Planarization coating and process with high crack threshold for filling wide and deep trenches in silicon wafers

Abstract

This disclosure provides a curable composition having a high crack threshold, comprising at least one polysiloxane resin, a solvent medium, and a crosslinking agent. The solvent medium may further comprise at least one solvent having a boiling point above 100°C and at least one solvent having a boiling point below 100°C.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims priority to U.S. Patent Application No. 18 / 664,268, filed May 14, 2024, which claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Patent Application No. 63 / 468,442, filed May 23, 2024, both of which are hereby incorporated by reference in their entireties.

[0002] (Field of the Invention) The present disclosure generally relates to planarizing materials, and more specifically to silicone - based planarizing compositions for coating semiconductor and display devices.

Background Art

[0003] In advanced semiconductor manufacturing, such as in microprocessors, memory devices, and displays employing light - emitting diodes, there is a need for a dielectric material that can be spin - coated onto the surface of a device to fill deep spaces or gaps between device structures and provide a relatively flat surface suitable for subsequent device layer processing.

[0004] Such a dielectric material is important to exhibit thermal stability at high temperatures and be crack - resistant at a thickness that allows the material to completely fill the trenches of a semiconductor device.

Summary of the Invention

[0005] The present disclosure provides a composition for planarizing a substrate, comprising at least one polysiloxane resin, a solvent medium, and a cross - linker comprising a siloxane compound. Each of the at least one polysiloxane resins has the following formula:

[0006]

Chemical Formula

[0007] Furthermore, the solvent medium includes at least one solvent having a boiling point above 100°C and at least one solvent having a boiling point below 100°C.

[0008] This disclosure further provides a method for planarizing a semiconductor substrate, comprising: applying a composition onto and within a plurality of channels in the semiconductor substrate; and curing the composition to form a coating that at least partially fills the channels in the substrate. The composition comprises at least one polysiloxane resin, a solvent medium, and a crosslinking agent comprising a siloxane compound. Each of the at least one polysiloxane resin comprises the following formula:

[0009] [ka] The reaction product comprises one or more monomers of (wherein R1 and R2 are each independently selected from alkyl groups and aryl groups having substituted or unsubstituted carbons).

[0010] Furthermore, the solvent medium includes at least one solvent having a boiling point above 100°C and at least one solvent having a boiling point below 100°C. [Brief explanation of the drawing]

[0011] By referring to the following description of exemplary embodiments in conjunction with the attached drawings, the above and other features and advantages of this disclosure, as well as the manner in which they are obtained, will become clearer and better understood. [Figure 1] An example of a semiconductor device having a trench with depth D and width W is provided. [Figure 2] An example of a semiconductor device coated with the composition of this disclosure is shown in Figure 1. [Figure 3]Figure 2 illustrates a coated semiconductor device including a liner composition and an overcoat composition. [Figure 4] An example of a method for applying a curable composition onto a substrate is provided. [Figure 5] Examples of methods for applying liners, curable compositions, overcoats, and combinations thereof onto a substrate are provided.

[0012] Corresponding reference letters indicate corresponding parts across several figures. The drawings illustrate various characteristics and components in accordance with this disclosure, but the drawings are not necessarily to scale, and certain characteristics may be exaggerated to better illustrate and explain this disclosure. The illustrations described herein are illustrative of embodiments of the invention and should not be construed as limiting the scope of the invention in any way. [Modes for carrying out the invention]

[0013] For the purpose of facilitating an understanding of the principles of this disclosure, embodiments illustrated in the drawings below will be referenced. The exemplary embodiments disclosed herein are not intended to be exhaustive or to limit this disclosure to the exact forms disclosed in the detailed description below. Rather, these exemplary embodiments have been selected and described so that those skilled in the art can utilize their teachings.

[0014] I. Coating Composition This disclosure provides a curable composition for planarizing the surface of a semiconductor device, such as a substrate, a semiconductor device, such as a microprocessor, a memory device, a display using light-emitting diodes, or other types of displays, thereby planarizing the surface of a semiconductor device. The composition can be applied by spin coating to form a planarization film on a semiconductor device. Planarization films formed from the curable composition of this disclosure have been found to exhibit high crack resistance, delamination resistance, and high heat resistance, even when the coating is applied in a layer having a relatively high thickness compared to known planarization coatings.

[0015] Figure 1 is a schematic diagram of a portion of a semiconductor device illustrating a surface to be planarized. The semiconductor 10 may include a substrate 12 and at least one surface feature 14, for example, a trench. The trench 14 may have a width W of 0.1 μm, 1 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm to 60 μm, 80 μm, 100 μm, 200 μm, 500 μm, 1000 μm, 2000 μm, or any range including any two of the above as endpoints, for example, 0.1 μm to 2000 μm, 1 μm to 1000 μm, 10 μm to 500 μm, 20 μm to 200 μm, 30 μm to 100 μm, 40 μm to 80 μm, or 50 μm to 60 μm. The trench 14 may have a depth D of 0.1 μm, 1 μm, 5 μm, 10 μm, 15 μm to 20 μm, 25 μm, 30 μm, 100 μm, 500 μm, or any range including any two of the above as endpoints, for example, 0.1 μm to 500 μm, 1 μm to 100 μm, 5 μm to 30 μm, 10 μm to 25 μm, or 15 μm to 20 μm.

[0016] Figure 2 illustrates a semiconductor device 10 having a planarization film formed from a cured composition 16 of the present disclosure. The composition 16 may fill trenches 14 to provide a substantially flat surface 18 on which subsequent device layers may be formed (not shown). The cured composition 16 may have a thickness on a portion of the semiconductor device of any range including 1 μm, 10 μm, 30 μm to 60 μm, 90 μm, 100 μm, or any two of the aforementioned as endpoints, for example, 1 μm to 100 μm, 10 μm to 90 μm, or 30 μm to 60 μm.

[0017] Figures 1 and 2 illustrate an example of a planarization film that may be formed. It is understood that the planarization film formed from the cured composition 16 may be coated on many other microstructures with different arrangements of conductive, nonconductive, and semiconductor materials. For ease of illustration, one surface feature 14 is shown in Figures 1 and 2. However, it is understood that the semiconductor 10 may contain multiple surface features 14.

[0018] The semiconductor device 10 can be further coated with a liner, an overcoat, or a combination thereof, as discussed below.

[0019] A planarization film formed from the cured composition 16 can be created by coating at least a portion of the semiconductor device 10 by spin coating a curable composition. The curable composition can include at least one polysiloxane resin, a solvent medium, and a crosslinking agent. The composition can additionally include a catalyst.

[0020] A. Polysiloxane Resin The curable composition can include at least one polysiloxane resin. The polysiloxane resin can include a polysilsesquioxane block and a polydisiloxane block. The polysilsesquioxane block can include any type of polysilsesquioxane having the formula [RSiO3 / 2]n, where R is hydrogen, an alkyl group, an aryl group, or an alkoxyl group. For example, the polysilsesquioxane block can include a poly(methylsilsesquioxane) block, a poly(phenylsilsesquioxane) block, poly(methylphenylsilsesquioxane), or any combination thereof.

