阅读说明：本技术 抗裂性硅基平整化组合物、方法和膜 (Crack resistant silicon-based planarization compositions, methods, and films ) 是由 黄红敏 海伦·晓·徐 于 2018-12-18 设计创作，主要内容包括：一种用于使半导体器件的表面平整化的组合物包括：硅基材料,硅基材料包括硅氧烷、倍半硅氧烷、聚硅氧烷、聚倍半硅氧烷和/或聚硅氧烷树脂；连同至少一种溶剂、催化剂以及交联剂,交联剂包括硅氧烷化合物。(A composition for planarizing a surface of a semiconductor device comprising: a silicon-based material comprising a siloxane, silsesquioxane, polysiloxane, polysilsesquioxane and/or polysiloxane resin; together with at least one solvent, a catalyst, and a crosslinker, the crosslinker comprises a siloxane compound.)

1. A composition for planarizing a surface of a semiconductor device, the composition comprising:

a silicon-based material comprising at least one of: siloxanes, silsesquioxanes, polysiloxanes, polysilsesquioxanes, and polysiloxane resins;

at least one solvent;

a catalyst; and

a crosslinking agent comprising a siloxane compound according to the general formula:

wherein R is an aliphatic containing group and R₁、R₂、R₃、R₄、R₅And R₆Each independently selected from the group consisting of: h or an alkyl group having a substituted or unsubstituted carbon.

2. The composition of claim 1, wherein the crosslinking agent comprises at least one of: bis- (trimethoxysilylpropyl) amine, bis (triethoxysilyl) methane, 1, 2-bis (triethoxysilyl) ethane, and 1- (triethoxysilyl) -2- (diethoxymethylsilyl) ethane.

3. The composition of claim 1, wherein the silicon-based material comprises a polysiloxane resin formed from monomers comprising at least one of: methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane.

4. The composition of claim 1, wherein the catalyst comprises at least one of: tetramethylammonium acetate, tetramethylammonium hydroxide, tetrabutylammonium acetate, hexadecyltrimethylammonium acetate and tetramethylammonium nitrate.

5. A method for preparing a planarization composition, the method comprising:

dissolving a silicon-based material in one or more solvents to form a silicon-based material solution, the silicon-based material comprising at least one of: siloxanes, silsesquioxanes, polysiloxanes, polysilsesquioxanes, and polysiloxane resins;

adding a catalyst to the silicon-based material solution; and

adding a cross-linking agent to the silicon-based material solution, the cross-linking agent comprising a siloxane compound according to the general formula:

wherein R is an aliphatic containing group and R₁、R₂、R₃、R₄、R₅And R₆Each independently selected from the group consisting of: h or an alkyl group having a substituted or unsubstituted carbon.

6. The method of claim 5, wherein the crosslinking agent comprises at least one of: bis- (trimethoxysilylpropyl) amine, bis (triethoxysilyl) methane, 1, 2-bis (triethoxysilyl) ethane, and 1- (triethoxysilyl) -2- (diethoxymethylsilyl) ethane.

7. The method of claim 5, wherein the silicon-based material comprises a polysiloxane resin formed from monomers comprising at least one of: methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane.

8. The method of claim 5, wherein the catalyst comprises at least one of: tetramethylammonium acetate, tetramethylammonium hydroxide, tetrabutylammonium acetate, hexadecyltrimethylammonium acetate and tetramethylammonium nitrate.

9. A planarizing film for a semiconductor device, the film comprising:

a cured silicon-based polymer comprising at least one of: polysiloxanes, polysilsesquioxanes and polysiloxane resins;

residues of the catalyst; and

residues of a crosslinking agent, said residues of said crosslinking agent comprising residues of a siloxane compound according to the general formula:

wherein R is an aliphatic containing group and R₁、R₂、R₃、R₄、R₅And R₆Each independently selected from the group consisting of: h or an alkyl group having a substituted or unsubstituted carbon.

10. The planarizing film of claim 9, wherein the residues of the cross-linking agent comprise residues of at least one of: bis- (trimethoxysilylpropyl) amine, bis (triethoxysilyl) methane, 1, 2-bis (triethoxysilyl) ethane, and 1- (triethoxysilyl) -2- (diethoxymethylsilyl) ethane.

Technical Field

The present invention relates to planarizing materials, and more particularly to planarizing dielectric materials for semiconductor and display fabrication.

