two separate hot plates at a surface temperature of 160°C and 180°C, respectively, to evaporate the solvent. The thickness of the baked coating on each wafer was measured and found to be 31,873 Å and 31,915 Å, respectively. One wafer was cured in a nitrogen atmosphere at 410°C for 30 minutes, and the other at 450°C for 30 minutes. Cracks in the cured coating were examined using optical and scanning electron microscopy. No cracks were observed in the cured coating on either wafer.

[0054] Example 9 – Poly(silsesquioxane) resin SST-3PM1 and dimethylsiloxane copolymer resin SST-3PM4 In a 200 ml flask, 45.0 g of SST-3PM1 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM1 resin solution. In another 200 ml flask, 45.0 g of SST-3PM4 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM4 resin solution. In another 200 ml flask, 0.5 g of the 10 wt% surfactant solution prepared as described above and 0.32 g of the TMAN catalyst solution prepared as described above were added to 20 g of the SST-3PM1 resin solution and 20 g of the SST-3PM4 resin solution, and stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was filtered through a 0.1 micron filter.

[0055] A filtered planarization composition was spin-coated onto two four-inch silicon wafers at 1,500 RPM. The wafers with the cast film were each baked for 60 seconds in air on two separate hot plates at a surface temperature of 160°C and 180°C, respectively, to evaporate the solvent. The thickness of the baked coating on each wafer was measured and found to be 31,897 Å and 31,896 Å, respectively. One wafer was cured at 410°C for 30 minutes in a nitrogen atmosphere, and the other at 450°C for 30 minutes in a nitrogen atmosphere. Cracks in the cured coating were examined using optical microscopy and scanning electron microscopy. No cracks were observed in the cured coating on either wafer.

[0056] Example 10 – Poly(silsesquioxane) resin SST-3PM1 and dimethylsiloxane copolymer resin SST-3PM4 In a 200 ml flask, 45.0 g of SST-3PM1 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM1 resin solution. In another 200 ml flask, 45.0 g of SST-3PM4 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM4 resin solution. In yet another 200 ml flask, 0.5 g of the 10 wt% surfactant solution prepared as described above and 0.32 g of the TMAN catalyst solution prepared as described above were added to 30 g of the SST-3PM1 resin solution and 10 g of the SST-3PM4 resin solution, and stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was filtered through a 0.1 micron filter.

[0057] A filtered planarization composition was spin-coated onto two four-inch silicon wafers at 1,500 RPM. The wafers with the cast film were each baked for 60 seconds in air on two separate hot plates at a surface temperature of 160°C and 180°C, respectively, to evaporate the solvent. The thickness of the baked coating on each wafer was measured and found to be 31,684 Å and 31,722 Å, respectively. One wafer was cured at 410°C for 30 minutes in a nitrogen atmosphere, and the other at 450°C for 30 minutes in a nitrogen atmosphere. Cracks in the cured coating were examined using optical microscopy and scanning electron microscopy. No cracks were observed in the cured coating on either wafer.

[0058] Example 11 – Dimethylsiloxane copolymer resins SST-3PM2 and SST-3PM4 In a 200 ml flask, 30.0 g of SST-3PM4 resin was added to 70.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM4 resin solution. In another 200 ml flask, 30.0 g of SST-3PM2 resin was added to 70.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM2 resin solution. In another 200 ml flask, 1.25 g of the 10 wt% surfactant solution prepared as described above and 0.8 g of the TMAN catalyst solution prepared as described above were added to 100 g of the SST-3PM4 resin solution and 1 g of the SST-3PM2 resin solution, and stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was filtered through a 0.1 micron filter.

[0059] A filtered planarization composition was spin-coated onto a four-inch silicon wafer at 1,500 RPM. The wafer with the cast film was then baked for 60 seconds each in air on two separate hot plates at a surface temperature of 160°C and 180°C, respectively, to evaporate the solvent. The thickness of the baked coating was measured and found to be 14,231 Å. The wafer with the baked coating was then cured at 350°C for 1 hour in a nitrogen atmosphere. The cured coating was examined for cracks using optical and scanning electron microscopy. No cracks were observed in the cured coating.

