Soluble polyimides and diimides for spin-on carbon applications

Abstract

A high temperature stable spin-on-carbon ("SOC") material is provided that fills in topographical features on a substrate while planarizing its surface in a one-step thin layer coating process. The material comprises a low molecular weight polyimide or diimide that is pre- imidized in solution rather than on a wafer. The SOC layer can survive harsh CVD conditions and is resistant to SC1, particularly on TiN and SiOx surfaces.

Description

Background Technology

[0001] Related applications

[0002] This application claims priority to U.S. Provisional Patent Application Serial No. 63 / 063,623, filed August 10, 2020, entitled "Soluble Polyimides and Diimides for Spin-on Carbon Applications," which is incorporated herein by reference in its entirety. Technical Field

[0003] This invention generally relates to methods for manufacturing microelectronic structures.

[0004] Description of related fields

[0005] According to Moore's Law, as feature sizes become smaller, photolithography techniques for semiconductor devices have shifted towards multilayer patterning. This approach involves patterning multiple layers on top of each other, such as a photoresist layer on top of a hard mask layer above a spin-coated carbon ("SOC") layer, to increase the etch resistance of smaller features. With each layer being deposited and patterned, depositing a uniform, planarized layer of material on top of it becomes crucial for accurate pattern transfer and critical dimension ("CD") control.

[0006] When depositing hard mask layers via chemical vapor deposition ("CVD"), a SOC layer with high-temperature stability is required. Polyimide is a well-known thermally stable polymer. It is typically coated onto a substrate as a polyamic acid precursor. During baking, typically at 200-300°C, the polyamic acid precursor is converted to polyimide. During this process, the coating thickness usually shrinks due to the loss of water and other small molecules. Simultaneously, the polymer crosslinks through intermolecular imidization and other side reactions. Both coating shrinkage and crosslinking negatively impact planarization because shrinkage causes the material in trench / via regions (where there is more SOC material) to "sink" more easily than the material in open areas or at the top of lines (where there is less SOC material). This leads to an increased deviation between these two regions, negatively affecting planarization. Unfortunately, thermal reflow is limited because the polyamic acid crosslinks prematurely through intermolecular imidization and other side reactions, causing the material to rapidly transition from a fluid state to a gel or solid state.

[0007] Furthermore, SOCs are frequently coated onto substrates formed or coated with SiO2, TiN, and other metals. Dry etching is a frequently preferred method for transferring patterns onto the substrate; however, the plasma used in dry etching can damage thin oxide and nitride layers. Therefore, when thin oxide or nitride layers are present, wet etching is often used to transfer patterns onto the substrate. Wet etching of titanium nitride (TiN) is performed at a mild temperature (50-70°C) in an SC1 cleaning solution, which is an aqueous solution of ammonium hydroxide and hydrogen peroxide. One problem with this wet etching is that, due to the weak adhesion between the SOC layer and TiN, the TiN in the protected area suffers undesirable undercutting by the SOC layer. As feature sizes continue to shrink, this undesirable etching becomes increasingly problematic.

[0008] Existing SOCs formed from polyamic acid are also insoluble in the common solvent PGMEA, which is used in photoresists, hard masks, and other SOC solutions. Due to this insolubility, existing SOCs may precipitate in coating equipment, leading to blockages in spin coater drain lines and / or sedimentation in waste tanks. Summary of the Invention

[0009] In one embodiment, this disclosure broadly relates to a method of forming a microelectronic structure. The method includes optionally forming one or more intermediate layers on a substrate surface. If one or more intermediate layers are present, a topmost intermediate layer is formed on the substrate surface. If a topmost intermediate layer is present, a composition is applied onto the topmost intermediate layer; if no intermediate layer is present, the composition is applied to the substrate surface. The composition comprises one or both of diimides or polyimides dissolved or dispersed in a solvent system. The composition is heated to form a carbon-rich layer that exhibits less than about 0.1 defects / cm upon CVD viability testing. 2 The surface area characteristics of the layer. The CVD viability test used to determine the presence of this characteristic involves forming a SiOx or SiNx layer on a carbon-rich layer by plasma-enhanced chemical vapor deposition (PECVD) in a vacuum at a temperature of approximately 400°C, and observing defects in the SiOx or SiNx layer.

[0010] In another embodiment, a method for forming a microelectronic structure is disclosed, wherein one or more intermediate layers are optionally formed on a substrate surface, and if one or more intermediate layers are present, a topmost intermediate layer is formed on the substrate surface. If a topmost intermediate layer is present, a composition is applied to the topmost intermediate layer; if no intermediate layer is present, the composition is applied to the substrate surface. The composition comprises one or both of diimide or polyimide dissolved or dispersed in a solvent system. The composition is heated to form a carbon-rich layer with SC1 resistance.

[0011] In another embodiment, a method for forming a microelectronic structure is provided, wherein the method includes optionally forming one or more intermediate layers on a substrate surface. If one or more intermediate layers are present, a topmost intermediate layer is formed on the substrate surface. If a topmost intermediate layer is present, a composition is applied to the topmost intermediate layer; if no intermediate layer is present, the composition is applied to the substrate surface. The composition comprises a component dissolved or dispersed in a solvent system and one or both of diimides or polyimides. The component is selected from: polyphenols containing at least four phenolic rings, polyhydroxy compounds, phosphorus compounds, and combinations thereof. The composition is heated to form a carbon-rich layer.

[0012] In another embodiment, the present invention provides a method for forming a microelectronic structure, wherein the method includes imidizing one or both of a diamic acid or a polyamic acid in a solvent system containing propylene glycol monomethyl ether, thereby forming a composition containing one or both of a diimide or a polyimide. Optionally, one or more intermediate layers are formed on a substrate surface, wherein if one or more intermediate layers are present, an uppermost intermediate layer is formed on the substrate surface. The composition is applied to the uppermost intermediate layer (if present) or to the substrate surface (if no intermediate layer is present) without removing any propylene glycol monomethyl ether. The composition is heated to form a carbon-rich layer.

[0013] The present invention also provides a method for forming a microelectronic structure, wherein the method includes optionally forming one or more intermediate layers on a substrate surface, wherein if one or more intermediate layers are present, a topmost intermediate layer is formed on the substrate surface. If a topmost intermediate layer is present, a composition is applied to the topmost intermediate layer; if no intermediate layer is present, the composition is applied to the substrate surface. The composition comprises a polyimide dissolved or dispersed in a solvent system having a weight-average molecular weight of about 2,000 Daltons to about 7,000 Daltons. The composition is heated to form a carbon-rich layer.

[0014] In another embodiment, a composition is provided comprising:

[0015] diimide

[0016] Selected from the following components:

[0017] Polyphenols containing at least four phenolic rings;

[0018] Polyhydroxy compounds;

[0019] Phosphorus compounds; and

[0020] The combination of the above components; and

[0021] Solvent system.

[0022] In another embodiment, a microelectronic structure is provided comprising a microelectronic substrate having a surface. Optionally, one or more intermediate layers are provided on the surface of the substrate, and if one or more intermediate layers are present, a topmost intermediate layer is present on the surface of the substrate. A composition layer is placed on the topmost intermediate layer (if present) or on the surface of the substrate (if no intermediate layer is present). The composition comprises:

[0023] One or both of diimide or polyimide;

[0024] Selected from the following components:

[0025] Polyphenols containing at least four phenolic rings;

[0026] Polyhydroxy compounds;

[0027] Phosphorus compounds; and

[0028] The combination of the above components; and

[0029] Solvent system.

[0030] In another embodiment, the present invention provides a microelectronic structure comprising:

[0031] A microelectronic substrate having a surface. Optionally, one or more intermediate layers are present on the surface of the substrate, and if one or more intermediate layers are present, an uppermost intermediate layer is present on the surface of the substrate. A carbon-rich layer is on the uppermost intermediate layer (if present), or on the surface of the substrate (if no intermediate layer is present). The carbon-rich layer comprises:

[0032] One or both of cross-linked diimide or cross-linked polyimide; and

[0033] Selected from the following components:

[0034] Polyphenols containing at least four phenolic rings;

[0035] Polyhydroxy compounds;

[0036] Phosphorus compounds; and

[0037] The combination of the above components.

[0038] Brief description of the attached figures

[0039] Figure 1 These are optical microscope images (500x on the left and 2000x on the right), showing examples of CVD viability test results;

[0040] Figure 2 This is a test flowchart illustrating an exemplary SC1 resistance test process;

[0041] Figure 3 The image is a scanning electron microscope ("SEM") image (200kx) of the chip coated with the formulation of Example 2 as described in Example 3;

[0042] Figure 4 The image is a SEM image (200kx) of the chip coated with the formulation of Example 2 as described in Example 3;

[0043] Figure 5 The image is a SEM image (200kx) of the chip coated with the formulation of Example 2 as described in Example 3;

[0044] Figure 6 These are SEM images of the chip coated with the formulation of Example 4 as described in Example 5;

[0045] Figure 7 These are SEM images of the chip coated with the formulation of Example 4 as described in Example 5;

[0046] Figure 8 These are SEM images of the chip coated with the formulation of Example 4 as described in Example 5;

[0047] Figure 9 These are SEM images of the chip coated with the formulation of Example 6 as described in Example 7;

[0048] Figure 10 These are SEM images of the chip coated with the formulation of Example 6 as described in Example 7;

[0049] Figure 11 These are SEM images of the chip coated with the formulation of Example 6 as described in Example 7;

[0050] Figure 12 The image is a SEM image (100kx) of the chip coated with the formulation of Example 8 as described in Example 9;

[0051] Figure 13 The image is a SEM image (200kx) of the chip coated with the formulation of Example 8 as described in Example 9;

[0052] Figure 14 The image is a SEM image (200kx) of the chip coated with the formulation of Example 8 as described in Example 9;

[0053] Figure 15 The image shows a SEM image (200kx) of a chip coated with the formulation of Example 20 as described in Example 23.

[0054] Figure 16The image is a SEM image (200kx) of the chip coated with the formulation of Example 21 as described in Example 23;

[0055] Figure 17 The image is a SEM image (200kx) of the chip coated with the formulation of Example 22 as described in Example 23;

[0056] Figure 18 The image is a SEM image (200kx) of the chip coated with the formulation of Example 12 as described in Example 23;

[0057] Figure 19 The image is a SEM image (200kx) of the chip coated with the control formulation as described in Example 28.

[0058] Figure 20 The image shows a SEM image (200kx) of the chip coated with the formulation of Example 24 as described in Example 28.

