Anti-reflection composition, anti-reflection film, patterning process, patterned substrate, semiconductor device and preparation method thereof

Abstract

The present application provides an anti-reflective composition, an anti-reflective film, a patterning process, a patterned substrate, a semiconductor device and a preparation method thereof. The present application can obtain an anti-reflective composition with a lower acid value by properly mixing two organic solvents with different acid values, thereby reducing its preparation cost, reducing the white edge phenomenon, suppressing the standing wave phenomenon, and improving its stability, which is conducive to obtaining a pattern with high resolution and low line width roughness. The anti-reflective composition can be applied in the preparation of semiconductor devices to improve the comprehensive performance of the semiconductor devices.

Description

Technical Field

[0001] The present application relates to the field of semiconductor preparation, and in particular to an anti-reflective composition, an anti-reflective film, a patterning process, a patterned substrate, a semiconductor device and a preparation method thereof. Background Art

[0002] With the continuous development of semiconductor technology, the industry has higher and higher requirements for the fineness of patterns, resulting in the wavelength of light required for exposure becoming shorter and shorter. However, short-wave light will aggravate the problems of diffuse reflection and standing waves of the substrate, which will seriously affect the clarity and resolution of the pattern. In the related art, an anti-reflection film is formed on the surface of the substrate using an anti-reflection composition to reduce the reflection phenomenon during the patterning process. Due to problems such as preparation process and raw material quality control, the acid value of the existing anti-reflection composition is generally high, and the preparation cost is high, resulting in reduced stability of the patterning process and poor line width roughness of the obtained pattern. Therefore, there is a need for an anti-reflection composition with low acid value and low preparation cost, which can improve the stability of the patterning process and reduce the line width roughness of the pattern. Summary of the invention

[0003] In view of this, the present application provides an anti-reflective composition, an anti-reflective film, a patterning process, a patterned substrate, a semiconductor device and a preparation method thereof. The anti-reflective composition reduces the acid value of the anti-reflective composition by regulating the ratio of organic solvents with different acid values ​​to obtain an anti-reflective composition with a lower acid value, which can reduce the standing wave phenomenon in the patterning process, improve the stability of the patterning process, enhance the resolution of the obtained pattern, and reduce the line width roughness of the pattern.

[0004] In a first aspect, the present application provides an anti-reflective composition, which includes a resin, a thermal acid generator, a cross-linking agent and an organic solvent; the organic solvent includes a first organic solvent and a second organic solvent, the acid value of the first organic solvent is 0.002 mgNaOH / g-0.056 mgNaOH / g, and the acid value of the second organic solvent is less than 0.002 mgNaOH / g and greater than or equal to 0.0005 mgNaOH / g; in the organic solvent, the mass percentage of the first organic solvent is 10%-80%, and the mass percentage of the second organic solvent is 20%-90%.

[0005] Optionally, among the organic solvents, the mass percentage of the first organic solvent is 15%-75%, and the mass percentage of the second organic solvent is 25%-85%.

[0006] Optionally, the first organic solvent includes one or more of propylene glycol methyl ether acetate, 2-ethyl-1,3-propanediol, 1,4-butyrolactone, methyl 2-hydroxyisobutyrate, propylene glycol methyl ether, ethyl lactate and cyclohexanone.

[0007] Optionally, the second organic solvent includes one or more of propylene glycol methyl ether acetate, 2-ethyl-1,3-propanediol, 1,4-butyrolactone, methyl 2-hydroxyisobutyrate, propylene glycol methyl ether, ethyl lactate and cyclohexanone.

[0008] Optionally, the resin includes one or more of polyhydroxystyrene resin, polyester resin and polyacrylate resin.

[0009] Optionally, the thermal acid generator includes one or more of p-toluenesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, dodecylsulfonic acid triethylamine salt, p-toluenesulfonic acid amine salt, p-toluenesulfonic acid triethylamine salt, trifluoromethanesulfonic acid amine salt, trifluoromethanesulfonic acid amine triethylamine salt, trifluoromethanesulfonic acid amine pyridine salt, p-toluenesulfonic acid pyridinium salt, N-benzyl-N,N-dimethylphenyl trifluoromethanesulfonic acid ammonium salt, cyclohexyl trifluoromethanesulfonate, methyl trifluoromethanesulfonate, 2,4,6-triisopropylbenzenesulfonic acid cyclohexyl ester, and 2-nitrobenzyl p-toluenesulfonate.

[0010] Optionally, in the anti-reflective composition, the mass percentage of the resin is 0.4%-5%, the mass percentage of the thermal acid generator is 0.01%-0.5%, the mass percentage of the cross-linking agent is 0.05%-1%, and the mass percentage of the organic solvent is 93.5%-99.5%.

[0011] Optionally, the anti-reflective composition further comprises a crosslinking agent, wherein the crosslinking agent comprises one or more of a melamine crosslinking agent, a urea crosslinking agent and a polymer crosslinking agent containing an epoxy group;

[0012] Optionally, in the anti-reflective composition, the mass percentage of the crosslinking agent is 0.05%-1%.

[0013] Optionally, the resin includes one or more of polyhydroxystyrene resin, polyester resin and polyacrylate resin; the polyhydroxystyrene resin includes a structural unit derived from hydroxystyrene, and the polyester resin and the polyacrylate resin both have a hydroxyl-containing structural unit.

[0014] Optionally, the anti-reflective composition further comprises an additive, wherein the additive comprises a first additive and / or a second additive.

[0015] Optionally, the first additive includes one or more of pyrazole, pyrrole, tetrahydropyrrole, pyrimidine, purine, adenine and 6-aminopurine; the second additive includes one or more of ammonia water, substituted or unsubstituted aniline, substituted or unsubstituted naphthylamine and alkylamine.

[0016] Optionally, the mass of the additive is less than or equal to 0.05% of the mass of the resin.

[0017] Optionally, the sum of the mass of the structural unit derived from hydroxystyrene and the mass of the structural unit containing a hydroxyl group accounts for 10% to 50% of the mass of the resin.

[0018] Optionally, the additive includes the first additive and the second additive, and the mass ratio of the first additive to the second additive is (1:9)-(9:1).

[0019] Optionally, the acid value of the anti-reflective composition is 0.003 mgNaOH / g-2 mgNaOH / g.

[0020] Optionally, the acid value of the anti-reflective composition is 0.192 mgNaOH / g-0.44 mgNaOH / g.

[0021] The anti-reflective composition provided in the present application controls two organic solvents with different acid values ​​so that the acid value of the anti-reflective composition is maintained at a relatively low level, thereby reducing the amount of resin used and thus reducing its preparation cost. At the same time, the stability of the patterning process can be improved, the line width roughness of the obtained pattern can be reduced, and the resolution of the pattern can be improved, thereby improving the overall performance of the semiconductor device.

[0022] In a second aspect, the present application provides an anti-reflection film, which comprises an anti-reflection film of a solid molded product of the anti-reflection composition described in the first aspect.

[0023] The anti-reflection composition provided in the present application has a low acid value, and the prepared anti-reflection film has a good anti-reflection effect.

[0024] In a third aspect, the present application provides a patterning process, comprising: coating the anti-reflective composition described in the first aspect on a substrate to form an anti-reflective film on the substrate; forming a photosensitive material film on the surface of the anti-reflective film; exposing and developing the photosensitive material film through a photomask to form a patterned film on the substrate.

[0025] Optionally, the line width roughness of the pattern on the patterned film with a resolution of 190 nm is less than or equal to 5 nm.