[0021] The polysiloxane resin can include the reaction product of one or more siloxane monomers of the following formula:

[0022]

Chemical formula

[0023] The siloxane monomer can be described according to the degree of oxygen substitution or functionality on the central silicon atom.

[0024]

Table 1

[0025] Polysiloxane resins may contain reaction products of monofunctional, difunctional, trifunctional, or tetrafunctional siloxane monomers, or any combination thereof.

[0026] The polysiloxane resin may contain at least one monofunctional siloxane monomer (Formula I) as an end-sealing agent, such as triphenylsiloxane block, phenyldimethylsiloxane block, trimethylsiloxane block, or a combination thereof. The polysiloxane resin may contain monofunctional siloxane block amounts in mol% based on the total moles of the polysiloxane resin, such as 0.1 mol%, 1 mol%, 5 mol% to 10 mol%, 20 mol%, 30 mol%, or any two of the aforementioned values ​​as endpoints, for example, 0.1 to 30 mol%, 1 to 20 mol%, or 5 to 10 mol%.

[0027] The polysiloxane resin may contain at least one of the following: a difunctional siloxane monomer (Formula II), such as a poly(diphenylsiloxane) block, a poly(phenylmethylsiloxane) block, a poly(dimethylsiloxane) block, or a combination thereof. The polysiloxane resin may contain a difunctional siloxane block amount in mol% based on the total moles of the polysiloxane resin, such as 0.1 mol%, 1 mol%, 5 mol% to 10 mol%, 20 mol%, 30 mol%, or any two of the aforementioned values ​​as endpoints, for example, 0.1 to 30 mol%, 1 to 20 mol%, or 5 to 10 mol%.

[0028] The polysiloxane resin may contain at least one of the following trifunctional siloxane monomers (Formula III), for example, poly(methylsiloxane) blocks, poly(phenylsiloxane) blocks, poly(propylsiloxane) blocks, poly(ethylsiloxane) blocks, or combinations thereof. The polysiloxane resin may contain trifunctional siloxane block amounts in mol% based on the total moles of the polysiloxane resin, such as 0.1 mol%, 1 mol%, 5 mol% to 10 mol%, 20 mol%, 30 mol%, or any two of the aforementioned values ​​as endpoints, for example, 0.1 to 30 mol%, 1 to 20 mol%, or 5 to 10 mol%.

[0029] The polysiloxane resin may contain at least one of the following: tetrafunctional siloxane monomers (formula IV), such as tetramethoxysilane, tetraethoxysilane, tetrachloride, silicon alkoxide, silicon tetraacetate, and combinations thereof. The polysiloxane resin may contain tetrafunctional siloxane block amounts in mol% based on the total moles of the polysiloxane resin, such as 0.1 mol%, 1 mol%, 5 mol% to 10 mol%, 20 mol%, 30 mol%, or any two of the aforementioned values ​​as endpoints, for example, 0.1 to 30 mol%, 1 to 20 mol%, or 5 to 10 mol%.

[0030] Polysiloxane resins formed from siloxane monomers may further contain end groups. Suitable end groups include hydroxysilanes, chlorosilanes, alkoxysilanes, acrylooxysilanes, epoxysilanes, and combinations thereof. These end groups may be further polymerizable. Further suitable end groups include non-reactive or chain-terminating end groups, such as trialkylsilanes.

[0031] The curable composition may contain polysiloxane resin in wt.% amounts of 1 wt.%, 15 wt.%, 30 wt.% to 45 wt.%, 60 wt.%, 90 wt.%, or any range including any two of the aforementioned values ​​as endpoints, based on the total weight of the curable composition, for example, 1 wt.% to 90 wt.%, 15 wt.% to 60 wt.%, or 30 wt.% to 45 wt.%.

[0032] B. Solvent medium The curable composition may contain a solvent medium. The solvent medium may contain at least one high-boiling point solvent and at least one low-boiling point solvent. The solvent medium may contain one or more high-boiling point solvents and one or more low-boiling point solvents. Specifically, the solvent medium may contain two different low-boiling point solvents.

[0033] A suitable high-boiling point solvent may have a boiling point of at least 100°C, at least 120°C, at least 140°C, at least 160°C, at least 180°C, or any range defined between any two of the aforementioned values. Examples of high-boiling point solvents include glycol ethers, such as dipropylene glycol methyl ether (DPM), tripropylene glycol methyl ether (TPM), propylene glycol monomethyl ether acetate (PGMEA), n-propoxypropanol (NPP), propylene carbonate, gamma-butyrolactone, ethyl lactate, propylene glycol propyl ether (PGPE), propylene glycol methyl ether (PGME), propylene carbonate, ethyl lactate, isobutyl lactate, indole-3-acetic acid (IAA), or combinations thereof.

[0034] Suitable low-boiling point solvents may have boiling points below 100°C, below 90°C, below 80°C, below 60°C, or within any range defined between any two of the aforementioned values. Examples of low-boiling point solvents include water, acetone, ethyl esters such as ethyl acetate, and low molecular weight alcohols such as methanol, ethanol, propanol, isopropyl alcohol (IPA), methyl acetate, butanol, or any combination thereof.

[0035] The curable composition may contain, in wt.%, solvent media amounts of 10 wt.%, 15 wt.%, 30 wt.% to 60 wt.%, 90 wt.%, 99 wt.%, or any range including any two of the aforementioned values ​​as endpoints, based on the total weight of the curable composition, for example, 10 wt.% to 99 wt.%, 15 wt.% to 90 wt.%, or 30 wt.% to 60 wt.%.

[0036] C. Crosslinking agent The curable composition may contain a crosslinking agent. The crosslinking agent is of general formula V:

[0037] [ka] The formula includes a siloxane compound comprising (wherein R is one of an aliphatic group and an aromatic group, and R1, R2, R3, R4, R5, and R6 are each independently selected from the group consisting of H or alkyl groups having substituted or unsubstituted carbons). R may also be an aliphatic group.

[0038] A suitable crosslinking agent is given by the following formula:

[0039] [ka] It may have one of the following.

[0040] The crosslinking agents are bis-(trimethoxysilylpropyl)amine (formula VI), N,N'bis(trimethoxysilylpropyl)ethylenediamine (formula VII), 1,2-bis(trimethoxysilyl)ethylene (formula VIII), bis[3-(triethoxysilyl)propyl]disulfide (formula IX), bis-(triethoxysilylpropyl)amine, bis-(methyldimethoxysilylpropyl)amine, bis-(methyldiethoxysilylpropyl)amine, bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, 1,2-bis( The crosslinking agent may be triethoxysilyl)ethane, bis(trimethoxysilyl)benzene, bis(triethoxysilyl)benzene, or 1-(triethoxysilyl)-2-(diethoxymethylsilyl)ethane, 1,8-bis(triethoxysilyl)octane (formula X), N,N'-bis(2-hydroxyethyl)-N,N'-bis(trimethoxysilylpropyl)ethylenediamine (formula XI), N,N'-bis-[(3-triethoxysilylpropyl)aminocarbonyl]polyethylene oxide (formula XII), or any combination thereof. Such crosslinking agents have high functional values, offering great potential for linking high molecular weight chains together and low molecular weight oligomers together.