[0059] Figure 21 The image shows a SEM image (200kx) of a chip coated with the formulation of Example 25 as described in Example 28.

[0060] Figure 22 SEM image (200kx) of the chip coated with the formulation of Example 26 as described in Example 28; and

[0061] Figure 23 The image shows a SEM image (200kx) of the chip coated with the formulation of Example 27 as described in Example 28. Detailed Implementation

[0062] This disclosure broadly relates to high-temperature stable spin-coated carbon compositions particularly suitable for multilayer lithography applications, as well as methods of using these compositions and the resulting structures.

[0063] Composition

[0064] These compositions typically contain diimide and / or polyimide dispersed or dissolved in a solvent system, as well as one or more optional components, depending on the implementation method.

[0065] 1. Polyimide

[0066] In one embodiment, commercially available polyimides can be used. In another embodiment, polyimides can be synthesized by imidizing polyamic acid in solution. The polyamic acid can be a commercially available polyamic acid or it can be synthetic, for example, by reacting one or more dianhydrides with one or more diamines in a suitable reaction solvent system, which may include only one solvent or multiple solvents.

[0067] In embodiments of the synthesis of polyamic acid, suitable dianhydrides comprise an aromatic moiety, and preferred aromatic dianhydrides have a flexible structure. As used herein, "flexible structure" refers to a structure with aliphatic linkages that allow for bond rotation and bending within the structure. Examples of such dianhydrides include those selected from benzophenone-3,3',4,4'-tetracarboxylic dianhydride ("BTDA"), 4,4'-biphthalic dianhydride, 4,4'-oxobisphthalic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride ("FDAH"), and combinations thereof.

[0068] Diamines suitable for polyamic acid synthesis contain an aromatic moiety, and preferred aromatic diamines have a flexible structure. Examples of such diamines include those selected from 4,4'-oxodiphenylamine ("ODA"), bis(4-aminophenyl) sulfone, 9,9-bis(4-aminophenyl)fluorene ("FDA"), and combinations thereof.

[0069] Polymerization can be carried out in any suitable reaction solvent system, examples of which are selected from dimethylformamide ("DMF"), dimethylacetamide ("DMAC"), N-methyl-2-pyrrolidone ("NMP"), γ-butyrolactone ("GBL"), propylene glycol monomethyl ether acetate ("PGMEA"), propylene glycol monomethyl ether ("PGME"), propylene glycol ethyl ether ("PGEE"), cyclopentanone, and combinations thereof. In one embodiment, a processing-friendly (fab-friendly) solvent such as PGMEA, PGME, and / or PGEE is used. In another embodiment, the reaction or polymerization solvent system consists essentially of or even entirely of PGMEA, PGME, and / or PGEE. In yet another embodiment, the solvent system is essentially free of DMF, DMAC, NMP, and / or GBL. In other words, the solvent system contains less than about 5%, preferably less than about 1%, more preferably about 0% of one or more of DMF, DMAC, NMP and / or GBL, or even more preferably a combination of less than about 5%, preferably less than about 1%, more preferably about 0% of DMF, DMAC, NMP and / or GBL.

[0070] In embodiments where it is desired to obtain polyamic acid having amino-terminal groups (or at least primarily amino-terminal groups), the ratio of dianhydride to diamine used is preferably from about 1:3 to about 4:5, more preferably from about 1:3 to about 2:3. In embodiments where it is desired to obtain polyamic acid having anhydride-terminal groups (or at least primarily anhydride-terminal groups), the ratio of dianhydride to diamine is preferably from about 4:3 to about 14:3, more preferably from about 5:3 to about 10:3. In any embodiment, the weight-average molecular weight of the polyamic acid, as determined by GPC, is preferably from about 500 Daltons to about 9,000 Daltons, more preferably from about 2,000 Daltons to about 7,000 Daltons.

[0071] Based on the total weight of the reaction system, the amounts of dianhydride and diamine monomer dissolved or dispersed in the reaction solvent are preferably from about 5% to about 20% by weight, more preferably from about 7% to about 15% by weight, and most preferably from about 10% by weight. The polycondensation reaction is carried out under nitrogen atmosphere with stirring at a temperature of about 10°C to about 40°C, preferably from about 20°C to about 30°C, for a time of about 12 hours to about 36 hours, preferably from about 16 hours to about 24 hours.

[0072] Next, the polyamic acid is preferably end-capped, which can extend the shelf life of the final polyimide, improve spin bowl compatibility, and increase thermal stability by introducing crosslinkable groups. In embodiments where the polyamic acid is amino-terminated, the end-capping agent is preferably an acid anhydride, such as selected from acetic anhydride, phthalic anhydride ("PTA"), succinic anhydride, trimellitic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 4-ethynylphthalic anhydride ("EPA"), 4-methylethynylphthalic anhydride ("MEPA"), 4-phenylethynylphthalic anhydride ("PEPA"), and combinations thereof.

[0073] In embodiments where polyamic acid is capped with an anhydride group, the capping agent is preferably a compound containing an amino group, such as aniline. Particularly preferred are compounds containing an aniline moiety, selected from 2,5-dimethoxyaniline, 3,5-dimethoxyaniline, 3,4,5-trimethoxyaniline, 5-amino-1-naphthol, 4'-aminoacetophenone, 1-aminoanthraquinone, 3-ethynylaniline, 4-ethynylaniline, 2-ethynylaniline, and combinations thereof.

[0074] The molar ratio of the capping agent to the major terminal group (i.e., anhydride capping agent to terminal amino group, or amino capping agent to terminal anhydride group) depends on the initial molar ratio of the dianhydride to the diamine, and is chosen such that the capping agent reacts completely (or at least substantially completely) with the terminal group. For anhydride capping agents, the molar ratio can be calculated as follows:

[0075] E / B = 2(1 - A / B)

[0076] Where A is the molar number of dianhydride, B is the molar number of diamine, and E is the molar number of anhydride capping agent. For example, if the initial molar ratio of dianhydride (A) to diamine (B) is approximately 2:5, then the molar ratio of anhydride capping agent (E) to diamine (B) is chosen to be approximately 6:5; or if the initial molar ratio of dianhydride (A) to diamine (B) is approximately 3:5, then the molar ratio of anhydride capping agent (E) to diamine (B) is chosen to be approximately 4:5.

[0077] Similarly, for amino-terminated agents, the molar ratio can be calculated as follows:

[0078] F / A = 2(1 - B / A)

[0079] Where A is the molar number of dianhydrides, B is the molar number of diamines, and F is the molar number of amino-capping agents. (The coefficient "2" is needed because the monomer is a bifunctional acid anhydride and a bifunctional amine, while the capping agent is a monofunctional acid anhydride or a monofunctional amine.)

[0080] Regardless of the type of capping agent chosen, the capping reaction is carried out under nitrogen atmosphere with stirring at a temperature of about 10°C to about 40°C, preferably about 20°C to about 30°C, for about 12 hours to about 36 hours, more preferably about 16 hours to 24 hours.

[0081] The polyamic acid is then converted to a polyimide by imidization of the polymer or the end-capped polymer (depending on whether end-capping is used) via a dehydration reaction. Since the dehydration / hydrolysis reaction is reversible, it is desirable to remove water by azeotropic distillation to achieve complete imidization. Water removal advances the equilibrium to achieve complete imidization. A solvent capable of azeotropic distillation with water, such as toluene or xylene, is then added to the reaction mixture in an amount of about 10% to about 40% by weight, preferably about 20% to about 30% by weight, based on 100% of the total weight of the reaction mixture. The mixture is heated in an inert atmosphere, such as nitrogen, at a temperature of about 150°C to about 200°C, preferably about 170°C to about 190°C, more preferably about 180°C. The distillation solvent (e.g., toluene, xylene) is distilled out along with the water and is condensed and collected, for example, in a DeanStark collector. The water then separates from the distillation solvent and settles to the bottom of the collector, while the distillation solvent flows back into the reaction vessel. The imidization is carried out for about 4 to about 24 hours, preferably about 8 to about 16 hours, or until the water collection stops.

[0082] The crude polyimide solution is then cooled to room temperature. In one embodiment, the polyimide precipitates from the reaction solution, preferably in methanol or a methanol / acetone mixture at a weight ratio of about 1:5. The precipitated polyimide is filtered and washed, preferably with methanol, acetone, or a combination thereof. The resulting polyimide can be air-dried or dried under vacuum, preferably at a temperature of about 60°C for about 10 hours to about 24 hours.

[0083] In another embodiment, the polyimide does not precipitate from the reaction solution. That is, advantageously, when using the processing-friendly solvents discussed above as the reaction solvent system, the crude polyimide solution can be used as is without the need for additional precipitation.

[0084] In one embodiment, the weight-average molecular weight of the resulting polyimide, as determined by GPC, is from about 500 Daltons to about 9,000 Daltons, preferably from about 2,000 Daltons to about 7,000 Daltons. In another embodiment, the weight-average molecular weight of the resulting polyimide, as determined by GPC, is from about 450 Daltons to about 8,100 Daltons, preferably from about 1,800 Daltons to about 6,300 Daltons.

[0085] 2. Diimide

[0086] In one embodiment, a commercially available diimide can be used. In another embodiment, the diimide can be synthesized by imidizing a diamic acid in solution. The diamic acid can be a commercially available diamic acid or it can be synthetic, for example, by reacting one or more dianhydrides with one or more monoamines, or by reacting one or more monohydrides with one or more diamines, in a suitable reaction solvent system, which may include only one solvent or multiple solvents.

[0087] In one embodiment of the synthesis of diamic acid, one or more dianhydrides and one or more monoamines (preferably crosslinkable) are reacted in a solvent system. Suitable dianhydrides include those selected from benzophenone-3,3',4,4'-tetracarboxylic acid dianhydride, 4,4'-oxobisphthalic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride and combinations thereof. Suitable monoamines are preferably crosslinkable and include those selected from 2-vinylaniline, 4-vinylaniline, 2-allylaniline, 4-allylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-ethynylaniline and combinations thereof. Suitable reaction solvents include those discussed in the previous polyimide embodiments, preferably processing-friendly solvents such as PGMEA, PGME, and / or PGEE. The molar ratio of the crosslinkable monoamine compound to the dianhydride is preferably from about 2:1 to about 2.2:1, more preferably from about 2:1 to about 2.1:1.