[0026] The patterning process provided by the present application is simple, and the patterned film obtained has a clear pattern, low line width roughness, and high pattern resolution.

[0027] In a fourth aspect, the present application provides a patterned substrate, wherein the patterned substrate is manufactured using the patterning process described in the third aspect.

[0028] The patterned substrate provided by the present application has high resolution and good overall performance.

[0029] In a fifth aspect, the present application provides a semiconductor device, comprising the patterned substrate described in the fourth aspect and a functional layer disposed on the patterned substrate.

[0030] The semiconductor device provided by the present application has high precision and excellent comprehensive performance.

[0031] In a sixth aspect, the present application provides a method for preparing a semiconductor device, comprising: coating the anti-reflective composition as described in the first aspect on a substrate to form an anti-reflective film on the substrate; forming a photosensitive material film on the surface of the anti-reflective film; exposing and developing the photosensitive material film through a photomask to form a patterned film on the substrate; etching to obtain a patterned substrate; preparing a functional layer to obtain a semiconductor device.

[0032] The semiconductor preparation method provided in the present application is simple and has low preparation cost, which is conducive to its industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0034] Figure 1 This is a scanning electron microscope image of the patterned film provided in Example 1 of the present application;

[0035] Figure 2 This is a scanning electron microscope image of the patterned film provided in Example 2 of the present application;

[0036] Figure 3 This is a scanning electron microscope image of the patterned film provided in Example 3 of the present application;

[0037] Figure 4 This is a scanning electron microscope image of the patterned film provided in Example 4 of the present application;

[0038] Figure 5 This is a scanning electron microscope image of the patterned film provided in Comparative Example 2 of the present application. DETAILED DESCRIPTION

[0039] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0040] Patterning: Lithography, patterning process, and lithography process are important steps in the semiconductor device manufacturing process. The exposure and development process of this step depicts the collective graphic structure on the patterned material, and the pattern on the mask is transferred to the substrate substrate through the etching process. The substrate substrate here includes not only silicon wafers, but also other metal layers, dielectric layers, and the above-mentioned substrates with surface modification or added supporting layers.

[0041] Photosensitive material: also known as photoresist or anti-etching agent, refers to an etching-resistant thin film material whose solubility in the developer changes when irradiated or radiated by light with a wavelength of 10nm-400nm, light with a wavelength of 200nm-350nm, X-rays, electron beams, ion beams, etc.

[0042] Developer: The developer is a pure or mixed solvent that dissolves the soluble areas after the solubility of the patterned material changes due to exposure.

[0043] Positive pattern: After development, the exposed part of the patterned material is washed away by the developer, and the pattern formed is a positive pattern.

[0044] Negative pattern: After development, the unexposed part of the patterned material is washed away by the developer, and the pattern formed is a negative pattern.

[0045] Spin coating process: Spin coating is a high-speed film-forming method that can produce uniform thin films and is widely used in the preparation of thin films such as semiconductor materials and chemical materials. It uses the centrifugal force generated by rotation to evenly spread sols, solutions or suspensions on the substrate surface.

[0046] Mask: During the patterning process, the mask acts as an optical element in the light path. The mask carries the design pattern, and the light selectively transmits or reflects through it, so that the design pattern can be projected onto the patterned material film layer.

[0047] With the continuous development of the semiconductor industry and the continuous miniaturization of semiconductor devices, the thickness of the patterned film layer is getting thinner and thinner, and the feature size is constantly decreasing. During the patterning process, when the exposure light is irradiated to the substrate, part of the light will be reflected, and the reflected light has the same frequency as the exposure light, so that the exposure light and the reflected light interfere with each other in the photosensitive material film layer to form a standing wave, resulting in a standing wave effect, which leads to uneven distribution of light intensity in the photosensitive material film layer, prone to overexposure, resulting in a decrease in the stability of the patterning process, and the resolution of the obtained pattern is poor, and the line width roughness increases. In the related art, by setting a bottom anti-reflection coating (BARC) on the surface of the substrate to absorb the reflected light at the bottom, thereby reducing the standing wave phenomenon in the photosensitive material film layer, the line width roughness of the pattern can be better controlled, and the resolution of the pattern can be improved. Due to problems such as the preparation process and raw material quality control, the existing anti-reflection composition has a high acid value and a high preparation cost, which is not conducive to further improving the stability of the patterning process, and the line width roughness of the obtained pattern is poor and the resolution is low.

[0048] The present application provides an anti-reflective composition, comprising a resin, a thermal acid generator, a cross-linking agent and an organic solvent; the organic solvent comprises a first organic solvent and a second organic solvent, the acid value of the first organic solvent is 0.002 mgNaOH / g-0.056 mgNaOH / g, the acid value of the second organic solvent is less than 0.002 mgNaOH / g and greater than or equal to 0.0005 mgNaOH / g; in the organic solvent, the mass percentage of the first organic solvent is 10%-80%, and the mass percentage of the second organic solvent is 20%-90%. In the present application, two types of organic solvents with different acid values ​​are added to the system at the same time, and the acid value of the anti-reflective composition is kept at a low level by controlling the ratio of the first organic solvent and the second organic solvent with different acid values, which can absorb reflected rays and suppress the standing wave effect, so that the obtained pattern has low line width roughness and high resolution; it can also improve the stability of the patterning process of the photosensitive material film layer, and reduce the probability of the occurrence of white edges in the patterned film layer; in addition, by controlling the ratio of the first organic solvent and the second organic solvent, the ideal anti-reflective film thickness can be achieved while reducing the amount of other components such as resin, thereby reducing the preparation cost of the anti-reflective composition. Therefore, the anti-reflective composition provided by the present application has low preparation cost and low acid value, is conducive to improving the stability of the patterning process, reducing the line width roughness of the pattern, and improving the resolution of the pattern, and is applied in the preparation of semiconductor devices, which is conducive to improving the comprehensive performance of semiconductor devices.

[0049] In the present application, the organic solvent includes a first organic solvent and a second organic solvent, and the acid value of the first organic solvent is 0.002mgNaOH / g-0.056mgNaOH / g. The acid value of the first organic solvent is relatively high, and the acid value of the anti-reflective composition can be integrated so that the acid value of the anti-reflective composition will not be too low, while avoiding the instability of the patterning process caused by too low acid value, reducing the probability of the occurrence of white edges of the pattern, and reducing the occurrence of standing wave phenomenon, improving the resolution of the pattern, and reducing the line width roughness. Specifically, the acid value of the first organic solvent can be, but is not limited to, 0.002mgNaOH / g, 0.005mgNaOH / g, 0.01mgNaOH / g, 0.03mgNaOH / g, 0.035mgNaOH / g, 0.04mgNaOH / g or 0.056mgNaOH / g, etc. In one embodiment of the present application, the acid value of the first organic solvent may be 0.002 mgNaOH / g-0.05 mgNaOH / g, which can further enhance the anti-reflection effect of the anti-reflection film, reduce the standing wave phenomenon, improve the stability of the patterning process, and improve the overall performance of the pattern. In another embodiment of the present application, the acid value of the first organic solvent may be 0.04 mgNaOH / g-0.056 mgNaOH / g. In some embodiments, the first organic solvent and the second organic solvent may be obtained by separating and purifying the anti-reflection composition by means of distillation, etc., but not limited thereto, to obtain the acid value of the first organic solvent.