[0041] While we do not wish to be bound by any theory, it is thought that in the absence of the crosslinking agent described above, high molecular weight chains would directly crosslink, creating a rigid structure that accumulates high stress after exposure to high temperatures. Furthermore, poorly bonded low molecular weight oligomers are thought to be more likely to result in a weaker coating and greater cracking due to the accumulation of high stress in the film. Highly functionalized crosslinking agents provide greater strength by bonding with high molecular weight chains at more positions, while the aliphatic groups in the crosslinking agent provide flexibility between chains, reducing film stress. Highly functionalized crosslinking agents also bond to more low molecular weight oligomers, which act as chain extenders, increasing the molecular weight of the film and enhancing its strength. Therefore, planarized films may be able to withstand cracking even with thicknesses exceeding 6 micrometers and after exposure to temperatures exceeding 400°C.

[0042] The curable composition may contain crosslinking agent amounts in wt.% of 0.0001 wt.%, 0.1 wt.%, 1 wt.% to 5 wt.%, 10 wt.%, 20 wt.%, or any range including any two of the aforementioned values ​​as endpoints, for example, 0.0001 wt.% to 20 wt.%, 0.1 wt.% to 10 wt.%, or 1 wt.% to 5 wt.% based on the total weight of the curable composition.

[0043] D. Additives This composition may contain one or more additives. Examples of additives include catalysts, surfactants, surface agents, fillers, pigments, and wetting agents, as well as combinations thereof. The curable composition may contain a total amount of additives in wt.% of 0.1 wt.%, 0.5 wt.%, 1 wt.% to 5 wt.%, 10 wt.%, 20 wt.%, or any range including any two of the aforementioned values ​​as endpoints, for example, 0.1 wt.% to 20 wt.%, 0.5 wt.% to 10 wt.%, or 1 wt.% to 5 wt.% based on the total weight of the curable composition.

[0044] i. Catalyst The curable composition may further contain a catalyst. Examples of catalysts include tetraalkylammonium salts, such as tetramethylammonium salts, tetrabutylammonium salts, cetyltrimethylammonium salts, and any combination thereof, of acetic acid, trifluic acid, trifluoroacetic acid, nitric acid, and other organic and inorganic acids. Such catalysts can be activated by heat after the composition is applied to a semiconductor device, causing polymerization and crosslinking of the curable composition to form a planar film.

[0045] Suitable catalysts include, for example, tetramethylammonium acetate (TMAA), tetramethylammonium hydroxide (TMAH), tetrabutylammonium acetate (TBAA), cetyltrimethylammonium acetate (CTAA), tetramethylammonium nitrate (TMAN), triphenylamine, trioctylamine, tododecylamine, triethanolamine, tetramethylphosphonium acetate, tetramethylphosphonium hydroxide, triphenylphosphine, trimethylphosphine, trioctylphosphine, aminopropyltriethoxysilane, aminopropyltriethoxysilane triflate, and any combination thereof. Such catalysts can be activated by heat after the composition is applied to a semiconductor device, causing polymerization and crosslinking of the curable composition to form a planarized film.

[0046] The curable composition may contain a catalyst amount in wt.% of 0.0001 wt.%, 0.1 wt.%, 0.5 wt.% to 1 wt.%, 5 wt.%, 10 wt.%, or any range including any two of the aforementioned values ​​as endpoints, based on the total weight of the curable composition, for example, 0.0001 wt.% to 10 wt.%, 0.1 wt.% to 5 wt.%, or 0.5 wt.% to 1 wt.%.

[0047] ii. Surfactants Surfactants can further reduce striations, which has been found to be particularly useful when compositions are spin-coated onto larger diameter semiconductor device wafers or display substrates. The surfactants may be polyether-modified polydimethylsiloxane surfactants, such as BYK®-306, BYK®-222, or BYK®-307 available from BYK-Chemie (Wesel, Germany), Novec® fluorosurfactant FC-4430 provided by 3M, and Tego® Flow 300 provided by Evonik Industries AG.

[0048] The curable composition may contain surfactant amounts in wt.% of 0.0001 wt.%, 0.1 wt.%, 0.5 wt.% to 1 wt.%, 5 wt.%, 10 wt.%, or any range including any two of the aforementioned values ​​as endpoints, based on the total weight of the curable composition, for example, 0.0001 wt.% to 10 wt.%, 0.1 wt.% to 5 wt.%, or 0.5 wt.% to 1 wt.%.

[0049] II. Method of applying and curing the composition A method for planarizing a substrate may include applying a curable composition onto and within multiple surface features, such as trenches or channels, in a substrate such as a semiconductor device, and curing the curable composition to form a coating or planarization film that at least partially fills the channels in the substrate. The curable composition may be applied to the substrate using spin coating or squeegee coating.

[0050] A. Spin coating Using a spin coating method, a coating can be applied to the surface of a substrate, i.e., a "wafer," to achieve a coating of a desired thickness. As shown in Figure 4, Method 40 includes a multi-step spin coating process. In block 42, the formulation can be distributed dynamically or statically onto the wafer. The wafer may be placed on a spin plate, and the coating solution of the planarizing composition is applied to the center of the wafer. The curable composition can then be applied to the center of the wafer. After application, the wafer may then be spun to allow the composition to cover the wafer surface. In an alternative embodiment, the composition may be applied to a location on the wafer surface away from the center of the wafer. The wafer can then be spun to achieve complete coverage of the wafer surface.

[0051] A suitable coating speed may be 100 revolutions per minute (rpm), 150 rpm, 200 rpm to 300 rpm, 400 rpm to 500 rpm, or any range including any two of the aforementioned values ​​as endpoints, for example, 100 rpm to 500 rpm, 150 rpm to 400 rpm, or 200 rpm to 300 rpm. A suitable spin time may be 2 seconds, 20 seconds, 30 seconds to 40 seconds, 50 seconds, 60 seconds, or any range including any two of the aforementioned values ​​as endpoints, for example, 1 second to 60 seconds, 20 seconds to 50 seconds, or 30 seconds to 40 seconds.

[0052] In block 44, the multi-step spin coating process then includes a diffusion time during which the wafer is rotated at a desired speed without applying any additional liquid formulation, and during which the low-boiling point solvent is evaporated. The diffusion time may allow the composition to flow and achieve a flat surface along the surface. A preferred diffusion speed may be 0 rpm, 100 rpm, 200 rpm to 300 rpm, 400 rpm, 500 rpm, or any range including any two of the aforementioned values ​​as endpoints, for example, 0 rpm to 500 rpm, 100 rpm to 400 rpm, or 200 rpm to 300 rpm. A preferred diffusion time may be 0 seconds, 20 seconds, 30 seconds to 40 seconds, 50 seconds, 60 seconds, or any range including any two of the aforementioned values ​​as endpoints, for example, 0 seconds to 60 seconds, 20 seconds to 50 seconds, or 30 seconds to 40 seconds.