[0088] In another embodiment of the synthesis of diamic acid, diamic acid is formed by reacting one or more diamines and one or more monohydric anhydrides in a solvent system. Suitable diamines include those selected from 4,4'-oxodiphenylamine, bis(4-aminophenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, and combinations thereof. Suitable monohydric anhydrides are preferably crosslinkable and include those selected from maleic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 4-ethynylphthalic anhydride ("EPA"), 4-methylethynylphthalic anhydride ("MEPA"), 4-phenylethynylphthalic anhydride ("PEPA"), and combinations thereof. Similarly, suitable reaction solvents include those discussed in the previous polyimide embodiments, preferably, for example, processing-friendly solvents such as PGMEA or PGME. The molar ratio of the monohydric anhydride compound to the diamine is preferably from about 2:1 to about 2.2:1, more preferably from about 2:1 to about 2.1:1.

[0089] In one embodiment, the reaction solvent system is substantially composed of or even entirely of PGMEA, PGME, and / or PGEE. In another embodiment, the solvent system is substantially free of DMF, DMAC, NMP, and / or GBL. In other words, the solvent system contains less than about 5% by weight, preferably less than about 1% by weight, and more preferably about 0% by weight of one or more of DMF, DMAC, NMP, and / or GBL. Additionally or alternatively, the total weight of DMF, DMAC, NMP, and GBL in the solvent system is less than about 5% by weight, preferably less than about 1% by weight, and more preferably about 0% by weight.

[0090] In any case, the reaction proceeds similarly to the reaction described above for the polyimide embodiment, but with several differences as described below. The reaction is also carried out under nitrogen atmosphere with stirring, preferably at a temperature of about 10°C to about 50°C, more preferably about 20°C to about 40°C, for about 12 hours to about 36 hours, more preferably about 16 to 24 hours.

[0091] Next, the diamic acid is converted to a diimide via a dehydration reaction, thereby imidizing it. Since the dehydration / hydrolysis reaction is reversible, azeotropic distillation is preferred to remove water for complete imidization. Water removal advances the equilibrium to achieve complete imidization. In one embodiment, a solvent capable of azeotropic distillation with water, such as toluene or xylene, is added to the reaction mixture in an amount from about 10% to about 40% by weight, preferably from about 20% to about 30% by weight, based on the total weight of the reaction mixture. The mixture is heated in an inert atmosphere, such as nitrogen, at a temperature from about 100°C to about 200°C, preferably from about 130°C to about 180°C. The distillation solvent (e.g., toluene, xylene) is distilled off along with the water and condensed and collected, for example, in a Dean Stark collector. The water then separates from the distillation solvent and settles to the bottom of the collector, while the distillation solvent flows back into the reaction vessel. In another embodiment, due to the rapid kinetics of the imidization reaction, distillation of the solvent is not required. The imidization is carried out for about 4 hours to about 24 hours, preferably about 8 hours to about 16 hours, or until the water collection stops.

[0092] The crude diimide solution is then cooled to room temperature and precipitated from the reaction solution. Precipitation is preferably carried out in deionized water or hexane at a weight ratio of approximately 1:5. The precipitated diimide is filtered and washed, preferably with water, hexane, or a combination thereof. The resulting polyimide can be air-dried or dried under vacuum, preferably at a temperature of approximately 60°C for approximately 10 hours to approximately 24 hours.

[0093] In another embodiment, the diimide does not precipitate from the reaction solution. That is, advantageously, when a processing-friendly solvent is used as the reaction solvent system, the crude polyimide solution can be used as is without the need for additional precipitation.

[0094] Regardless of the implementation method, the weight-average molecular weight of the formed diimide is preferably less than about 1,000 Daltons, more preferably about 500 Daltons to about 1,000 Daltons, and even more preferably about 600 Daltons to about 800 Daltons.

[0095] 3. Composition formulation

[0096] In embodiments involving polyimides and diimides, the compositions of the present invention comprise the polyimides and / or diimides dispersed or dissolved in a solvent system as described above. In any embodiment, each composition may individually comprise optional components, such as those selected from crosslinking agents, surfactants, polymers, catalysts, additives, and mixtures thereof.

[0097] In each of the above compositions, the amount of polyimide and / or diimide present in the specific composition is preferably about 2% to about 50% by weight, more preferably about 3% to about 30% by weight, and even more preferably about 5% to about 10% by weight, based on the total weight of the composition as 100%.

[0098] In one embodiment, the composition may contain one or more additives. A suitable additive is selected from polyphenols, particularly polyphenols containing four, five, six or more phenolic rings. In one embodiment, the polyphenol contains at least two unsubstituted phenolic rings.

[0099] Some preferred polyphenols are those disclosed in US 2021 / 0040290, which is incorporated herein by reference, and those supplied by Mitsubishi Gas Chemical Corporation under the trade names NeoFARIT 7177C and 7177D ("NF7177C" and "NF7177D"). A particularly preferred polyphenol includes:

[0100]

[0101] Where n is 5. In the above structure, the repeating unit is shown to be bonded to carbon α. ​​In some embodiments, the repeating unit may be bonded to carbon α' instead of α. In other embodiments, both carbon α and carbon α' may include repeating units, each n independently selected from 1 to 5.

[0102] Another suitable additive includes hydroxyl compounds, particularly polyhydroxyl compounds. In one embodiment, a preferred hydroxyl compound has three or more hydroxyl groups, more preferably three to six hydroxyl groups. In another embodiment, the hydroxyl compound comprises an aromatic moiety (e.g., a benzene ring) substituted with a hydroxyl group. Examples of suitable hydroxyl compounds include those selected from gallic acid, methyl gallate, 4-hydroxybenzoic acid, 1,2-dihydroxybenzene, pyrogallol, 2,3,4,3',4',5'-hexahydroxybenzophenone ["6HBP"], 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol [TMOM-BP], poly(4-vinylphenol), and combinations thereof.

[0103] Phosphorus compounds are another type of additive that can be used in some embodiments of the compositions of the present invention. Preferred phosphorus compounds include phosphine, phosphine oxide, phosphonate, and / or phosphate groups. Examples of suitable phosphorus compounds include those selected from: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, dimethyl phenylphosphonate, phenyl phosphate, phenylphosphonic acid, phytic acid, and combinations thereof.

[0104] With the total solid weight as 100%, the level at which each of the included additives is present individually in the specific composition is preferably from about 0.5% to about 10% of solid weight, more preferably from about 1% to about 3% of solid weight. Alternatively or additionally, the total weight of all present additive combinations preferably falls within the above range.

[0105] In some embodiments, surfactants may be included in the composition to improve coating quality. Particularly preferred are nonionic surfactants such as R30N (DIC Corporation, Japan) and FS3100 (The Chemours Company FC, LLC, USA). The surfactant is preferably present in a particular composition at about 0.05% to about 0.5% by weight of solids, more preferably about 0.1% to about 0.3% by weight of solids, based on 100% of the total solids.

[0106] The aforementioned components (polyimide and / or diimide, and any additives and / or surfactants) are mixed in a solvent system to form a specific composition. Preferred solvent systems include those selected from cyclopentanone, cyclohexanone, or PGMEA, PGME, PGEE, ethyl lactate, GBL, and mixtures thereof. With the total weight of the composition being 100%, the solvent system used is preferably about 50% to about 98% by weight, more preferably about 60% to about 95% by weight, and even more preferably about 85% to about 95% by weight. It should be understood that when the reaction solvent is also the formulation solvent (such as PGME, PGMEA, or PGEE), further separation or precipitation may not be required after synthesis. That is, no solvent removal is required (thus avoiding the need for removal of, for example, NMP, as in the prior art) or removal of the polymer from the solvent. With the total weight of the composition being 100% by weight, the composition can be simply further diluted with a desired solvent to achieve a final solvent content of about 50% to about 98% by weight, preferably about 85% to about 95% by weight, with the total solids range being the aforementioned balance, so that the composition reaches 100% by weight. The material is preferably filtered before use, such as with a 0.1μm or 0.2μm PTFE filter.

[0107] In one embodiment, the composition consists essentially of, or even entirely of, polyimide and / or diimide dispersed or dissolved in a solvent system. In another embodiment, the composition consists essentially of, or even entirely of, polyimide and / or diimide dispersed or dissolved in a solvent system, and one, two, three, four, or all five of a crosslinking agent, surfactant, polymer, catalyst, and / or additive.

[0108] Using the composition method

[0109] More specifically, the present invention provides a method for forming microelectronic structures particularly suitable for photolithography. In the method of the present invention, a substrate having a surface is provided. Any microelectronic substrate can be used. The substrate is preferably a semiconductor substrate, such as silicon, SiGe, SiO2, Si3N4, SiON, aluminum, tungsten, tungsten silicide, gallium arsenide, germanium, tantalum, tantalum nitride, Ti3N4, hafnium, HfO2, ruthenium, indium phosphide, a combination of tetramethylsilicate and tetramethylcyclotetrasiloxane (as sold under the name CORAL), SiCOH (as sold under the name Black Diamond by SVM of Santa Clara, California, USA), glass, or mixtures thereof. An optional intermediate layer can be formed on the substrate prior to processing, one particularly preferred intermediate layer being TiN. The substrate can be planar or may include morphological features (vias, trenches, contact holes, protrusions, lines, etc.). As used herein, "morphology" refers to the height or depth of a structure within or on the surface of the substrate.

[0110] The SOC composition layer of the present invention is formed on a substrate or any intermediate layer. The SOC layer can be formed by any known application method, a preferred method being spin coating at a speed of about 1,000 rpm to about 2,000 rpm, preferably about 1,200 rpm to about 1,500 rpm, for a duration of about 30 seconds to about 90 seconds, preferably about 45 seconds to 60 seconds. Preferably, the composition of the present invention has good spin cup compatibility, i.e., it does not react or form precipitates with common photoresist solvents such as PGME, PGMEA, ethyl lactate, cyclohexanone, or combinations thereof.

[0111] After applying the carbon-rich composition, it is preferably heated to about 100°C to about 250°C, more preferably about 170°C to about 230°C, for about 30 seconds to about 90 seconds, more preferably about 45 seconds to about 60 seconds, to evaporate the solvent. Advantageously, the SOC composition exhibits rapid thermal reflux. That is, at temperatures above about 200°C, the viscosity of the composition, as measured by a rheometer, is less than about 10 cP.

[0112] The average thickness of the baked SOC or carbon-rich layer is preferably from about 50 nm to about 2.5 μm, more preferably from about 80 nm to about 150 nm, and even more preferably from about 100 nm to about 120 nm. The average thickness is determined by averaging thickness measurements at five different locations on the SOC layer, which are obtained using an ellipsometry.

