Composition capable of removing imprint adhesive and reinforcing and protecting optical grating

Abstract

The invention provides a composition capable of removing imprint glue and reinforcing and protecting optical gratings. The composition comprises 5-30% of a compound surfactant, 20-70% of a compound organic solvent and 0.1-5% of a metal corrosion inhibitor, and the 20-70% of the compound organic solvent comprises 1-10% of unsaturated hydrocarbon and derivatives thereof and 20-60% of aromatic compounds. The composition disclosed by the invention is used for rapidly and efficiently removing the imprinting glue in a nano imprinting process, solves the problem that residues are generated due to too strong crosslinking property of the glue, and has compatible protectiveness on a grating structure at the bottom. In addition, the composition disclosed by the invention does not cause damage to equipment such as a filter element in a recycling process.

Description

Technical Field

[0001] The invention belongs to the field of semiconductors, and in particular relates to a cleaning liquid for quickly and efficiently removing embossing glue and enhancing protection of gratings. Background Art

[0002] Semiconductor microelectronics technology uses optical lithography to form very fine feature patterns. However, due to the limitation of the diffraction limit of the exposure wavelength, optical lithography technology can no longer meet the requirements of nano-manufacturing technology for line width and high resolution. Nano-imprint lithography (NIL) does not require exposure, but transfers the pattern on the mask by mechanical means, avoiding the limitation of the diffraction limit of the exposure wavelength, so it can achieve ultra-high resolution.

[0003] After curing, the imprint glue in the nanoimprint process will form polymer hinges to generate high molecular polymers, which are difficult to be removed by general organic solvents. The presence of residual glue will affect subsequent processes. Oxygen plasma bombardment is usually used to treat residual glue. However, insufficient bombardment time will result in incomplete removal of residual glue, and excessive bombardment may damage the substrate and grating morphology, ultimately affecting the performance of the device.

[0004] Therefore, developing a composition that can remove embossing glue and enhance the protection of gratings has become an urgent problem to be solved in the art. Summary of the invention

[0005] To solve the above problems, the present invention provides a composition for quickly and efficiently removing cross-linked adhesive colloids, and has compatible protection for the bottom grating structure. The present invention solves the above technical problems through the following technical solutions.

[0006] A composition for removing embossed glue and enhancing the protection of gratings, characterized in that the composition comprises 5-30% of a compound surfactant, 1-10% of unsaturated hydrocarbons and their derivatives, 20-60% of aromatic compounds and 0.1-5% of metal corrosion inhibitors, accounting for 5-30% of the total weight of the composition, and the sum of the mass fractions of the components is 100%.

[0007] Furthermore, the present invention relates to the above-mentioned compound surfactant which is composed of 10-30% of a main surfactant and 0.1-0.5% of a secondary surfactant.

[0008] Furthermore, the present invention relates to the main surfactant being a dodecynediol surfactant. Dodecynediol can permanently suppress foam and remove microbubbles, which can avoid damage to the filter element due to bubbles during the circulation process and make the overall composition have good storage stability.

[0009] Furthermore, the present invention relates to one or more of the secondary surfactant selected from sodium dodecylbenzene sulfonate, dodecylbenzene sulfonic acid, polyoxyethylene dodecylene glycol ether, polyoxyethylene phosphate, tertiary phosphate, sucrose fatty acid ester, benzalkonium chloride, benzalkonium bromide, benzalkonium chloride, and sulfobetaine. The primary and secondary surfactants are compounded, and their synergistic solubilization effect can greatly reduce the surface tension and promote the peeling and dissolution of the film.

[0010] Further, the present invention relates to one or more of the unsaturated hydrocarbons and their derivatives selected from 1,2-dibromoethylene, 1-octene, tetrapropylene, 3-bromopropylene, isoprene, polybutene, styrene, 1-octyne, 3,6-dimethyl-4-octyne-3,6-diol. The unsaturated olefins promote the chain scission of the polymer caused by the crosslinking agent.

