Patterning materials, patterning compositions, patterned films, patterned substrates, semiconductor devices and methods for their preparation

Abstract

Embodiments of the present application provide a patterned material, a patterned composition, a patterned film, a patterned substrate, a semiconductor device, and a method for preparing the same. The method for preparing the patterned material includes: mixing a first monomer, a second monomer, an iodine-containing initiator, and an organic iodide catalyst, and subjecting the mixture to a polymerization reaction to form an iodine-containing polymer; performing a deiodination treatment on the iodine-containing polymer to obtain the patterned material, where the patterned material includes a first repeating unit represented by formula (I) and a second repeating unit represented by formula (II), where R1 is selected from polar groups, R2 is selected from acid-decomposable groups, #imgabs0# formula (I), #imgabs1# formula (II). In the preparation of the patterned material, an iodine-containing initiator and an organic iodide catalyst are used, and a deiodination treatment is performed, avoiding the influence of impurity elements on the performance of the obtained patterned material, which is beneficial to the preparation and use of semiconductor devices.

Description

Technical Field

[0001] Embodiments of the present application relate to the field of semiconductor manufacturing technology, and in particular to a patterned material, a patterning composition, a patterned film, a patterned substrate, a semiconductor device, and a method for preparing the same. Background Art

[0002] The patterned materials for semiconductor devices are mostly radiation-sensitive resin materials. However, the residual impurity elements in the patterned materials affect the preparation and use of semiconductor devices. For example, using a chain transfer agent containing sulfur elements and a catalyst containing copper elements in the polymerization reaction will result in the residual sulfur and copper in the obtained patterned materials, affecting the stability of the patterned materials and the adhesion performance, exposure performance, etc. of the film layers formed by the patterned materials. Therefore, how to avoid the influence of impurity elements in the patterned materials on the preparation and use of semiconductor devices is an urgent problem to be solved. Summary of the Invention

[0003] In view of this, embodiments of the present application provide a patterned material, a patterning composition, a patterned film, a patterned substrate, a semiconductor device, and a method for preparing the same. In the preparation of the patterned material, an iodine-containing initiator and an organic iodide catalyst are used, and deiodination treatment is also carried out, avoiding the influence of impurity elements on the performance of the obtained patterned material, which is beneficial to the preparation and use of semiconductor devices.

[0004] In a first aspect, embodiments of the present application provide a patterned material, including:

[0005] Mixing a first monomer, a second monomer, an iodine-containing initiator, and an organic iodide catalyst, and forming an iodine-containing polymer through a polymerization reaction;

[0006] Performing deiodination treatment on the iodine-containing polymer to obtain a patterned material, where the patterned material includes a first repeating unit represented by formula (I) and a second repeating unit represented by formula (II), where R1 is selected from polar groups and R2 is selected from acid-labile groups,

[0007] Formula (I),

[0008] Formula (II).

[0009] In the preparation of the patterned material of the present application, an iodine-containing initiator and an organic iodide catalyst are used, and deiodination treatment is also carried out, avoiding the influence of impurity elements on the performance of the obtained patterned material, and the obtained patterned material has excellent performance.

[0010] In an embodiment of the present application, the polydispersity index of the patterned material is less than 1.4.

[0011] In an embodiment of the present application, the molar fraction of the first repeating unit in the patterned material is 35% - 65%.

[0012] In an embodiment of the present application, the molar fraction of the second repeating unit in the patterned material is 35% - 65%.

[0013] In an embodiment of the present application, the weight - average molecular weight of the patterned material is 4000 Da - 12000 Da.

[0014] In an embodiment of the present application, the sulfur element content in the patterned material is less than 1 ppm, and the copper element content is less than 100 ppb.

[0015] In an embodiment of the present application, in the polymerization reaction, the molar ratio of the iodine - containing initiator to the sum of the molar amounts of the first monomer and the second monomer is 1:(30 - 100).

[0016] In an embodiment of the present application, in the polymerization reaction, the molar ratio of the first monomer to the second monomer is (3:7)-(7:3).

[0017] In an embodiment of the present application, the reaction temperature of the polymerization reaction is 50°C - 90°C, and the reaction time is 1 h - 24 h.

[0018] In an embodiment of the present application, the first monomer, the second monomer, the iodine - containing initiator, and the organic iodide catalyst are mixed to form a polymerization reaction solution, and the polymerization reaction solution further includes a first solvent. The mass ratio of the total mass of the first monomer and the second monomer to the mass of the first solvent is 1:(0.5 - 5).

[0019] In an embodiment of the present application, the chemical structural formula of the iodine - containing initiator is as shown in formula (III).

[0020] Formula (III).

[0021] In an embodiment of the present application, the chemical structural formula of the organic iodide catalyst is as shown in formula (IV), where R6, R7, R8, and R9 are independently selected from substituted or unsubstituted alkyl groups or substituted or unsubstituted cycloalkyl groups.

[0022] Formula (IV).

[0023] In an embodiment of the present application, the polar group is selected from the group shown in formula (V) or the group shown in formula (VI), where is the connection site, n1, n2, n3, and n4 are independently selected from integers from 1 to 4, and R 1 is selected from H, substituted or unsubstituted alkyl groups, or substituted or unsubstituted alkoxy groups.2 Selected from O or -(CHR 4 )-, R 4 is selected from H, substituted or unsubstituted alkyl or substituted or unsubstituted alkoxy, R 3 is selected from H, substituted or unsubstituted alkyl or substituted or unsubstituted alkoxy. When n1 is greater than or equal to 2, a plurality of said R 1 can be interconnected to form a cyclic structure. When n3 is greater than or equal to 2, a plurality of said R 3 can be interconnected to form a cyclic structure,

[0024] Formula (V),

[0025] Formula (VI).

[0026] In the embodiments of the present application, the acid-labile group is selected from the groups shown in Formula (VII), wherein is a linking site, n5 and n6 independently selected from integers from 1 to 4, R 5 is selected from substituted or unsubstituted alkyl, R 6 is selected from H or substituted or unsubstituted alkyl, and when n5 is greater than or equal to 2, a plurality of said R 6 can be interconnected to form a cyclic structure,

[0027] Formula (VII).

[0028] In the embodiments of the present application, the chemical structural formula of the first monomer is as shown in Formula (IX),

[0029] Formula (IX).

[0030] In the embodiments of the present application, the first monomer forms the first repeating unit shown in Formula (I) in the patterned material after the polymerization reaction and the deiodination treatment.

[0031] In the embodiments of the present application, the chemical structural formula of the second monomer is as shown in Formula (X),

[0032] Formula (X).

[0033] In the embodiments of the present application, the second monomer forms the second repeating unit shown in Formula (II) in the patterned material after the polymerization reaction and the deiodination treatment.

[0034] In the embodiments of the present application, the deiodination treatment of the iodine-containing polymer includes:

[0035] The iodine-containing polymer is mixed with the compound represented by formula (VIII) for the deiodination treatment, where R 7 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted arylalkyl,

[0036] Formula (VIII).

[0037] In the embodiments of the present application, the molar ratio of the iodine-containing polymer to the compound represented by formula (VIII) in the deiodination treatment is 1:(1 - 20).

[0038] In the embodiments of the present application, the reaction temperature of the deiodination treatment is 20°C - 100°C, and the reaction time is 1 h - 24 h.

[0039] In a second aspect, the embodiments of the present application provide a patterned material prepared by the preparation method described in the first aspect.

[0040] In a third aspect, the embodiments of the present application provide a patterning composition, comprising the patterned material described in the second aspect, a photoacid generator, and a second solvent.

[0041] In a fourth aspect, the embodiments of the present application provide a patterned film, and the patterned film is formed from the patterning composition described in the third aspect.

[0042] In a fifth aspect, the embodiments of the present application provide a patterned substrate, and the pattern on the patterned substrate is formed from the patterning composition described in the third aspect.

[0043] In a sixth aspect, the embodiments of the present application provide a semiconductor device prepared using the patterned film described in the fourth aspect, or prepared using the patterned substrate described in the fifth aspect.