[0113] After baking, the formed SOC layer, with the weight of the baked layer as 100%, preferably comprises more than about 75% by weight of carbon, more preferably more than about 80% by weight of carbon, and even more preferably about 85% to about 90% by weight of carbon. The SOC layer preferably exhibits high-temperature stability, with almost no thermal decomposition below about 500°C. For example, as measured using thermogravimetric analysis, the SOC layer described herein exhibits less than about 10% weight loss when heated to about 400°C for about 10 minutes, and even more preferably, less than about 10% weight loss when heated to about 500°C for about 10 minutes.

[0114] Furthermore, the SOC layer contains most of the additives included in the SOC composition that forms the layer. That is, the baked SOC layer will retain at least about 50% by weight, preferably at least about 80% by weight, more preferably at least about 90% by weight, and even more preferably at least about 95% by weight of the initial additive dose.

[0115] In one embodiment, taking the total weight of the layer as 100%, the final SOC layer will contain about 0.25% to about 9.5% by weight, preferably about 0.4% to about 8% by weight, more preferably about 0.6% to about 5% by weight, and even more preferably about 0.8% to about 2.5% of one or more of the previously described additives. Alternatively or additionally, the total weight of the combination of all additives present in the final layer is preferably within the above range.

[0116] The SOC layer preferably exhibits little or no shrinkage. That is, after being heated to about 400°C for about 10 minutes, the average thickness decreases by less than about 5%, and even more preferably, after being heated to about 500°C for about 10 minutes, the thickness decreases by less than about 5%. In some cases, the shrinkage of the SOC layer may be negative, i.e., the thickness of the layer increases under the aforementioned baking conditions, indicating expansion of the SOC layer. (In these cases, it is presumed that the SOC layer may become less dense after high-temperature baking, resulting in minimal weight loss and slight film expansion.) In one embodiment, the SOC layer has good resistance to SC1 because it is unaffected by exposure to SC1 cleaning solution at around 60°C for more than 30 minutes.

[0117] A hard mask layer can be applied adjacent to the SOC layer or any intermediate layer that may exist on the SOC layer. The hard mask layer can be formed by any known application method, such as chemical vapor deposition ("CVD") or plasma-enhanced chemical vapor deposition ("PECVD"). Another preferred method involves spin coating at a speed of about 1,000 rpm to about 5,000 rpm, preferably about 1,250 rpm to about 1,750 rpm, for a time of about 30 seconds to about 120 seconds, preferably about 45 seconds to about 75 seconds. A suitable hard mask layer should have a high etch deviation relative to the underlying layer. Based on the total weight of the mask layer, a preferred hard mask layer has a high silicon content material, preferably at least about 30% by weight silicon, more preferably about 35% by weight silicon to about 40% by weight silicon. Suitable hard mask layers are commercially available and can be formed from compositions comprising polymers or oligomers (e.g., silanes, siloxanes, silsesquioxanes, silicon oxynitride, silicon nitride, polycrystalline silicon, amorphous silicon, and combinations thereof) dissolved or dispersed in a solvent system. Some preferred monomers or polymers for hard mask layers are selected from the group consisting of phenethyltrimethoxysilane ("PETMS"), 2-(carbonmethoxy)ethyltrimethoxysilane ("CMETMS"), tetraethoxysilane ("TEOS"), methyltrimethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane ("MTMS"), ethyltrimethoxysilane ("ETMS"), (3-glycidyloxypropyl)triethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane ("ECHTMS"), and mixtures thereof. Any optional components (such as surfactants, acid catalysts, base catalysts, and / or crosslinking agents) are dissolved together with the polymer, monomers, and / or oligomers in the solvent system. Based on a total weight of 100% of the composition, the preferred hard mask composition preferably has a solid content of about 0.1% to about 70%, more preferably about 0.5% to about 10%, and even more preferably about 0.5% to about 1%.

[0118] After applying the hard mask composition, it is preferably heated to a temperature of about 100°C to about 300°C, more preferably about 150°C to about 250°C, for about 30 seconds to about 120 seconds, more preferably about 45 seconds to about 60 seconds, to evaporate the solvent. The average thickness of the hard mask layer after baking (measured by elliptic polarization at five locations and averaged) is preferably about 5 nm to about 50,000 nm, more preferably about 5 nm to about 1,000 nm, and even more preferably about 10 nm to about 30 nm.

[0119] Advantageously, the SOC layer of the present invention can withstand harsh CVD processes, such as those used to apply the aforementioned hard mask layer onto the SOC layer. To determine whether the SOC layer can survive in typical CVD semiconductor manufacturing processes, a "CVD viability test" is performed by coating a chip with a specific morphology (preferably a chip with various morphological features, including but not limited to 50 nm lines / spacing, loosely spaced features, large features, 50-μm lines with a large pitch of about 50 μm and / or contact holes / vias with a depth of 100 nm or 200 nm) with the SOC composition to be tested, then baking it on a hot plate at 170°C for about 1 minute, and then baking it in an oven in a N2 atmosphere at about 450°C for about 4 minutes to form a cured SOC layer with an average thickness of about 180 nm. Then, a SiOx or SiNx test film is deposited on the coated chip using PECVD at a high vacuum of about 400°C. After PECVD deposition, the chip is observed using an optical microscope. Failure or success is determined by the number of defects (bubbles, delamination, wrinkles, and / or cracks) appearing in the CVD-deposited film. Films that successfully pass the CVD viability test have fewer than approximately 0.1 defects / cm² when observed under an optical microscope. 2 CVD thin films (i.e., fewer than about 15 defects per 8-inch wafer), preferably fewer than about 0.05 defects / cm. 2 CVD thin films (i.e., fewer than about 7.5 defects per 8-inch wafer), more preferably about 0 defects / cm 2 CVD thin films. Figure 1 Examples of failed and passed CVD viability tests are shown. A SOC or carbon-rich composition or layer exhibiting CVD viability characteristics with at least one SiOx or SiNx test film within these parameter ranges is considered to have CVD viability. In a particularly preferred embodiment, the SOC layer exhibits CVD viability when tested with both SiOx and SiNx test films.

[0120] The photoresist (i.e., the imaging layer) can then be applied to the SOC or any intermediate layer to form a photoresist layer. The photoresist layer can be formed by any conventional method, one preferred method being spin-coating the photoresist composition at a speed of about 350 rpm to about 4000 rpm (preferably about 1000 rpm to about 2500 rpm) for a duration of about 10 seconds to about 60 seconds (preferably about 10 seconds to about 30 seconds). Then, optionally, the photoresist layer is subjected to a post-application bake ("PAB") at a temperature of at least about 70°C, preferably about 80°C to about 150°C, more preferably about 100°C to about 150°C, for a duration of about 30 seconds to about 120 seconds. The average thickness of the baked photoresist layer (as described above) is typically about 5 nm to about 120 nm, preferably about 10 nm to about 50 nm, more preferably about 20 nm to about 40 nm.

[0121] The photoresist layer was then exposed to a dose of approximately 10 mJ / cm 2 Approximately 200 mJ / cm 2 The preferred value is approximately 15 mJ / cm. 2 Approximately 100 mJ / cm 2 More preferably about 20 mJ / cm 2 Approximately 50 mJ / cm 2 Patterning is performed under radiation. More specifically, the photoresist layer is exposed using a mask positioned above its surface. The mask has regions designed to allow radiation to be reflected from or pass through the mask and to contact the surface of the photoresist layer. The remainder of the mask is designed to absorb light to prevent radiation from contacting the surface of the photoresist layer in certain areas. It will be readily understood by those skilled in the art that the arrangement of the reflective and absorbing portions is designed according to the desired pattern formed on the photoresist layer and ultimately on the substrate or any intermediate layer.

[0122] After exposure, the photoresist layer is subjected to post-exposure baking ("PEB") at a temperature below about 180°C, preferably about 60°C to about 140°C, more preferably about 80°C to about 130°C, for a duration of about 30 seconds to about 120 seconds (preferably about 30 seconds to about 90 seconds).

[0123] The photoresist layer is then brought into contact with a developer to form a pattern. Depending on whether the photoresist used is positive-working or negative-working, the developer will remove either the exposed or unexposed portions of the photoresist layer to form the pattern. The pattern is then transferred through the layers and finally onto the substrate. This pattern transfer can be performed using plasma etching (such as CF4 etchant, O2 etchant) or wet etching or development processes.

[0124] In one embodiment, once the layer of the present invention is patterned, SC1 etching can be used to open a metal layer (such as TiN) that serves as another hard mask, thereby further transferring the pattern into the substrate. The SOC layer of the present invention will exhibit little or no undercut, meaning it will protect the metal layer from dissolution where the SOC layer is present.

[0125] The "SC1 resistance test" was performed by spin-coating a 180 nm thick carbon-rich composition onto a TiN substrate, followed by baking on a hot plate at approximately 170 °C for about 1 minute, and then baking in an N2 atmosphere oven at approximately 450 °C for about 4 minutes. The layer was then etched back using O2 plasma to partially remove material from the depth of the intermediate trenches. The substrate was then immersed in an SC1 etch solution at approximately 60 °C for approximately 100 seconds. SEM (200 kx) cross-sectional analysis was performed to determine the undercut depth. Figure 2 The procedure for the SC1 test and the method for measuring the undercut depth are shown. Figure 2 The wafer in this example is an SC1 wafer, whose TiN ALD layer features 50 nm lines / spaces and a depth of 200 nm. Preferably, the undercut depth is less than about 60 nm, more preferably less than about 30 nm, and even more preferably from about 0.1 nm to about 20 nm. SOCs or carbon-rich compositions or layers exhibiting these parameter ranges are considered to have SC1 resistance.

[0126] Other advantages of the various embodiments will become apparent to those skilled in the art after reviewing the disclosure herein and the following working examples. It should be understood that, unless otherwise indicated herein, the various embodiments described herein are not necessarily mutually exclusive. For example, a feature described or depicted in one embodiment may be included in other embodiments, but is not necessarily required to be included in other embodiments. Therefore, the present invention encompasses various combinations and / or integrations of the specific embodiments described herein.

[0127] The term "and / or" as used herein, when used in a list of two or more items, means that any one of the listed items may be used alone, or any combination of two or more of the listed items may be used. For example, if a composition is described as containing or not containing components A, B and / or C, then the composition may contain or not contain: A only; B only; C only; a combination of A and B; a combination of A and C; a combination of B and C; or a combination of A, B and C.