[0053] The period from the distribution of the composition onto the wafer to the completion of the diffusion time of block 44 may constitute the evaporation time of the coating. Evaporation block 44 may include baking the coated wafer at a series of temperatures to evaporate the solvent. The wafer is baked for three evaporation times at three different temperatures. Preferred evaporation temperatures may be 60°C, 80°C, 100°C to 140°C, 180°C, 200°C, or any range including any two of the aforementioned values ​​as endpoints, for example, 60°C to 200°C, 80°C to 180°C, or 100°C to 140°C. Evaporation times may be 0 seconds, 40 seconds, 60 seconds to 80 seconds, 100 seconds, 120 seconds, or any range including any two of the aforementioned values ​​as endpoints, for example, 0 seconds to 120 seconds, 40 seconds to 100 seconds, or 60 seconds to 80 seconds.

[0054] After the evaporation time has elapsed, the composition may have a thickness greater than 1,000 angstroms (Å), greater than 5,000 Å, greater than 10,000 Å, greater than 20,000 Å, greater than 30,000 Å, greater than 50,000 Å, greater than 80,000 Å, greater than 100,000 Å, greater than 500,000 Å, greater than 1,000,000 Å, or any range defined between any two of the aforementioned values, the thickness of which is measured using an ellipsometer or a simplified evaporation method (SEM).

[0055] The multi-step spin coating process may include high-rpm spinning in block 46 while rotating the wafer without applying additional liquid formulations to establish the desired film thickness. If the spin coating process does not include high-rpm spinning, the method may proceed from block 44 to block 48.

[0056] Suitable high-rpm speeds may be 200 rpm, 500 rpm, 1000 rpm to 1500 rpm, 2000 rpm, 3000 rpm, or any range including any two of the aforementioned values ​​as endpoints, for example, 200 rpm to 3000 rpm, 500 rpm to 2000 rpm, or 1000 rpm to 1500 rpm. Suitable high-rpm spin times may be 2 seconds, 20 seconds, 30 seconds to 40 seconds, 50 seconds, 60 seconds, or any range including any two of the aforementioned values ​​as endpoints, for example, 1 second to 60 seconds, 20 seconds to 50 seconds, or 30 seconds to 40 seconds.

[0057] In block 48, the multi-step spin coating process may include a pause time to facilitate the flow of a viscous fluid of the high-boiling point solvent along the coated surface of the substrate. A preferred duration for the pause time may be 2 seconds, 20 seconds, 30-40 seconds, 50 seconds, 60 seconds, or any range including any two of the aforementioned values ​​as endpoints, for example, 1-60 seconds, 20-50 seconds, or 30-40 seconds.

[0058] B. Hardening When the curable composition is applied to the surface of a substrate, the composition can cure to form a planar film. Referring further to the method in Figure 4, in block 49, the composition can cure on the applied surface. Preferred curing temperatures may be 160°C, 190°C, 200°C to 250°C, 300°C, 400°C, or any range including any two of the aforementioned values ​​as endpoints, for example, 160°C to 400°C, 190°C to 300°C, or 200°C to 250°C. The curable composition may be cured at the aforementioned temperatures for 30 seconds, 1 minute, 30 minutes, 40 minutes to 60 minutes, 90 minutes, 180 minutes, 360 minutes, or any range defined between any two of the aforementioned values, for example, 30 seconds to 360 minutes, 1 minute to 180 minutes, 30 minutes to 90 minutes, or 40 minutes to 60 minutes.

[0059] C. Reiner A method for applying a curable composition may include applying a liner to the surface of the substrate before applying the curable composition 16. As shown in Figure 3, the liner layer 20 may be applied to the surface 12 of the semiconductor 10. The liner may be SiN, SiO x This may be a polysiloxane coating, or any other spin-on glass coating such as Honeywell polysiloxane coating product T41C.

[0060] The liner may be coated via a spin coating process, as described above, with respect to the coating of the curable composition. Referring to method 50 in Figure 5, the liner may be coated onto the wafer before coating the curable composition in block 52. The liner may be coated statically or dynamically using spin coating. Blocks 42-49 in Figure 5 include the same steps as above, referring to method 40 in Figure 4. Following the coating process, the liner may be optionally cured or baked before coating the substrate with the curable composition.

[0061] Once applied and cured, the liner may have a thickness within any range defined between 10 Å, 20 Å, 40 Å, 45 Å, 50 Å, 55 Å–60 Å, 65 Å, 100 Å, 200 Å, 500 Å, 1000 Å, or any two of the aforementioned values, for example, 10 Å–1000 Å, 20 Å–500 Å, 40 Å–200 Å, 45 Å–100 Å, 50 Å–65 Å, or 55 Å–60 Å, and the thickness is measured using an ellipsometer.

[0062] In addition to a liner that functions as an adhesion promoter, a surface treatment is applied to the substrate to improve adhesion between the substrate and the coating. A suitable surface treatment may be plasma treatment.

[0063] D. Overcoat A method for applying a curable composition may further include applying an overcoat after curing the curable composition to form a planar film. As shown in Figure 3, the overcoat layer 22 may be applied on top of the cured composition 16 inside the surface features 14 of the semiconductor 10. The overcoat may include a dielectric material, such as a nanoporous silica film. Suitable overcoat compositions include silicon dioxide (SiO2), silicon nitride (SiN), and silicon oxynitride (SiO2). x N y Examples include polysiloxane or other spin-on glass coatings.

[0064] The overcoat can be applied to the planarized film by spin coating, dip coating, spray coating, or chemical vapor deposition (CVD). Referring to method 50 in Figure 5, after the curable composition has cured, the overcoat can be applied to the curable composition in block 54. Then, in block 56, the overcoat can be cured.

[0065] The overcoat may be applied to have a thickness of 0.1 μm, 0.5 μm, 1 μm, 1.5 μm to 2 μm, 2.5 μm, 3 μm, 5 μm, or any range defined between any two of the aforementioned values, for example, 0.1 μm to 5 μm, 0.5 μm to 3 μm, 1 μm to 2.5 μm, or 1.5 μm to 2 μm.

[0066] The overcoat may be cured to form an overcoat film. Preferred curing temperatures for forming the overcoat film may be 160°C, 190°C, 200°C to 250°C, 300°C, 400°C, or any range including any two of the aforementioned values ​​as endpoints, for example, 160°C to 400°C, 190°C to 300°C, or 200°C to 250°C. The overcoat may be cured at the aforementioned temperatures for 1 minute, 10 minutes, 20 minutes to 25 minutes, 30 minutes, 40 minutes, or any range defined between any two of the aforementioned values, for example, 1 minute to 40 minutes, 10 minutes to 30 minutes, or 20 minutes to 25 minutes. [Examples]

[0067] Aspects of this disclosure are further illustrated by reference to the following examples. It will be apparent to those skilled in the art that many modifications to both materials and methods can be practiced without departing from the scope of this disclosure.