[0050] In the present application, in the organic solvent, the mass percentage of the first organic solvent is 10%-50%, that is, the first organic solvent accounts for 10%-50% of the total mass of the organic solvent. The first organic solvent of the appropriate proportion can make the anti-reflection composition have excellent anti-reflection effect, reduce the risk of white edge of the pattern, improve the stability of the patterning process, reduce the line width roughness of the pattern, and provide the resolution of the pattern. Specifically, in the organic solvent, the mass percentage of the first organic solvent can be, but not limited to, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70% or 80%, etc. In one embodiment of the present application, in the organic solvent, the mass percentage of the first organic solvent is 15%-35%, which can further improve the anti-reflection ability of the anti-reflection composition, reduce the standing wave effect, and reduce the preparation cost of the anti-reflection film. In another embodiment of the present application, in the organic solvent, the mass percentage of the first organic solvent is 50%-80%. In some embodiments, the mass percentage of the first organic solvent can be tested by, but not limited to, gas chromatography, liquid chromatography, nuclear magnetic resonance, etc.

[0051] In one embodiment of the present application, the first organic solvent may include, but is not limited to, one or more of propylene glycol methyl ether acetate (PGMEA), 2-ethyl-1,3-propanediol (PGEE), 1,4-butyrolactone (GBL), 2-hydroxyisobutyric acid methyl ester (HBM), propylene glycol methyl ether (PGME), ethyl lactate (EL) and cyclohexanone. In one embodiment of the present application, the first organic solvent may be propylene glycol methyl ether acetate (PGMEA). In another embodiment of the present application, the first organic solvent may be propylene glycol methyl ether acetate (PGMEA) and 1,4-butyrolactone (GBL). In some embodiments, when the first organic solvent includes multiple solvents, the two solvents may be mixed in any proportion.

[0052] In the present application, the acid value of the second organic solvent is less than 0.002 mgNaOH / g and greater than or equal to 0.0005 mgNaOH / g. The acid value of the second organic solvent is low, and the acid value of the anti-reflective composition can be appropriately reduced to maintain a suitable level to avoid excessive acid value, which has an adverse effect on the resolution and line width roughness of the pattern, and can also improve the stability of the patterning process. Specifically, the acid value of the second organic solvent can be, but is not limited to, 0.0019 mgNaOH / g, 0.0017 mgNaOH / g, 0.0015 mgNaOH / g, 0.0012 mgNaOH / g, 0.001 mgNaOH / g, 0.0008 mgNaOH / g, 0.0006 mgNaOH / g or 0.0005 mgNaOH / g, etc. In one embodiment of the present application, the acid value of the second organic solvent can be 0.0005 mgNaOH / g-0.0015 mgNaOH / g, which can further improve the stability of the patterning process. In some embodiments, the anti-reflective composition may be separated and purified by, but not limited to, distillation or other means to obtain the first organic solvent and the second organic solvent, thereby obtaining the acid value of the second organic solvent.

[0053] In the present application, in the organic solvent, the mass percentage of the second organic solvent is 50%-90%, that is, the second organic solvent accounts for 50%-90% of the total mass of the organic solvent. The second organic solvent of the appropriate proportion can make the anti-reflection composition reduce the line width roughness of the pattern, provide the resolution of the pattern, and have excellent anti-reflection effect, reduce the risk of white edge of the pattern, and improve the stability of the patterning process. Specifically, in the organic solvent, the mass percentage of the second organic solvent can be, but not limited to, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%, etc. In one embodiment of the present application, in the organic solvent, the mass percentage of the second organic solvent can also be 65%-85%, which can further improve the anti-reflection ability of the anti-reflection composition, reduce the standing wave effect, and reduce the preparation cost of the anti-reflection film. In another embodiment of the present application, in the organic solvent, the mass percentage of the second organic solvent can be 20%-70%. In some embodiments, the mass percentage of the second organic solvent can be tested by, but not limited to, gas chromatography, liquid chromatography, nuclear magnetic resonance, etc.

[0054] In one embodiment of the present application, the second organic solvent may include, but is not limited to, one or more of propylene glycol methyl ether acetate (PGMEA), 2-ethyl-1,3-propanediol (PGEE), 1,4-butyrolactone (GBL), 2-hydroxyisobutyric acid methyl ester (HBM), propylene glycol methyl ether (PGME), ethyl lactate (EL), and cyclohexanone. In one embodiment of the present application, the second organic solvent may be propylene glycol methyl ether (PGME). In another embodiment of the present application, the second organic solvent may be ethyl lactate (EL).

[0055] It should be noted that due to differences in production methods, preparation processes, storage conditions, etc., the acid value of the same organic solvent may deviate. In the present application, the first organic solvent must meet the acid value in the range of 0.002mgNaOH / g-0.056mgNaOH / g, and the second organic solvent must meet the acid value in the range of less than 0.002mgNaOH / g and greater than or equal to 0.0005mgNaOH / g, regardless of the type of organic solvent. For example: when the acid value of propylene glycol methyl ether acetate is 0.04mgNaOH / g, at this time, propylene glycol methyl ether acetate is the first organic solvent; when the acid value of propylene glycol methyl ether acetate is 0.001mgNaOH / g, at this time, propylene glycol methyl ether acetate is the second organic solvent. In some embodiments, the anti-reflective composition can be separated by means such as distillation, but not limited to, to obtain the first organic solvent and the second organic solvent, thereby obtaining its acid value.

[0056] In one embodiment of the present application, in the anti-reflection composition, the mass percentage of the organic solvent is 93.5%-99.5%. An appropriate amount of organic solvent can reduce the viscosity of the anti-reflection composition, improve the coating ability of the anti-reflection composition, and is conducive to forming a uniform anti-reflection film, thereby improving the anti-reflection ability of the anti-reflection film, reducing the occurrence of standing wave phenomenon, improving the stability of patterning, and improving the fineness of the pattern. Specifically, in the anti-reflection composition, the mass percentage of the organic solvent can be but not limited to 93.5%, 94%, 95%, 96%, 97%, 98% or 99.5%, etc. In one embodiment of the present application, in the anti-reflection composition, the mass percentage of the organic solvent can be 93.5%-95%. In another embodiment of the present application, in the anti-reflection composition, the mass percentage of the organic solvent can be 94%-99.5%.

[0057] In the present application, the resin enables the anti-reflection composition to have film-forming properties, can form an anti-reflection film with excellent uniformity, and improve the structural stability of the anti-reflection film. Achieve anti-reflection effect and reduce standing wave phenomenon. In one embodiment of the present application, the resin may include but is not limited to one or more of polyhydroxystyrene resins, polyester resins and polyacrylate resins. For example, the polyhydroxystyrene resin includes modified or unmodified polyhydroxystyrene, wherein the unmodified polyhydroxystyrene may be, for example, a homopolymer of hydroxystyrene; the modified polyhydroxystyrene includes copolymers of hydroxystyrene and other monomers, and / or, hydroxystyrene homopolymers or copolymers modified by other groups or compounds, and other monomers copolymerized with hydroxystyrene may be but are not limited to styrene, etc. In one embodiment of the present application, the polyhydroxystyrene resin includes structural units derived from hydroxystyrene, wherein the structural units derived from hydroxystyrene include structural units obtained by breaking the carbon-carbon double bonds of the vinyl groups in hydroxystyrene and undergoing addition polymerization. ; Polyester resins include resins whose main chains contain structural units obtained by polycondensation of polyols and polyacids, resins containing another kind of polyester formed by ester exchange reaction of polyols, polyacids, polyesters and other polyesters, and resins containing structural units obtained by ring opening of polyols or polyacids with epoxy monomers; that is, polyester resins include modified or unmodified polyester resins; polyacrylate resins include resins whose main chains contain structural units derived from substituted or unsubstituted acrylates, that is, polyacrylate resins include modified or modified polyacrylates, and it can be understood that polymethacrylate resins also belong to polyacrylate resins. In one embodiment of the present application, the film-forming resin may be a polyacrylate. In another embodiment of the present application, the film-forming resin may be a polyester resin.

[0058] In one embodiment of the present application, in the anti-reflection composition, the mass percentage of the resin is 0.4%-5%, and an appropriate amount of resin can improve the storage stability and film-forming properties of the anti-reflection composition. Specifically, in the anti-reflection composition, the mass percentage of the resin can be, but is not limited to, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%. In one embodiment of the present application, in the anti-reflection composition, the mass percentage of the resin can be 0.4%-3.5%. In another embodiment of the present application, in the anti-reflection composition, the mass percentage of the resin can be 3%-5%.

[0059] In the embodiments of the present application, the anti-reflective composition may be subjected to freeze-drying or other treatments to remove the solvent, the solid matter obtained after freeze-drying is dissolved in a quantitative deuterated reagent and subjected to nuclear magnetic resonance testing, the nuclear magnetic resonance test results are normalized, and then the content of the resin in the anti-reflective composition is calculated and determined.

[0060] In one embodiment of the present application, in the resin, the polyhydroxystyrene resin includes a structural unit derived from hydroxystyrene, the polyester resin and the polyacrylate resin both have a structural unit containing a hydroxyl group, the above resin has an absorption capacity for light with a wavelength of 100 nm-400 nm, and the film layer formed by it can effectively reduce the reflection of the substrate to the exposure light source. At this time, the anti-reflective composition also includes an additive. The first structural unit in the resin has a high absorbance to a light source with a wavelength of 193 nm or 248 nm, which is particularly beneficial to weaken the reflection of the substrate or the bottom film layer of the photosensitive material film to the above light source, and improve the fineness of the pattern after development. In particular, under the synergistic effect of the resin and the specific amount of the additive, the line width roughness of the patterned film can be effectively reduced, and the phenomenon of patterned white edges can be improved, which is beneficial to optimize the patterning effect in the semiconductor device process and is beneficial to the preparation and application of high-performance semiconductor devices. The introduction of the above additives can also assist the organic solvent, so that the anti-reflective composition obtains a lower acid value, further improving the fineness of the patterned film.

[0061] In one embodiment of the present application, the hydroxyl-containing structural unit includes a structural unit having an exposed hydroxyl group. In the polyacrylate resin, the hydroxyl-containing structural unit can be, for example, a structural unit derived from an acrylic ester having an exposed hydroxyl group in a substituent, wherein the carbon-carbon double bond of the acrylic ester is broken and added. Specifically, the acrylic ester having a hydroxyl group can be represented as , then the hydroxyl-containing structural unit is expressed as ; Among them, R 1 has a naked hydroxyl group; in some specific embodiments, R 1 The hydroxyl groups in the connection), △ indicates the connection site. Specifically, R 1 For example, it can be a substituted alkyl, a substituted cycloalkyl, a substituted alkenyl, a substituted cycloalkenyl, or a substituted lactone; the substituents in the substituted alkyl, substituted cycloalkyl, substituted alkenyl, substituted cycloalkenyl, or substituted lactone groups include hydroxyl (-OH); the present application does not limit the connection position of the hydroxyl group on the above-mentioned substituted groups, and any position that can be substituted by a hydroxyl group can be used. In the embodiment of the present application, one R 1 In some specific embodiments, one R 1 The number of hydroxyl groups in is 1. Of course, the above R 1 The substituents in the polyacrylate resin may also include other substituent groups, for example, fluorine atoms. It is understandable that the polyacrylate resin may contain multiple hydroxyl-containing structural units. In this case, the multiple hydroxyl-containing structural units may be the same or different; for example, the R 1 Both ; R may also be part of a hydroxyl-containing structural unit 1 for , the other part of the hydroxyl-containing structural unit , this application does not limit this; the above △ all represent the connection position. In this application, the above R 2 Including but not limited to hydrogen atom, substituted or unsubstituted C1-C4 alkyl and the like.

[0062] In one embodiment of the present application, in the polyester resin, the hydroxyl-containing structural unit also refers to a structural unit with exposed hydroxyl groups; wherein the hydroxyl group can be located on the side chain or on the main chain of the polyester resin. In some embodiments of the present application, in the polyester resin, the hydroxyl-containing structural unit can be, for example, In the polyester resin, the number of hydroxyl groups in a hydroxyl-containing structural unit can be, for example, 1, 2, 3, or 4; in some specific embodiments, in the polyester resin, a hydroxyl-containing structural unit contains 1 hydroxyl group.

[0063] In one embodiment of the present application, the sum of the mass of the structural unit derived from hydroxystyrene and the hydroxyl-containing structural unit accounts for 10%-50% of the mass of the resin. In this way, the anti-reflective composition has good film-forming properties, is conducive to forming a uniform film layer, and is conducive to the coating and molding of the photosensitive material film; more importantly, the anti-reflective film formed by it has a high absorbance to the aforementioned specific wavelength of light, which is more conducive to reducing the line width roughness of the pattern and eliminating the white edge. Specifically, the sum of the mass of the structural unit derived from hydroxystyrene and the hydroxyl-containing structural unit in the resin can be, but is not limited to, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, 50%, etc. In one embodiment of the present application, the sum of the mass of the structural unit derived from hydroxystyrene and the hydroxyl-containing structural unit accounts for 25%-45% of the mass of the resin. In another embodiment of the present application, the sum of the mass of the structural units derived from hydroxystyrene and the hydroxyl-containing structural units accounts for 15%-35% of the mass of the resin.

[0064] In one embodiment of the present application, the additive includes a first additive and / or a second additive. The first additive may include, but is not limited to, one or more of pyrazole, pyrrole, tetrahydropyrrole, pyrimidine, purine, adenine and 6-aminopurine; the second additive may include, but is not limited to, one or more of ammonia water, substituted or unsubstituted aniline, substituted or unsubstituted naphthylamine, and alkylamine. The first additive can synergize with the hydroxyl-containing structural unit in the resin topological structure and the structural unit derived from hydroxystyrene, and will not volatilize after being treated by baking in the semiconductor process, and can assist the organic solvent to adjust the acid value of the anti-reflective composition to a certain extent, which is beneficial to reduce the line width roughness of the pattern and improve the white edge phenomenon; the second additive can assist the organic solvent to adjust the acid value of the anti-reflective composition to a certain extent, which is beneficial to reduce the line width roughness of the pattern and improve the white edge phenomenon. In one embodiment of the present application, the additive may be pyrimidine. In another embodiment of the present application, the additive may be ammonia water.

[0065] In one embodiment of the present application, the mass of the additive relative to the total mass of the resin is less than or equal to 0.05%. Specifically, the mass of the additive relative to the total mass of the resin may be, but is not limited to, 0.05%, 0.048%, 0.046%, 0.045%, 0.042%, 0.04%, 0.038%, 0.036%, 0.035%, 0.032%, 0.03%, 0.028%, 0.026%, 0.025%, 0.022%, 0.02%, 0.018%, 0.016%, 0.015%, 0.012%, 0.01%, 0.009%, 0.008%, 0.007%, 0.006%, 0.005%, 0.0045%, 0.004%, 0.0035%, 0.003%, 0.002%, 0.0025%, 0.001%, etc. If the additive accounts for too large a proportion of the resin mass (>0.05%), it will result in insufficient exposure of the upper layer of photosensitive material in subsequent processes, and the photosensitive material will be difficult to remove after development.