[0128] This description also uses numerical ranges to quantify certain parameters relating to the various embodiments. It should be understood that when a numerical range is provided, the range should be interpreted as providing written support for claims that specify only the lower limit of the range and claims that specify only the upper limit of the range. For example, the disclosed numerical range of about 10 to about 100 provides written support for claims that specify "about greater than 10" (no upper limit) and claims that specify "about less than 100" (no lower limit).

[0129] Example

[0130] The following embodiments illustrate the method of the present invention. However, it should be understood that these embodiments are provided by way of illustration and should not be construed as limiting the overall scope of the present invention.

[0131] Example 1

[0132] 1. Synthesis of polyamic acid

[0133] In this embodiment, 12.866 g of 9,9-bis(4-aminophenyl)fluorene ("FDA", JFE, Japan) was dissolved in 115.741 g of N-methyl-2-pyrrolidone ("NMP", Sigma-Aldrich, St. Louis, Missouri) in a 500 ml round-bottom flask. 7.144 g of benzophenone-3,3',4,4'-tetracarboxylic dianhydride ("BTDA", Sigma-Aldrich, St. Louis, Missouri) was dissolved in 64.081 g of NMP, and this solution was added to a dropping funnel connected to the round-bottom flask. The system was purged with nitrogen for 10 minutes. Then, the BTDA solution was added dropwise to the FDA solution, and the mixture was magnetically stirred in nitrogen for 20 minutes. The reaction was allowed to proceed at room temperature with magnetic stirring in nitrogen for 32 hours.

[0134] 2. End-capping of polyamic acid

[0135] A solution of 3.443 g of phthalic anhydride ("PTA", Sigma-Aldrich, St. Louis, Missouri) dissolved in 31.033 g of NMP was added to the polyamic acid solution obtained in Part 1 above under nitrogen atmosphere and magnetically stirred. The reaction was carried out at room temperature under nitrogen atmosphere with magnetic stirring for 21 hours.

[0136] 3. Solution imidization of polyamic acid

[0137] 50 g of toluene (Sigma-Aldrich, St. Louis, Missouri) was added to the end-capped polyamic acid solution obtained in Part 2. A Dean-Stark collector was attached to the reaction flask. The oil bath in which the flask was immersed was heated to 180 °C. Azeotropic distillation of water-toluene was initiated when imidization began between 150 °C and 160 °C. The reaction was magnetically stirred under nitrogen at these temperatures for 8 hours, after which the system was cooled to room temperature.

[0138] Example 2

[0139] 1. Purification of polyimide

[0140] In this process, 20 g of the polyimide solution obtained in Example 1 was precipitated in 100 g of acetone (Sigma-Aldrich, St. Louis, Missouri). The precipitated polyimide was filtered, washed with acetone, and then air-dried. GPC analysis using polystyrene standards showed a single peak with Mw = 8637, Mn = 6229, and PDI = 1.39.

[0141] 2. Coating formulations

[0142] Next, 0.536 g of the polymer solid obtained in Part 1 was dissolved in 9.536 g of cyclopentanone (Sigma-Aldrich, St. Louis, Missouri). The solution was filtered through a 0.1 μm PTFE membrane filter (General Electric, UK).

[0143] Example 3

[0144] Flattening test

[0145] The solution prepared in Example 2 was spin-coated onto a chip containing lines of varying densities (220 nm CD, line / space ratios of 1:1, 1:2, or 1:5, 100 nm high feature) at 1,500 rpm for 60 seconds. The chip was then baked on a hot plate at 170°C for 1 minute and in an oven at 450°C for 4 minutes. The chip was examined using SEM. The results showed that the lines were well planarized (see...). Figure 3 (1:1 lines / spaces), 4 (1:2 lines / spaces) and 5 (1:5 lines / spaces)).

[0146] Example 4

[0147] 1. Synthesis of polyamic acid

[0148] In this embodiment, 6.33 g of FDA was dissolved in 56.11 g of NMP in a 500 ml round-bottom flask. 4.996 g of 9,9-bis(3,4-dicarboxyphenyl)fluorene dihydride (FDAH, JFE, Japan) was dissolved in 45.367 g of NMP, and this solution was added to a dropping funnel connected to the round-bottom flask. The system was purged with nitrogen for 10 minutes. Then, the FDAH solution was added dropwise to the FDA solution, and the mixture was magnetically stirred under nitrogen for 17 minutes. The reaction was allowed to proceed at room temperature with magnetic stirring under nitrogen for 19 hours.

[0149] 2. End-capping of polyamic acid

[0150] Under nitrogen atmosphere, 2.19 g of acetic anhydride (Sigma-Aldrich, St. Louis, Missouri) was added to the polyamic acid solution obtained in Part 1 with magnetic stirring. The reaction was carried out at room temperature with magnetic stirring under nitrogen atmosphere for 24 hours.

[0151] 3. Solution imidization of polyamic acid

[0152] 27.40 g of toluene was added to the capped polyamic acid solution. A Dean-Stark collector was connected to the reaction flask. The oil bath in which the flask was immersed was heated to 180 °C. Azeotropic distillation of water-toluene was initiated when imidization began between 150 °C and 160 °C. The reaction was carried out at these temperatures with magnetic stirring under nitrogen for 8 hours. The system was then cooled to room temperature.

[0153] 4. Purification of polyimide

[0154] Next, 100 g of the polyimide solution obtained in Part 3 was precipitated in 500 g of an acetone / methanol (50:50) mixture (Sigma-Aldrich, St. Louis, Missouri). The precipitated polyimide was filtered, washed with acetone / methanol (50:50), and then air-dried. GPC showed a single peak, Mw = 3772, Mn = 3145, PDI = 1.20.

[0155] 5. Coating formulations

[0156] To prepare the coating formulation, 1.021 g of the polymer solid obtained in Part 5 was dissolved in 15.585 g of cyclopentanone. 0.104 g of 1% R30N surfactant (DIC Corporation, Japan) was added. The solution was filtered through a 0.1 μm PTFE membrane filter.

[0157] Example 5

[0158] Flattening test

[0159] The solution prepared in Example 4 was spin-coated onto a chip containing lines of varying densities at 1,500 rpm for 60 seconds. The chip was then baked on a hot plate at 170°C for 1 minute and in an oven at 450°C for 4 minutes. The chip was examined using SEM. Figure 6-8 As shown, the results demonstrate good flattening. Figure 6 On the left side of the chip are lines of 50nm and spacing of 250nm, a 1.5μm spacing, and then lines of 50nm and spacing of 50nm. Figure 7 It is a more magnified image of the 1:1 region. Figure 8 The left side is a 1:1 region, and the right side is a 50μm oxide pad. There is a 500nm trench between the dense area and the pad.

[0160] Example 6

[0161] 1. Synthesis of polyamic acid

[0162] In this embodiment, 9.507 g of FDA was dissolved in 60.25 g of NMP in a 500 ml round-bottom flask. 5.002 g of FDAH was dissolved in 99.50 g of NMP, and this solution was added to a dropping funnel connected to the round-bottom flask. The system was purged with nitrogen for 10 minutes. Then, the FDAH solution was added dropwise to the FDA solution, and the mixture was magnetically stirred under nitrogen for 20 minutes. The reaction was allowed to proceed at room temperature with magnetic stirring under nitrogen for 24 hours.

[0163] 2. End-capping of polyamic acid

[0164] 8.136 g of 4-phenylethynyl phthalic anhydride ("PEPA", TCI, Portland, OR, USA) was added to the polyamic acid solution prepared in Part 1 above under nitrogen atmosphere, while magnetic stirring was performed. The reaction was carried out at room temperature under nitrogen atmosphere with magnetic stirring for 28 hours.

[0165] 3. Solution imidization of polyamic acid

[0166] Add 40.36 g of toluene to the polyamic acid solution obtained in Part 1 above. Connect the Dean-Stark collector to the reaction flask. Heat the oil bath into which the flask is immersed to 180 °C. Initiate azeotropic distillation of water-toluene when imidization begins between 150 °C and 160 °C. Stir the reaction magnetically under nitrogen at these temperatures for 8 hours, then cool the system to room temperature.

[0167] 4. Purification of polyimide

[0168] Next, the 100 g polyimide solution obtained in Part 3 above was precipitated in 500 g of methanol. The precipitated polyimide was filtered, washed with methanol, and then air-dried. GPC analysis showed Mw = 2567, Mn = 1716, and PDI = 1.49.

[0169] 5. Coating formulations

[0170] To prepare the coating formulation, 5.014 g of the polymer solid obtained in Part 4 was dissolved in 134.445 g of cyclopentanone. Next, 7.508 g of 2% NF7177C (for improving adhesion; Mitsubishi Gas Company; Japan) and 0.501 g of 1% R30N surfactant were added. The solution was filtered through a 0.1 μm PTFE membrane filter.

[0171] Example 7

[0172] Flattening test

[0173] The solution from Example 6 was spin-coated onto a chip containing lines of varying densities at 1,500 rpm for 60 seconds. The chip was then baked on a hot plate at 170°C for 1 minute and in an oven at 450°C for 4 minutes. The chip was inspected using SEM. Figure 9-11 As shown, the results demonstrate good flattening. Figure 9 On the left side of the chip, there are 50nm lines and 250nm spacing, 1.5μm spacing, and then 50nm lines and 50nm spacing. Figure 10 It is a more magnified image of the 1:1 region. Figure 11 The left side is a 1:1 region, and the right side is a 50μm oxide pad. There is a 500nm trench between the dense area and the pad.

[0174] Example 8

[0175] 1. Synthesis of diamic acid in NMP

[0176] In this embodiment, 9.169 g of FDAH was added to a 500 ml round-bottom flask. 4.747 g of 3-ethynylaniline (3-EA, TCI, Oportland, OR, USA) was dissolved in 155.00 g of NMP, and this solution was added to a dropping funnel connected to the round-bottom flask. The system was purged with nitrogen for 10 minutes. Then, the 3-EA solution was added dropwise to the flask, and the mixture was magnetically stirred under nitrogen for 5 minutes. The reaction was allowed to proceed at room temperature with magnetic stirring under nitrogen for 24 hours.

[0177] 2. Solution imidization of diamic acid

[0178] Then, 166 g of toluene was added to the solution obtained in Part 1 above. A Dean-Stark collector was connected to the reaction flask. The oil bath in which the flask was immersed was heated to 180 °C. Azeotropic distillation of water-toluene was initiated when imidization began between 150 °C and 160 °C. The reaction was magnetically stirred under nitrogen at these temperatures for 8 hours, after which the system was cooled to room temperature.

[0179] 3. Purification of diimide

[0180] The diimide solution was rotary evaporated to remove toluene. It was then precipitated in deionized water (1:10 weight ratio). The precipitated diimide was filtered and washed with deionized water. It was dried in a nitrogen stream. GPC analysis with NMP as the mobile phase showed Mw = 1168, Mn = 973, and PDI = 1.20.

[0181] 4. Coating formulations

[0182] To prepare the coating formulation, 1.672 g of the diimide solid obtained in Part 3 was dissolved in 22.237 g of cyclopentanone. Next, 2.516 g of 2% NF7177C and 1.675 g of 0.1% R30N surfactant were added. The solution was filtered through a 0.1 μm PTFE membrane filter.

[0183] Example 9

[0184] Flattening test

[0185] The solution prepared in Example 8 was spin-coated onto a chip containing lines of varying densities at 1,500 rpm for 60 seconds. The chip was then baked on a hot plate at 170°C for 1 minute and in an oven at 450°C for 4 minutes. The chip was inspected using SEM. Figure 12-14 As shown, the results demonstrate good flattening. Figure 12 On the left side of the chip are 50nm lines with 50nm spacing, a 1.5μm spacing, and then 50nm lines with 250nm spacing. Figure 13 It is a more magnified image of the 1:1 region. Figure 14 On the left is a 50μm oxide block, and on the right is a 1:1 region, with a 500nm trench between them.

[0186] Example 10

[0187] 1. Synthesis of diamic acid in PGMEA

[0188] In this embodiment, 27.18 g of FDAH was added to a 500 ml round-bottom flask. 13.94 g of 3-EA was dissolved in 163.56 g of PGMEA (General Chemical Corporation, USA), and this solution was added to a dropping funnel connected to the round-bottom flask. The system was purged with nitrogen for 10 minutes. Then, the 3-EA solution was added dropwise to the flask, and the mixture was magnetically stirred in nitrogen for 4 minutes. The reaction was allowed to proceed with magnetic stirring in nitrogen at room temperature for 4 hours, then the flask was connected to a condenser, and the reaction temperature was raised to 150 °C. The imidization reaction was carried out at 150 °C with magnetic stirring in nitrogen for 8 hours.

[0189] 2. Purification of diimide

[0190] The diimide solution obtained in Part 1 was precipitated in hexane (1:5 by weight, Sigma-Aldrich, St. Louis, Missouri). The precipitated diimide was filtered and washed with hexane (Tedia high-purity solvent, Fairfield, Ohio), and then dried overnight in a vacuum oven at 70°C.

[0191] Example 11

[0192] 1. Synthesis of diamic acid in PGME

[0193] In this embodiment, 26.43 g of FDAH was added to a 500 ml round-bottom flask. 13.57 g of 3-EA was dissolved in 60 g of PGME (General Chemicals, USA), and this solution was added to a dropping funnel connected to the round-bottom flask. The system was purged with nitrogen for 10 minutes, and then the 3-EA solution was added dropwise to the flask, with magnetic stirring under nitrogen for 4 minutes. The reaction was carried out at 50°C with magnetic stirring under nitrogen for 8 hours. The flask was then connected to a condenser, and the reaction temperature was raised to 130°C. The imidization reaction was carried out at 150°C with magnetic stirring under nitrogen for 16 hours.

[0194] 2. Purification of diimide

[0195] The diimide solution obtained in Part 1 was precipitated in hexane (1:5 by weight, Sigma-Aldrich, St. Louis, Missouri). The precipitated diimide was filtered and washed with hexane (Tedia high-purity solvent, Fairfield, Ohio), and then dried overnight in a vacuum oven at 70°C.

[0196] Example 12

[0197] Coating formulations

[0198] To prepare the coating formulation, 3.88 g of diimide solid was dissolved in 81.7 g of PGMEA and 4.8 g of PGME. Next, 5.82 g of 2% NF7177C and 3.8 g of 0.1% R30N surfactant were added. The solution was filtered through a 0.1 μm PTFE membrane filter.

[0199] Example 13

[0200] Coating test

[0201] The coating formulation prepared in Example 12 was spin-coated onto a silicon wafer at 1,500 rpm for 60 seconds. The wafer was then baked on a hot plate at 170°C for 1 minute and in an oven at 450°C for 4 minutes. After baking at 170°C for 1 minute, the coating thickness was 114.6 nm. After baking at 450°C for 4 minutes, the coating thickness was 112.9 nm, with a loss of less than 5% of the total thickness.

[0202] Example 14

[0203] Coating formulations

[0204] In this embodiment, 5.03 g of diimide solid obtained in Example 10 was dissolved in 85.45 g of PGMEA and 4.6 g of PGME. Next, 0.146 g of gallic acid and 4.8 g of 0.1% R30N surfactant were added. The solution was filtered through a 0.1 μm PTFE membrane filter.

[0205] Example 15

[0206] Coating test

[0207] The coating formulation from Example 14 was spin-coated onto a silicon wafer at 1,500 rpm for 60 seconds. The wafer was then baked on a hot plate at 170°C for 1 minute and in an oven at 450°C for 4 minutes. After baking at 170°C for 1 minute, the coating thickness was 99.8 nm. After baking at 450°C for 4 minutes, the coating thickness was 101.4 nm, indicating no thickness loss; however, the coating may have exhibited some slight expansion.

[0208] Example 16

[0209] Coating formulations

[0210] In this embodiment, 5.00 g of diimide solid obtained in Example 10 was dissolved in 85.25 g of PGMEA and 4.75 g of PGME. Then, 5.0 g of 0.1% R30N surfactant was added. The solution was filtered through a 0.1 μm PTFE membrane filter.

[0211] Example 17

[0212] Coating test

[0213] The solution from Example 16 was spin-coated onto a silicon wafer at 1,500 rpm for 60 seconds. The wafer was then baked on a hot plate at 170°C for 1 minute and in an oven at 450°C for 4 minutes. After baking at 170°C for 1 minute, the coating thickness was 119.5 nm. After baking at 450°C for 4 minutes, the coating thickness was 122.7 nm, indicating no thickness loss; however, the coating may have exhibited some slight expansion.

[0214] Example 18

[0215] 1. Synthesis of diimides using FDA and EPA standards

[0216] In a 200 mL round-bottom flask, 3.48 g of FDA and 3.44 g of 4-ethynyl phthalic anhydride ("EPA", Neximid 200, Nexam Chemical Holdings AB, Lockheed Martin, Sweden) were added, followed by 27.68 g of PGMEA. The flask was then connected to a condenser, and nitrogen was purged through the system. The flask was then placed in an oil bath at 150 °C for 80 minutes. Once the reaction was complete, the flask was removed from the oil bath and cooled to room temperature. The resulting solution was precipitated in approximately 0.5 L of n-hexane, and the solid was filtered off. The resulting polymer solid was dried overnight under vacuum at 40 °C.

[0217] 2. Coating formulations

[0218] In this embodiment, 0.5988 g of the finally dried solid, 14.28 g of cyclopentanone, and 0.12 g of FS3100 (a 1% solution of cyclopentanone) surfactant (Cholmours FC, LLC, USA) were stirred until dissolved. The solution was filtered through a 0.1 μm end-point filter and bottled for further use.

[0219] Example 19

[0220] Coating test

[0221] The coating formulation prepared in Example 18 was spin-coated onto a 100 mm silicon wafer for 60 seconds at 1,500 rpm. The wafer was then baked on a hot plate at 170°C for 1 minute and in an oven at 450°C for 4 minutes. After baking at 170°C for 1 minute, the coating thickness was 157.3 nm. After baking at 450°C for 4 minutes, the coating thickness was 163.0 nm, indicating no thickness loss; however, the coating may have exhibited some slight expansion.

[0222] Example 20

[0223] Coating formulations

[0224] In this embodiment, 4.72 g of diimide solid obtained in Example 10 was dissolved in 90.3 g of PGMEA and 4.8 g of PGME. Next, 0.14 g of NF7177C, 0.14 g of gallic acid, and 4.7 g of 0.1% R30N surfactant were added. The solution was filtered through a 0.1 μm PTFE membrane filter.

[0225] Example 21

[0226] Coating formulations

[0227] In this embodiment, 4.72 g of diimide solid obtained in Example 10 was dissolved in 90.3 g of PGMEA and 4.8 g of PGME. Next, 0.14 g of NF7177C, 0.14 g of 2,3,4,3',4',5'-hexahydroxybenzophenone (“6-HBP”), and 4.7 g of 0.1% R30N surfactant were added. The solution was filtered through a 0.1 μm PTFE membrane filter.

[0228] Example 22

[0229] Coating formulations

[0230] In this embodiment, 4.71 g of diimide solid obtained in Example 10 was dissolved in 28.5 g of PGMEA. Next, 68.5 g of PGMEA, 0.14 g of NF7177C, 0.14 g of 3,3,5,5-tetramethoxymethyl-[1,1'-biphenyl]-4,4'-diol ("TMOM-BP"), and 4.7 g of 0.1% R30N surfactant were added. The solution was filtered through a 0.1 μm PTFE membrane filter.

[0231] Example 23

[0232] SC1 resistance test

[0233] The coating formulations from Examples 12, 20, 21, and 22 were spin-coated at 1,500 rpm onto TiN substrate chips containing narrow trenches (each example having 50 nm lines, 50 nm spacing, and 200 nm deep trenches) for 60 seconds. The chips were then baked on a hot plate at 170°C for 1 minute, followed by an oven bake at 450°C for 4 minutes, and then subjected to plasma etching to remove the coating in the open areas and partially remove the coating within the trenches. Next, the chips were immersed in SC1 etchant (ammonium hydroxide, hydrogen peroxide, and deionized water in a 1:1:5 ratio) at 50°C for 100 seconds. After air drying, the chips were inspected using SEM. Results ( Figure 15-18 The results show that on chips coated with the formulations of Examples 20, 21 and 22, there is almost no undercut (i.e. less than 20 nm), which makes these formulations particularly suitable for use in processes including SC1 etching.

[0234] Example 24

[0235] Coating formulations

[0236] In this embodiment, 4.71 g of diimide solid obtained in Example 10 was dissolved in 90.25 g of PGMEA and 4.75 g of PGME. Next, 0.14 g of NF7177C, 0.14 g of phenyl phosphate, and 0.1 g of R30N surfactant were added. The solution was mixed for 4 hours and then filtered through a 0.2 μm PTFE membrane filter.

[0237] Example 25

[0238] Coating formulations

[0239] In this embodiment, 4.71 g of diimide solid obtained in Example 10 was dissolved in 90.25 g of PGMEA and 4.75 g of PGME. Next, 0.14 g of NF7177C, 0.14 g of dimethyl phenyl phosphate, and 0.1 g of R30N surfactant were added. The solution was mixed for 4 hours and then filtered through a 0.2 μm PTFE membrane filter.

[0240] Example 26

[0241] Coating formulations

[0242] In this embodiment, 4.71 g of diimide solid obtained in Example 10 was dissolved in 90.25 g of PGMEA and 4.75 g of PGME. Next, 0.14 g of NF7177C, 0.14 g of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and 0.1 g of R30N surfactant were added. The solution was mixed for 4 hours and then filtered through a 0.2 μm PTFE membrane filter.

[0243] Example 27

[0244] Coating formulations

[0245] In this embodiment, 4.71 g of diimide solid obtained in Example 10 was dissolved in 90.25 g of PGMEA and 4.75 g of PGME. Next, 0.14 g of NF7177C, 0.14 g of phenylphosphonic acid, and 0.1 g of R30N surfactant were added. The solution was mixed for 4 hours and then filtered through a 0.2 μm PTFE membrane filter.

[0246] Example 28

[0247] SC1 resistance test

[0248] The coating formulations from Examples 24-27 were spin-coated at 1,500 rpm for 60 seconds on TiN substrate chips containing narrow trenches (each example having 50 nm lines, 50 nm spacing, and 200 nm deep trenches). The chips were then baked on a hot plate at 170°C for 1 minute, followed by baking in a nitrogen-filled oven at 450°C for 4 minutes, and then subjected to plasma etching to remove the coating in the open areas and partially remove the coating within the trenches. Next, the chips were immersed in SC1 etchant (ammonium hydroxide, hydrogen peroxide, and deionized water in a 1:1:5 ratio) at 60°C for 100 seconds. After air drying, the chips were examined using SEM. The results showed that the undercut on the chips coated with the solutions from Examples 24-27 was significantly less than that on the chips coated with the comparative solution without additives (i.e., the comparative solution comprised 4.71 g of the diimide solid obtained in Example 10 dissolved in 90.25 g of PGMEA and 4.75 g of PGME). Figure 19-23 The SEM cross-sectional view of the coated substrate is shown.

Claims

1. A method for forming a microelectronic structure, the method comprising: Optionally, one or more intermediate layers are formed on the surface of the substrate; if one or more intermediate layers are present, the uppermost intermediate layer is formed on the surface of the substrate. If an uppermost intermediate layer exists, the composition is applied to the uppermost intermediate layer; or if no intermediate layer exists, the composition is applied to the surface of the substrate. The composition comprises a diimide dissolved or dispersed in a solvent system, the diimide being formed from a diamidic acid derived from the following compounds: (i) dianhydrides and crosslinkable monoamines; (ii) can crosslink monohydric anhydrides and diamines; or (iii)(i) and (ii) both; and The composition is heated to form a carbon-rich layer, which exhibits less than 0.1 defects / cm upon CVD viability testing. 2 Characteristics of layer surface area.

2. The method of claim 1, further comprising: Optionally, one or more additional intermediate layers are formed on the carbon-rich layer, and if one or more additional intermediate layers exist, the carbon-rich layer has an uppermost additional intermediate layer. If one or more additional intermediate layers exist, the imaging layer is applied to the one or more additional intermediate layers; or if no additional intermediate layers exist, it is applied to the carbon-rich layer. The imaging layer is patterned to form a pattern therein; If one or more additional intermediate layers exist, the pattern is transferred to one or more additional intermediate layers on the carbon-rich layer, and then transferred to the carbon-rich layer; as well as The carbon-rich layer is brought into contact with SC1.

3. The method of claim 1 or 2, wherein the substrate surface comprises an intermediate layer, and the intermediate layer is selected from TiN or SiO2.

4. The method of claim 1 or 2, wherein the carbon-rich layer has SC1 resistance.

5. The method of claim 1 or 2, wherein the composition further comprises a component selected from: Polyphenols, wherein the polyphenols are selected from Where n is 1 to 5, and the molecular chain can be bonded to carbon α', replacing or supplementing carbon α; The polyhydroxy compound is selected from: gallic acid, methyl gallate, 4-hydroxybenzoic acid, pyrogallol, 2,3,4,3',4',5'-hexahydroxybenzophenone, boronized polystyrene, 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol, poly(4-vinylphenol), or combinations thereof; Phosphorus compounds, wherein the phosphorus compounds are selected from: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and dimethyl phenylphosphonate, phenyl phosphate, phenylphosphonic acid, phytic acid, and combinations thereof; or The combination of the above components.

6. The method of claim 1 or 2, wherein the solvent system comprises propylene glycol monomethyl ether, and the application of the composition is performed without removing some or all of the propylene glycol monomethyl ether prior to the application.

7. The method of claim 1, wherein: The dianhydride is selected from benzophenone-3,3'4,4'-tetracarboxylic acid dianhydride, 4,4'-oxobisphthalic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride or a combination thereof; The crosslinkable monoamine is selected from 2-vinylaniline, 4-vinylaniline, 2-allylaniline, 4-allylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-ethynylaniline, or combinations thereof; The crosslinkable monohydric anhydride is selected from 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, or combinations thereof; and The diamine is selected from 4,4'-oxodiphenylamine, bis(4-aminophenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, or combinations thereof.

8. A method for forming a microelectronic structure, the method comprising: Optionally, one or more intermediate layers are formed on the surface of the substrate; if one or more intermediate layers are present, the uppermost intermediate layer is formed on the surface of the substrate. If an uppermost intermediate layer exists, the composition is applied to the uppermost intermediate layer; or if no intermediate layer exists, the composition is applied to the surface of the substrate. The composition comprises a diimide dissolved or dispersed in a solvent system, the diimide being formed from a diamidic acid derived from the following compounds: (i) dianhydrides and crosslinkable monoamines; (ii) can crosslink monohydric anhydrides and diamines; or (iii)(i) and (ii) both; Heating the composition to form a carbon-rich layer; Optionally, one or more additional intermediate layers are formed on the carbon-rich layer, and if one or more additional intermediate layers exist, the carbon-rich layer has an uppermost additional intermediate layer. If one or more additional intermediate layers exist, the imaging layer is applied to the one or more additional intermediate layers; or if no additional intermediate layers exist, it is applied to the carbon-rich layer. The imaging layer is patterned to form a pattern therein; If one or more additional intermediate layers exist, the pattern is transferred to one or more additional intermediate layers on the carbon-rich layer, and then transferred to the carbon-rich layer; as well as The carbon-rich layer is brought into contact with SC1.

9. The method of claim 8, wherein the substrate surface comprises an intermediate layer selected from TiN or SiO2.

10. The method of claim 8 or 9, wherein the carbon-rich layer has SC1 resistance.

11. The method of claim 8 or 9, wherein the composition further comprises a component selected from: Polyphenols, wherein the polyphenols are selected from Where n is 1 to 5, and the molecular chain can be bonded to carbon α', replacing or supplementing carbon α; The polyhydroxy compound is selected from: gallic acid, methyl gallate, 4-hydroxybenzoic acid, pyrogallol, 2,3,4,3',4',5'-hexahydroxybenzophenone, boronized polystyrene, 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol, poly(4-vinylphenol), or combinations thereof; Phosphorus compounds, wherein the phosphorus compounds are selected from: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and dimethyl phenylphosphonate, phenyl phosphate, phenylphosphonic acid, phytic acid, and combinations thereof; or The combination of the above components.

12. The method of claim 8 or 9, wherein the solvent system comprises propylene glycol monomethyl ether, and the application of the composition is performed without removing some or all of the propylene glycol monomethyl ether prior to the application.

13. The method of claim 8, wherein: The dianhydride is selected from benzophenone-3,3'4,4'-tetracarboxylic acid dianhydride, 4,4'-oxobisphthalic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride or a combination thereof; The crosslinkable monoamine is selected from 2-vinylaniline, 4-vinylaniline, 2-allylaniline, 4-allylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-ethynylaniline, or combinations thereof; The crosslinkable monohydric anhydride is selected from 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, or combinations thereof; and The diamine is selected from 4,4'-oxodiphenylamine, bis(4-aminophenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, or combinations thereof.

14. A method for forming a microelectronic structure, the method comprising: Optionally, one or more intermediate layers are formed on the surface of the substrate; if one or more intermediate layers are present, the uppermost intermediate layer is formed on the surface of the substrate. If an uppermost intermediate layer exists, the composition is applied to the uppermost intermediate layer; or if no intermediate layer exists, the composition is applied to the surface of the substrate. The composition comprises a diimide dissolved or dispersed in a solvent system, the diimide being formed from a diamidic acid derived from the following compounds: (i) dianhydrides and crosslinkable monoamines; (ii) can crosslink monohydric anhydrides and diamines; or (iii)(i) and (ii) both; and The composition is heated to form a carbon-rich layer with SC1 resistance.

15. The method of claim 14, wherein the substrate surface comprises an intermediate layer selected from TiN or SiO2.

16. The method of claim 14 or 15, wherein the composition further comprises a component selected from: Polyphenols, wherein the polyphenols are selected from Where n is 1 to 5, and the molecular chain can be bonded to carbon α', replacing or supplementing carbon α; The polyhydroxy compound is selected from: gallic acid, methyl gallate, 4-hydroxybenzoic acid, pyrogallol, 2,3,4,3',4',5'-hexahydroxybenzophenone, boronized polystyrene, 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol, poly(4-vinylphenol), or combinations thereof; Phosphorus compounds, wherein the phosphorus compounds are selected from: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and dimethyl phenylphosphonate, phenyl phosphate, phenylphosphonic acid, phytic acid, and combinations thereof; or The combination of the above components.

17. The method of claim 14 or 15, wherein the solvent system comprises propylene glycol monomethyl ether, and the application of the composition is performed without removing some or all of the propylene glycol monomethyl ether prior to the application.

18. The method of claim 14, wherein: The dianhydride is selected from benzophenone-3,3'4,4'-tetracarboxylic acid dianhydride, 4,4'-oxobisphthalic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride or a combination thereof; The crosslinkable monoamine is selected from 2-vinylaniline, 4-vinylaniline, 2-allylaniline, 4-allylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-ethynylaniline, or combinations thereof; The crosslinkable monohydric anhydride is selected from 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, or combinations thereof; and The diamine is selected from 4,4'-oxodiphenylamine, bis(4-aminophenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, or combinations thereof.