[0068] Comparative Examples Comparative composition 1 In a 250 mL flask, 45.0 g of GR950F resin was added to 55.0 g of PGMEA, and the mixture was stirred overnight at room temperature to form a 45% GR950F resin solution. In a 250 mL flask, 1.25 g of 10 wt.% BYK-307 surfactant solution prepared in ethanol and 0.8 g of tetramethylammonium nitrate (TMAN) solution prepared in deionized water were added to 100 g of GR950F resin solution, and the mixture was stirred at room temperature for 3 hours to form a planar composition.

[0069] The planarization composition was filtered through a 0.1 micrometer filter. The filtered planarization composition was coated onto a 4-inch silicon wafer by spin coating at 1,000 RPM.

[0070] A wafer with a cast film was baked in an air atmosphere on a series of three hot plates (a first hot plate with a surface temperature of 80°C, a second hot plate with a surface temperature of 160°C, and a third hot plate with a surface temperature of 180°C) for 60 / 60 / 120 seconds, respectively, to evaporate the solvent. The film thickness was measured to be 41430 Å using an ellipsometer. The wafer with the baked coating was cured in a nitrogen atmosphere inside a furnace at 300°C for 30 minutes.

[0071] When a standard spin coating process was used to coat the solution at a spin speed of 600 rpm, a uniform coating was not obtained.

[0072] The solution was spin-coated at 1000 rpm onto a wafer coupon having a trench pattern with a depth of 20 μm and a width of 80 μm.

[0073] The coupon was baked under the same conditions as when it was used on a 4-inch wafer, and then cured on a hot plate at 250°C for 5 minutes.

[0074] A cross-sectional view of the pattern was examined under SEM, which indicated incomplete trench filling and revealed severe membrane cracks in the film.

[0075] Comparative Composition 2 In a 250 mL flask, 45.0 g of SST-3PM4 resin was added to 55.0 g of PGMEA, and the mixture was stirred overnight at room temperature to form a 45% SST-3PM4 resin solution. In another 250 mL flask, 45.0 g of SST-3PM2 resin was added to 55.0 g of PGMEA, and the mixture was stirred overnight at room temperature to form a 45% SST-3PM2 resin solution. In yet another 250 mL flask, 1.25 g of 10 wt.% BYK-307 surfactant solution prepared in ethanol, 0.8 g of tetramethylammonium nitrate (TMAN) solution prepared in deionized water, 0.225 g of trifluoroacetic acid, and 0.45 g of bis-(trimethoxysilylpropyl)amine were added to 100 g of SST-3PM4 resin solution and 1 g of SST-3PM2 resin solution, and the mixture was stirred at room temperature for 3 hours to form a planarized composition.

[0076] The planarization composition was filtered through a 0.1 micrometer filter. The filtered planarization composition was coated onto a 4-inch silicon wafer by spin coating at 1,000 RPM.

[0077] Wafers with a cast film were baked in an air atmosphere on a series of three hot plates (a first hot plate with a surface temperature of 80°C, a second hot plate with a surface temperature of 160°C, and a third hot plate with a surface temperature of 180°C) for 60 / 60 / 120 seconds, respectively, to evaporate the solvent. The film thickness was measured at 43354 Å using an ellipsometer. The wafers with the baked coating were cured in a nitrogen atmosphere inside a furnace at 300°C for 30 minutes.

[0078] When a standard spin coating process was used to coat the solution at a spin speed of 600 rpm, a uniform coating was not obtained.

[0079] The solution was spin-coated at 1000 rpm onto a wafer coupon having a trench pattern with a depth of 20 μm and a width of 80 μm.

[0080] The coupon was baked under the same conditions as when it was used on a 4-inch wafer, and then cured on a hot plate at 250°C for 5 minutes.

[0081] A cross-section of the pattern was examined under SEM, which indicated incomplete trench filling and the absence of membrane cracks.

[0082] Comparative composition 3 In a 250 mL flask, 35.0 g of SST-3PM4 resin was added to 65.0 g of PGMEA, and the mixture was stirred overnight at room temperature to form a 35% SST-3PM4 resin solution. In another 250 mL flask, 35.0 g of SST-3PM2 resin was added to 35.0 g of PGMEA, and the mixture was stirred overnight at room temperature to form a 35% SST-3PM2 resin solution. In yet another 250 mL flask, 5 g of a 10 wt.% BYK-307 surfactant solution prepared in ethanol, 0.8 g of a tetramethylammonium nitrate (TMAN) solution prepared in deionized water, 0.175 g of trifluoroacetic acid, and 0.35 g of bis-(trimethoxysilylpropyl)amine were added to 100 g of the SST-3PM4 resin solution and 1 g of the SST-3PM2 resin solution, and the mixture was stirred at room temperature for 3 hours to form a planarized composition.

[0083] The planarization composition was filtered through a 0.1 micrometer filter. The filtered planarization composition was coated onto a 4-inch silicon wafer by spin coating at 1,000 RPM.

[0084] A wafer with a cast film was baked in an air atmosphere on a series of three hot plates (a first hot plate with a surface temperature of 80°C, a second hot plate with a surface temperature of 160°C, and a third hot plate with a surface temperature of 180°C) for 60 / 60 / 120 seconds, respectively, to evaporate the solvent. The film thickness was measured to 30546 Å using an ellipsometer. The wafer with the baked coating was cured in a nitrogen atmosphere inside a furnace at 300°C for 30 minutes.

[0085] The solution was spin-coated in a double-coating manner at 1000 rpm onto a wafer coupon having a trench pattern with a depth of 20 μm and a width of 80 μm.

[0086] The coupon was baked under the same conditions as when it was used on a 4-inch wafer, and then cured on a hot plate at 250°C for 5 minutes.

[0087] A cross-sectional view of the pattern was examined under SEM, which indicated incomplete trench filling and observed delamination between film layers.

[0088] Comparative composition 4 PTSRE50C is a planarization composition (comparative composition 4) obtained from Honeywell Electronic Materials (Santa Clara, California), and consists of a polysiloxane resin containing 50% wt% GR150F and 50% wt% GR950.

[0089] The planarization composition was filtered through a 0.1 micrometer filter. The filtered planarization composition was coated onto a 4-inch silicon wafer by spin coating at 1,000 RPM.

[0090] A wafer with a cast film was baked in an air atmosphere on a series of two hot plates (a first hot plate with a surface temperature of 160°C and a second hot plate with a surface temperature of 180°C) for 60 / 60 seconds each to evaporate the solvent.

[0091] The wafers received a second and a third coating, and were spun at the same speed as the first coating, and then baked again on a hot plate as described above.

[0092] The film thickness was measured to 53929 Å using an ellipsometer. The wafer with the baked coating was cured in a nitrogen atmosphere inside a furnace at 360°C for 30 minutes.

[0093] Film cracks were observed at the edges of the wafer.