[0066] In the embodiments of the present application, the mass ratio of the first structural unit and / or the second structural unit may be tested by using, but not limited to, a carbon spectrum of a nuclear magnetic resonance spectroscopy (NMR).

[0067] In some embodiments of the present application, the additive includes a first additive and a second additive, wherein the mass ratio of the first additive to the second additive is (1:9)-(9:1). In this way, it is more conducive to reducing the line width roughness of the pattern, while also helping to eliminate the white edge phenomenon and control the acid value of the anti-reflective composition. Specifically, the mass ratio of the first additive to the second additive may be, but is not limited to, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2 or 9:1, etc. In one embodiment of the present application, the mass ratio of the first additive to the second additive may be (3:7)-(7:3). In another embodiment of the present application, the mass ratio of the first additive to the second additive may be (1:1)-(7:3).

[0068] In the present application, the thermal acid generator is susceptible to thermal decomposition to produce acidic substances, which improves the fineness of the patterning process and is beneficial to improving the resolution of the pattern. Specifically, the thermal acid generator may include, but is not limited to, p-toluenesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, dodecylsulfonic acid triethylamine salt, p-toluenesulfonic acid amine salt, p-toluenesulfonic acid triethylamine salt, trifluoromethanesulfonic acid amine salt, trifluoromethanesulfonic acid amine triethylamine salt, trifluoromethanesulfonic acid amine pyridine salt, p-toluenesulfonic acid pyridinium salt, N-benzyl-N,N-dimethylphenyl trifluoromethanesulfonic acid ammonium salt, cyclohexyl trifluoromethanesulfonate, trifluoromethanesulfonic acid methyl ester, 2,4,6-triisopropylbenzenesulfonic acid cyclohexyl ester, 2-nitrobenzyl p-toluenesulfonate. In one embodiment of the present application, the thermal acid generator may be p-toluenesulfonic acid pyridine salt. In another embodiment of the present application, the thermal acid generator may be amine p-toluenesulfonic acid salt.

[0069] In one embodiment of the present application, in the anti-reflective composition, the mass percentage of the thermal acid generator is 0.01%-0.5%. An appropriate amount of the thermal acid generator can further improve the fineness of the pattern, which is beneficial to improving the overall performance of the semiconductor device. Specifically, in the anti-reflective composition, the mass percentage of the thermal acid generator can be, but is not limited to, 0.01%, 0.002%, 0.05%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4% or 0.5%, etc. In one embodiment of the present application, in the anti-reflective composition, the mass percentage of the thermal acid generator can be 0.01%-0.2%. In another embodiment of the present application, in the anti-reflective composition, the mass percentage of the thermal acid generator can be 0.1%-0.5%.

[0070] In the embodiments of the present application, the anti-reflective composition may be subjected to freeze-drying or other treatments to remove the solvent, and the solid matter obtained after freeze-drying is dissolved in a quantitative deuterated reagent and subjected to nuclear magnetic resonance testing. The nuclear magnetic resonance test results are normalized, and then the content of the thermal acid generator in the anti-reflective composition is calculated and determined.

[0071] In one embodiment of the present application, the crosslinking agent can improve the film-forming properties of the anti-reflection composition, which is beneficial to improve the curing of the anti-reflection film and improve the structural stability of the anti-reflection film. Specifically, the anti-reflection composition may include, but is not limited to, one or more of a melamine crosslinking agent, a urea crosslinking agent, and a polymer crosslinking agent containing an epoxy group. Exemplarily, the crosslinking agent may include, but is not limited to, one or more of N,N-dimethoxymethyl-melamine, tetramethoxymethyl glycoluril, and tris(2-hydroxyethyl)isocyanurate. In one embodiment of the present application, the crosslinking agent may be a melamine crosslinking agent. In another embodiment of the present application, the crosslinking agent may be a polymer crosslinking agent containing an epoxy group.

[0072] In one embodiment of the present application, in the anti-reflective composition, the mass percentage of the cross-linking agent is 0.05%-1%, and an appropriate amount of the cross-linking agent can further improve the structural stability of the anti-reflective film, which is conducive to improving the stability of the patterning process. Specifically, in the anti-reflective composition, the mass percentage of the cross-linking agent can be, but is not limited to, 0.05%, 0.1%, 0.15%, 0.2%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%, etc. In one embodiment of the present application, in the anti-reflective composition, the mass percentage of the cross-linking agent can be 0.05%-0.85%. In another embodiment of the present application, in the anti-reflective composition, the mass percentage of the cross-linking agent can be 0.6%-1%.

[0073] In the embodiments of the present application, the anti-reflective composition may be subjected to freeze-drying or other treatments to remove the solvent, the solid matter obtained after freeze-drying is dissolved in a quantitative deuterated reagent and subjected to nuclear magnetic resonance testing, the nuclear magnetic resonance test results are normalized, and then the content of the cross-linking agent in the anti-reflective composition is calculated and determined.

[0074] In one embodiment of the present application, the acid value of the anti-reflective composition is 0.003 mgNaOH / g-2 mgNaOH / g. The appropriate acid value of the anti-reflective composition can enable the anti-reflective composition to absorb bottom rays and suppress the standing wave effect, so that the obtained pattern has low line width roughness and high resolution; it can also improve the stability of the patterning process of the photosensitive material film layer, and at the same time reduce the probability of the occurrence of white edges in the patterned film layer. Specifically, the acid value of the anti-reflective composition may be, but is not limited to, 0.003 mg NaOH / g, 0.005 mg NaOH / g, 0.01 mg NaOH / g, 0.02 mg NaOH / g, 0.03 mg NaOH / g, 0.04 mg NaOH / g, 0.06 mg NaOH / g, 0.08 mg NaOH / g, 0.1 mg NaOH / g, 0.2 mg NaOH / g, 0.8 mg NaOH / g, 1 mg NaOH / g, 1.2 mg NaOH / g, 1.5 mg NaOH / g or 2 mg NaOH / g, etc. In one embodiment of the present application, the acid value of the anti-reflective composition may be 0.192 mg NaOH / g-0.44 mg NaOH / g, which may further reduce the standing wave phenomenon, reduce the pattern line width roughness, improve the stability of the patterning process, and reduce the white edge phenomenon in the patterned film layer. In another embodiment of the present application, the acid value of the anti-reflective composition may be 0.4 mgNaOH / g-2 mgNaOH / g.

[0075] In one embodiment of the present application, the anti-reflective composition may further include other additives, such as a leveling agent, a defoaming agent, an adhesion promoter, a plasticizer, etc., so as to improve the coating performance of the anti-reflective composition. Those skilled in the art may determine the amount of the above-mentioned additives added to the anti-reflective composition according to actual production needs.

[0076] One embodiment of the present application provides a method for preparing an anti-reflective composition, comprising: mixing a resin, a thermal acid generator, a cross-linking agent and an organic solvent to obtain an anti-reflective composition. In use, the anti-reflective composition of the present application is applied to a substrate in the form of a coating by any of a variety of methods such as spin coating. The anti-reflective composition generally forms an anti-reflective coating thickness between about 0.01 μm and 0.5 μm, preferably an anti-reflective coating thickness between about 0.02 μm and 0.2 μm, applied to the substrate. The substrate is preferably any substrate used in a process involving photosensitive materials. The preparation method provided by the present application is simple, has a low preparation cost, and realizes industrial production.