[0060] Example 12 – Dimethylsiloxane copolymer resins SST-3PM2 and SST-3PM4 In a 200 ml flask, 45.0 g of SST-3PM4 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM4 resin solution. In another 200 ml flask, 45.0 g of SST-3PM2 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM2 resin solution. In another 200 ml flask, 1.25 g of the 10 wt% surfactant solution prepared as described above and 0.8 g of the TMAN catalyst solution prepared as described above were added to 100 g of the SST-3PM4 resin solution and 1 g of the SST-3PM2 resin solution, and stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was filtered through a 0.1 micron filter.

[0061] The filtered planarization composition was spin-coated onto five four-inch silicon wafers, two at 1,000 RPM, two at 1,500 RPM, and one at 2,400 RPM. The wafers with the cast film were each baked in air for 60 seconds on two hot plates in a series of conditions to evaporate the solvent; the first hot plate had a surface temperature of 160°C, and the second hot plate had a surface temperature of 180°C. One of the two wafers coated at 1,000 RPM, one of the two wafers coated at 1,500 RPM, and the wafer coated at 2,400 RPM each underwent a second coating, each rotating at the same speed as their first coating, and then baked again on the hot plates as described above. The thickness of the baked coating on several wafers was measured, revealing a thickness of 43,458 Å for a single coating at 1,000 RPM, 93,494 Å for a double coating at 1,000 RPM, 32,440 Å for a single coating at 1,500 RPM, and 54,973 Å for a double coating at 2,400 RPM. Five wafers with the baked coating were cured at 410 °C for 30 minutes in a nitrogen atmosphere. Cracks in the cured coating were examined using optical and scanning electron microscopy. No cracks were observed in the cured coating on wafers with a coating thickness up to 54,973 Å. Cracks were observed only on wafers with a coating thickness of 93,494 Å.

[0062] Example 13 – Dimethylsiloxane copolymer resins SST-3PM2 and SST-3PM4 In a 100 ml flask, 0.5 g of tetrabutylammonium nitrate (TBAA) catalyst was added to 24.5 g of deionized water and stirred at room temperature for 1 hour to prepare a 2 wt% TBAA catalyst solution. In a 200 ml flask, 45.0 g of SST-3PM4 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM4 resin solution. In another 200 ml flask, 45.0 g of SST-3PM2 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM2 resin solution. In yet another 200 ml flask, 0.675 g of the 10 wt% surfactant solution prepared as described above, 0.4 g of TBAA catalyst solution, and 0.025 g of trifluoroacetic acid were added to 50 g of SST-3PM4 resin solution and 0.5 g of SST-3PM2 resin solution, and stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was filtered through a 0.1 micron filter.

[0063] The filtered planarization composition was spin-coated onto three four-inch silicon wafers, one at 600 RPM, one at 1,000 RPM, and one at 1,500 RPM. The wafers with the cast film were then baked in air for 60 seconds each on two hot plates in a series of two hot plates, with a surface temperature of 160°C and 180°C, respectively, to evaporate the solvent. The thickness of the baked coating on the wafers was measured, revealing a single coating thickness of 37,020 Å at 1,500 RPM and 50,012 Å at 1,000 RPM. The thickness of the single coating at 600 RPM could not be measured because the spin speed was too low to produce a uniform coating. The three wafers with the baked coating were cured at 410°C for 30 minutes in a nitrogen atmosphere. Cracks in the cured coating were examined using optical microscopy and scanning electron microscopy. No cracks were observed in the cured coating on the wafer coated at 1,500 RPM. Cracks were observed on wafers coated at 1,000 RPM.

[0064] Example 14 – Dimethylsiloxane copolymer resins SST-3PM2 and SST-3PM4 In a 200 ml flask, 45.0 g of SST-3PM4 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM4 resin solution. In another 200 ml flask, 45.0 g of SST-3PM2 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM2 resin solution. In another 200 ml flask, 1.25 g of the 10 wt% surfactant solution prepared as described above, 0.8 g of the TMAN catalyst solution prepared as described above, and 0.45 g of crosslinking agent were added to 100 g of SST-3PM4 resin solution and 1 g of SST-3PM2 resin solution, and stirred at room temperature for 3 hours to form a planarized composition. The crosslinking agent was Silquest, purchased from Momentive Performance Materials, Waterford, New York. ® A-1170 (bis-(trimethoxysilylpropyl)amine). The planarization composition was filtered through a 0.1-micron filter.

[0065] The filtered planarization composition was spin-coated onto twelve four-inch silicon wafers, three at 1,000 RPM, three at 1,300 RPM, three at 1,800 RPM, and three at 2,400 RPM. The wafers with the cast film were each baked for 60 seconds in air on a series of two hot plates with a surface temperature of 160°C and 180°C, respectively, to evaporate the solvent. Each wafer underwent a second coating, each rotating at the same speed as its first coating, and was baked again on the hot plates as described above. The thickness of the baked coating on each wafer was measured. The twelve wafers were cured in a nitrogen atmosphere for 30 minutes. Four of the twelve wafers (one of each of the four spin-coated wafers) were cured at 360°C. The remaining four of the twelve wafers (one of each of the four spin-coated wafers) were cured at 380°C. The remaining four of the twelve wafers (one of each of the four types coated at four different rotational speeds) were cured at 410 °C. Cracks in the cured coating were examined using optical and scanning electron microscopy. The thickness and crack detection results are shown in Table 1 below. As shown in Table 1, no cracks were observed in the cured coating on wafers with a coating thickness exceeding 10 micrometers (100,000 Å) at temperatures up to 380 °C. No cracks were observed in the cured coating on wafers with a coating thickness exceeding 7 micrometers (77,679 Å) at temperatures up to 410 °C.

[0066] Table 1

[0067] Example 15 – Dimethylsiloxane copolymer resins SST-3PM2 and SST-3PM4 In a 200 ml flask, 45.0 g of SST-3PM4 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM4 resin solution. In another 200 ml flask, 45.0 g of SST-3PM2 resin was added to 55.0 g of PGMEA and stirred at room temperature for 1 hour to form an SST-3PM2 resin solution. In another 200 ml flask, 1.25 g of the 10 wt% surfactant solution prepared as described above, 0.8 g of the TMAN catalyst solution prepared as described above, and 0.45 g of the above-described bis-(trimethoxysilylpropyl)amine crosslinking agent were added to 100 g of SST-3PM4 resin solution and 1 g of SST-3PM2 resin solution, and stirred at room temperature for 3 hours to form a planarization composition. The planarization composition was filtered through a 0.1 micron filter.

[0068] A filtered planarization composition was spin-coated onto a four-inch silicon wafer at 1,500 RPM. The wafer with the cast film was then baked for 60 seconds each in air on two separate hot plates in a series of two hot plates, one with a surface temperature of 160°C and the other with a surface temperature of 180°C. The wafer with the baked coating was then cured in a nitrogen atmosphere at 410°C for 30 minutes.

[0069] The cured coating was collected from the wafer and analyzed by TGA on a Discovery TGA system. The sample was heated in N2 from room temperature (25°C) to approximately 360°C and held for 24 hours. Results are shown below. Figure 3 middle. Figure 3 The temperature distribution of the TGA is shown 20 (refer to the right axis), and the weight of the coating 22 is shown as a percentage of the initial coating weight (refer to the left axis). Figure 3 As shown, the coating is thermally stable, losing less than 1% of its weight after being heated at 360°C for 24 hours.