[0044] In a seventh aspect, the embodiments of the present application provide a method for preparing a semiconductor device, comprising:[[]]

[0045] Coating the patterning composition described in the third aspect on a substrate to form a film layer on the substrate;

[0046] Developing the film layer through a photomask to form a patterned film on the substrate. Description of the Drawings

[0047] Figure 1 is a schematic flow chart of a patterning method provided by an embodiment of the present application;

[0048] Figure 2 is an electron micrograph of the patterned film obtained in Example C1;

[0049] Figure 3SEM image of the patterned film obtained in Example C2;

[0050] Figure 4 SEM image of the patterned film obtained in Example C3;

[0051] Figure 5 SEM image of the patterned film obtained in Comparative Example C1;

[0052] Figure 6 SEM image of the patterned film obtained in Comparative Example C2;

[0053] Figure 7 SEM image of the patterned film obtained in Comparative Example C3. Detailed implementation manners

[0054] The embodiments of the present application will be described below with reference to the accompanying drawings in the embodiments of the present application.

[0055] The embodiments of the present application provide a patterned material, comprising:

[0056] Mixing a first monomer, a second monomer, an iodine-containing initiator, and an organoiodide catalyst, and subjecting them to a polymerization reaction to form an iodine-containing polymer;

[0057] The iodine-containing polymer is subjected to deiodination treatment to obtain a patterned material, which comprises a first repeating unit represented by formula (I) and a second repeating unit represented by formula (II), wherein R1 is selected from polar groups, and R2 is selected from acid-decomposable groups.

[0058] Formula (I)

[0059] Formula (II).

[0060] In the present application, the first monomer, the second monomer, the iodine-containing initiator, and the organoiodide catalyst are subjected to a radical polymerization reaction to obtain an iodine-containing polymer, and the iodine element present in the iodine-containing polymer is removed by deiodination treatment, thereby avoiding the influence of impurity elements on the performance of the patterned material and obtaining a patterned material with excellent performance, which is beneficial to the use of the patterned material.

[0061] In the embodiment of the present application, the chemical structural formula of the first monomer is as shown in formula (IX), wherein R1 is selected from polar groups.

[0062] Formula (IX).

[0063] The first monomer forms the first repeating unit represented by formula (I) in the patterned material after polymerization reaction and deiodination treatment; the addition of the above-mentioned first monomer ensures the use performance of the patterned material and is beneficial to the preparation of semiconductor devices.

[0064] In some embodiments of the present application, the polar group is selected from the group represented by formula (V) or the group represented by formula (VI), where is a linking site, n1, n2, n3, n4 are independently selected from integers from 1 to 4, and R 1 is selected from H, substituted or unsubstituted alkyl, or substituted or unsubstituted alkoxy, and R 2 is selected from O or -(CHR 4 )-, and R 4 is selected from H, substituted or unsubstituted alkyl, or substituted or unsubstituted alkoxy, and R 3 is selected from H, substituted or unsubstituted alkyl, or substituted or unsubstituted alkoxy. When n1 is greater than or equal to 2, multiple Rs 1 can be connected to each other to form a cyclic structure. When n3 is greater than or equal to 2, multiple Rs 3 can be connected to each other to form a cyclic structure.

[0065] Formula (V)

[0066] Formula (VI).

[0067] The first monomer having the group represented by formula (V) or the group represented by formula (VI) is beneficial to improving the adhesion performance between the patterned material and the substrate during use, and avoiding the damage to the film layer formed by the unexposed patterned composition during the development process. Thus, it is beneficial to the preparation of semiconductor devices.

[0068] In some embodiments, n1 can be 1, 2, 3, or 4, n2 can be 1, 2, 3, or 4, n3 can be 1, 2, 3, or 4, and n4 can be 1, 2, 3, or 4. Exemplarily, n1 can be 1 or 2, and n2 can be 1 or 2. It can be understood that when n1 is an integer from 2 to 4, multiple Rs 1 can be connected to the same carbon atom or to different carbon atoms; when n2 is an integer from 2 to 4, multiple -OH groups can be connected to the same carbon atom or to different carbon atoms; when n3 is an integer from 2 to 4, multiple Rs 3 can be connected to the same carbon atom or to different carbon atoms.

[0069] In some embodiments, when there are multiple Rs 1 in the group represented by formula (V), multiple Rs 1 can be connected to each other to form a cyclic structure or may not be connected to each other to form a ring. In some embodiments, when there are multiple Rs 3 in the group represented by formula (VI), multiple Rs 3 can be connected to each other to form a cyclic structure or may not be connected to each other to form a ring.

[0070] In some embodiments, the polar group may, but is not limited to, be any one selected from the groups represented by Formula (1) to Formula (15):

[0071] Formula (1), Formula (2), Formula (3), Formula (4), Formula (5), Formula (6), Formula (7), Formula (8), Formula (9), Formula (10), Formula (11), Formula (12), Formula (13), Formula (14), Formula (15).

[0072] In the embodiments of the present application, the chemical structural formula of the second monomer is as shown in Formula (X), wherein R2 is selected from acid-labile groups,

[0073] Formula (X).

[0074] After the second monomer undergoes a polymerization reaction and a deiodination treatment, a second repeating unit as shown in Formula (II) in the patterned material is formed; the addition of the second monomer makes the patterned material sensitive to acid and can decompose in the presence of acid, which is beneficial to the exposure and development process, and thus is beneficial to the preparation of semiconductor devices.

[0075] In some embodiments of the present application, the acid-labile group is selected from the group represented by Formula (VII), wherein is a linking site, n5 and n6 independently selected from integers from 1 to 4, R 5 is selected from substituted or unsubstituted alkyl groups, R 6 is selected from H or substituted or unsubstituted alkyl groups, and when n5 is greater than or equal to 2, multiple Rs 6 can be connected to each other to form a cyclic structure,

[0076] Formula (VII).

[0077] The second monomer having the group represented by Formula (VII) is beneficial to improving the strength of the patterned material and the patterned film, avoiding problems such as the collapse of the film layer formed by the unexposed patterned composition during the development process. At the same time, the addition of the second monomer makes the patterned material sensitive to acid and can decompose in the presence of acid, which is beneficial to the exposure and development process, and thus is beneficial to the preparation of semiconductor devices.

[0078] In some embodiments, n5 can be 1, 2, 3 or 4, and n6 can be 1, 2, 3 or 4. It can be understood that when n5 is an integer from 2 to 4, multiple Rs 6 can be connected to the same carbon atom or to different carbon atoms.

[0079] In some embodiments, when there are multiple Rs in the group represented by formula (VII), 6 multiple Rs 6 can be connected to form a cyclic structure or not connected to each other to form a ring.

[0080] In some embodiments, the acid-labile deprotecting group can be, but is not limited to, any one of the groups represented by formula (16) to formula (26):

[0081] Formula (16), Formula (17), Formula (18), Formula (19), Formula (20), Formula (21), Formula (22), Formula (23), Formula (24), Formula (25), Formula (26).

[0082] In the embodiments of the present application, the molar ratio of the first monomer to the second monomer in the polymerization reaction is (3:7)-(7:3), which is beneficial to improving the performance of the formed patterned material, helps its use in the patterning composition, and improves the use performance of the patterning composition. In some embodiments, the molar ratio of the first monomer to the second monomer in the polymerization reaction can be, but is not limited to, 3:7, 2:3, 1:1, 3:2 or 7:3, etc.

[0083] In the polymerization reaction of the present application, an iodine-containing initiator is used to polymerize to form an iodine-containing polymer, and the iodine in the iodine-containing polymer can be removed by deiodination treatment to obtain a patterned material; due to the high deiodination rate and simple operation of the deiodination treatment, the influence of iodine atoms on the performance of the patterned material can be avoided.

[0084] In the embodiments of the present application, the iodine-containing initiator is an organic iodide. In some embodiments of the present application, the chemical structural formula of the iodine-containing initiator is as shown in formula (III),

[0085] Formula (III).

[0086] The above iodine-containing initiator polymer has excellent activity and is easily obtained, which is more beneficial to the preparation of the patterned material.