[0094] Examples Composition 1 of the present invention In a 250 mL flask, 33.0 g of SST-3PM4 resin was added to 33.5 g of PGMEA and 33.5 g of IPA, and the mixture was stirred overnight at room temperature to form a 33% SST-3PM4 resin solution. In another 250 mL flask, 33.0 g of SST-3PM2 resin was added to 67.0 g of PGMEA, and the mixture was stirred overnight at room temperature to form a 33% SST-3PM2 resin solution. In a separate 250 mL flask, 5 g of a 10 wt.% BYK-307 surfactant solution prepared in ethanol, 0.8 g of tetramethylammonium nitrate (TMAN) solution prepared in deionized water, 0.165 g of trifluoroacetic acid, and 0.33 g of bis-(trimethoxysilylpropyl)amine were added to 100 g of SST-3PM4 resin solution and 1 g of SST-3PM2 resin solution, and the mixture was stirred at room temperature for 3 hours to form a planarized composition.

[0095] The planarization composition was filtered through a 0.1 micrometer filter. The filtered planarization composition was coated onto a 4-inch silicon wafer by spin coating at 1,000 RPM.

[0096] A wafer with a cast film was baked in an air atmosphere on a series of three hot plates (a first hot plate with a surface temperature of 80°C, a second hot plate with a surface temperature of 160°C, and a third hot plate with a surface temperature of 180°C) for 60 / 60 / 120 seconds, respectively, to evaporate the solvent. The film thickness was measured to 31701 Å using an ellipsometer, and striations were observed on the film.

[0097] A wafer with a baked coating was cured in a nitrogen atmosphere inside a furnace at 300°C for 30 minutes, and the film thickness after curing was 30989 Å.

[0098] For this formulation, the slow diffusion process was investigated by adding a 300 rpm spin step before the main spin speed of 1000 rpm. The film thickness increased from 31701 Å without diffusion to 65639 Å with diffusion at 300 rpm for 60 seconds before spinning at 1000 rpm for 20 seconds.

[0099] [Table 2]

[0100] The solution was spin-coated in a double-coating manner at 1000 rpm onto a wafer coupon having a trench pattern with a depth of 20 μm and a width of 80 μm.

[0101] The coupon was baked under the same conditions as when it was used on a 4-inch wafer, and then cured on a hot plate at 250°C for 5 minutes.

[0102] A cross-sectional view of the pattern was examined under SEM, which indicated incomplete trench filling and revealed several minor delaminations between film layers.

[0103] Incomplete trench / channel filling refers to planarization compositions that partially fill trenches / channels to a depth of 20 μm for lower film thicknesses, but is not an indicator of thermal / crack failure otherwise. Coatings may fill trenches / channels to lower depths.

[0104] Delamination refers to a situation where the stress is higher than the adhesive strength between the composition and the substrate. Delamination can sometimes be resolved by using a composition with lower stress levels or by reducing the process temperature, and minor delamination is not an indicator of failure.

[0105] Composition 2 of the present invention In a 250 mL flask, 25.0 g of SST-3PM4 resin was added to 25.0 g of PGMEA, 25.0 g of acetone, and 25.0 g of IPA, and the mixture was stirred overnight at room temperature to form a 25% SST-3PM4 resin solution. In another 250 mL flask, 25.0 g of SST-3PM2 resin was added to 75.0 g of PGMEA, and the mixture was stirred overnight at room temperature to form a 25% SST-3PM2 resin solution. In a separate 250 mL flask, 5 g of a 10 wt.% BYK-307 surfactant solution prepared in ethanol, 0.8 g of tetramethylammonium nitrate (TMAN) solution prepared in deionized water, 0.125 g of trifluoroacetic acid, and 0.25 g of bis-(trimethoxysilylpropyl)amine were added to 100 g of SST-3PM4 resin solution and 1 g of SST-3PM2 resin solution, and the mixture was stirred at room temperature for 3 hours to form a planarized composition.

[0106] The planarization composition was filtered through a 0.1 micrometer filter. The filtered planarization composition was coated onto a 4-inch silicon wafer by spin coating at 1,000 rpm.

[0107] Wafers with a cast film were baked in an air atmosphere on a series of three hot plates (a first hot plate with a surface temperature of 80°C, a second hot plate with a surface temperature of 160°C, and a third hot plate with a surface temperature of 180°C) for 60 / 60 / 120 seconds, respectively, to evaporate the solvent. The film thickness was measured at 20498 Å using an ellipsometer. The wafers with the baked coating were cured in a nitrogen atmosphere inside a furnace at 300°C for 30 minutes.

[0108] The solution was spin-coated onto a wafer coupon having a trench pattern with a depth of 20 μm and a width of 80 μm at 300 rpm for 10 seconds, and then at 1000 rpm for 20 seconds.

[0109] The coupon was baked under the same conditions as when it was used on a 4-inch wafer, and then cured on a hot plate at 250°C for 5 minutes.

[0110] Examination of the pattern's cross-section under SEM revealed incomplete trench filling. Incomplete trench / channel filling refers to a planarization composition that partially fills trenches / channels to a depth of 20 μm for lower film thicknesses, but is not an indicator of thermal / crack defects. The coating may fill trenches / channels to lower depths.

[0111] In another coupon coating, the solution was spin-coated in a double-coating manner at 300 rpm, and the coupon was baked under the same conditions as when it was used on a 4-inch wafer to evaporate the solvent. The coupon with the baked coating was cured in a nitrogen atmosphere inside a furnace at 300°C for 30 minutes.

[0112] A cross-section of the pattern was examined under SEM, which indicated that the trench was completely filled, with only minor delamination observed between the membrane and the trench wall.

[0113] Composition 3 of the present invention In a 250 mL flask, 30.0 g of SST-3PM4 resin was added to 23.3 g of PGMEA, 23.3 g of acetone, and 23.3 g of IPA, and the mixture was stirred overnight at room temperature to form a 30% SST-3PM4 resin solution. In another 250 mL flask, 30.0 g of SST-3PM2 resin was added to 70.0 g of PGMEA, and the mixture was stirred overnight at room temperature to form a 30% SST-3PM2 resin solution. In a separate 250 mL flask, 5 g of a 10 wt.% BYK-307 surfactant solution prepared in ethanol, 0.8 g of tetramethylammonium nitrate (TMAN) solution prepared in deionized water, 0.125 g of trifluoroacetic acid, and 0.25 g of bis-(trimethoxysilylpropyl)amine were added to 100 g of SST-3PM4 resin solution and 1 g of SST-3PM2 resin solution, and the mixture was stirred at room temperature for 3 hours to form a planarized composition.

[0114] The planarization composition was filtered through a 0.1 micrometer filter. The filtered planarization composition was coated onto a 4-inch silicon wafer by spin coating at 1,000 RPM.

[0115] A wafer with a cast film was baked in an air atmosphere on a series of three hot plates (a first hot plate with a surface temperature of 80°C, a second hot plate with a surface temperature of 160°C, and a third hot plate with a surface temperature of 180°C) for 60 / 60 / 120 seconds, respectively, to evaporate the solvent. The film thickness was measured to 38966 Å using an ellipsometer. The wafer with the baked coating was cured in a nitrogen atmosphere inside a furnace at 300°C for 30 minutes.

[0116] The solution was spin-coated onto a wafer coupon having a trench pattern with a depth of 20 μm and a width of 80 μm at 300 rpm for 10 seconds, followed by 1000 rpm for 20 seconds. The coupon was baked under the same conditions as used for a 4-inch wafer, and then cured at 300°C for 30 minutes in a nitrogen atmosphere inside the furnace.

[0117] A cross-section of the pattern was examined under SEM, which indicated that the trench was completely filled, with only minor delamination observed between the membrane and the trench wall.

[0118] Composition 4 of the present invention In a 100 mL flask, 12.5 g of SST-3PM4 and 0.125 g of SST-3PM2 were added to 12.5 g of PGMEA, 12.5 g of acetone, and 9.13 g of IPA, and the mixture was stirred overnight at room temperature to form a clear solution. 2.5 g of a 10 wt.% BYK-307 surfactant solution prepared in ethanol, 0.16 g of a tetramethylammonium nitrate (TMAN) solution prepared in deionized water, 1.25 g of 10% trifluoroacetic acid prepared in IPA, 2.5 g of 10% (bis-(trimethoxysilylpropyl)amine) prepared in IPA, and 1.01 g of methyltriacetoxysilane were added to the solution as end-sealing agents for the polymer, and the solution was stirred at room temperature for 3 hours to form a planarized composition.

[0119] The planarization composition was filtered through a 0.1 micrometer filter.

[0120] The solution was spin-coated onto a wafer coupon having a trench pattern with a depth of 20 μm and a width of 80 μm at 300 rpm for 30 seconds.

[0121] The coupon was baked on a first hot plate at 80°C for 1 minute, on a second hot plate at 130°C for 1 minute, and on a third hot plate at 180°C for 2 minutes, followed by curing in an oven at 300°C for 30 minutes.

[0122] A cross-section of the pattern was examined using SEM, which showed that the trench was completely filled and there were no cracks.

[0123] Composition 5 of the present invention In another embodiment, a solution prepared with Composition 1 of the present invention was coated onto an 8-inch blanket wafer using squeegee coating. The wafer with the cast film was baked in an air atmosphere on a series of three hot plates (a first hot plate with a surface temperature of 80°C, a second hot plate with a surface temperature of 160°C, and a third hot plate with a surface temperature of 180°C) for 60 / 60 / 120 seconds, respectively, to evaporate the solvent. A film thickness of less than 10 μm was obtained.

[0124] A wafer with a baked coating was cured in a nitrogen atmosphere inside a furnace at 300°C for 30 minutes. A 2 μm layer of CVD SiO2 was deposited on one of the cured wafers using the P5000 CVD SiOx deposition tool supplied by Applied Materials.

[0125] The wafer was placed in a furnace, and the curing process at 300°C for 30 minutes was repeated 10 times. For comparison, a wafer with the same polymer coating but without CVD SiO was cured using the same process.

[0126] After 10 thermal curing cycles, no cracks were observed when the CVD-coated wafers were examined by SEM. For comparison, other wafers without CVD SiO showed severe film cracking. As demonstrated by the thermal curing cycles, wafers coated with the planarization composition and CVD are more resistant to cracking than wafers without CVD.

[0127] Composition 6 of the present invention In another example, the Honeywell polysiloxane coating product T41C was diluted and spin-coated onto a coupon having a trench pattern with a depth of 20 μm and a width of 80 μm to form a liner coating with a thickness of 53 Å. The spin-coating solution prepared with composition 1 of the present invention was then spin-coated onto a wafer coupon having a trench pattern with a depth of 20 μm and a width of 80 μm in a double coating process: 300 rpm for 10 seconds, followed by 1000 rpm for 20 seconds.

[0128] The coupon was baked under the same conditions as when it was used on a 4-inch wafer, and then cured in a nitrogen atmosphere inside the furnace at 300°C for 30 minutes.

[0129] A cross-section of the pattern was examined using SEM, which showed that the trench was completely filled and there was no delamination.

[0130] While specific embodiments of the present invention have been described for illustrative purposes, it will be apparent to those skilled in the art that numerous modifications can be made to the details of the present invention without departing from the invention as defined in the appended claims. Accordingly, this application is intended to encompass any variations, uses, or adaptations of the disclosure that utilize its general principles. Furthermore, this application is intended to encompass any deviations from the disclosure that belong to known or customary practices in the art to which the disclosure relates and which fall within the scope of the appended claims.

[0131] Composition 7 of the present invention In a 100 mL flask, 0.06 g of 1,4-bis-triethoxysilylbenzene was added to 30 g of PTSRE50C, and the mixture was stirred at room temperature for 1 hour to form a planar composition. The planar composition was filtered through a 0.1 micrometer filter.

[0132] The filtered planarization composition was coated onto three 4-inch silicon wafers by spin coating at 1,300 RPM.

[0133] A wafer with a cast film was baked in an air atmosphere on a series of two hot plates (a first hot plate with a surface temperature of 160°C and a second hot plate with a surface temperature of 180°C) for 60 / 60 seconds each to evaporate the solvent.

[0134] Each of the three wafers underwent a second coating and hot plate baking as described above. Two of the three wafers underwent a third coating and hot plate baking as described above. One of the two wafers having the third coating underwent a fourth coating and hot plate baking as described above.

[0135] When the thickness of each baked coating on the wafer was measured, it was found to be 29587 Å for double coating, 44823 Å for triple coating, and 61150 Å for quadruple coating.

[0136] A wafer with a baked coating was cured in a nitrogen atmosphere inside a furnace at 410°C for 30 minutes.

[0137] No film cracks were observed on the three wafers having double, triple, or quadruple coatings.

[0138] Composition 8 of the present invention In a 100 mL flask, 0.12 g of 1,4-bis-triethoxysilylbenzene was added to 30 g of PTSRE50C and stirred at room temperature for 1 hour to form a planarization composition. The planarization composition was filtered through a 0.1 micrometer filter. The filtered planarization composition was coated onto three 4-inch silicon wafers by spin coating at 1,300 RPM.

[0139] A wafer with a cast film was baked in an air atmosphere on a series of two hot plates (a first hot plate with a surface temperature of 160°C and a second hot plate with a surface temperature of 180°C) for 60 / 60 seconds each to evaporate the solvent.

[0140] Each of the three wafers underwent a second coating and hot plate baking as described above. Two of the three wafers underwent a third coating and hot plate baking as described above. One of the two wafers having the third coating underwent a fourth coating and hot plate baking as described above.

[0141] When the thickness of each baked coating on the wafer was measured, it was found to be 29556 Å for double coating, 45525 Å for triple coating, and 63529 Å for quadruple coating.

[0142] A wafer with a baked coating was cured in a nitrogen atmosphere inside a furnace at 410°C for 30 minutes.