Background

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

It is desirable to improve the planarizing dielectric material to provide planarization for advanced semiconductor devices having trenches six microns deep or deeper. It is important that such dielectric materials have crack resistance at such thicknesses, even when exposed to temperatures in excess of 400 ℃. It is also important for optoelectronic applications that such dielectric materials have high optical transmission. The dielectric material should also be thermally stable when exposed to temperatures in excess of 400 ℃.

Disclosure of Invention

A composition for planarizing a surface of a semiconductor device comprising a silicon-based material and a crosslinking agent comprising a siloxane compound according to the general formula:

wherein R is an aliphatic containing group and R₁、R₂、R₃、R₄、R₅And R₆Each independently selected from the group consisting of: h or an alkyl group having a substituted or unsubstituted carbon.

Various embodiments relate to a composition for planarizing a semiconductor device. The composition includes a silicon-based material, at least one solvent, a catalyst, and a crosslinker. The silicon-based material comprises at least one of: siloxanes, silsesquioxanes, polysiloxanes, polysilsesquioxanes, and polysiloxane resins. The crosslinking agent includes a siloxane compound according to the general formula:

wherein R is an aliphatic containing group and R₁、R₂、R₃、R₄、R₅And R₆Each independently selected from the group consisting of: h or an alkyl group having a substituted or unsubstituted carbon. In some embodiments, the crosslinking agent comprises at least one of: bis- (trimethoxysilylpropyl) amine, bis (triethoxysilyl) methane, 1, 2-bis (triethoxysilyl) ethane, and 1- (triethoxysilyl) -2- (diethoxymethylsilyl) ethane. In some further embodiments, the crosslinking agent consists of bis- (trimethoxysilylpropyl) amine. In some embodiments, the silicon-based material comprises a polysiloxane resin formed from monomers comprising at least one of: methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane. In some further embodiments, the polysiloxane resin is formed from monomers consisting of: methyltriethoxysilane, dimethyldiethoxysilane, and phenyltriethoxysilane. In some embodiments, the concentration of the crosslinking agent is from 0.1 weight percent to 5 weight percent of the composition. In some embodiments, the at least one solvent comprises at least one of: 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: tetramethylammonium acetate, tetramethylammonium hydroxide, tetrabutylammonium acetate, hexadecyltrimethylammonium acetate and tetramethylammonium nitrate. In some embodiments, the composition further comprises a surfactant.

Various embodiments relate to a method for preparing a planarization composition. The method comprises the following steps: dissolving a silicon-based material in one or more solvents to form a silicon-based material solution, adding a catalyst to the silicon-based material solution, and adding a cross-linking agent to the silicon-based material solution. The silicon-based material comprises at least one of: siloxanes, silsesquioxanes, polysiloxanes, polysilsesquioxanes, and polysiloxane resins. The crosslinking agent includes a siloxane compound according to the general formula:

wherein R is an aliphatic containing group and R₁、R₂、R₃、R₄、R₅And R₆Each independently selected from the group consisting of: h or an alkyl group having a substituted or unsubstituted carbon. In some embodiments, the crosslinking agent comprises at least one of: bis- (trimethoxysilylpropyl) amine, bis (triethoxysilyl) methane, 1, 2-bis (triethoxysilyl) ethane, and 1- (triethoxysilyl) -2- (diethoxymethylsilyl) ethane. In some further embodiments, the crosslinking agent consists of bis- (trimethoxysilylpropyl) amine. In some embodiments, the silicon-based material comprises a polysiloxane resin formed from monomers comprising at least one of: methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane. In some further embodiments, the polysiloxane resin is formed from monomers consisting of: methyltriethoxysilane, dimethyldiethoxysilane, and phenyltriethoxysilane. In some embodiments, the catalyst comprises at least one of: tetramethylammonium acetate, tetramethylammonium hydroxide, tetrabutylammonium acetate, hexadecyltrimethylammonium acetate and tetramethylammonium nitrate. In some embodiments, the concentration of the crosslinking agentThe degree is 0.1 to 5 weight percent of the composition.