[0011] Furthermore, the present invention relates to one or more of the aromatic compounds selected from benzene, p-xylene, styrene, phenol, catechol, pyrogallol, 3,4,5-trihydroxybenzoic acid, polyvinylphenol, chlorobenzene, and bromobenzene. -OH- and -Cl have a conjugated effect, which accelerates the reaction between the composition and the film and promotes its dissolution; when a group such as -CH=CHR is conjugated with an aromatic ring, each carbon also gives out a p electron, and usually does not increase the density of the aromatic ring electron cloud, but it will expand the conjugated system of the reaction intermediate, increase the stability of the intermediate, and thus reduce the activation energy of the reaction.

[0012] Furthermore, the present invention relates to the above metal corrosion inhibitor selected from one or more of 2-mercaptobenzimidazole, quinoline, 5-phenyltetrazolyl, 5-aminotetrazolyl, and 1H-1,2,3-triazole. Azoles provide charge through hyperconjugation and inductive effects, concentrating the charge density on nitrogen atoms, thereby increasing their adsorption at the metal anode position.

[0013] The reagents and raw materials used in the present invention are commercially available.

[0014] The technical solution of the present invention can realize the cleaning of polymer hinges generated by the imprint glue in the nanoimprint process after solidification, and at the same time avoid the influence on the grating during the cleaning process.

[0015] The present invention has the following beneficial effects: 1. Liquid unsaturated hydrocarbons and their derivatives, aromatic compounds are selected as organic solvents and additives. One cleaning can not only completely peel off the hard-to-remove embossed adhesive within 10 minutes, but also dissolve the adhesive filaments quickly and efficiently, which will simplify the traditional multi-stage cleaning process and avoid filter element clogging during recycling.

[0016] 2. The pH value of the composition is relatively weak and will not corrode various types of grating film structures and silicon substrates.

[0017] 3. The compound surfactant used in a specific proportion can reduce the surface tension of the composition, and has micellar and solubilizing effects, making the degumming effect excellent and leaving no residue.

[0018] 4. Azoles provide charges through hyperconjugation and inductive effects, concentrating the charge density on nitrogen atoms, thereby increasing their adsorption at the metal anode position and protecting the metal-doped grating structure. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 SEM of the specimen before cleaning.

[0020] Figure 2 SEM of the test piece of Example 1 after cleaning.

[0021] Figure 3 SEM of the test piece of Comparative Example 1 after cleaning.

[0022] Figure 4 SEM of the test piece of Comparative Example 2 after cleaning.

[0023] Figure 5 SEM of the test piece of Comparative Example 3 after cleaning.

[0024] Figure 6 SEM of the test piece of Comparative Example 4 after cleaning.

[0025] Figure 7 SEM of the test piece of Comparative Example 5 after cleaning.

[0026] Figure 8 SEM of the test piece of Comparative Example 6 after cleaning. DETAILED DESCRIPTION

[0027] In order to better understand the present invention, the following will fully describe the embodiments in combination with tables, but the scope of protection claimed by the present invention is not limited to the scope shown in the embodiments.

[0028] In the embodiments and comparative examples of the present invention, the debonding temperature is kept constant at 70°C, and the cleaning method is to cut the test piece into a size of 3×3cm and then soak it in 60g of the composition for a fixed time of 5min, and observe whether the adhesive film is completely peeled off and completely dissolved. SEM is used to observe whether there is adhesive thread sticking back to the test piece, and the morphology of the adhesive film and grating on the surface of the test piece. The composition after cleaning is filtered using a sand core funnel to observe whether there is adhesive thread on the filter paper. The types of components of the compositions of Examples 1-12 and Comparative Examples 1-6 are shown in Table 1, and the contents are shown in Table 2.

[0029] Table 1

[0030] Table 2

[0031] The cleaning time unit is min. The adhesive thread is indicated by “□” if it is sticky, and “Δ” if it is not. The adhesive film is completely peeled off from the test piece. " " indicates that the grating is not damaged, and "ΔΔ" indicates that it is not damaged; "√" indicates that the glue filaments are completely dissolved, and "×" indicates that there are glue filaments in the solution; "◇" indicates that the grating morphology is intact, and "××" indicates that it is corroded. The above experimental results are shown in Table 3.

[0032] Table 3

[0033] As can be seen from Tables 1-3, the types of compound surfactants, unsaturated hydrocarbons and their derivatives, aromatic compounds and metal corrosion inhibitors affect the time for the colloid to be completely peeled off and dissolved, but they can all achieve the purpose of completely removing the glue and enhancing the protection of the grating within 10 minutes. Additives also directly determine whether there are glue threads in the composition after cleaning and filtration. Figure 1 The SEM of the test piece before cleaning shows that the strips are the gratings and the upper layer is the colloid. Figure 2 This is the SEM image of Example 1 after cleaning. It can be seen that the structure sheet is very clear, while it can be seen from Comparative Example 1 that it is not completely cleaned. Figure 7 , 8 There is still some wear in Comparative Examples 5 and 6.

[0034] When using general-purpose DMSO and NMP as organic solvents and IPA as surfactant, the film cannot be peeled off from the surface of the test piece. This is because the cross-linking of the colloid is too strong and the molecular arrangement is too close. In addition, the corrosion inhibitor protects the integrity of the grating structure.

[0035] Obviously, the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the above embodiments have many variations or combinations, and it is not necessary and impossible to cite all the embodiments here. Therefore, the variations or changes made based on the above embodiments are still within the protection scope of the present invention.

Claims

1. A composition for removing embossing glue and strengthening grating protection, characterized in that: The composition comprises 5-30% of the total weight of the composition of a compound surfactant, 1-10% of unsaturated hydrocarbons and their derivatives, 20-60% of aromatic compounds, and 0.1-5% of metal corrosion inhibitors, and the mass fraction of each component is 100%.

2. The composition according to claim 1, characterized in that The compound surfactant in the composition is composed of 10-30% of a main surfactant and 0.1-0.5% of a secondary surfactant.

3. The composition according to claim 2, characterized in that The main surfactant is dodecyne diol surfactant.

4. The composition according to claim 2, characterized in that The secondary surfactant is selected from one or more of sodium dodecylbenzene sulfonate, dodecylbenzene sulfonic acid, polyoxyethylene phosphate, tertiary phosphate, sucrose fatty acid ester, benzalkonium chloride, benzalkonium bromide, benzalkonium chloride, and sulfobetaine.

5. The composition according to claim 1, characterized in that The unsaturated hydrocarbon and its derivatives are selected from one or more of 1,2-dibromoethylene, 1-octene, tetrapropylene, 3-bromopropylene, isoprene, polybutene, styrene, 1-octyne, and 3,6-dimethyl-4-octyne-3,6-diol.

6. The composition according to claim 1, characterized in that The aromatic compounds are aromatic hydrocarbons, phenolic substances and aromatic halogenated hydrocarbons.

7. The composition according to claim 6, characterized in that The aromatic hydrocarbon is selected from one or more of toluene, p-xylene, and styrene; the phenolic substance is selected from one or more of phenol, catechol, pyrogallol, 3,4,5-trihydroxybenzoic acid, and polyvinylphenol; and the aromatic halogenated hydrocarbon is selected from one or more of chlorobenzene and bromobenzene.

8. The composition according to claim 1, characterized in that The metal corrosion inhibitor is selected from one or more of 2-mercaptobenzimidazole, quinoline, 5-phenyltetrazolyl, 5-aminotetrazolyl, and 1H-1,2,3-triazole.

9. A method for preparing a composition capable of removing embossing glue and strengthening grating protection, characterized in that: A composition comprising any one of the raw material compositions of claims 1 to 8, 5-30% of a compound surfactant, 1-10% of unsaturated hydrocarbons and their derivatives, 20-60% of aromatic compounds, and 0.1-5% of a metal corrosion inhibitor are uniformly mixed in proportion so that the sum of the mass fractions of the components is 100%, thereby obtaining a composition capable of removing the embossed glue and enhancing the protection of the grating.

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