[0087] In the embodiments of the present application, in the polymerization reaction, the molar amount (n 引 ) of the iodine-containing initiator and the sum of the molar amounts (n 和 ) of the first monomer and the second monomer, the ratio (n 引 / n 和 ) is 1:(30 - 100). This is beneficial to the progress of the polymerization reaction, is also conducive to obtaining a patterned material with a suitable molecular weight, helps the use of the patterning composition and the patterned film, and is also beneficial to obtaining a patterned material with a low polydispersity index (PDI). In some embodiments, in the polymerization reaction, the ratio of the molar amount of the iodine-containing initiator to the sum of the molar amounts of the first monomer and the second monomer can be, but is not limited to, 1:30, 1:40, 1:45, 1:50, 1:60, 1:75, 1:80, 1:90, or 1:100, etc. In some embodiments of the present application, in the polymerization reaction, the ratio of the molar amount of the iodine-containing initiator to the sum of the molar amounts of the first monomer and the second monomer can be 1:(30 - 50). In some embodiments of the present application, in the polymerization reaction, the ratio of the molar amount of the iodine-containing initiator to the sum of the molar amounts of the first monomer and the second monomer can be 1:(50 - 100).

[0088] In the embodiments of the present application, the chemical structural formula of the organic iodide catalyst is shown in Formula (IV), where R6, R7, R8, and R9 are independently selected from substituted or unsubstituted alkyl groups or substituted or unsubstituted cycloalkyl groups,

[0089] Formula (IV).

[0090] The above-mentioned organic iodide catalyst has excellent catalytic performance and solubility, which is beneficial to the efficient and rapid preparation of iodine-containing polymers. Among them, the selection of any two groups among R6, R7, R8, and R9 can be the same or different.

[0091] In some embodiments, the organic iodide catalyst can be, but is not limited to, at least one selected from tetrabutylammonium iodide, tetramethylammonium iodide, tetraethylammonium iodide, and tetra-n-octylammonium iodide.

[0092] In the embodiments of the present application, in the polymerization reaction, the ratio of the molar amount of the iodine-containing initiator, the molar amount of the organic iodide catalyst, and the sum of the molar amounts of the first monomer and the second monomer is 1:(1 - 10):(30 - 100), which is beneficial to accelerating the polymerization reaction and at the same time is also beneficial to obtaining a patterned material with a low PDI. In some embodiments, in the polymerization reaction, the ratio of the molar amount of the iodine-containing initiator, the molar amount of the organic iodide catalyst, and the sum of the molar amounts of the first monomer and the second monomer can be 1:(1 - 8):(35 - 90), 1:(2 - 8):(35 - 80), 1:(1 - 7):(40 - 70), 1:(2 - 6):(40 - 60), 1:(2 - 5):(40 - 55), etc. Specifically, in the polymerization reaction, the ratio of the molar amount of the iodine-containing initiator, the molar amount of the organic iodide catalyst, and the sum of the molar amounts of the first monomer and the second monomer can be, but is not limited to, 1:1:30, 1:2:35, 1:2:50, 1:2:75, 1:3:40, 1:3:60, 1:3:90, 1:5:50, 1:5:75, 1:5:100, 1:7:40, 1:7:60, 1:7:95, 1:8:75, 1:9:90, 1:10:65, 1:10:75, or 1:10:100, etc.

[0093] In the embodiments of the present application, the first monomer, the second monomer, the iodine-containing initiator, and the organic iodide catalyst are mixed to form a polymerization reaction solution, and the polymerization reaction solution further includes a first solvent. The first solvent is used to disperse the first monomer, the second monomer, the iodine-containing initiator, and the organic iodide catalyst, and the first solvent is selected from substances that can disperse the first monomer, the second monomer, the iodine-containing initiator, and the organic iodide catalyst and do not react with the first monomer, the second monomer, the iodine-containing initiator, and the organic iodide catalyst. For example, the first solvent does not contain active hydrogen, such as alcohols, water, etc. Exemplarily, ethers, furans, esters, etc. can be selected as the first solvent, such as diethylene glycol dimethyl ether, tetrahydrofuran, 1,2-propylene glycol methyl ether acetate, etc.

[0094] In the embodiments of the present application, the ratio of the total mass of the first monomer and the second monomer to the mass of the first solvent is 1:(0.5 - 5), which is beneficial to obtaining an iodine-containing polymer and a patterned material with a more uniform molecular weight distribution, and helps to obtain a patterned material with a low PDI. For example, a patterned material with a PDI less than 1.4 can be obtained. In some embodiments, the ratio of the total mass of the first monomer and the second monomer to the mass of the first solvent can be, but is not limited to, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, or 1:5, etc.

[0095] In the embodiments of the present application, the polymerization reaction is carried out under an inert atmosphere, which is beneficial to the preparation of the iodine-containing polymer. Exemplarily, the inert atmosphere can be selected from nitrogen, argon, etc.

[0096] In the embodiments of the present application, the reaction temperature of the polymerization reaction is 50°C - 90°C, and the reaction time is 1h - 24h, which can improve the synthesis rate of the iodine-containing polymer and accelerate the polymerization reaction efficiency. In some embodiments, the reaction temperature of the polymerization reaction can be, but is not limited to, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or 90°C, etc.; the reaction time of the polymerization reaction can be, but is not limited to, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, etc.

[0097] In the iodine-containing polymer formed by the polymerization reaction, iodine atoms are located at the ends of the molecular chain segments. By deiodination treatment, the iodine atoms in the iodine-containing polymer can be removed to obtain a patterned material, and at the same time, the influence of iodine atoms on the patterned material is avoided.

[0098] In the embodiments of the present application, the iodine-containing polymer can be mixed with a nucleophile for deiodination treatment to obtain a patterned material.

[0099] In some embodiments of the present application, the molar ratio of the iodine-containing polymer to the nucleophile in the deiodination treatment is 1:(1 - 20), which is beneficial to the rapid and efficient removal of iodine atoms and ensures the performance of the obtained patterned material. In some embodiments, the molar ratio of the iodine-containing polymer to the nucleophile in the deiodination treatment can be, but is not limited to, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19 or 1:20, etc.

[0100] In some embodiments of the present application, the reaction temperature of the deiodination treatment is 20°C - 100°C, and the reaction time is 1h - 24h, which is conducive to the rapid and efficient removal of iodine atoms and also ensures the performance of the obtained patterned material. In some embodiments, the reaction temperature of the deiodination treatment can be, but is not limited to, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 60°C, 63°C, 65°C, 70°C, 80°C, 90°C or 100°C, etc.; the reaction time of the deiodination treatment can be, but is not limited to, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, etc.

[0101] In some embodiments of the present application, the deiodination treatment of the iodine-containing polymer includes:

[0102] The iodine-containing polymer is mixed with the compound shown in formula (VIII) for deiodination treatment, where R 7 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted arylalkyl,

[0103] Formula (VIII).

[0104] In some embodiments of the present application, the molar ratio of the iodine-containing polymer to the compound shown in formula (VIII) in the deiodination treatment is 1:(1 - 20), which is beneficial to the rapid and efficient removal of iodine atoms and ensures the performance of the obtained patterned material.

[0105] In the embodiments of the present application, the deiodination rate of the deiodination treatment reaches more than 99%. In some embodiments of the present application, the deiodination rate of the deiodination treatment reaches more than 99.9%.

[0106] In the embodiments of the present application, after the deiodination treatment, reprecipitation can be carried out for purification, which is beneficial to improving the service performance of the obtained patterned material. Specifically, methanol or a mixed solution of methanol and water can be used for reprecipitation.