19. A method for forming a microelectronic structure, the method comprising: Optionally, one or more intermediate layers are formed on the surface of the substrate; if one or more intermediate layers are present, the uppermost intermediate layer is formed on the surface of the substrate. If an uppermost intermediate layer exists, the composition is applied to the uppermost intermediate layer; or if no intermediate layer exists, the composition is applied to the surface of the substrate. The composition comprises a diimide dissolved or dispersed in a solvent system and a component, wherein: The components are selected from: Polyphenols, wherein the polyphenols are selected from Where n is 1 to 5, and the molecular chain can be bonded to carbon α', replacing or supplementing carbon α; The polyhydroxy compound is selected from: gallic acid, methyl gallate, 4-hydroxybenzoic acid, pyrogallol, 2,3,4,3',4',5'-hexahydroxybenzophenone, boronized polystyrene, 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol, poly(4-vinylphenol), or combinations thereof; Phosphorus compounds, wherein the phosphorus compounds are selected from: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and dimethyl phenylphosphonate, phenyl phosphate, phenylphosphonic acid, phytic acid, and combinations thereof; or The combination of the above components; and The diimide is formed from a diamido acid derived from the following compounds: (i) dianhydrides and crosslinkable monoamines; (ii) can crosslink monohydric anhydrides and diamines; or (iii)(i) and (ii) both; and The composition is heated to form a carbon-rich layer.

20. The method of claim 19, wherein the substrate surface comprises an intermediate layer selected from TiN or SiO2.

21. The method of claim 19 or 20, wherein the solvent system comprises propylene glycol monomethyl ether, and the application of the composition is performed without removing some or all of the propylene glycol monomethyl ether prior to the application.

22. The method of claim 19, wherein: The dianhydride is selected from benzophenone-3,3'4,4'-tetracarboxylic acid dianhydride, 4,4'-oxobisphthalic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride or a combination thereof; The crosslinkable monoamine is selected from 2-vinylaniline, 4-vinylaniline, 2-allylaniline, 4-allylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-ethynylaniline, or combinations thereof; The crosslinkable monohydric anhydride is selected from 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, or combinations thereof; and The diamine is selected from 4,4'-oxodiphenylamine, bis(4-aminophenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, or combinations thereof.

23. A method for forming a microelectronic structure, the method comprising: A diamide acid is imidized in a solvent system containing propylene glycol monomethyl ether to form a composition containing a diimide, wherein the diamide acid is formed from the following compounds: (i) dianhydrides and crosslinkable monoamines; (ii) can crosslink monohydric anhydrides and diamines; or (iii)(i) and (ii) both; Optionally, one or more intermediate layers are formed on the surface of the substrate; if one or more intermediate layers are present, the uppermost intermediate layer is formed on the surface of the substrate. Without removing some or all of the propylene glycol monomethyl ether, if an uppermost intermediate layer is present, the composition is applied to the uppermost intermediate layer, or if no intermediate layer is present, the composition is applied to the surface of the substrate. as well as The composition is heated to form a carbon-rich layer.

24. The method of claim 23, further comprising: Optionally, one or more additional intermediate layers are formed on the carbon-rich layer, and if one or more additional intermediate layers exist, the carbon-rich layer has an uppermost additional intermediate layer. If one or more additional intermediate layers exist, the imaging layer is applied to the one or more additional intermediate layers; if no additional intermediate layers exist, it is applied to the carbon-rich layer. The imaging layer is patterned to form a pattern therein; If one or more additional intermediate layers exist, the pattern is transferred to one or more additional intermediate layers on the carbon-rich layer, and then transferred to the carbon-rich layer; as well as The carbon-rich layer is brought into contact with SC1.

25. The method of claim 23 or 24, wherein the substrate surface comprises an intermediate layer, and the intermediate layer is selected from TiN or SiO2.

26. The method of claim 23, wherein: The dianhydride is selected from benzophenone-3,3'4,4'-tetracarboxylic acid dianhydride, 4,4'-oxobisphthalic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride or a combination thereof; The crosslinkable monoamine is selected from 2-vinylaniline, 4-vinylaniline, 2-allylaniline, 4-allylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-ethynylaniline, or combinations thereof; The crosslinkable monohydric anhydride is selected from 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, or combinations thereof; and The diamine is selected from 4,4'-oxodiphenylamine, bis(4-aminophenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, or combinations thereof.

27. Use of a composition for forming a microelectronic structure, said composition comprising: Diimide, wherein the diimide is formed from a diamido acid derived from the following compounds: (i) dianhydrides and crosslinkable monoamines; (ii) can crosslink monohydric anhydrides and diamines; or (iii)(i) and (ii) both; Selected from the following components: Polyphenols, wherein the polyphenols are selected from Where n is 1 to 5, and the molecular chain can be bonded to carbon α', replacing or supplementing carbon α; The polyhydroxy compound is selected from: gallic acid, methyl gallate, 4-hydroxybenzoic acid, pyrogallol, 2,3,4,3',4',5'-hexahydroxybenzophenone, boronized polystyrene, 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol, poly(4-vinylphenol), or combinations thereof; Phosphorus compounds, wherein the phosphorus compounds are selected from: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and dimethyl phenylphosphonate, phenyl phosphate, phenylphosphonic acid, phytic acid, and combinations thereof; or The combination of the above components; and Solvent system.

28. The use as described in claim 27, wherein, The solvent system contains propylene glycol monomethyl ether.

29. The use as described in claim 27, wherein: The dianhydride is selected from benzophenone-3,3'4,4'-tetracarboxylic acid dianhydride, 4,4'-oxobisphthalic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride or a combination thereof; The crosslinkable monoamine is selected from 2-vinylaniline, 4-vinylaniline, 2-allylaniline, 4-allylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-ethynylaniline, or combinations thereof; The crosslinkable monohydric anhydride is selected from 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, or combinations thereof; and The diamine is selected from 4,4'-oxodiphenylamine, bis(4-aminophenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, or combinations thereof.

30. A microelectronic structure comprising: Microelectronic substrates, which have a surface; Optionally, one or more intermediate layers are present on the surface of the substrate; if one or more intermediate layers are present, the uppermost intermediate layer is present on the surface of the substrate. If an uppermost intermediate layer exists, a composition layer is placed on the uppermost intermediate layer; or if no intermediate layer exists, a composition layer is placed on the surface of the substrate, the composition comprising: Diimide, wherein the diimide is formed from a diamido acid derived from the following compounds: (i) dianhydrides and crosslinkable monoamines; (ii) can crosslink monohydric anhydrides and diamines; or (iii)(i) and (ii) both; Selected from the following components: Polyphenols, wherein the polyphenols are selected from Where n is 1 to 5, and the molecular chain can be bonded to carbon α', replacing or supplementing carbon α; The polyhydroxy compound is selected from: gallic acid, methyl gallate, 4-hydroxybenzoic acid, pyrogallol, 2,3,4,3',4',5'-hexahydroxybenzophenone, boronized polystyrene, 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol, poly(4-vinylphenol), or combinations thereof; Phosphorus compounds, wherein the phosphorus compounds are selected from: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and dimethyl phenylphosphonate, phenyl phosphate, phenylphosphonic acid, phytic acid, and combinations thereof; or The combination of the above components; and Solvent system.

31. The structure of claim 30, wherein the substrate surface includes an intermediate layer, and the intermediate layer is selected from TiN or SiO2.

32. The structure as described in claim 30 or 31, wherein, The solvent system contains propylene glycol monomethyl ether.

33. The structure as described in claim 30, wherein: The dianhydride is selected from benzophenone-3,3'4,4'-tetracarboxylic acid dianhydride, 4,4'-oxobisphthalic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride or a combination thereof; The crosslinkable monoamine is selected from 2-vinylaniline, 4-vinylaniline, 2-allylaniline, 4-allylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-ethynylaniline, or combinations thereof; The crosslinkable monohydric anhydride is selected from 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, or combinations thereof; and The diamine is selected from 4,4'-oxodiphenylamine, bis(4-aminophenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, or combinations thereof.

34. A microelectronic structure comprising: Microelectronic substrates, which have a surface; Optionally, one or more intermediate layers are present on the surface of the substrate; if one or more intermediate layers are present, the uppermost intermediate layer is present on the surface of the substrate. If an uppermost intermediate layer exists, a carbon-rich layer is formed on the uppermost intermediate layer; or if no intermediate layer exists, a carbon-rich layer is formed on the surface of the substrate, the carbon-rich layer comprising: Cross-linked diimides, wherein the cross-linked diimides are formed from diamidic acids derived from the following compounds: (i) dianhydrides and crosslinkable monoamines; (ii) can crosslink monohydric anhydrides and diamines; or (iii)(i) and (ii) both; and Selected from the following components: Polyphenols, wherein the polyphenols are selected from Where n is 1 to 5, and the molecular chain can be bonded to carbon α', replacing or supplementing carbon α; The polyhydroxy compound is selected from: gallic acid, methyl gallate, 4-hydroxybenzoic acid, pyrogallol, 2,3,4,3',4',5'-hexahydroxybenzophenone, boronized polystyrene, 3,3',5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol, poly(4-vinylphenol), or combinations thereof; Phosphorus compounds, wherein the phosphorus compounds are selected from: phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and dimethyl phenylphosphonate, phenyl phosphate, phenylphosphonic acid, phytic acid, and combinations thereof; or The combination of the above components.

35. The structure of claim 34, wherein the substrate surface includes an intermediate layer, and the intermediate layer is selected from TiN or SiO2.

36. The structure as described in claim 34, wherein: The dianhydride is selected from benzophenone-3,3'4,4'-tetracarboxylic acid dianhydride, 4,4'-oxobisphthalic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride or a combination thereof; The crosslinkable monoamine is selected from 2-vinylaniline, 4-vinylaniline, 2-allylaniline, 4-allylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-ethynylaniline, or combinations thereof; The crosslinkable monohydric anhydride is selected from 4-ethynylphthalic anhydride, 4-methylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, or combinations thereof; and The diamine is selected from 4,4'-oxodiphenylamine, bis(4-aminophenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, or combinations thereof.

37. The structure as described in any one of claims 34 to 36, further comprising: One or more additional intermediate layers on the carbon-rich layer, and if one or more additional intermediate layers exist, then there is an uppermost additional intermediate layer on the carbon-rich layer; as well as If one or more additional intermediate layers are present, an imaging layer is formed on the one or more additional intermediate layers; or if no additional intermediate layers are present, an imaging layer is formed on the carbon-rich layer.

Images