[0077] The present application also provides an anti-reflection film, which includes a solid molded product of the anti-reflection composition provided by any one of the above embodiments. The anti-reflection film provided by the present application has a good anti-reflection effect, can reduce the occurrence of standing wave effect, improve the stability of the patterning process, avoid light interference, improve the resolution of the pattern, and is conducive to reducing the appearance of white edges in the patterned film layer, reducing the line width roughness of the pattern, and improving the comprehensive performance of the semiconductor device.

[0078] In one embodiment of the present application, the thickness of the anti-reflection film is 0.01μm-0.5μm. The appropriate thickness of the anti-reflection film can improve the anti-reflection effect, reduce standing waves, improve the resolution of the pattern, and enhance the overall performance of the semiconductor device. Specifically, the thickness of the anti-reflection film may be, but is not limited to, 0.02μm, 0.05μm, 0.1μm, 0.2μm, 0.4μm, 0.5μm, etc. In one embodiment of the present application, the thickness of the anti-reflection film may be 0.02μm-0.1μm. In another embodiment of the present application, the thickness of the anti-reflection film may be 0.1μm-0.5μm. In some embodiments, the number of layers of the anti-reflection film is not limited, and can be selected according to actual conditions, and may be, but is not limited to, 1 layer, 2 layers, 3 layers, 5 layers, 6 layers, etc.

[0079] The present application provides a patterning process, comprising:

[0080] S101: coating an anti-reflection composition on a substrate to form an anti-reflection film on the substrate;

[0081] S102: forming a photosensitive material film on the surface of the anti-reflection film;

[0082] S103: Expose and develop the photosensitive material film through a photomask to form a patterned film on the substrate. The patterning process provided by the present application is simple, has good anti-reflection effect, poor standing wave phenomenon, and the patterned film obtained has clear patterns, low line width roughness, and high pattern resolution.

[0083] In one embodiment of the present application, the substrate may include, but is not limited to, silicon or a silicon substrate covered with a coating. For example, the coating may be an anti-etching coating, an epitaxial layer, a metal layer, a dielectric layer, a modified layer or a matching layer. Other coatings may be obtained by pre-treating the substrate. The pre-treatment method may be: 2 Plasma surface hydrophilic activation; or in Piranha solution (H 2 O: 30% ammonia: 30% H 2 O 2 = 5:1:1) for 15mins-20mins, and then washed with deionized water and isopropanol to complete the hydrophilic treatment; or hexamethyldisilazane (HMDS) is covered on the substrate by evaporation or spin coating to perform surface hydrophobic treatment on the substrate; the hydrophobic treatment can be after the hydrophilic treatment; or a bottom carbon coating (Spin on carbon, SOC) or a bottom silicon coating (Spin on glass, SOG).

[0084] In one embodiment of the present application, after the anti-reflective composition is applied, it needs to be baked and heated, and the heating temperature is 90°C-300°C. Heating can make the anti-reflective composition cure quickly to form an anti-reflective film with high stability, avoid mixing of the subsequent photosensitive material film with the anti-reflective film, and improve the stability of the patterning process. Specifically, the heating temperature can be, but is not limited to, 90°C, 100°C, 120°C, 150°C, 160°C, 180°C, 200°C, 220°C, 240°C, 260°C, 280°C or 300°C, etc. In one embodiment of the present application, the heating temperature can be 90°C-200°C. In another embodiment of the present application, the heating temperature can be 150°C-250°C.

[0085] In one embodiment of the present application, the line width roughness of the pattern on the patterned film is less than or equal to 5nm. The lower the line width roughness, the lower the edge roughness of the pattern, and the higher the fineness of the pattern, which is beneficial to improving the overall performance of the semiconductor device. Specifically, the line width roughness of the pattern on the patterned film can be, but is not limited to, 5nm, 4.5nm, 4nm, 3.5nm, etc. In one embodiment of the present application, the line width roughness of the pattern on the patterned film with a resolution of 190 nm can be 3.5nm-4.5nm. In another embodiment of the present application, the line width roughness of the pattern on the patterned film with a resolution of 190 nm can be 4nm-5nm.

[0086] The present application also provides a patterned substrate, which is manufactured using the patterning process described in any of the above embodiments. The patterned substrate can be used in the preparation of semiconductor devices, thereby improving the manufacturing progress and quality of semiconductor devices and helping to improve the overall performance of semiconductor devices.

[0087] The present application provides a semiconductor device, which includes a patterned substrate as described in any one of the above embodiments and a functional layer arranged on the patterned substrate, or is manufactured using any of the patterning processes described in any one of the above embodiments. The semiconductor device provided by the present application has high precision, good miniaturization, and excellent comprehensive performance.

[0088] In one embodiment of the present application, the semiconductor device comprises: a structure obtained by etching or electron injection into a patterned substrate. In one embodiment of the present application, the semiconductor device is a structure obtained by etching or electron injection into a patterned substrate whose substrate is a silicon wafer.

[0089] In the present application, there is no limitation on the specific type of semiconductor device. In one embodiment of the present application, the semiconductor device may be an integrated circuit device including a chip. During the preparation of the chip, other functional layers may be prepared after the aforementioned patterning process is completed.

[0090] The present application also provides a method for preparing a semiconductor device, comprising:

[0091] S201: coating an anti-reflective composition on a substrate to form an anti-reflective film on the substrate;

[0092] S202: forming a photosensitive material film on the surface of the anti-reflection film;

[0093] S203: exposing and developing the photosensitive material film through a photomask to form a patterned film on the substrate;

[0094] S204: etching to obtain a patterned substrate;

[0095] S205: Prepare a functional layer to obtain a semiconductor device. The preparation method provided in the present application is simple, and the obtained semiconductor device has excellent comprehensive performance, which is conducive to its commercial application.

[0096] In one embodiment of the present application, the substrate may be cleaned before coating to remove impurities and dust on the surface of the substrate. Specifically, the cleaning method may be, but is not limited to, using a solvent, acid, ultrasound or spray cleaning. In one embodiment of the present application, the cleaning method may be ultrasonic cleaning.

[0097] In one embodiment of the present application, the light source for exposure may be, but is not limited to, light with a wavelength of 100 nm-400 nm, X-rays, electron beams, ion beams, and the like.

[0098] In one embodiment of the present application, after coating, baking treatment can be performed before exposure to remove excess solvent in the film layer and improve the structural reliability of the anti-reflective composition; baking treatment can also be performed after exposure and before development to promote the chemical reaction in the etching-resistant coating. The baking temperature is 60°C-250°C, and the baking time is 20s-120s. Specifically, the baking temperature can be but not limited to 60°C, 80°C, 100°C, 120°C, 140°C, 160°C, 200°C or 250°C, and the baking time can be but not limited to 20s, 40s, 60s, 80s, 100s or 120s, etc. In one embodiment of the present application, the baking temperature can be 60°C-150°C, and the baking time can be 20s-80s. In one embodiment of the present application, the baking temperature can be 100°C-250°C, and the baking time can be 60s.

[0099] In one embodiment of the present application, a developing solution is used for developing treatment. Since the chemical properties of the exposed area in the photosensitive material film layer change and the solubility changes, the exposed photosensitive material film layer needs to be cleaned with a developing solution to obtain a patterned film. The cleaning time is 10s-300s, which can be divided into single-step cleaning and multi-step cleaning. After cleaning, if the exposed area in the photosensitive material film layer is washed away, it is positive development to form a positive pattern. At this time, the patterned composition is a positive anti-reflective composition; if the exposed area is not washed away, it is negative development to form a negative pattern. At this time, the patterned composition is a negative patterning composition.