Various embodiments relate to a planarizing film for a semiconductor device. The planarizing film includes a cured silicon-based polymer, residues of a catalyst, and residues of a crosslinking agent. The polymer comprises at least one of: polysiloxanes, polysilsesquioxanes and polysiloxane resins. The residues of the crosslinking agent include residues of a siloxane compound according to the general formula:

wherein R is an aliphatic containing group and R₁、R₂、R₃、R₄、R₅And R₆Each independently selected from the group consisting of: h or an alkyl group having a substituted or unsubstituted carbon. In some embodiments, the residue of the crosslinking agent comprises a residue of at least one of: bis- (trimethoxysilylpropyl) amine, bis (triethoxysilyl) methane, 1, 2-bis (triethoxysilyl) ethane, and 1- (triethoxysilyl) -2- (diethoxymethylsilyl) ethane. In some embodiments, the residue of the catalyst comprises at least one of: tetramethylammonium acetate, tetramethylammonium hydroxide, tetrabutylammonium acetate, hexadecyltrimethylammonium acetate and tetramethylammonium nitrate. In some embodiments, the planarizing film has a film thickness greater than 6 microns within a portion of the semiconductor device.

The above-mentioned and other features of this invention and the manner of attaining them will become more apparent and the invention itself will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings.

Drawings

Fig. 1 is a schematic cross-section of a portion of a semiconductor device showing the topography of a surface to be planarized.

Fig. 2 is a schematic cross-section of the portion of the semiconductor device of fig. 1 illustrating planarization of a surface feature by a planarizing film in accordance with an embodiment of the present disclosure.

Detailed Description

Embodiments of the present disclosure may employ a composition comprising a silicon-based material and a crosslinker, as described below, to coat it onto the surface of a semiconductor device, such as microprocessors, memory devices, and displays employing light emitting diodes or other types of displays, to planarize the semiconductor device surface. The coating may be applied, for example, by spin coating or slot coating. It has been found that a planarized film formed by curing a composition according to embodiments of the present disclosure exhibits excellent crack resistance at thicknesses greater than 6 microns, even when subjected to temperatures in excess of 400 ℃. It has also been found that a planarized film formed by curing a composition according to embodiments of the present disclosure exhibits high intensity and high optical transmittance. It has also been found that planarizing films formed by curing compositions according to embodiments of the present disclosure are thermally stable when exposed to temperatures in excess of 400 ℃.

Fig. 1 is a schematic cross-section of a portion of a semiconductor device showing the topography of a surface to be planarized. Fig. 1 illustrates a semiconductor device 10 including a substrate 12 and at least one surface feature 14. Substrate 12 may include, for example, silicon dioxide, silicon nitride, aluminum, copper, or any other material in various layers of various thicknesses and arrangements of semiconductor devices as desired. In some embodiments, the surface features 14 may be trenches formed into the substrate 12.

The surface features 14 may be described as having a width W and a depth D. In some embodiments, the depth D of the surface features 14 may be as small as 0.01 microns, 0.1 microns, 0.5 microns, or 1 micron, as large as 3 microns, 5 microns, 10 microns, 100 microns. In some embodiments, the depth D of the surface features 14 may be in a range of 0.01 microns to 100 microns, 0.1 microns to 10 microns, 0.5 microns to 5 microns, or 1 micron to 3 microns. In some embodiments, the width W of the surface features 14 may be as small as 0.01 microns, 0.1 microns, 1 micron, 10 microns, or as large as 50 microns, 100 microns, 500 microns, 1000 microns. In some embodiments, the width W of the surface features 14 may be in a range of 0.01 microns to 1000 microns, 0.1 microns to 500 microns, 1 micron to 100 microns, or 10 microns to 50 microns.

Fig. 2 is a schematic cross-section of the portion of semiconductor device 10 of fig. 1 illustrating planarization of surface features 14 by planarizing film 16 in accordance with an embodiment of the present disclosure. Fig. 2 illustrates semiconductor device 10 after a planarizing film 16 is formed from a silicon-based material and a crosslinker composition in accordance with an embodiment of the present disclosure. Planarizing film 16 can fill surface features 14 to provide a substantially planar surface 18 on which subsequent device layers (not shown) can be formed. In some embodiments, planarizing film 16 can have a thickness T greater than 6 microns within a portion of a semiconductor device.

Fig. 1 and 2 show an example in which a planarizing film 16 according to an embodiment of the present disclosure can be formed. It should be understood that planarizing film 16 in accordance with embodiments of the present disclosure can be formed over many other topographies involving different arrangements of conductive, non-conductive, and semiconductive materials. For ease of illustration, only one surface feature 14 is shown in fig. 1 and 2. However, it should be understood that embodiments may include a plurality of surface features 14.

Planarizing film 16 can be formed by coating at least a portion of semiconductor device 10 (e.g., by spin-coating or slot-coating a composition comprising a silicon-based material, at least one solvent, a catalyst, and a crosslinker, as described below). In some embodiments, the composition may also include a surfactant. In some embodiments, the composition consists essentially of a composition comprising a silicon-based material, at least one solvent, a catalyst, a surfactant, and a crosslinker, as described below.

