Anti-reflective composition, anti-reflective film, patterning method, patterned substrate, semiconductor device, and method for manufacturing same

Abstract

The embodiment of the invention provides an anti-reflection composition, an anti-reflection film, a patterning method, a patterned substrate, a semiconductor device and a preparation method of the semiconductor device. When a film layer formed by the anti-reflection composition is applied to the manufacturing process of a semiconductor device, reflection and diffraction of parts such as a substrate on the lower layer of a photosensitive material film to a light source can be effectively reduced, the line width roughness of a patterned film can be further reduced, and the white edge phenomenon of the patterned film is improved.

Description

Technical Field

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

[0002] With the rapid development of semiconductor integrated circuits in recent years, the requirements for the critical dimensions of chips have also been continuously reduced. The patterning process usually includes forming a photosensitive material film on a substrate, so that the exposure light source irradiates the above-mentioned photosensitive material film through a mask with a predetermined pattern, and then selectively dissolves the photosensitive material film through development to form a patterned film, and then etches the substrate with the patterned film to achieve the transfer of the pattern. However, the substrate under the photosensitive material film will reflect the light source or cause the light source to diffract, resulting in the inability to control the critical dimensions. In order to reduce the damage to the patterned film caused by reflected light and diffracted light, an anti-reflective film layer can be introduced between the photosensitive material film and the substrate. In recent years, the industry has often used organic resin anti-reflective films, but as the critical dimensions of chips continue to develop towards smaller sizes, the performance of current anti-reflective films is still expected to be improved to further enhance the pattern fineness of the photosensitive material film. Summary of the invention

[0003] In view of this, the embodiments of the present application provide an anti-reflection composition, an anti-reflection film, a patterning method, a patterned substrate, a semiconductor device and a method for preparing the same. The film layer formed by the anti-reflection composition is applied in the process of manufacturing semiconductor devices, which can not only effectively reduce the reflection and diffraction of the light source by the substrate and other components under the photosensitive material film, but also further reduce the line width roughness of the patterned film and improve the footing phenomenon of the patterned film.

[0004] The first aspect of the embodiment of the present application provides an anti-reflective composition, comprising a resin, an additive and a solvent; the resin comprises one or more of a polyhydroxystyrene resin, a polyester resin and a polyacrylate resin; the polyhydroxystyrene resin comprises a structural unit derived from hydroxystyrene, and the polyester resin and the polyacrylate resin both have a structural unit containing a hydroxyl group;

[0005] The additive includes a first additive, and / or the additive includes a second additive;

[0006] The first additive includes one or more of pyrazole, pyrrole, tetrahydropyrrole, pyrimidine, purine, adenine and 6-hydroxypurine;

[0007] The second additive includes one or more of ammonia, substituted or unsubstituted aniline, substituted or unsubstituted naphthylamine, and substituted or unsubstituted alkylamine;

[0008] The mass of the additive is less than or equal to 0.05% of the total mass of the resin.

[0009] When the coating formed by the above-mentioned anti-reflective composition is set at the bottom of the photosensitive material layer, under the synergistic effect of the resin and the specified additives in a specific amount, the line width roughness (LWR) of the patterned film can be effectively reduced, and the white edge phenomenon of the patterned film can be improved, thereby facilitating the optimization of the patterning effect in the semiconductor device process and facilitating the preparation and application of high-performance semiconductor devices.

[0010] In some embodiments of the present application, the sum of the mass of the structural unit derived from hydroxystyrene and the structural unit containing hydroxyl accounts for 10%-50% of the total mass of the resin. This is more conducive to reducing the LWR of the pattern and reducing or even eliminating the white edge of the pattern.

[0011] In some embodiments of the present application, the additive accounts for 0.005%-0.05% of the total mass of the resin. This is more conducive to reducing the LWR of the pattern formed after the photosensitive material film is exposed, and reducing or even eliminating the white edge phenomenon of the pattern.

[0012] In some embodiments of the present application, the resin accounts for 0.4%-5% of the mass of the anti-reflection composition. In this way, the anti-reflection composition has good coating performance and is conducive to forming an anti-reflection film with appropriate thickness and good uniformity.

[0013] In some embodiments of the present application, the 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; the solvent accounts for 93.5%-99.5% of the mass of the anti-reflective composition. The above solvent has good compatibility with the resin and the first additive, the second additive and other components used in the anti-reflective composition of the present application, and can form a uniform and stable solution, which is conducive to the application of the anti-reflective composition.

[0014] In some embodiments of the present application, a crosslinking agent is further included; the crosslinking agent accounts for 0.05%-1% of the mass of the anti-reflective composition. The crosslinking agent is used to cause a crosslinking reaction of the resin.

[0015] In some embodiments of the present application, a compound that can provide an acid is also included; the compound that can provide an acid accounts for 0.01%-0.5% of the mass of the anti-reflective composition. In this way, the reaction between the crosslinking agent and the resin can be catalyzed, and the risk of the acid generated by the compound that can provide an acid diffusing into the photosensitive material film in the subsequent process can also be reduced.

[0016] In some embodiments of the present application, the additive includes the first additive and the second additive. Under the synergistic effect of the first additive and the second additive, it is more conducive to assisting in reducing the LWR of the pattern formed by the photosensitive material film and improving the white edge phenomenon.