[0100] In one embodiment of the present application, the developing solution includes a developer. The developer can be selected according to the properties of the anti-reflective composition and used in combination to improve the etching effect. The developing time is 10s-120s. Specifically, the developer can include but is not limited to organic solutions, inorganic solutions, pure solvents, mixed solvents, solvents containing other additives, etc.; illustratively, the organic solvent can be but is not limited to one or more of ketones, alcohols, ethers, esters, lactones and high-boiling alcohols; among them, ketones can be but are not limited to cyclohexanone or methyl-2-n-pentyl ketone, etc.; alcohols can be but are not limited to 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol or diacetone alcohol, etc.; ethers can be but are not limited to propylene glycol monomethyl ether. Ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether or diethylene glycol dimethyl ether, etc.; esters may be, but are not limited to, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, n-butyl acetate, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, tert-butyl acetate, tert-butyl propionate or propylene glycol monotert-butyl ether acetate, etc.; lactones may be, but are not limited to, γ-butyrolactone; high boiling point alcohol solvents may be, but are not limited to, diethylene glycol, propylene glycol, glycerol, 1,4-butanediol or 1,3-butanediol, etc. In one embodiment of the present application, the developer may be a tetramethylammonium hydroxide (TMAH) aqueous solution with a concentration of 0.5%-5% and n-butyl acetate. In some embodiments, the development further includes rinsing and baking to remove impurities on the surface of the anti-reflection film and improve the structural reliability of the anti-reflection film.

[0101] The effect of the technical solution of the present application is further illustrated below through specific examples.

[0102] Example 1

[0103] The anti-reflective composition includes 3.3% by weight of a resin (polyacrylic resin), 0.05% by weight of a thermal acid generator, 0.45% by weight of a cross-linking agent, and 96.2% by weight of an organic solvent, wherein the organic solvent includes 25% by weight of a first organic solvent (propylene glycol methyl ether acetate (PGMEA) having an acid value of 0.004 mgNaOH / g) and 75% by weight of a second organic solvent (ethyl lactate (EL) having an acid value of 0.0012 mgNaOH / g).

[0104] Example 2

[0105] The difference from Example 1 is that the organic solvent includes a first organic solvent with a mass percentage of 15% (2-hydroxyisobutyric acid methyl ester (HBM) with an acid value of 0.05 mgNaOH / g), a first organic solvent with a mass percentage of 32% (1,4-butyrolactone (GBL) with an acid value of 0.0035 mgNaOH / g), and a second organic solvent with a mass percentage of 53% (propylene glycol methyl ether (PGME) with an acid value of 0.0009 mgNaOH / g).

[0106] Example 3

[0107] The difference from Example 1 is that in the organic solvent, the mass percentage of the first organic solvent (1,4-butyrolactone (GBL) with an acid value of 0.0035 mgNaOH / g) is 10%, and the mass percentage of the second organic solvent (ethyl lactate (EL) with an acid value of 0.0012 mgNaOH / g) is 90%.

[0108] Example 4

[0109] The difference from Example 1 is that in the organic solvent, the mass percentage of the first organic solvent (2-hydroxyisobutyric acid methyl ester (HBM) with an acid value of 0.002 mgNaOH / g) is 80%, and the mass percentage of the second organic solvent (cyclohexanone with an acid value of 0.0015 mgNaOH / g) is 20%.

[0110] Example 5

[0111] The difference from Example 1 is that the resin is a polyacrylate resin, and the resin (specifically a polymethacrylate resin, and the hydroxyl-containing structural unit is derived from hydroxyethyl methacrylate, the mass content of the hydroxyl-containing structural unit in the resin is 40%, and the structural unit derived from hydroxyethyl methacrylate is as shown in Formula A, Formula A), the first additive is pyrrole, and the mass content is 0.0004%.

[0112] Example 6

[0113] The difference from Example 5 is that the anti-reflective composition further includes a second additive (triethylamine), and the mass ratio of the first additive to the second additive is 6:4.

[0114] Comparative Example 1

[0115] The difference from Example 1 is that the organic solvent is propylene glycol methyl ether acetate (PGMEA with an acid value of 0.024 mgNaOH / g).

[0116] Comparative Example 2

[0117] The difference from Example 1 is that the mass percentage of resin (polyacrylic resin) is 2.8%, the mass percentage of thermal acid generator is 0.05%, the mass percentage of cross-linking agent is 0.45%, and the mass percentage of organic solvent is 96.7%. Among the organic solvents, the mass percentage of the first organic solvent (propylene glycol methyl ether acetate (PGMEA) with an acid value of 0.004 mgNaOH / g) is 5%, and the mass percentage of the second organic solvent (ethyl lactate (EL) with an acid value of 0.0012 mgNaOH / g) is 95%.

[0118] Comparative Example 3

[0119] The difference from Example 1 is that the mass percentage of resin (polyacrylic resin) is 3.9%, the mass percentage of thermal acid generator is 0.05%, the mass percentage of cross-linking agent is 0.45%, and the mass percentage of organic solvent is 95.6%. Among the organic solvents, the mass percentage of the first organic solvent (propylene glycol methyl ether acetate (PGMEA) with an acid value of 0.004 mgNaOH / g) is 80%, and the mass percentage of the second organic solvent (propylene glycol methyl ether (PGME) with an acid value of 0.0009 mgNaOH / g) is 20%.

[0120] Comparative Example 4

[0121] The difference from Example 1 is that, among the organic solvents, the first organic solvent is propylene glycol methyl ether acetate (PGMEA) having an acid value of 0.0015 mgNaOH / g, and the second organic solvent is ethyl lactate (EL) having an acid value of 0.0002 mgNaOH / g.

[0122] Comparative Example 5

[0123] The difference from Example 1 is that, among the organic solvents, the first organic solvent is propylene glycol methyl ether acetate (PGMEA) having an acid value of 0.006 mgNaOH / g, and the second organic solvent is ethyl lactate (EL) having an acid value of 0.003 mgNaOH / g.

[0124] Performance Testing

[0125] The acid value of the anti-reflective composition prepared in the above Examples 1-6 and Comparative Examples 1-5 was tested, and the sample was titrated to neutrality using the principle of acid-base neutralization, and the titration endpoint was determined by the color change phenomenon under the action of the indicator. The test results are shown in Table 1.

[0126] The anti-reflection compositions prepared in the above-mentioned Examples 1-6 and Comparative Examples 1-5 were coated on the surface of a substrate to form an anti-reflection substrate, and then a patterned composition was coated on the anti-reflection substrate to form a photosensitive material film layer; the anti-reflection composition film layer was exposed and developed through a photomask to form a patterned film on the surface of the substrate, and the line width of the patterned film was 190 nm (that is, the resolution of the patterned film was 190 nm). The exposure performance of the above-mentioned patterned film was tested. Figure 1 This is a scanning electron microscope image of the patterned film provided in Example 1 of the present application. Figure 2 This is a scanning electron microscope image of the patterned film provided in Example 2 of the present application. Figure 3 This is a scanning electron microscope image of the patterned film provided in Example 3 of the present application. Figure 4 This is a scanning electron microscope image of the patterned film provided in Example 4 of the present application. Figure 5 This is a scanning electron microscope image of the patterned film provided in Comparative Example 2 of the present application. Figure 5 The white borders on both sides of the patterned film are heavier, namely white edges. Among them, the test results of the best exposure energy BE, the best focal length BF, the exposure energy margin EL, the depth of focus DOF, and the line width roughness LWR are shown in Table 2.

[0127] Table 1 Acid value performance test

[0128]

[0129] Table 2 Exposure performance test

[0130]

[0131] According to the examples 1-6 and comparative examples 1-5 provided by the present application, it can be seen that the anti-reflective composition provided by the present application reduces the acid value of the anti-reflective composition by regulating the ratio of organic solvents with different acid values ​​to obtain an anti-reflective composition with a lower acid value, which can reduce the standing wave phenomenon in the patterning process, improve the stability of the patterning process, improve the resolution of the obtained pattern, and reduce the line width roughness of the pattern. According to Example 1 and Examples 2-6, it can be seen that the appropriate ratio of the first organic solvent and the second organic solvent, the addition and ratio of the first additive and the second additive can reduce the acid value of the anti-reflective composition, so that the anti-reflective composition has excellent anti-reflective performance, reduces the standing wave phenomenon, reduces the line width roughness of the patterned film, and can avoid the generation of white edges, and improve the stability of the patterning process. According to Example 1 and Comparative Example 1, it can be seen that by the ratio of organic solvents with different acid values, the acid value of the anti-reflective composition is reduced, the resolution of the pattern is improved, and the line width roughness of the pattern is reduced. It can be seen from Example 1 and Comparative Examples 2-5 that a suitable ratio of the first organic solvent to the second organic solvent and a moderate acid value can obtain an anti-reflective composition with a suitable acid value, which reduces the pattern line width roughness and reduces the amount of other components such as resin, which is beneficial to reducing the preparation cost and promoting the industrial preparation of semiconductor devices.

[0132] It should be understood that the first, second and various numerical numbers involved in this document are only distinguished for the convenience of description and are not used to limit the scope of the present application.

[0133] In this application, "and / or" describes the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone, where A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0134] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple.

[0135] In this application, “-” represents a range value, including the endpoint values ​​at both ends. For example, the value of a can be 0.5-15, which means that the value of a can be between 0.5 and 15, and includes the endpoint values ​​0.5 and 15.

[0136] The above is a preferred embodiment of the present application, but it should not be understood as limiting the scope of the present application. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present application, and these improvements and modifications are also considered to be within the scope of protection of the present application.

Claims

1. An antireflective composition, characterized in that: The anti-reflective composition comprises a resin, a thermal acid generator, a cross-linking agent and an organic solvent; the organic solvent comprises a first organic solvent and a second organic solvent, the acid value of the first organic solvent is 0.002 mgNaOH / g-0.056 mgNaOH / g, and the acid value of the second organic solvent is less than 0.002 mgNaOH / g and greater than or equal to 0.0005 mgNaOH / g; Among the organic solvents, the mass percentage of the first organic solvent is 10%-80%, and the mass percentage of the second organic solvent is 20%-90%; the acid value of the anti-reflective composition is 0.192 mgNaOH / g-0.44 mgNaOH / g.

2. The antireflective composition according to claim 1, wherein In the organic solvent, the mass percentage of the first organic solvent is 15%-75%, and the mass percentage of the second organic solvent is 25%-85%.

3. The antireflective composition according to claim 1, wherein The first organic solvent includes one or more of propylene glycol methyl ether acetate, 2-ethyl-1,3-propanediol, 1,4-butyrolactone, methyl 2-hydroxyisobutyrate, propylene glycol methyl ether, ethyl lactate and cyclohexanone, and the second organic solvent includes one or more of propylene glycol methyl ether acetate, 2-ethyl-1,3-propanediol, 1,4-butyrolactone, methyl 2-hydroxyisobutyrate, propylene glycol methyl ether, ethyl lactate and cyclohexanone.

4. The antireflective composition according to claim 1, wherein The resin includes one or more of polyhydroxystyrene resin, polyester resin and polyacrylate resin.

5. The antireflective composition according to claim 1, wherein The thermal acid generator includes one or more of p-toluenesulfonic acid, trifluoromethanesulfonic acid, dodecylbenzenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, dodecylsulfonic acid triethylamine salt, p-toluenesulfonic acid amine salt, p-toluenesulfonic acid triethylamine salt, trifluoromethanesulfonic acid amine salt, trifluoromethanesulfonic acid amine triethylamine salt, trifluoromethanesulfonic acid amine pyridine salt, p-toluenesulfonic acid pyridinium salt, N-benzyl-N,N-dimethylphenyl trifluoromethanesulfonic acid ammonium salt, cyclohexyl trifluoromethanesulfonate, trifluoromethanesulfonic acid methyl ester, 2,4,6-triisopropylbenzenesulfonic acid cyclohexyl ester, and 2-nitrobenzyl p-toluenesulfonate.

6. The antireflective composition according to claim 1, wherein In the anti-reflective composition, the mass percentage of the resin is 0.4%-5%, the mass percentage of the thermal acid generator is 0.01%-0.5%, the mass percentage of the cross-linking agent is 0.05%-1%, and the mass percentage of the organic solvent is 93.5%-99.5%.

7. The antireflective composition according to claim 1, wherein The crosslinking agent includes one or more of a melamine crosslinking agent, a urea crosslinking agent and a polymer crosslinking agent containing an epoxy group.

8. The antireflective composition according to any one of claims 1 to 7, characterized in that The resin includes one or more of polyhydroxystyrene resin, polyester resin and polyacrylate resin; the polyhydroxystyrene resin includes a structural unit derived from hydroxystyrene, and the polyester resin and the polyacrylate resin both have a structural unit containing a hydroxyl group.

9. The antireflective composition according to claim 8, wherein The anti-reflective composition further comprises an additive, wherein the additive comprises a first additive and / or a second additive; The first additive includes one or more of pyrazole, pyrrole, tetrahydropyrrole, pyrimidine, purine, adenine and 6-aminopurine; The second additive includes one or more of ammonia, substituted or unsubstituted aniline, substituted or unsubstituted naphthylamine and alkylamine; The mass of the additive is less than or equal to 0.05% of the mass of the resin; The sum of the mass of the structural unit derived from hydroxystyrene and the structural unit containing a hydroxyl group accounts for 10% to 50% of the mass of the resin.

10. The antireflective composition according to claim 9, characterized in that The additives include the first additive and the second additive, and the mass ratio of the first additive to the second additive is (1:9)-(9:1).

11. An antireflection film, characterized in that: The antireflection film comprises a solid formed article of the antireflection composition according to any one of claims 1 to 10.

12. A patterning process, characterized in that: include: Coating the anti-reflective composition according to any one of claims 1 to 10 on a substrate to form an anti-reflective film on the substrate; forming a photosensitive material film on the surface of the anti-reflection film; The photosensitive material film is exposed and developed through a photomask to form a patterned film on the substrate.

13. The patterning process according to claim 12, characterized in that: The line width roughness of the pattern on the patterned film with a resolution of 190 nm is less than or equal to 5 nm.

14. A patterned substrate, characterized in that: The patterned substrate is manufactured by the patterning process as claimed in claim 12 or 13.

15. A semiconductor device, characterized in that: The semiconductor device comprises the patterned substrate according to claim 14 and a functional layer disposed on the patterned substrate.

16. A method for preparing a semiconductor device, characterized in that: include: Applying the antireflection composition according to any one of claims 1 to 10 on a substrate to form an antireflection film on the substrate; forming a photosensitive material film on the surface of the anti-reflection film; exposing and developing the photosensitive material film through a photomask to form a patterned film on the substrate; Etching to obtain a patterned substrate; A functional layer is prepared to obtain a semiconductor device.

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