[0070] In a 100 ml flask, 20.0 g of the planarization composition was added to 25.0 g of PGMEA, and the mixture was stirred at room temperature for 1 hour to form a diluted planarization composition. The diluted planarization composition was then filtered through a 0.1 micron filter.

[0071] A filtered, diluted planarization composition was spin-coated onto an 8-inch silicon wafer and a 2-inch by 2-inch clear glass substrate at 1,500 RPM. The silicon wafer and glass substrate with the cast film were then baked in air for 60 seconds each on two hot plates with a surface temperature of 160°C and 180°C, respectively, to evaporate the solvent. The wafer with the baked coating was then cured in air at 250°C for 60 minutes.

[0072] The transmittance of glass and coated glass was measured using a Hitachi U-3900 UV-Vis spectrophotometer. The optical transmittance of the uncoated glass substrate was measured to be 92.1%, while the transmittance of the cured coating on the glass substrate was measured to be 91.6%, demonstrating the high transmittance of the cured coating.

[0073] Through Hysiron ® Nanoindentation testing on a nanomechanical testing system was used to measure the nanohardness of an 8-inch silicon wafer with a cured coating and to perform a reduction in elastic modulus analysis. A high nanohardness of 145.1 MPa and a reduced elastic modulus of 3.49 GPa were measured for the cured coating on the silicon wafer.

Claims

1. A composition for planarizing the surface of a semiconductor device, the composition comprising: catalyst; At least one solvent; and At least one polysiloxane resin, said at least one polysiloxane resin comprising polysilsesquioxane blocks and polydisiloxane blocks, said polydisiloxane blocks conforming to the following general formula: ， R1 and R2 are each independently selected from aryl groups or alkyl groups having substituted or unsubstituted carbon atoms.

2. The composition according to claim 1, wherein the polydisiloxane block comprises at least one of the following: poly(diphenylsiloxane) block, poly(phenylmethylsiloxane) block, and poly(dimethylsiloxane) block.

3. The composition according to claim 1, wherein the polysilsesquioxane block comprises at least one of the following: poly(methylsilsesquioxane) block and poly(phenylsilsesquioxane) block.

4. The composition according to claim 1, wherein the concentration of the polydisiloxane block is from 0.1 mol% to 50 mol% of the polysiloxane resin.

5. The composition according to claim 1, wherein the polydisiloxane block in the composition has a weight-average molecular weight of 100 Da to 5,000 Da.

6. The composition according to claim 1, wherein the at least one polysiloxane resin is a first polysiloxane resin, and further comprises a second polysiloxane resin, the second polysiloxane resin being composed of a poly(silsesquioxane) resin.

7. A method for preparing a planarization composition, the method comprising: At least one polysiloxane resin is dissolved in one or more solvents to form a resin solution, said at least one polysiloxane resin comprising polysilsesquioxane blocks and polydisiloxane blocks, said polydisiloxane blocks conforming to the following general formula: ， R1 and R2 are each independently selected from: aryl groups or alkyl groups having substituted or unsubstituted carbon atoms; and The catalyst is added to the resin solution.

8. The method according to claim 7, wherein the polydisiloxane block comprises at least one of the following: poly(diphenylsiloxane) block, poly(phenylmethylsiloxane) block, and poly(dimethylsiloxane) block.

9. A planarization film for a semiconductor device, the film comprising: Catalyst residues; and A cured polysiloxane, wherein the cured polysiloxane comprises polysilsesquioxane blocks and polydisiloxane blocks, the polydisiloxane blocks conforming to the following general formula: ， R1 and R2 are each independently selected from aryl groups or alkyl groups having substituted or unsubstituted carbon atoms.

10. The planarization film according to claim 9, wherein the polydisiloxane block comprises at least one of the following: poly(diphenylsiloxane) block, poly(phenylmethylsiloxane) block, and poly(dimethylsiloxane) block.

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