[0017] In some embodiments of the present application, the mass ratio of the first additive to the second additive is 1:9 to 9:1. In this way, it is more conducive to reducing the LWR of the pattern formed by the photosensitive material film, and at the same time, it is conducive to improving or even eliminating the white edge phenomenon of the patterned film.

[0018] A second aspect of the embodiments of the present application provides an anti-reflection film, which includes a solid molded product of the anti-reflection composition provided in the first aspect of the embodiments of the present application.

[0019] During the patterning process, setting the above-mentioned anti-reflection film on the lower layer of the photosensitive material film can effectively reduce the line width roughness of the pattern formed after the photosensitive material film is exposed and developed, and can also effectively improve or eliminate the white edge phenomenon of the patterned film, thereby facilitating the preparation of highly integrated semiconductor devices.

[0020] A third aspect of the embodiment of the present application provides a patterning process, including:

[0021] Applying the anti-reflection composition provided in the embodiment of the present application on a substrate to form an anti-reflection film on the substrate;

[0022] forming a photosensitive material film on the surface of the anti-reflection film;

[0023] exposing and developing the photosensitive material film through a photomask to form a patterned film on the substrate;

[0024] Etching to obtain a patterned substrate.

[0025] The fourth aspect of the embodiment of the present application provides a patterned substrate, which is made by the patterning process provided by the embodiment of the present application. The critical dimension of the pattern on the patterned substrate and the line width roughness of the pattern can reach the industry-leading level, and can be used to provide high-precision and high-reliability semiconductor devices, such as high-precision and high-reliability integrated circuits.

[0026] A fifth aspect of an embodiment of the present application provides a semiconductor device, which includes a patterned substrate provided by an embodiment of the present application and a functional layer arranged on the patterned substrate.

[0027] Since the semiconductor device provided by the embodiment of the present application is manufactured using the patterned substrate provided by the embodiment of the present application, the semiconductor device provided by the embodiment of the present application can have both high precision and high reliability.

[0028] In the embodiments of the present application, there is no special restriction on the structure of the semiconductor device. Those skilled in the art can design it according to the actual application needs, and prepare it according to the acid-sensitive resin, photosensitive composition, patterned film, or patterned substrate provided in the embodiments of the present application. In the embodiments of the present application, the semiconductor device includes but is not limited to integrated circuit devices such as chips. It is understandable that the semiconductor device provided in the embodiments of the present application also includes a functional layer, and the functional layer may include any structure that can be applied to the semiconductor device, for example, metal wiring, active devices, passive devices, etc.

[0029] A sixth aspect of the embodiments of the present application provides a method for preparing a semiconductor device, comprising:

[0030] The anti-reflection composition provided in the embodiment of the present application is coated on a substrate to form an anti-reflection film on the substrate;

[0031] forming a photosensitive material film on the surface of the anti-reflection film;

[0032] exposing and developing the photosensitive material film through a photomask to form a patterned film on the substrate;

[0033] Etching to obtain a patterned substrate;

[0034] A functional layer is prepared to obtain a semiconductor device.

[0035] The preparation method is suitable for large-scale industrial production and can produce semiconductor devices with high precision and high reliability. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is a scanning electron microscope (SEM) photograph of a patterned film obtained by performing exposure performance test 1 using the anti-reflective composition of Example 1 of the present application;

[0037] Figure 2 This is a SEM photograph of a patterned film obtained by performing exposure performance test 1 using the anti-reflective composition of Example 2 of the present application;

[0038] Figure 3 This is a SEM photograph of a patterned film obtained by performing exposure performance test 1 using the anti-reflective composition of Example 3 of the present application;

[0039] Figure 4 This is a SEM photograph of a patterned film obtained by performing exposure performance test 1 using the anti-reflective composition of comparative example 1;

[0040] Figure 5 This is a SEM photograph of a patterned film obtained by performing exposure performance test 2 using the anti-reflective composition of Example 4. DETAILED DESCRIPTION

[0041] As the critical dimensions of semiconductor integrated circuits have been moving towards a smaller direction in recent years, the requirements for the degree of refinement of each process stage in the semiconductor process have been continuously improved. The patterning process is one of the key processes in the semiconductor process, which usually includes forming a photosensitive material film on a substrate, so that the exposure light source irradiates the above-mentioned photosensitive material film through a mask with a predetermined pattern, and then selectively dissolves the photosensitive material film through development to form a patterned film, and then etches the substrate with the patterned film to achieve the transfer of the pattern. The fineness of the pattern determines the lower limit of the refinement of the chip to a certain extent. During the above exposure, the substrate (for example, a silicon wafer) under the photosensitive material film will reflect the light source, and the reflected light and the incident light will interfere, forming a standing wave effect and multiple exposures inside the photosensitive material film, resulting in the key dimensions of the pattern being uncontrollable, damaging the clarity and resolution of the pattern, and damaging the etching accuracy. In addition, the patterned film will also produce footing, which is manifested as white edges on the edges of the pattern in the SEM top view of the patterned film. The more obvious the white edges, the more serious the footing problem. In order to reduce the damage of reflected light and diffracted light to the patterned film, an anti-reflection film layer can be introduced between the photosensitive material film and the substrate, or between the photosensitive material film and other bottom film layers. In recent years, the industry often uses organic resin anti-reflection compositions to form bottom anti-reflection coatings, but its performance is still expected to be improved. The anti-reflection performance of the bottom anti-reflection coating commonly used in the industry mainly depends on the resin with light absorption ability, thereby reducing the reflectivity of the substrate.

[0042] The embodiment of the present application provides an anti-reflective composition, including a resin, an additive and a solvent; the resin includes one or more of a polyhydroxystyrene resin, a polyester resin and a 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; the resin has the ability to absorb light with a wavelength of 100nm-400nm, and the film layer formed by the resin can effectively reduce the reflection of the substrate to the exposure light source. The polyhydroxystyrene resin includes modified or unmodified polyhydroxystyrene, wherein the unmodified polyhydroxystyrene can be, for example, a homopolymer of hydroxystyrene; the modified polyhydroxystyrene includes a copolymer of hydroxystyrene and other monomers, and / or a homopolymer or copolymer of hydroxystyrene modified by other groups or compounds, and other monomers copolymerized with hydroxystyrene can be but are not limited to styrene, etc. In the embodiment of the present application, the polyhydroxystyrene resin includes a structural unit derived from hydroxystyrene, wherein the structural unit derived from hydroxystyrene includes a structural unit obtained by breaking the carbon-carbon double bond of the vinyl group in hydroxystyrene and undergoing addition polymerization. Polyester resins include resins whose main chains contain structural units obtained by condensation of polyols and polyacids, resins including another kind of polyester generated by ester exchange reaction of polyols, polyacids, polyesters and other polyesters, and resins including 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. It can be understood that polymethacrylate resins also belong to polyacrylate resins.

[0043] In the present application, the hydroxyl-containing structural unit includes a structural unit with exposed hydroxyl groups. In polyacrylate resins, the hydroxyl-containing structural unit can be, for example, a structural unit derived from an acrylic ester having exposed hydroxyl groups 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 The hydroxyl-containing structural unit is represented by Among them, R 1 has exposed hydroxyl groups; 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 a part of the hydroxyl-containing structural unit. 1 for Another part of the hydroxyl-containing structural unit This application does not limit this; the above * indicates the connection position. 2Including but not limited to hydrogen atom, substituted or unsubstituted C1-C4 alkyl and the like.

[0044] In polyester resins, hydroxyl-containing structural units also refer to structural units with exposed hydroxyl groups; wherein the hydroxyl groups may be located on the side chains or on the main chains of the polyester resins. In some embodiments of the present application, in polyester resins, hydroxyl-containing structural units may 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.

[0045] The additive includes a first additive and / or a second additive;

[0046] The first additive includes one or more of pyrazole, pyrrole, tetrahydropyrrole, pyrimidine, purine, adenine and 6-hydroxypurine; the above-mentioned first additive can synergistically react with the hydroxyl-containing structural units in the resin topological structure and the structural units derived from hydroxystyrene, and will not volatilize after treatment such as baking in the semiconductor process.

[0047] The second additive includes one or more of ammonia water, substituted or unsubstituted aniline, substituted or unsubstituted naphthylamine, and substituted or unsubstituted alkylamine; the second additive has a certain stability. In the embodiment of the present application, the aniline can be, for example, aniline or diphenylamine; the substituted aniline can be, for example, N-methylaniline; the substituted naphthylamine can be, for example, N-methylnaphthylamine; the alkylamine can be, for example, R 3 -NH 2 , R 4 -NH-R 5 , where R 3 , R 4 , R 5 Each is independently a C2-C8 alkyl group; the alkyl group may be, for example, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc.; the alkylamine may be, for example, one or more of diethylamine, triethylamine, di-n-propylamine, n-butylamine, etc. The substituted alkylamine may be, for example, ethylenediamine.

[0048] The mass of the additive is less than or equal to 0.05% of the total mass of the resin.

[0049] In the anti-reflection composition, the resin has a high absorbance to a light source with a wavelength of 193nm or 248nm, which is particularly beneficial to weaken the reflection of the substrate or the bottom film layer of the photosensitive material film to the light source, and improve the fineness of the pattern after development. In particular, when the coating formed by the anti-reflection composition is arranged at the bottom of the photosensitive material layer, under the synergistic effect of the resin and the specified additive in a specific amount, the line width roughness (LWR) of the obtained patterned film can be effectively reduced, and the white edge phenomenon of the patterned film can be improved, thereby facilitating the optimization of the patterning effect in the semiconductor device manufacturing process and facilitating the preparation and application of high-performance semiconductor devices.

[0050] Specifically, the mass of the additive relative to the total mass of the resin can be, for example, 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 mass ratio of the additive to the resin is too large (>0.05%), it will lead to insufficient exposure of the upper layer of photosensitive material in the subsequent process, and the photosensitive material will be difficult to remove after development.

[0051] In the present application, it includes but is not limited to using methods such as nuclear magnetic resonance and mass spectrometry to test the presence of the resin, including but not limited to using nuclear magnetic resonance, mass spectrometry, infrared, etc. to characterize the presence of hydroxyl-containing structural units and structural units derived from hydroxystyrene; it includes but is not limited to using methods such as nuclear magnetic resonance and mass spectrometry to characterize the presence of additives.

[0052] In the embodiments of the present application, high performance liquid chromatography (HPLC) is used to characterize the mass ratio of the additive to the resin.

[0053] In some embodiments of the present application, the additive accounts for 0.005%-0.05% of the total mass of the resin. When the mass ratio of the two is controlled within the above range, when the anti-reflective composition is applied in the patterning process, it is more conducive to reducing the LWR of the pattern formed after the photosensitive material film is exposed, and reducing or even eliminating the white edge phenomenon of the pattern; for example, the LWR of the pattern with a resolution of 190nm is ≤3.7nm. Specifically, based on the total mass of the resin in the anti-reflective composition, the mass proportion of the additive can be, for example, 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%, or 0.005%.

[0054] In some embodiments of the present application, the sum of the mass of the structural units derived from hydroxystyrene and the hydroxyl-containing structural units accounts for 10%-50% of the total mass of the resin. Specifically, the hydroxyl-containing structural units refer to hydroxyl-containing structural units in polyacrylate resins and polyester resins. 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 LWR of the pattern and reducing or even eliminating the white edge of the pattern. Specifically, based on the total mass of the resin in the anti-reflective composition, the mass proportion of the sum of the mass of the structural units derived from hydroxystyrene and the mass of the structural units containing hydroxyl groups can be, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, etc. Specifically, the following situations may be included: 1) The resin is a copolymer of hydroxystyrene and other monomers, in which case the structural units derived from hydroxystyrene account for 10%-50% of the mass of the resin; 2) The resin is a polyacrylic resin and / or a polyester resin, in which case the hydroxyl-containing structural units account for 10%-50% of the mass of the resin; 3) The resin includes a copolymer of hydroxystyrene and other monomers, as well as a polyacrylic resin and / or a polyester resin, in which case the sum of the mass of the hydroxyl-containing structural units and the structural units derived from hydroxystyrene accounts for 10%-50% of the total mass of the resin.

[0055] In the embodiments of the present application, it is included but not limited to testing the structural units derived from hydroxystyrene and the mass proportion of the above-mentioned hydroxyl-containing structural units in the resin by using a carbon spectrum of a nuclear magnetic resonance spectroscopy (NMR).

[0056] In some embodiments of the present application, the resin accounts for 0.4%-5% of the mass of the anti-reflective composition. In this way, the anti-reflective composition has good coating performance and is conducive to forming an anti-reflective film with suitable thickness and good uniformity. Specifically, the mass proportion of the resin in the anti-reflective composition can be, for example, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.

[0057] In the embodiments of the present application, the anti-reflective composition is freeze-dried or subjected to other treatments to remove the solvent, the solid matter obtained after freeze-drying is dissolved in a quantitative deuterated reagent and subjected to a nuclear magnetic resonance test, the nuclear magnetic resonance test results are normalized, and then the content of the resin in the anti-reflective composition is determined by calculation.

[0058] In some embodiments of the present application, the solvent of the anti-reflective composition 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. The above-mentioned solvent has good compatibility with the resin and the first additive, the second additive and other components used in the anti-reflective composition of the present application, and can form a uniform and stable solution, which is conducive to the application of the anti-reflective composition. In some embodiments of the present application, the solvent accounts for 93.5%-99.5% of the mass of the anti-reflective composition. Specifically, the mass proportion of the solvent in the anti-reflective composition can be, for example, 93.5%, 94%, 95%, 96%, 97%, 98%, 99%, 99.5%, etc.

[0059] In the patterning process, the anti-reflection composition is generally coated on the substrate, baked, and the solvent is removed to obtain an anti-reflection film. However, in order to form a subsequent photosensitive material film and avoid the resin in the anti-reflection film being dissolved by the solvent of the photosensitive material, the resin in the anti-reflection composition needs to be cross-linked during the baking process to form an anti-reflection film with certain mechanical properties. In order to cross-link the resin, the anti-reflection composition also includes a cross-linking agent, which is used to cause the resin to undergo a cross-linking reaction. The cross-linking agent needs to be determined according to the selected resin, for example, it can include but is not limited to melamine, glycoluril, isocyanurate, benzoguanamine-based substances and urea-based substances. In some specific embodiments, the cross-linking agent can be, for example, one or more of N,N-dimethoxymethyl-melamine, tetramethoxymethyl glycoluril, and tris (2-hydroxyethyl) isocyanurate.

[0060] In some embodiments of the present application, in order to control the crosslinking degree of the resin within a suitable range, so as to have a certain mechanical strength and facilitate its removal from the substrate in the subsequent process, the mass proportion of the crosslinking agent in the anti-reflective composition is controlled to be 0.1%-1%. Specifically, the mass proportion of the crosslinking agent in the anti-reflective composition can be, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%.

[0061] In the embodiments of the present application, the anti-reflective composition is freeze-dried or subjected to other treatments to remove the solvent, the solid matter obtained after freeze-drying is dissolved in a quantitative deuterated reagent and subjected to a nuclear magnetic resonance test, 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.

[0062] In some cases, in order to initiate or catalyze the crosslinking reaction between the crosslinking agent and the resin, the anti-reflective composition also includes a thermal acid generator. After the anti-reflective composition is coated on the substrate, during the baking process, the thermal acid generator generates acid under heat, thereby initiating a reaction between the resin and the crosslinking agent to form an anti-reflective film that is insoluble in the solvent for the photosensitive material. In order to fully initiate and catalyze the reaction between the crosslinking agent and the resin, in some embodiments of the present application, the mass proportion of the thermal acid generator in the anti-reflective composition is controlled to be 0.05%-0.5%; in this way, the risk of the acid generated by the thermal acid generator not reacting completely and diffusing into the photosensitive material film in the subsequent process can also be reduced. Specifically, the mass proportion of the thermal acid generator in the anti-reflective composition can be, for example, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%.

[0063] In some embodiments of the present application, the compound capable of providing acid includes, but is not limited to, one or more of an acid compound and an acid generator. Specifically, the acid compound may include, for example, one or more of sulfonic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, and dodecylbenzenesulfonic acid, and / or one or more of carboxylic acid compounds such as salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, and hydroxybenzoic acid, but is not limited thereto. The acid generator may include: one or more of sulfonate acid generators such as triethylamine dodecylsulfonate, ammonium p-toluenesulfonate, ammonium trifluoromethanesulfonate, pyridinium p-toluenesulfonate, iodonium diphenyl hexafluorophosphate, iodonium bis(4-tert-butylphenyl)trifluoromethanesulfonate, and sulfonium triphenyltrifluoromethanesulfonate; and / or one or more of acid generators generated by light or heat such as cyclohexyl trifluoromethanesulfonate, methyl trifluoromethanesulfonate, cyclohexyl 2,4,6-triisopropylbenzenesulfonate, and 2-nitrobenzyl p-toluenesulfonate.

[0064] In the embodiments of the present application, the anti-reflective composition is freeze-dried or subjected to other treatments to remove the solvent, the solid matter obtained after freeze-drying is dissolved in a quantitative deuterated reagent and subjected to a nuclear magnetic resonance test, the nuclear magnetic resonance test results are normalized, and then the content of the thermal acid generator in the anti-reflective composition is determined by calculation.

[0065] In some embodiments of the present application, the additive includes a first additive and a second additive. The introduction of the first additive and the second additive simultaneously can make it easier to adjust the pH value of the anti-reflective composition and the film formed by coating it to a certain extent, and it is easier to adjust the acidity and alkalinity of the interface between the anti-reflective coating and the photosensitive material film. Under the combined effect of the second additive, the first additive and the resin, it is more conducive to assisting in reducing the LWR of the pattern formed by the photosensitive material film and improving the white edge phenomenon.

[0066] In some embodiments of the present application, the mass ratio of the second additive to the first additive is 1:9 to 9:1; that is, the mass ratio of the second additive to the first additive is 1:0.11 to 1:9. In some specific embodiments, the mass ratio of the second additive to the first additive is 3:7 to 7:3; that is, the mass ratio of the second additive to the first additive is 1:0.428 to 1:2.33. In this way, it is more conducive to reducing the LWR of the pattern formed by the photosensitive material film, and at the same time, it is conducive to improving or even eliminating the white edge phenomenon of the patterned film. In addition, controlling the amount of the two within the above range is conducive to controlling the pH of the anti-reflective composition, or in other words, it can broaden the tolerance of the amount of the first additive and the second additive added to the anti-reflective composition on the pH value of the composition, which is conducive to the preparation of the anti-reflective composition. In the present application, the mass ratio of the second additive to the first additive can be, for example, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 1:0.43, 1:0.45, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.1, 1:2.2, 1:2.3.

[0067] In the embodiment of the present application, the anti-reflective composition may further include other auxiliary agents, such as a leveling agent, a defoaming agent, 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 auxiliary agents added to the anti-reflective composition according to actual production needs.

[0068] The embodiment of the present application also provides an anti-reflection film, which includes a solid molded product of the anti-reflection composition provided in the embodiment of the present application. In some embodiments of the present application, the anti-reflection film includes a cross-linked resin, and a first additive and / or a second additive. In some embodiments of the present application, the thickness of the anti-reflection film can be, for example, 10nm-300nm, and the present application does not limit this. A person skilled in the art can determine the thickness of the anti-reflection film according to actual production needs.

[0069] The anti-reflection film provided in the embodiment of the present application can be removed by using a dry etching process.

[0070] In some embodiments of the present application, the preparation of the anti-reflection film includes:

[0071] The anti-reflection composition is coated on the substrate and baked to obtain an anti-reflection film. The baking temperature can be, for example, 100°C-250°C, and the baking time can be, for example, 10s-120s. The above baking can remove the solvent, and cause the thermal acid generator to generate acid and initiate the cross-linking reaction between the cross-linking agent and the resin. The anti-reflection film finally obtained includes a solid molded product of the anti-reflection composition. Specifically, the above baking temperature can be, for example, 100°C, 120°C, 150°C, 180°C, 200°C, 220°C, 230°C, 240°C, 250°C, etc., and the above baking time can be, for example, 15s, 30s, 60s, 90s, 120s, etc. It should be noted that the anti-reflection composition contains a second additive, and when the second additive includes ammonia water, although the ammonia water will partially volatilize during the above baking process, it can still effectively reduce the line width roughness of the final patterned film and improve the white edge phenomenon.

[0072] During the patterning process, the anti-reflection film is set on the lower layer of the photosensitive material film, which can effectively reduce the line width roughness of the pattern formed after the photosensitive material film is exposed and developed; for example, the line width roughness of the pattern with a resolution of 190nm is reduced to 3.7nm and below, and the white edge phenomenon of the patterned film can be effectively improved or even eliminated.

[0073] The present application also provides a patterning process, including:

[0074] S11, coating the anti-reflection composition provided in the embodiment of the present application on a substrate to form an anti-reflection film on the substrate;

[0075] S12, forming a photosensitive material film on the surface of the anti-reflection film;

[0076] S13, exposing and developing the photosensitive material film through a photomask to form a patterned film on the substrate;

[0077] S14, etching to obtain a patterned substrate.

[0078] In some embodiments of the present application, the substrate may be, for example, a silicon wafer. In other embodiments, the substrate includes a silicon wafer on which other film layers are stacked, for example, an epitaxial layer, a metal layer, a dielectric layer, a modified layer or a matching layer.

[0079] In some embodiments of the present application, in step S01, the anti-reflection composition may be coated on the surface of the substrate by spin coating. Specifically, according to the size of the substrate, an appropriate volume of the anti-reflection composition is taken and coated on the substrate by spin coating.

[0080] In the embodiment of the present application, in step S01, after the above spin coating, the substrate with the anti-reflective composition coating is further subjected to baking treatment. The baking temperature can be, for example, 100°C-250°C, and the baking time can be, for example, 10s-120s. The above baking can remove the solvent, and cause the thermal acid generator to generate acid and initiate a cross-linking reaction between the cross-linking agent and the resin, and the anti-reflective film finally obtained includes a solid molded product of the anti-reflective composition. Specifically, the above baking temperature can be, for example, 100°C, 120°C, 150°C, 180°C, 200°C, 220°C, 230°C, 240°C, 250°C, etc., and the above baking time can be, for example, 15s, 30s, 60s, 90s, 120s, etc.

[0081] In some embodiments of the present application, in step S02, forming a photosensitive material film on the surface of the anti-reflective film includes: spin coating a photosensitive material composition on the surface of the anti-reflective film, and the photosensitive material composition may include, for example, a polyacrylate resin, a photoacid generator, and a solvent. In some specific embodiments, the photosensitive material composition also includes a photodecomposition base and / or an acid quencher, and the acid quencher is used to capture acid. In some embodiments of the present application, after coating the photosensitive material composition, a baking treatment may be performed to remove the solvent in the photosensitive composition coating to form a photosensitive material film.

[0082] In some embodiments of the present application, in S03, the photosensitive material film is exposed and developed through a photomask, which may be to expose the photosensitive material film to an exposure light source through a photomask so that the solubility of the photosensitive material changes, and then perform a development process to transfer the pattern on the photomask or its complementary pattern to the photosensitive material film. In some embodiments, the wavelength of the exposure light source may be, for example, 150nm-350nm.

[0083] The development may be to develop the exposed photosensitive material film with a developer to form a patterned film on the substrate. The developer may be, for example, a developer that changes the chemical properties of the exposed portion of the photosensitive material film and changes the solubility. The irradiated film layer may be cleaned with a developer to obtain a preset pattern. The cleaning time ranges from 10s to 300s, and may be a single-step cleaning or a multi-step cleaning.

[0084] In the above step S03, a suitable developer can be selected in the development process according to the properties of the photosensitive composition film layer; for example, an alkaline developer or an organic solvent. In some embodiments of the present application, the developer includes a 0.5-5% by mass tetramethylammonium hydroxide (TMAH) aqueous solution and n-butyl acetate. The developer is in contact with the exposed film layer for a development time of 10s-120s.

[0085] In some embodiments of the present application, the line width roughness of the patterned film obtained in step S03 with a resolution of 190nm is ≤3.7nm; specifically, the line width roughness of the patterned film with a resolution of 190nm can be, for example, 3.70nm, 3.68nm, 3.65nm, 3.60nm, 3.58nm, 3.55nm, 3.52nm, 3.50nm, 3.48nm, 3.45nm, 3.42nm, 3.40nm, 3.38nm, 3.35nm, 3.32nm, 3.30nm, 3.28nm, 3.27nm, 3.26nm, 3.25nm, 3.24nm, 3.22nm, 3.21nm, 3.2nm, etc.

[0086] In step S04, the patterned film selectively protects the underlying substrate material during the etching process. After etching under certain conditions, part of the patterned film and the unprotected substrate material are etched, but the etching speed of the protected part is slower than that of the unprotected part, and finally a pattern is formed on the substrate material, that is, the pattern is transferred to the substrate to obtain a patterned substrate. The etching process can specifically transfer the pattern to the substrate through HF etching, ion etching or ion implantation process.

[0087] The present application also provides a patterned substrate, which is made by the patterning process provided in the present application. The critical dimensions of the pattern on the patterned substrate and the line width roughness of the pattern can reach the industry-leading level, and can be used to provide high-precision and high-reliability semiconductor devices, such as high-precision and high-reliability integrated circuits.

[0088] The embodiment of the present application further provides a semiconductor device, which includes the patterned substrate provided by the embodiment of the present application and a functional layer arranged on the patterned substrate.

[0089] Since the semiconductor device provided by the embodiment of the present application is manufactured using the patterned substrate provided by the embodiment of the present application, the semiconductor device provided by the embodiment of the present application can have both high precision and high reliability.

[0090] In the embodiments of the present application, there is no special restriction on the structure of the semiconductor device. Those skilled in the art can design it according to the actual application needs, and prepare it according to the acid-sensitive resin, photosensitive composition, patterned film, or patterned substrate provided in the embodiments of the present application. In the embodiments of the present application, the semiconductor device includes but is not limited to integrated circuit devices such as chips. It is understandable that the semiconductor device provided in the embodiments of the present application also includes a functional layer, and the functional layer may include any structure that can be applied to the semiconductor device, for example, metal wiring, active devices, passive devices, etc.

[0091] The present application also provides a method for preparing a semiconductor device, comprising:

[0092] S21, coating the anti-reflection composition provided in the embodiment of the present application on a substrate to form an anti-reflection film on the substrate;

[0093] S22, forming a photosensitive material film on the surface of the anti-reflection film;

[0094] S23, exposing and developing the photosensitive material film through a photomask to form a patterned film on the substrate;

[0095] S24, etching to obtain a patterned substrate;

[0096] S25, preparing a functional layer to obtain a semiconductor device.

[0097] The preparation method is suitable for large-scale industrial production and can produce semiconductor devices with high precision and high reliability.

[0098] The above steps S21, S22, S23, and S24 can refer to the relevant description of the patterning process in the previous text, and will not be repeated here. S25 can be performed using any process familiar to technicians in the field, and this application does not limit this.

[0099] The technical solution of the present application is described in detail below with multiple embodiments.

[0100] Example 1

[0101] An antireflective composition comprising the following components in amounts by weight:

[0102] 2.8% of a resin (specifically a polymethacrylate resin, and a hydroxyl-containing structural unit is derived from hydroxyethyl methacrylate, and the mass content of the hydroxyl-containing structural unit in the resin is 40%), 0.0004% of a first additive (specifically pyrrole), 0.1% of a thermal acid generator (specifically pyridinium p-toluenesulfonate), 0.5% of a cross-linking agent (specifically tetramethoxymethyl glycoluril), and the remainder of a solvent;

[0103] Specifically, the structural unit derived from hydroxyethyl methacrylate is shown in Formula A, Formula A.

[0104] Example 2

[0105] An antireflective composition comprising the following components in amounts by weight:

[0106] 2.8% of resin (specifically polymethacrylate resin, and the mass content of hydroxyl-containing structural units in the resin is 40%, and the hydroxyl-containing structural units are derived from hydroxyethyl methacrylate), 0.0002% of the first additive (specifically pyrrole), 0.0002% of the second additive (specifically triethylamine), 0.1% of the thermal acid generator (specifically pyridinium p-toluenesulfonate), 0.5% of the cross-linking agent (specifically tetramethoxymethyl glycoluril), and the remainder of the solvent (specifically PGME).

[0107] Example 3

[0108] 2.8% of resin (specifically polymethacrylate resin, and the hydroxyl-containing structural unit is derived from hydroxyethyl methacrylate, and the mass content of the hydroxyl-containing structural unit in the resin is 40%), 0.0004% of the second additive (specifically ammonia water), 0.1% of a thermal acid generator (specifically pyridinium p-toluenesulfonate), 0.5% of a cross-linking agent (specifically tetramethoxymethyl glycoluril), and the remainder of a solvent (specifically PGME).

[0109] Example 4

[0110] 2.8% of resin (specifically polymethacrylate resin, and the hydroxyl-containing structural unit is derived from hydroxyethyl methacrylate, and the mass content of the hydroxyl-containing structural unit in the resin is 40%), 0.0006% of the second additive (specifically 6-hydroxypurine), 0.1% of the thermal acid generator (specifically pyridinium p-toluenesulfonate), 0.5% of the cross-linking agent (specifically tetramethoxymethyl glycoluril), and the remainder of the solvent (specifically PGME).

[0111] The following comparative examples were set.

[0112] Comparative Example 1

[0113] The difference from Example 1 is that the antireflective composition of Comparative Example 1 does not contain the first additive.

[0114] Exposure performance test 1

[0115] A 12-inch silicon wafer was used as a substrate, and the antireflection compositions of the embodiments and comparative examples were coated on the substrate surface, respectively, and baked at 205° C. for 60 seconds to obtain a substrate with an antireflection film on the surface.