In some embodiments, the silicon-based material may include a siloxane, silsesquioxane, polysiloxane, or polysilsesquioxane, or any combination thereof. In some embodiments, the silicon-based resin may include, for example, methylsiloxane, methylsilsesquioxane, phenylsiloxane, phenylsilsesquioxane, methylphenylsiloxane, methylphenylsilsesquioxane, dimethylsiloxane, diphenylsiloxane, methylphenylsiloxane, polyphenylsilsesquioxane, polyphenylsiloxane, polymethylphenylsiloxane, polymethylphenylsilsesquioxane, polymethylsiloxane, or polymethylsilsesquioxane, or any combination thereof.

In some embodiments, the silicon-based material may additionally or alternatively include one or more silicone resins, such as one or more of the glass resins silicone resins available from Techneglas, Perrysburg, Ohio, Techneglas, pellegurg. In some embodiments, the polysiloxane resin is a silicon-based oligomer formed from limited hydrolysis and condensation reactions of one or more silicon-based monomers. In some embodiments, the silicon-based monomer may include an organoalkoxysilane having a Si-C bond, such as methyltrimethoxysilane (MTMOS), Methyltriethoxysilane (MTEOS), dimethyldiethoxysilane (DMDEOS), Phenyltriethoxysilane (PTEOS), dimethyldimethoxysilane, or phenyltrimethoxysilane, or any combination thereof. In some embodiments, the silicon-based monomer may include an organoalkoxysilane that does not contain Si-C bonds, such as Tetraethylorthosilicate (TEOS).

In some embodiments, the concentration of the silicon-based material in the composition can be as low as 5 weight percent (wt%), 10 wt%, 20 wt%, or 30 wt%, or as high as 40 wt%, 50 wt%, 60 wt%, 70 wt%, or 80 wt%, or within any range defined by any two of the foregoing values, for example, in some embodiments, the concentration of the silicon-based material in the composition can be in a range from 5 wt% to 80 wt%, 10 wt% to 60 wt%, or 20 wt% to 40 wt%, of the total weight of the composition.

The at least one solvent may comprise a single solvent such as a glycol ether, a glycol ether acetate, n-butyl acetate, a ketone, or an alcohol. Glycol ethers may include, for example, propylene glycol propyl ether or propylene glycol methyl ether. The glycol ether acetate may include, for example, Propylene Glycol Methyl Ether Acetate (PGMEA), ethyl 2-ethoxyacetate, or methoxyethyl 2-acetate. The ketone may include, for example, acetone or diethyl ketone. The alcohol may include, for example, isopropanol, butanol, or ethanol. In other embodiments, the at least one solvent comprises a mixture of two or more of the foregoing solvents.

The crosslinking agent includes a siloxane compound according to the following general formula:

formula (I)

Wherein R is an aliphatic containing group and R₁、R₂、R₃、R₄、R₅And R₆Each independently selected from the group consisting of: h or an alkyl group having a substituted or unsubstituted carbon. In some embodiments, R is an aliphatic group.

For example, in some embodiments, the crosslinking agent can be bis- (trimethoxysilylpropyl) amine, bis (triethoxysilyl) methane, 1, 2-bis (triethoxysilyl) ethane, or 1- (triethoxysilyl) -2- (diethoxymethylsilyl) ethane, or any combination thereof. Such crosslinkers have high functionality to provide greater opportunity to chain high molecular weight chains together as well as low molecular weight oligomers. Without wishing to be bound by any theory, it is believed that the high molecular weight chains crosslink directly without a crosslinking agent as described above, thereby creating a rigid structure that accumulates high stresses after high temperature exposure. It is also believed that insufficiently bonded low molecular weight oligomers weaken the coating and are more likely to crack due to the accumulation of high stresses in the film. High functionality crosslinkers bond high molecular weight chains together at more sites to provide additional strength, while the aliphatic-containing groups of the crosslinker provide flexibility between chains to reduce film stress. The high functionality crosslinker also bonds to more of the low molecular weight oligomers, thereby acting as a chain extender to increase the molecular weight of the membrane and increase the membrane strength. Accordingly, the planarizing film according to the embodiment of the present disclosure can resist cracking even at a thickness of more than 6 μm and after exposure to a temperature of more than 400 ℃.