[0143] No film cracks were observed on the three wafers having double, triple, or quadruple coatings.

[0144] Composition 9 of the present invention In a 100 mL flask, 0.30 g of 1,4-bis-triethoxysilylbenzene was added to 30 g of PTSRE50C and stirred at room temperature for 1 hour to form a planarization composition. The planarization composition was filtered through a 0.1 micrometer filter. The filtered planarization composition was coated onto three 4-inch silicon wafers by spin coating at 1,300 RPM.

[0145] A wafer with a cast film was baked in an air atmosphere on a series of two hot plates (a first hot plate with a surface temperature of 160°C and a second hot plate with a surface temperature of 180°C) for 60 / 60 seconds each to evaporate the solvent.

[0146] Each of the three wafers underwent a second coating and hot plate baking as described above. Two of the three wafers underwent a third coating and hot plate baking as described above. One of the two wafers having the third coating underwent a fourth coating and hot plate baking as described above.

[0147] When the thickness of each baked coating on the wafer was measured, it was found to be 29288 Å for double coating, 45159 Å for triple coating, and 60922 Å for quadruple coating.

[0148] A wafer with a baked coating was cured in a nitrogen atmosphere inside a furnace at 410°C for 30 minutes.

[0149] No film cracks were observed on the three wafers having double, triple, or quadruple coatings.

[0150] While specific embodiments of the present invention have been described for illustrative purposes, it will be apparent to those skilled in the art that numerous modifications can be made to the details of the present invention without departing from the invention as defined in the appended claims. Accordingly, this application is intended to encompass any variations, uses, or adaptations of the disclosure that utilize its general principles. Furthermore, this application is intended to encompass any deviations from the disclosure that belong to known or customary practices in the art to which the disclosure relates and which fall within the scope of the appended claims.

Claims

1. A composition for planarizing a substrate, The following formula: 【Chemistry 1】 A polysiloxane resin comprising the reaction product of one or more monomers (wherein R is independently selected from unsubstituted or substituted alkyl groups and unsubstituted or substituted aryl groups), A solvent medium, At least one solvent having a boiling point greater than 100°C, and A solvent medium comprising at least one solvent having a boiling point below 100°C, A composition comprising a crosslinking agent.

2. The monomer of formula I, Triphenylsiloxane block, Phenyldimethylsiloxane block, and The trimethylsiloxane block comprises at least one of the following: The monomer of formula II is Poly(diphenylsiloxane) block, Poly(phenylmethylsiloxane) block, and The poly(dimethylsiloxane) block comprises at least one of the following: The monomer of formula III, Poly(methylsiloxane) block, Poly(phenylsiloxane) block, Poly(propylsiloxane) block, and It comprises at least one of the poly(ethylsiloxane) blocks, and The monomer of formula IV, Tetramethoxysilane, Tetraethoxysilane, Silicon tetrachloride, Silicon alkoxides, and The composition according to claim 1, comprising at least one of silicon tetraacetate.

3. The aforementioned crosslinking agent has a general formula: 【Chemistry 2】 (In the formula, R' is one of an aliphatic group and an aromatic group, R １ , R ２ , R ３ , R ４ , R ５ , and R ６ The composition according to claim 1 or 2, wherein each is independently selected from hydrogen and alkyl groups having substituted or unsubstituted carbons.

4. The crosslinking agent is given by the following formula: 【Transformation 3】 A composition according to any one of claims 1 to 3, selected from a combination of the above.

5. The composition according to any one of claims 1 to 4, further comprising a catalyst, wherein the catalyst is selected from tetraalkylammonium salts, such as tetramethylammonium salts, tetrabutylammonium salts, cetyltrimethylammonium salts, and combinations thereof of acetic acid, trifluic acid, trifluoroacetic acid, nitric acid, and the aforementioned.

6. Each of the compositions, based on the total weight of the composition, 1-90 wt.% polysiloxane resin, The catalyst in an amount of 0.0001 to 10 wt.% and 10 to 99 wt.% of the above at least one solvent, The composition according to claim 5, comprising 0.0001 to 20 wt.% of the crosslinking agent.

7. The composition according to any one of claims 1 to 6, wherein the at least one solvent having a boiling point above 100°C is selected from dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol monomethyl ether acetate, n-propoxypropanol, and propylene carbonate, gamma butyrolactone, and combinations thereof.

8. The composition according to any one of claims 1 to 7, wherein the at least one solvent having a boiling point of less than 100°C comprises at least two different solvents.

9. The composition according to claim 8, wherein each of the two different solvents having a boiling point below 100°C is independently selected from acetone, ethyl acetate, methanol, ethanol, propanol, butanol, and isopropyl alcohol.

10. The composition according to any one of claims 1 to 9, wherein the polysiloxane resin further comprises terminal groups derived from hydroxysilane, chlorosilane, alkoxysilane, acrylicoxysilane, epoxysilane, non-reactive or chain termination terminal groups, and combinations thereof.

11. A semiconductor article coated with the cured composition according to any one of claims 1 to 10.

12. A method for planarizing a semiconductor substrate, The method involves coating a composition onto and within a plurality of channels in the semiconductor substrate, wherein the composition is The following formula: 【Chemistry 4】 A polysiloxane resin comprising the reaction product of one or more monomers (wherein R is independently selected from unsubstituted or substituted alkyl groups and unsubstituted or substituted aryl groups), A solvent medium, At least one solvent having a boiling point greater than 100°C, and A solvent medium comprising at least one solvent having a boiling point below 100°C, The application of a crosslinking agent, A method comprising curing the composition to form a coating that at least partially fills the channels in the substrate.

13. The aforementioned crosslinking agent has a general formula: 【Transformation 5】 (wherein, R' is one of an aliphatic-containing group and an aromatic-containing group, and R １ , R ２ , R ３ , R ４ , R ５ , and R ６ are each independently selected from hydrogen and an alkyl group having substituted or unsubstituted carbon), the method according to claim 12, which is a siloxane compound.

14. The crosslinking agent is given by the following formula: 【Transformation 6】 The method according to claim 12 or 13, selected from a combination of the above.

15. The method according to any one of claims 12 to 14, further comprising applying the composition by spin-coating the composition into the interior of the plurality of channels in the semiconductor substrate at a speed of 100 rpm to 500 rpm for a period of 2 seconds to 60 seconds.

16. The method according to claim 15, further comprising the additional step of further spinning the substrate at a speed of 200 to 3000 rpm for a period of 2 to 60 seconds after the coating step.

17. The method according to any one of claims 12 to 16, further comprising curing the composition at a temperature of 160°C to 400°C for a period of 60 seconds to 60 minutes.

18. The method according to any one of claims 12 to 17, further comprising the additional step of depositing a liner coating inside the channel of the substrate before the coating step.

19. The method according to any one of claims 12 to 18, further comprising the additional step of depositing an overcoat on the plurality of channels in the substrate after the curing step.

20. The method according to any one of claims 12 to 19, wherein the coating has a thickness of 1 μm to 100 μm inside the plurality of channels of the substrate.

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