[0116] The photosensitive composition is evenly applied to the above-mentioned substrate by a spin coater, and baked at 120°C for 60 seconds to form a photosensitive material film with a thickness of 150nm. Dry exposure is performed using a krypton fluoride excimer laser, and the medium is air. After that, it is baked at 95°C for 60 seconds, and developed at 23°C for 60 seconds using a tetramethylammonium hydroxide aqueous solution with a mass concentration of 2.38%, washed with water and dried to form a patterned film; the line width of the patterned film is 190nm (that is, the resolution of the patterned film is 190nm). The line width roughness of the patterned films prepared in each embodiment and comparative example is tested using a scanning electron microscope (SEM), which is summarized in Table 1-1, and the optimal exposure energy BE, optimal focal length BF, depth of focus DOF, and exposure energy margin EL of each embodiment and comparative example 1 are summarized in Table 1; the SEM photos of the patterned films of Examples 1 to 3 and Comparative Example 1 are shown in turn. Figures 1 to 4 .

[0117] Exposure performance test 2

[0118] The photosensitive composition of Example 4 was evenly applied to the above substrate by a spin coater and baked at 110°C for 60 seconds to form a photosensitive material film with a film thickness of 90nm. Wet exposure was performed using an argon fluoride excimer laser, and the medium was water. The line width of the patterned film was 110nm (that is, the resolution of the patterned film was 110nm), and the other conditions were the same as those in the exposure performance test 1; the results are shown in Table 1-2, and the SEM photos of the obtained patterned film are shown in Figure 5 .

[0119] Table 1-1

[0120] Case LWR / nm <![CDATA[BE(mJ / cm 2 )]]> BF / μm DOF / nm <![CDATA[EL(nm / (mJ·cm -2 ))]]> Example 1 3.53 29.53 0 220 24.36％ Example 2 3.21 29.58 0 220 24.33％ Example 3 3.76 30.67 0 220 26.21％ Example 4 3.63 30.02 0 220 25.01％ Comparative Example 1 4.08 30.91 0 220 27.20％

[0121] Table 1-2

[0122] Case LWR / nm <![CDATA[BE(mJ / cm 2 )]]> BF / μm DOF / nm <![CDATA[EL(nm / (mJ·cm -2 ))]]> Example 4 3.02 36.91 0 280 38.32％

[0123] It can be seen from the data in Table 1-1 and Table 1-2 that the anti-reflective composition provided in the embodiment of the present application can effectively reduce the line width roughness of the patterned film without significantly affecting other exposure properties of the photosensitive material film, and is conducive to improving the pattern white edge phenomenon in the top view of the patterned film. Figures 1 to 4 It can be seen that the white edge phenomenon of the pattern prepared in Comparative Example 1 is the most serious.

[0124] 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.

[0125] 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.

[0126] 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, respectively.

[0127] 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.

Claims

1. An antireflective composition, characterized in that Comprising resin, additives and solvent; the resin comprises one or more of polyhydroxystyrene resin, polyester resin and polyacrylate resin; the polyhydroxystyrene resin comprises structural units derived from hydroxystyrene, and the polyester resin and the polyacrylate resin both have structural units containing hydroxyl groups; The additive includes a first additive, and / or the additive includes a second additive; The first additive includes one or more of pyrazole, pyrrole, tetrahydropyrrole, pyrimidine, purine, adenine and 6-hydroxypurine; The second additive includes one or more of ammonia, substituted or unsubstituted aniline, substituted or unsubstituted naphthylamine, and substituted or unsubstituted alkylamine; The mass of the additive is less than or equal to 0.05% of the total mass of the resin.

2. The antireflective composition according to claim 1, characterized in that 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 total mass of the resin.

3. The antireflective composition according to claim 1, characterized in that The additive accounts for 0.005%-0.05% of the total mass of the resin.

4. The antireflective composition according to claim 1, characterized in that The resin accounts for 0.4% to 5% by weight of the antireflective composition.

5. The antireflective composition according to claim 1, characterized in that The 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; the solvent accounts for 93.5%-99.5% of the mass of the anti-reflective composition.

6. The antireflective composition according to claim 1, characterized in that The composition further comprises a crosslinking agent, and the crosslinking agent accounts for 0.05% to 1% of the mass of the anti-reflective composition.

7. The antireflective composition according to claim 1, characterized in that The composition further comprises a compound capable of providing acid; the compound capable of providing acid accounts for 0.01% to 0.5% by weight of the anti-reflective composition.

8. The antireflective composition according to any one of claims 1 to 7, characterized in that: The additives include the first additive and the second additive.

9. The antireflective composition according to claim 8, characterized in that The mass ratio of the first additive to the second additive is 1:9 to 9:

1.

10. 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 9.

11. A patterning process, characterized in that: include: Coating the anti-reflective composition according to any one of claims 1 to 9 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; exposing and developing the photosensitive film through a photomask to form a patterned film on the substrate; Etching to obtain a patterned substrate.

12. A patterned substrate, characterized in that: The patterned substrate is manufactured by the patterning process as claimed in claim 11.

13. A semiconductor device, characterized in that: The semiconductor device comprises the patterned substrate according to claim 12 and a functional layer disposed on the patterned substrate.

14. A method for preparing a semiconductor device, characterized in that: include: Applying the antireflective composition according to any one of claims 1 to 9 on a substrate to form an antireflective 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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