[0107] In the present application, the above-mentioned substituted or unsubstituted alkyl is a chain alkyl, which can be a straight-chain alkyl or a branched-chain alkyl. In the embodiments of the present application, the substituted or unsubstituted alkyl can be a substituted or unsubstituted C1-C 15 alkyl. For example, the substituted or unsubstituted alkyl can be a substituted or unsubstituted C1-C 14 alkyl, a substituted or unsubstituted C1-C 12 alkyl, a substituted or unsubstituted C1-C 10 alkyl, a substituted or unsubstituted C1-C9 alkyl, a substituted or unsubstituted C1-C6 alkyl, or a substituted or unsubstituted C1-C5 alkyl; specifically, the substituted or unsubstituted alkyl can be a substituted or unsubstituted methyl, a substituted or unsubstituted ethyl, a substituted or unsubstituted n-propyl, a substituted or unsubstituted isopropyl, a substituted or unsubstituted n-butyl, a substituted or unsubstituted isobutyl, a substituted or unsubstituted tert-butyl, a substituted or unsubstituted 1-methylpentyl, a substituted or unsubstituted 2,2-dimethylheptyl, a substituted or unsubstituted 4-methylhexyl, etc. In some embodiments, R 1 can be selected from substituted or unsubstituted C1-C5 alkyl. For example, R 1 can be a substituted or unsubstituted C1-C2 alkyl, a substituted or unsubstituted C1-C3 alkyl, or a substituted or unsubstituted C1-C4 alkyl. In some embodiments, R 3 can be selected from substituted or unsubstituted C1-C5 alkyl. For example, R 3may be a substituted or unsubstituted C1-C2 alkyl group, a substituted or unsubstituted C1-C3 alkyl group, or a substituted or unsubstituted C1-C4 alkyl group. In some embodiments, R 4 may be selected from substituted or unsubstituted C1-C5 alkyl groups. For example, R 4 may be a substituted or unsubstituted C1-C2 alkyl group, a substituted or unsubstituted C1-C3 alkyl group, or a substituted or unsubstituted C1-C4 alkyl group. In some embodiments, R 5 may be selected from substituted or unsubstituted C1-C5 alkyl groups. For example, R 5 may be a substituted or unsubstituted C1-C2 alkyl group, a substituted or unsubstituted C1-C3 alkyl group, or a substituted or unsubstituted C1-C4 alkyl group. In some embodiments, R 6 may be selected from substituted or unsubstituted C1-C5 alkyl groups. For example, R 6 may be a substituted or unsubstituted C1-C2 alkyl group, a substituted or unsubstituted C1-C3 alkyl group, or a substituted or unsubstituted C1-C4 alkyl group. In some embodiments, R6, R7, R8 and R9 may independently be selected from substituted or unsubstituted C1-C6 alkyl groups. For example, R6, R7, R8 and R9 may independently be selected from substituted or unsubstituted C1-C5 alkyl groups, substituted or unsubstituted C1-C4 alkyl groups, or substituted or unsubstituted C1-C3 alkyl groups. In some embodiments, R 7 may be selected from substituted or unsubstituted C1-C 12 alkyl groups. For example, R 7 may be a substituted or unsubstituted C1-C 10 alkyl group, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C1-C8 alkyl group, or a substituted or unsubstituted C1-C5 alkyl group.

[0108] In the present application, the above-mentioned substituted or unsubstituted alkoxy groups may be straight-chain alkoxy groups or branched-chain alkoxy groups. In the embodiments of the present application, the substituted or unsubstituted alkoxy groups may be substituted or unsubstituted C1-C 15 alkoxy groups. For example, the substituted or unsubstituted alkoxy groups may be substituted or unsubstituted C1-C 14 alkoxy groups, substituted or unsubstituted C1-C 12 alkoxy groups, substituted or unsubstituted C1-C 10 alkoxy groups, substituted or unsubstituted C1-C9 alkoxy groups, substituted or unsubstituted C1-C6 alkoxy groups, or substituted or unsubstituted C1-C5 alkoxy groups; specific substituted or unsubstituted alkoxy groups may be substituted or unsubstituted methoxy (-OCH3), substituted or unsubstituted ethoxy (-OCH2CH3), substituted or unsubstituted propoxy, substituted or unsubstituted tert-butoxy, etc. In some embodiments, R 1may be selected from substituted or unsubstituted C1-C5 alkoxy groups. For example, R 1 may be a substituted or unsubstituted C1-C2 alkoxy group, a substituted or unsubstituted C1-C3 alkoxy group, or a substituted or unsubstituted C1-C4 alkoxy group. In some embodiments, R 3 may be selected from substituted or unsubstituted C1-C5 alkoxy groups. For example, R 3 may be a substituted or unsubstituted C1-C2 alkoxy group, a substituted or unsubstituted C1-C3 alkoxy group, or a substituted or unsubstituted C1-C4 alkoxy group. In some embodiments, R 4 may be selected from substituted or unsubstituted C1-C5 alkoxy groups. For example, R 4 may be a substituted or unsubstituted C1-C2 alkoxy group, a substituted or unsubstituted C1-C3 alkoxy group, or a substituted or unsubstituted C1-C4 alkoxy group.

[0109] In the present application, cycloalkyl may refer to a cyclic alkyl group having a single ring or a polycyclic ring system including fused, bridged, and spiro ring systems. In the embodiments of the present application, the substituted or unsubstituted cycloalkyl group may be a substituted or unsubstituted C3-C 15 cycloalkyl group. For example, the substituted or unsubstituted cycloalkyl group may be a substituted or unsubstituted C3-C 12 cycloalkyl group, a substituted or unsubstituted C3-C 10 cycloalkyl group, a substituted or unsubstituted C3-C9 cycloalkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, or a substituted or unsubstituted C3-C5 cycloalkyl group; specifically, the substituted or unsubstituted cycloalkyl group may be a substituted or unsubstituted cyclopropyl group, a substituted or unsubstituted cyclobutyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclooctyl group, a substituted or unsubstituted adamantyl group, etc. In some embodiments, R6, R7, R8, and R9 may independently be selected from substituted or unsubstituted C3-C 10 cycloalkyl groups. For example, R6, R7, R8, and R9 may independently be selected from substituted or unsubstituted C3-C7 cycloalkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, or substituted or unsubstituted C3-C5 cycloalkyl groups. In some embodiments, R 7 may be selected from substituted or unsubstituted C3-C 12 cycloalkyl groups. For example, R 7 may be a substituted or unsubstituted C3-C 10 cycloalkyl group, a substituted or unsubstituted C3-C9 cycloalkyl group, a substituted or unsubstituted C3-C8 cycloalkyl group, or a substituted or unsubstituted C3-C5 cycloalkyl group.

[0110] In the present application, an aryl group may refer to a monovalent aromatic carbocyclic group having a single ring (such as that present in a phenyl group) or a ring system having multiple fused rings (examples of such aromatic ring systems include naphthyl, anthracenyl, and indenyl), where the fused rings may or may not be aromatic, provided that the point of attachment is via an atom of an aromatic ring. In embodiments of the present application, a substituted or unsubstituted aryl group may be a substituted or unsubstituted C6-C 15 aryl group. For example, a substituted or unsubstituted aryl group may be a substituted or unsubstituted C6-C 13 aryl group, a substituted or unsubstituted C6-C 12 aryl group, a substituted or unsubstituted C6-C 11 aryl group, a substituted or unsubstituted C6-C 10 aryl group, a substituted or unsubstituted C6-C8 aryl group, or a substituted or unsubstituted C6-C7 aryl group; specifically, a substituted or unsubstituted aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, etc. In some embodiments, R 7 may be selected from substituted or unsubstituted C6-C 12 aryl groups. For example, R 7 may be a substituted or unsubstituted C6-C 10 aryl group, a substituted or unsubstituted C6-C9 aryl group, a substituted or unsubstituted C6-C8 aryl group, or a substituted or unsubstituted C6-C7 aryl group.

[0111] In embodiments of the present application, a substituted or unsubstituted arylalkyl group may be a substituted or unsubstituted C7-C 15 arylalkyl group. For example, a substituted or unsubstituted arylalkyl group may be a substituted or unsubstituted C7-C 13 arylalkyl group, a substituted or unsubstituted C7-C 12 arylalkyl group, a substituted or unsubstituted C7-C 11 arylalkyl group, a substituted or unsubstituted C7-C 10 arylalkyl group, a substituted or unsubstituted C7-C9 arylalkyl group, or a substituted or unsubstituted C7-C8 arylalkyl group; specifically, a substituted or unsubstituted arylalkyl group may be a substituted or unsubstituted phenylalkyl group, a substituted or unsubstituted biphenylalkyl group, a substituted or unsubstituted polycyclic arylalkyl group, etc. In some embodiments, R 7 may be selected from substituted or unsubstituted C7-C 12 arylalkyl groups. For example, R 7 may be a substituted or unsubstituted C7-C 10 arylalkyl group, a substituted or unsubstituted C7-C9 arylalkyl group, or a substituted or unsubstituted C7-C8 arylalkyl group.

[0112] In the present application, "substituted or unsubstituted" may mean unsubstituted or substituted by one or more substituents selected from the following: deuterium atom, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), oxygen atom, nitrogen atom, phosphorus atom, sulfur atom, cyano group, nitro group, hydroxyl group, carbonyl group, ester group, imide group, amide group, phosphine oxide group, alkyl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkenyl group, silyl group, boron group, amino group, arylphosphine group, aryl group, arylalkyl group, arylalkenyl group, heteroaryl group, heteroarylamino group, arylamino group, heterocyclic group. "Substituted or unsubstituted" may also mean unsubstituted or substituted by a substituent formed by connecting at least two of the substituents exemplified above. For example, the "substituent formed by connecting at least two of the substituents exemplified above" may be a biphenyl group, which can be regarded as an aryl group in the embodiments of the present application and can also be understood as a substituent formed by connecting two phenyl groups.

[0113] The patterned material of the present application includes a first repeating unit represented by formula (I) and a second repeating unit represented by formula (II), wherein R1 is selected from polar groups and R2 is selected from acid-labile groups. The selection of polar groups and acid-labile groups is as described above and will not be elaborated here. The patterned material of the present application is a binary copolymer. Additionally, when using multiple first monomers with different structures or multiple second monomers with different structures to prepare the patterned material, that is, when the patterned material contains multiple first repeating units with different structures or multiple second repeating units with different structures, the patterned material can also be regarded as a terpolymer, a quaternary copolymer, a quinary copolymer, etc. For example, when the patterned material uses a first monomer with one structure and a second monomer with one structure, the patterned material is a binary copolymer; when the patterned material uses a first monomer with one structure and one or two second monomers with different structural formulas, or when the patterned material uses one or two first monomers with different structural formulas and a second monomer with one structure, the patterned material can be regarded as a binary copolymer or a terpolymer; when the patterned material uses two first monomers with different structural formulas and two second monomers with different structural formulas, the patterned material can be regarded as a binary copolymer or a quaternary copolymer.

[0114] In the embodiments of the present application, the sulfur element content in the patterned material is less than 1 ppm. In the related art, in a radical polymerization reaction, for example, in reversible addition-fragmentation chain transfer polymerization (RAFT), a chain transfer agent containing a sulfur element is used, resulting in the presence of sulfur element in the prepared patterned material, which affects the stability of the patterned material and the light absorption during use; at the same time, during the process of removing the sulfur element, mercapto groups are easily formed and dimerize to generate disulfide bonds, which still affects the performance of the patterned material. However, the present application uses an iodine-containing initiator, which can generate iodine atoms as a chain transfer agent during the polymerization reaction and is easily removed during the deiodination treatment, avoiding the influence of sulfur element on the performance of the patterned material. The sulfur element content in the patterned material of the present application is less than 1 ppm, that is, it can be considered that the patterned material hardly contains sulfur element, avoiding the problem of the influence of sulfur element on the performance of the patterned material and being beneficial to the use of the patterned material. In some embodiments, the sulfur element content in the patterned material can be but is not limited to less than 0.9 ppm, less than 0.8 ppm, less than 0.7 ppm, less than 0.5 ppm, less than 0.3 ppm or less than 0.1 ppm, etc.

[0115] In the embodiments of the present application, the copper element content in the patterned material is less than 100 ppb. In the related art, in a radical polymerization reaction, for example, in atom transfer radical polymerization (ATRP), a catalyst containing a copper element is used to catalyze the polymerization reaction, resulting in the presence of copper element in the prepared patterned material, which affects the performance of the patterned material, such as the adhesion performance and exposure performance of the patterned thin film formed by the patterned material. However, in the present application, an organic iodide catalyst is used, which does not contain copper element, avoiding the influence of copper element on the performance of the patterned material. The copper element content in the patterned material of the present application is less than 100 ppb, that is, it can be considered that the patterned material hardly contains copper element, avoiding the problem of the influence of copper element on the performance of the patterned material and being beneficial to the use of the patterned material. In some embodiments, the copper element content in the patterned material can be but is not limited to less than 90 ppb, less than 85 ppb, less than 80 ppb, less than 70 ppb, less than 60 ppb, less than 50 ppb, less than 45 ppb, less than 40 ppb or less than 30 ppb, etc.

[0116] In the embodiments of the present application, the iodine element content in the patterned material is less than 5 ppm, thus avoiding the influence of iodine element on the performance of the patterned material and being beneficial to the use of the patterned material. In some embodiments, the iodine element content in the patterned material can be but is not limited to less than 4 ppm, less than 3 ppm, less than 2 ppm, less than 1 ppm or less than 0.5 ppm, etc.

[0117] The polydispersity index (PDI) is used to describe the molecular weight distribution of a polymer and is the ratio of the weight-average molecular weight to the number-average molecular weight. In the embodiments of the present application, the polydispersity index of the patterned material is less than 1.4, the molecular weight distribution of the patterned material is relatively narrow, and the uniformity is better, so that the patterned composition with the patterned material can form patterns with higher resolution and lower edge roughness, which is beneficial to the preparation and use of semiconductor devices. Specifically, the PDI of the patterned material can be, but is not limited to, less than 1.3, less than 1.2, less than 1.1, or less than 1.05, etc.

[0118] In the embodiments of the present application, the molar fraction of the first repeating unit in the patterned material is 35% - 65%, which is beneficial to improving the adhesion and strength properties of the patterned film formed by the patterned material, and at the same time does not affect the development speed. In some embodiments, the molar fraction of the first repeating unit in the patterned material can be, but is not limited to, 35%, 40%, 45%, 50%, 55%, 60% or 65%, etc. In the embodiments of the present application, the molar fraction of the second repeating unit is 35% - 65%, which is beneficial to improving the development speed of the patterned film formed by the patterned material, and at the same time does not affect the properties of the patterned film. In some embodiments, the molar fraction of the second repeating unit in the patterned material can be, but is not limited to, 35%, 40%, 45%, 50%, 55%, 60% or 65%, etc.

[0119] In the embodiments of the present application, the weight-average molecular weight of the patterned material is 4000 Da - 12000 Da, so that the film-forming performance and resolution of the patterned film formed by the patterned composition are excellent. In some embodiments, the weight-average molecular weight of the patterned material can be, but is not limited to, 4000 Da, 5000 Da, 6000 Da, 7000 Da, 8000 Da, 9000 Da, 10000 Da, 11000 Da or 12000 Da, etc.

[0120] The embodiments of the present application also provide a patterned material prepared by the above preparation method. The patterned material of the present application includes a first repeating unit represented by formula (I) and a second repeating unit represented by formula (II), wherein R1 is selected from polar groups and R2 is selected from acid-labile groups. This patterned material avoids the influence of impurity elements on its properties and is beneficial to its use.

[0121] The embodiments of the present application provide a patterned composition, which includes the above-mentioned patterned material, a photoacid generator (PAG) and a second solvent. Among them, the patterned material avoids the influence of impurity elements on its properties, which is beneficial to improving the use performance of the patterned composition. When the patterned composition is irradiated or radiated with light such as ultraviolet light, deep ultraviolet light, X-rays, electron beams, ion beams, etc., its solubility in the developer will change.

[0122] In the embodiments of the present application, the mass content of the patterning material in the patterning composition is 0.7% - 6%, which is beneficial to the uniform dispersion of the patterning material in the patterning composition and also beneficial to improving the performance of the patterned film formed by the patterning composition. In some embodiments, the mass content of the patterning material in the patterning composition can be but is not limited to 0.7%, 0.8%, 1%, 1.2%, 1.5%, 1.6%, 1.9%, 2%, 2.1%, 2.3%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.7%, 4%, 4.3%, 4.5%, 5%, 5.2%, 5.7% or 6%, etc.

[0123] The photoacid generator in the patterning composition can generate acid after illumination, thereby decomposing the acid-labile groups in the patterning material, resulting in a change in the dissolution property of the patterning material, which is beneficial to the formation of the patterned film. In the embodiments of the present application, the mass content of the photoacid generator in the patterning composition is 0.01% - 1%, which is beneficial to the application of the patterning composition in the preparation of the patterned film and does not affect the performance of the formed patterned film, being beneficial to the preparation of semiconductor devices. In some embodiments, the mass content of the photoacid generator in the patterning composition can be but is not limited to 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%, etc. In the embodiments of the present application, the mass ratio of the patterning material to the photoacid generator is 20:(1 - 4), which can improve the interaction between the photoacid generator and the patterning material during exposure and also ensure the strength of the formed patterned film. In some embodiments, the mass ratio of the patterning material to the photoacid generator can be but is not limited to 20:1, 100:9, 10:1, 25:3, 20:3, 100:17 or 5:1, etc.

[0124] In the embodiments of the present application, the photoacid generator contains a cation and an anion. In some embodiments of the present application, the structure of the cation in the photoacid generator is shown in formula (27), and Rs1, Rs2, and Rs3 are independently selected from H, substituted or unsubstituted alkyl groups, or substituted or unsubstituted cycloalkyl groups.

[0125] Formula (27).

[0126] In some embodiments, when Rs1, Rs2, and Rs3 are selected from substituted or unsubstituted alkyl groups or substituted or unsubstituted cycloalkyl groups, the number of carbon atoms in the alkyl group can be less than or equal to 5, and the number of carbon atoms in the cycloalkyl group can be less than or equal to 5. Specifically, Rs1, Rs2, and Rs3 can independently be selected from substituted or unsubstituted methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, or cyclopentyl, etc. In some embodiments of the present application, the structure of the anion in the photoacid generator can, but is not limited to, be selected from any one of formulas (28) to (38).

[0127] Formula (28), Formula (29), Formula (30), Formula (31), Formula (32), Formula (33), Formula (34), Formula (35), Formula (36) Formula (37), Formula (38).

[0128] In the present application, the second solvent of the patterning composition is selected from substances that can dissolve and disperse other components of the patterning composition. In some embodiments, the second solvent can, but is not limited to, be selected from at least one of propylene glycol methyl ether acetate (PGMEA), γ-butyrolactone (GBL), and cyclohexanone. In the embodiments of the present application, the mass content of the second solvent in the patterning composition can be 94% - 99%, which is beneficial to the uniform mixing and dispersion of other components in the patterning composition, and is also beneficial to the leveling of the patterning composition, facilitating coating into a film to form a film layer with a smooth surface. In some embodiments, the mass content of the second solvent in the patterning composition can, but is not limited to, be 94%, 95%, 96%, 97%, 98%, or 99%, etc.

[0129] In the embodiments of the present application, the patterning composition further includes a protective agent. The protective agent can protect the patterning composition, especially protect the unexposed areas during the process of forming a patterned film from the patterning composition, improve the exposure and development effects, and enhance the performance of the obtained patterned film. In some embodiments of the present application, the mass content of the protective agent in the patterning composition is 0.01%-1%, which can not only exert the protective effect of the protective agent, but also will not affect other properties such as the strength and adhesion of the formed patterned film. In some embodiments, the mass content of the protective agent in the patterning composition can be but is not limited to 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%, etc. In some embodiments of the present application, the mass ratio of the patterning material to the protective agent is 20:(1-4), which can not only enhance the protective effect of the protective agent, but also ensure other properties such as the strength and adhesion of the formed patterned film. In some embodiments, the mass ratio of the patterning material to the protective agent can be but is not limited to 20:1, 100:9, 10:1, 25:3, 20:3, 100:17 or 5:1, etc. In some embodiments of the present application, the protective agent includes at least one of photo-decomposable base (PDB) and quencher. In some implementations of the present application, the photo-decomposable base (PDB) includes a triphenylsulfonium salt with or without a photosensitive group substitution or a diphenyliodonium salt with or without a substitution or a photosensitive group substitution, and a basic group. In some embodiments, the basic group can include at least one of a carboxylate anion, a secondary amine group, and a tertiary amine group. In some implementations of the present application, the quencher is a benzimidazole substituted with a substituent. In some embodiments, the photo-decomposable base can be but is not limited to any one of the compounds shown in Formula (39) to Formula (46), and the quencher can be but is not limited to any one of the compounds shown in Formula (47) to Formula (50).

[0130] Formula (39), Formula (40), Formula (41), Formula (42), Formula (43), Formula (44), Formula (45), Formula (46), Formula (47), Formula (48), Formula (49), Formula (50).

[0131] In the embodiments of the present application, in order to improve the comprehensive performance of the patterning composition, the patterning composition may further include an auxiliary agent, and the auxiliary agent may be at least one of a leveling agent and a surfactant. The addition of the leveling agent and the surfactant can improve the uniformity of the coated film layer. The content of the auxiliary agent in the patterning composition can be adjusted according to actual needs. In some embodiments, the mass ratio of the patterning material to the auxiliary agent can be greater than or equal to 20.

[0132] In the embodiments of the present application, the patterning composition may further include a fluororesin. The addition of the fluororesin can improve the hydrophobicity of the film layer formed by the patterning composition, which is beneficial to the preparation of the patterned thin film under different process conditions. In some embodiments, the mass ratio of the patterning material to the fluororesin can be greater than or equal to 10.

[0133] In the embodiments of the present application, the solid content of the patterning composition can be 1% - 6%, which is beneficial to both the leveling of the patterning composition and the improvement of the performance of the formed patterned thin film. In some embodiments, the solid content of the patterning composition can be, but is not limited to, 1%, 2%, 3%, 4%, 5% or 6%, etc.

[0134] In the embodiments of the present application, the copper element content in the patterning composition is less than 5 ppb. The copper element content in the patterning material used in the present application is low, avoiding the influence of the copper element on the performance of the patterning material, and the copper element content in the formed patterning composition still remains at a very low level, which is beneficial to the preparation of the patterned thin film.

[0135] The embodiments of the present application also provide an application of the above-mentioned patterning composition in the field of patterning. The above-mentioned patterning composition can be applied to the semiconductor patterning process to obtain high-quality patterns and improve the precision and preparation efficiency of components.

[0136] The embodiments of the present application also provide a patterning method, as Figure 1 shown, and its patterning process includes:

[0137] S101: Coating the patterning composition of the embodiments of the present application on a substrate to form a patterning material film layer on the substrate.

[0138] As Figure 1 shown, a patterning material film layer 20 is formed on the substrate 10.

[0139] In the embodiments of the present application, the substrate may but is not limited to be a silicon wafer. Other coatings may also be covered on the substrate, and the other coatings may be an antireflection coating, an etching-resistant coating, an epitaxial layer, a metal layer, a dielectric layer, a modification layer or a matching layer. Generally, the other coatings can be obtained by preprocessing the substrate, and the preprocessing methods can be: performing O2 plasma surface hydrophilic activation on the silicon wafer substrate; or cleaning in a Piranha solution (H2O: 30% ammonia water: 30% H2O2 = 5: 1: 1) for 15 min - 20 min, and then completing the hydrophilic treatment through deionized water washing and isopropyl alcohol washing; or performing surface hydrophobic treatment on the substrate by covering hexamethyldisilazane (HMDS) on the substrate by evaporation or spin coating; the hydrophobic treatment can be after the hydrophilic treatment; or adding a bottom antireflection layer (BARC), a bottom carbon-containing coating (SOC), or a bottom silicon-containing coating (SOG).

[0140] According to the size of the substrate, an appropriate volume of the patterning composition is applied onto the substrate through a spin coating process to form a patterned material film layer with a thickness of 5 nm - 200 nm, and the surface roughness of the film layer can be lower than 2 nm. Exemplarily, for a 4-inch substrate, 1 mL - 5 mL of the patterning composition can be taken for spin coating.

[0141] In the embodiments of the present application, after spin coating, the second solvent remaining in the patterned material film layer can be selectively removed through a baking process before exposure. In some embodiments of the present application, the baking temperature can be 90°C - 150°C, and the time can be 30 s - 120 s. In some embodiments, the baking temperature can be 100°C - 120°C, and the time can be 40 s - 90 s.

[0142] S102: Expose the patterned material film layer to an exposure light source through a photomask.

[0143] As Figure 1 shown, the patterned material film layer 20 is exposed to the exposure light source through the photomask 30, so that the patterned material film layer 20 has an exposed portion 21 and a non-exposed portion 22.

[0144] Specifically, the exposure light source can be ultraviolet light, deep ultraviolet light, extreme ultraviolet light, X-ray or electron beam. In some embodiments, the exposure light source can be deep ultraviolet light, such as deep ultraviolet light of 193 nm (ArFi). The patterning material and the patterned material film layer provided by the present application can be applicable to deep ultraviolet light such as ArFi, which is beneficial to improving the exposure and development effect. Among them, the exposure doses of ultraviolet light, deep ultraviolet light, extreme ultraviolet light, and X-ray can be 10 mJ / cm 2 - 300 mJ / cm 2 , and the dose of electron beam irradiation can be 50 μC / cm 2 - 5000 μC / cm2 . After the patterned material film layer is selectively exposed to a light source, a chemical reaction occurs in the exposed part, and the solubility changes.

[0145] In the embodiment of the present application, the patterned material film layer can be selectively baked after exposure and before development. The baking temperature can be 80°C - 150°C, and the time can be 30s - 120s. This baking operation can promote the further completion of the uncompleted chemical reactions in the film layer.

[0146] S103: Use a developer to develop the exposed patterned material film layer to form a patterned thin film on the substrate.

[0147] As Figure 1 shown, a patterned thin film 40 is formed on the substrate 10 after development.

[0148] Since the chemical properties of the exposed part of the patterned material film layer change and the solubility changes, the irradiated patterned material is cleaned with a developer. The cleaning time ranges from 10s to 300s and can be single-step cleaning or multi-step cleaning; after cleaning, the irradiated part of the patterned material film layer is washed away.

[0149] The developing process can select a suitable developer according to the properties of the patterned material. The developer is a pure or mixed solvent that dissolves the soluble regions after the solubility change of the patterned material film layer caused by exposure. The developer can be selected from organic solutions, inorganic solutions, pure solvents, mixed solvents, solvents containing additives, etc. Specifically, in some embodiments of the present application, the developer can be an aqueous solution of tetramethylammonium hydroxide (TMAH) with a concentration of 0.5% - 5%, or can be an organic solvent such as ketones, alcohols, ethers, esters, lactones, high-boiling-point alcohols, etc. Among them, the ketones can be, for example, cyclohexanone and methyl-2-n-amyl ketone; the alcohols can be, for example, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; the ethers can be, for example, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether; the esters can be, for example, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monoter-butyl ether acetate; the lactones can be, for example, γ-butyrolactone; the high-boiling-point alcohol solvents can be, for example, diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, 1,3-butanediol. The developer can be a mixture of one or more of the above solvents. The developing can be achieved by soaking or coating (such as spin coating). Among them, the contact developing time between the developer and the film layer after exposure can be 10s - 120s. After development, a water rinsing process can be selectively added, and the rinsing time can be 20s - 120s. Rinsing can make the film layer cleaner; a baking process can also be selectively added. The baking temperature can be between 80°C and 150°C, and the time can be between 30s and 120s; baking can make the pattern structure more stable and not easily collapse.

[0150] In some embodiments, development can also be carried out by using steam or etching.

[0151] S104: After development, etch the substrate to transfer the pattern of the patterned thin film onto the substrate to obtain a patterned substrate.

[0152] As Figure 1 shown, after development and etching, a patterned substrate 50 is obtained.

[0153] The pattern formed by the patterned material forms a selective protection effect on the substrate material in the etching step. After etching under certain conditions, the patterned material and the unprotected substrate material are etched, but the etching rate at the protected part by the patterned material is slower than that at the unprotected part. Finally, a pattern is formed on the substrate material, that is, the pattern of the patterned thin film is transferred onto the substrate. The etching process can specifically be carried out by hydrofluoric acid etching, ion etching, or ion implantation process to transfer the pattern onto the substrate.

[0154] The patterning method provided by the embodiments of the present application, by using the patterning composition of the embodiments of the present application, can be applied to the patterning process in the preparation of semiconductor integrated circuits, obtaining a smaller critical dimension of chip patterning, which is beneficial to the development of high integration and high precision of semiconductors.

[0155] The embodiments of the present application further provide a patterned film, which is formed by the above-mentioned patterning composition or obtained by the above-mentioned patterning method. The patterned film can be used as a high-precision mask in the integrated circuit patterning process, and the pattern of the patterned film can be transferred to a substrate such as a silicon wafer by etching, so as to form a preset pattern on the substrate.

[0156] In the embodiments of the present application, the patterned film includes a patterning material and a photoacid generator. In some embodiments, the mass ratio of the patterning material to the photoacid generator can be 20:(1 - 4). In the embodiments of the present application, the patterned film further includes a protective agent. In some embodiments, the mass ratio of the patterning material to the protective agent can be 20:(1 - 4).

[0157] The embodiments of the present application further provide a patterned substrate, on which the pattern is formed by the above-mentioned patterning composition or obtained by the above-mentioned patterning method. The patterned substrate can be used for the preparation of semiconductor devices such as chips, improving the manufacturing precision and quality of the devices, and further enhancing the performance of semiconductor devices.

[0158] The embodiments of the present application further provide a semiconductor device, which is prepared by using the above-mentioned patterned film or the above-mentioned patterned substrate.

[0159] The semiconductor device provided by the embodiments of the present application can be applied in terminal devices, such as tablet computers, laptop computers, mobile phones, digital cameras, wearable electronic devices, virtual reality devices, etc.

[0160] The embodiments of the present application further provide a method for preparing a semiconductor device, including:

[0161] Coating the above-mentioned patterning composition on a substrate to form a film layer on the substrate;

[0162] Developing the film layer through a photomask to form a patterned film on the substrate.

[0163] Specifically, the method for preparing a semiconductor device includes using the above-mentioned patterning method. The semiconductor device can include chips, etc. In the preparation process of the chips, after the patterning process is completed, the preparation of other functional layers can be carried out.

[0164] The technical solutions of the embodiments of the present application are further described below through specific embodiments.

[0165] Example A1

[0166] The initiator ( ), the catalyst (tetrabutylammonium iodide), monomer IX-1 ( ), monomer X-1 ( ), and monomer X-2 ( ) were added to a 1 L polymerization reactor in amounts of 6.5 g, 49.3 g, 102.1 g, 121.5 g, and 26.2 g respectively. 200 mL of the solvent diglyme was added. Under a nitrogen atmosphere, the mixture was heated at 70 °C for polymerization for 10 h, then 60 g of dodecylamine was added, and stirring was continued at 80 °C for 10 h for deiodination treatment; after the reaction was completed, the mixed solution was dropped into 3 L of methanol, and then filtered and dried to obtain the patterned material; the patterned material included the repeating unit I-1 ( ), the repeating unit II-1 ( ), and the repeating unit II-2 ( ).

[0167] The contents of sulfur and copper elements in the obtained patterned material were detected by inductively coupled plasma mass spectrometry (ICP-MS). The sulfur element content in the patterned material was less than 1 ppm, the copper element content was less than 100 ppb, and the iodine element content was less than 5 ppm.

[0168] Comparative Example A1

[0169] In a 1 L glass reactor, 306 parts by weight of PGMEA was added under a nitrogen atmosphere, and the temperature was controlled at a constant 91 °C in an oil bath; then a mixed solution containing 97 parts by weight of monomer IX-1, 168 parts by weight of monomer X-1, 35 parts by weight of monomer X-2, 295 parts by weight of the solvent PGMEA, and 18 parts by weight of initiator V601 (dimethyl 2,2'-azobis(2-methylpropionate)) was added dropwise into the reactor through an injection pump at a certain dropping rate over 3 h. After the dropping was completed, the reaction was continued for 2 h. Subsequently, the resin solution was cooled and diluted, and dropped into a solvent of about 5 times the amount of methanol and water (90 / 10 V / V). Then the sedimentation mixture was heated to 45 °C and slurried for 30 min, and the wet powder polymer was obtained by filtration. The wet powder of the polymer was placed in a vacuum drying oven at 65 °C and dried for about 24 h to obtain the patterned material; the patterned material included the repeating unit I-1, the repeating unit II-1, and the repeating unit II-2.

[0170] The weight-average molecular weight (M W ) and number-average molecular weight (M n)(Detection was carried out with tetrahydrofuran as the mobile phase and polymethyl methacrylate (PMMA) as the standard sample, and the PDI value of the patterned material was calculated; the molar fractions of the repeating units in the patterned materials prepared in Example A1 and Comparative Example A1 were detected by carbon-13 nuclear magnetic resonance, and the results are shown in Table 1.)

[0171] Table 1 Properties of the Patterned Material

[0172]

[0173] Example B1

[0174] (The patterned material prepared in Example A1, a photoacid generator, a photo-decomposable base, and a solvent (including PGMEA and GBL, with a mass ratio of PGMEA to GBL of 10:1) were mixed to form a patterned composition.)

[0175] Comparative Example B1

[0176] (The difference from Example B1 is that the patterned material used the substance prepared in Comparative Example A1.)

[0177] Example C1

[0178] (The patterned composition of Example B1 was spin-coated on the surface of a silicon substrate to form a patterned material film layer with a thickness of 85 nm.)

[0179] (Pre-exposure baking: The patterned material film layer was baked at 110 °C for 2 min.)

[0180] (Radiation exposure: The patterned material film layer was masked and exposed with 193 nm deep ultraviolet light. The pattern selected had a line width of 30 nm and a repeating size of 76 nm line-space pattern, and the irradiation dose was 22 mJ / cm 2 -32 mJ / cm 2 ;

[0181] (Development: Development was carried out with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 s to form a patterned thin film on the silicon wafer.)

[0182] Example C2

[0183] (The difference from Example C1 is that the pattern selected had a line width of 33 nm and a repeating size of 78 nm line-space pattern.)

[0184] Example C3

[0185] (The difference from Example C1 is that the pattern selected had a line width of 37 nm and a repeating size of 80 nm line-space pattern.)

[0186] Comparative Example C1

[0187] It is different from Example C1 in that the patterning composition provided by Comparative Example B1 is used.

[0188] Comparative Example C2

[0189] It is different from Example C2 in that the patterning composition provided by Comparative Example B1 is used.

[0190] Comparative Example C3

[0191] It is different from Example C3 in that the patterning composition provided by Comparative Example B1 is used.

[0192] The patterned films obtained after the above exposure and development were detected using a scanning electron microscope for feature size measurement (CD-SEM) to obtain line sizes at different focal lengths and different energies. According to the target sizes of different masks, the best energy (Best E), best focal length (Best F), exposure latitude (EL), depth of focus (DOF), and line width roughness (LWR) of different patterning compositions under different masks were calculated. The results are shown in Table 2; Figure 2 is the electron micrograph of the patterned film obtained in Example C1, Figure 3 is the electron micrograph of the patterned film obtained in Example C2, Figure 4 is the electron micrograph of the patterned film obtained in Example C3, Figure 5 is the electron micrograph of the patterned film obtained in Comparative Example C1, Figure 6 is the electron micrograph of the patterned film obtained in Comparative Example C2, Figure 7 is the electron micrograph of the patterned film obtained in Comparative Example C3.

[0193] Table 2 Performance of the Patterned Films

[0194]

[0195] It can be seen that under the same exposure conditions and masks, the patterned films formed using the patterning materials and patterning material compositions provided in the embodiments of the present application have lower exposure energy, higher exposure latitude (EL), and lower line width roughness (LWR), and have excellent exposure and development performance, which is beneficial to the use of the patterning materials and patterning material compositions in the preparation of semiconductor devices.

Claims

1. A patterned composition, characterized in that, It includes a patterned material, a photoacid generator, and a second solvent. The patterned material includes a first repeating unit represented by formula (I) and a second repeating unit represented by formula (II), where R1 is selected from polar groups, R2 is selected from acid-labile groups, and the polydispersity index of the patterned material is less than 1.4; Formula (I), Formula (II); The polar group is selected from the groups represented by formula (V), where is a linking site, n1 is selected from integers from 1 to 4, R 1 is selected from H, substituted or unsubstituted alkyl or substituted or unsubstituted alkoxy, R 2 is selected from O, Formula (V), The acid-labile moiety is selected from the group represented by formula (VII), wherein is a linking site, n5 is an integer selected from 1 to 4, n6 is an integer selected from 2 to 4, R 5 is selected from substituted or unsubstituted alkyl, R 6 is selected from H or substituted or unsubstituted alkyl, Formula (VII); The preparation method of the patterned material includes: Mixing a first monomer, a second monomer, an iodine-containing initiator, and an organic iodide catalyst to form a polymerization reaction solution, and forming an iodine-containing polymer through a polymerization reaction; in the polymerization reaction, the molar ratio of the first monomer to the second monomer is (3:7)-(7:3); The iodine-containing polymer is subjected to deiodination treatment to obtain a patterned material. The chemical structural formula of the iodine-containing initiator is as shown in formula (III). Formula (III); The chemical structural formula of the organic iodide catalyst is as shown in formula (IV), where R6, R7, R8, and R9 are independently selected from substituted or unsubstituted alkyl groups or substituted or unsubstituted cycloalkyl groups. Formula (IV).

2. The patterned composition according to claim 1, wherein The molar fraction of the first repeating unit in the patterned material is 35%-65%; The molar fraction of the second repeating unit in the patterned material is 35%-65%; The weight-average molecular weight of the patterned material is 4000 Da - 12000 Da.

3. The patterned composition according to claim 1, wherein The sulfur element content in the patterned material is less than 1 ppm, and the copper element content is less than 100 ppb.

4. The patterned composition according to claim 1, wherein In the polymerization reaction, the molar ratio of the iodine-containing initiator to the sum of the molar amounts of the first monomer and the second monomer is 1:(30 - 100); The reaction temperature of the polymerization reaction is 50°C - 90°C, and the reaction time is 1 h - 24 h.

5. The patterned composition according to claim 1, wherein The polymerization reaction solution further includes a first solvent, and the mass ratio of the total mass of the first monomer and the second monomer to the mass of the first solvent is 1:(0.5 - 5).

6. The patterned composition according to claim 1, wherein, The chemical structural formula of the first monomer is as shown in formula (IX), and the chemical structural formula of the second monomer is as shown in formula (X). Formula (IX), Formula (X).

7. The patterned composition according to claim 1, wherein The iodine-containing polymer is subjected to deiodination treatment, including: The iodine-containing polymer is mixed with the compound represented by formula (VIII) for the deiodination treatment, where R 7 is selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted arylalkyl, Formula (VIII); In the deiodination treatment, the molar ratio of the iodine-containing polymer to the compound represented by formula (VIII) is 1:(1 - 20); The reaction temperature of the deiodination treatment is 20°C - 100°C, and the reaction time is 1 h - 24 h.

8. A patterned film, characterized in that, The patterned thin film is formed from the patterned composition according to any one of claims 1 - 7.

9. A patterned substrate, characterized in that, The pattern on the patterned substrate is formed from the patterned composition according to any one of claims 1 - 7.

10. A semiconductor device, characterized in that, It is prepared by using the patterned thin film according to claim 8, or by using the patterned substrate according to claim 9.

11. A method for manufacturing a semiconductor device, characterized in that, It includes: Coating the patterned composition according to any one of claims 1 - 7 on a substrate to form a film layer on the substrate; Developing the film layer through a photomask to form a patterned thin film on the substrate.

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