In some embodiments, the concentration of the crosslinking agent in the composition can be as low as 0.01, 0.1, 0.4, 0.6, or 0.8 weight percent of the total weight of the composition, or as high as 1,2, 3, 4, or 5 weight percent of the total weight of the composition, or within any range defined by any two of the foregoing values, e.g., in some embodiments, the concentration of the crosslinking agent in the composition can be in a range of 0.01 to 5, 0.1 to 4, 0.4 to 3, 0.6 to 2, 0.8 to 1, or 0.4 to 0.8 weight percent of the total weight of the composition.

The catalyst may include, for example, tetramethylammonium acetate (TMAA), tetramethylammonium hydroxide (TMAH), tetrabutylammonium acetate (TBAA), cetyltrimethylammonium acetate (CTAA), tetramethylammonium nitrate (TMAN), triphenylamine, trioctylamine, dotrialkylamine, triethanolamine, tetramethylphosphonium acetate, tetramethylphosphonium hydroxide, triphenylphosphine, trimethylphosphine, trioctylphosphine, aminopropyltriethoxysilane triflate, and any combination thereof. Such catalysts may be activated by heat after the composition is applied to semiconductor device 10 to cause the composition to polymerize and crosslink to form planarizing film 16.

In some embodiments, the composition may further comprise a surfactant. It has been found that surfactants can further reduce striations, which can be particularly useful when spin coating the composition onto larger diameter semiconductor device wafers or display substrates. In some embodiments, the surfactant can be a polyether modified polydimethylsiloxane surfactant, such as that available from BYK-Chemie, Wesel, Germany, BYK chemical company-306 or

-307。

In some embodiments, the concentration of surfactant in the composition can be as low as 0.01, 0.1, 0.4, 0.6, or 0.8 weight percent of the total weight of the composition, or as high as 1,5, 10, 15, or 20 weight percent of the total weight of the composition, or within any range defined by any two of the foregoing values, e.g., in some embodiments, the concentration of surfactant in the composition can be in a range of 0.01 to 20, 0.1 to 15, 0.4 to 10, 0.6 to 5, or 0.8 to 1 weight percent of the total weight of the composition.

In some embodiments, the composition may also include an organic acid that may volatilize or decompose at elevated 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 0.1, 0.2, 0.3, or 0.4 weight percent of the total weight of the composition, or as much as 0.5, 0.6, 0.8, or 1 weight percent of the total weight of the composition, or within any range defined by any two of the foregoing values, for example, in some embodiments, the concentration of the organic acid in the composition may be within a range of 0.1 to 1, 0.2 to 0.8, 0.3 to 0.6, or 0.4 to 0.5 weight percent of the total weight of the composition.

A method for preparing a planarization composition according to an embodiment of the present disclosure may include: providing a silicon-based material as described above, and dissolving the silicon-based material in one or more solvents to form a silicon-based material solution. Dissolving the silicon-based material may be facilitated by mixing the silicon-based material into one or more solvents for one to four hours. The crosslinking agent as described above and the catalyst as described above may be added to the silicon-based material solution. The silicon-based material solution may be stirred for several hours (e.g., three hours) to form the composition. The composition may then be filtered through a 0.1 micron filter.

In use, a planarizing composition in accordance with embodiments of the present disclosure can be applied to semiconductor device 10 (fig. 1) by, for example, spin coating. The coated device 10 may then be baked at a temperature in the range of about 160 ℃ to about 180 ℃ to remove substantially all of the at least one solvent and form an uncured film. Once the at least one solvent is substantially removed, the catalyst may be activated by heat to cure the film by polymerizing and crosslinking the silicon-based material and the crosslinking agent to form the planarizing film 16. Residues of the crosslinking agent and catalyst may remain after curing.

In some embodiments, the planarizing film 16 can be cured at a temperature as low as 250 ℃, 260 ℃, 280 ℃,300 ℃, or 350 ℃, or as high as 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, or 450 ℃, or at any temperature between any two of the foregoing temperatures. For example, in some embodiments, the planarizing film 16 may be cured at a temperature in a range of 250 ℃ to 450 ℃, 260 ℃ to 440 ℃, 280 ℃ to 430 ℃,300 ℃ to 420 ℃, or 350 ℃ to 410 ℃.

In some embodiments, planarizing film 18 can also include surfactant residues that include polyether modified polydimethylsiloxane surfactants such as, for example, in accordance with any of the above embodiments

-307 residues.

While this invention has been described with respect to an exemplary design, the present invention may be further modified within the spirit and scope of this disclosure. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains.