CN115947885A - Resin and ArF immersion photoresist composition containing same - Google Patents
Resin and ArF immersion photoresist composition containing same Download PDFInfo
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- CN115947885A CN115947885A CN202111172218.1A CN202111172218A CN115947885A CN 115947885 A CN115947885 A CN 115947885A CN 202111172218 A CN202111172218 A CN 202111172218A CN 115947885 A CN115947885 A CN 115947885A
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Abstract
The invention discloses a resin and an ArF immersion photoresist composition containing the same. The resin is obtained by polymerizing the following monomers in parts by weight: 40-50 parts of monomer A, 1-7.5 parts of monomer B, 0.25-2.5 parts of monomer C and 0.25-2.5 parts of monomer D. The photoresist containing the resin has the advantages of high resolution, high sensitivity and low line width roughness.
Description
Technical Field
The present invention relates to a resin and an ArF immersion photoresist composition comprising the same.
Background
The photolithography technique is a fine processing technique for transferring a pattern designed on a mask plate to a pattern on a substrate by using the chemical sensitivity of a photolithography material (particularly a photoresist) under the action of visible light, ultraviolet rays, electron beams and the like through the processes of exposure, development, etching and the like. The photoresist material (specifically referred to as photoresist), also called photoresist, is the most critical functional chemical material involved in the photolithography technology, and its main components are resin, photo Acid Generator (PAG), and corresponding additives and solvents. The photo-acid generator is a light-sensitive compound, which is decomposed under illumination to generate acid, and the generated acid can make acid-sensitive resin generate decomposition or cross-linking reaction, so that the dissolution contrast of the illuminated part and the non-illuminated part in a developing solution is increased, and the photo-acid generator can be used in the technical field of pattern micro-machining.
Three important parameters of the photoresist include resolution, sensitivity, line width roughness, which determine the process window of the photoresist during chip fabrication. With the increasing performance of semiconductor chips, the integration level of integrated circuits has increased exponentially, and the patterns in integrated circuits have been shrinking. In order to make patterns with smaller dimensions, the performance indexes of the three photoresists must be improved. The use of a short wavelength light source in a photolithography process can increase the resolution of the photoresist according to the rayleigh equation. The light source wavelength of the photolithography process is developed from 365nm (I-line) to 248nm (KrF), 193nm (ArF), and 13nm (EUV). In order to improve the sensitivity of the photoresist, the current KrF, arF and EUV photoresists are mainly made of chemically amplified photosensitive resin. Thus, photosensitizers (photoacid generators) compatible with chemically amplified photopolymer resins are widely used in high-end photoresists.
As the photolithography process is gradually developed, the process complexity is increased to 193nm immersion process, and higher requirements are made on the resist (i.e. photoresist). Developing a photoresist capable of improving resolution, sensitivity and line width roughness becomes a problem to be solved urgently in the industry.
Disclosure of Invention
The invention aims to overcome the defect of few resin types used in photoresist in the technology, and provides a resin and an ArF immersion photoresist composition containing the resin. The photoresist containing the resin has the advantages of high resolution, high sensitivity and low line width roughness.
The invention provides a resin, which is obtained by polymerizing the following monomers in parts by weight: 40-50 parts of monomer A, 1-7.5 parts of monomer B, 0.25-2.5 parts of monomer C and 0.25-2.5 parts of monomer D;
wherein R is 1 Is C 1-10 Alkyl groups of (a);
R 2 is H or C 1-10 Alkyl groups of (a);
R 3 is C 1-10 Alkyl groups of (a);
R 4 is C 2-4 Alkenyl of (a);
R 5 and R 6 Independently is H or C 1-5 Alkyl group of (1).
In some embodiments, R 1 In (b), the C 1-10 Alkyl of (A) is C 1-5 The alkyl group of (b) is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group or a tert-butyl group.
In some embodiments, R 2 In (b), the C 1-10 Alkyl of (A) is C 1-5 The alkyl group of (b) is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group or a tert-butyl group.
In some embodiments, R 3 In (b), the C 1-10 Alkyl of (A) is C 1-5 The alkyl group of (b) is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group or a tert-butyl group.
In some embodiments, R 4 In (b), the C 2-4 Alkenyl of (A) is C 2-3 The alkenyl group of (1) is preferably an ethenyl group or an isopropenyl group.
In some embodiments, R 5 In (b), the C 1-5 The alkyl group of (b) is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group or a tert-butyl group.
In some embodiments, R 2 Is C 1-10 Alkyl group of (1).
In some embodiments, R 5 And R 6 Is C 1-10 The alkyl group of (1).
In some embodiments, the monomer A is
In some embodiments, the monomer C is
In some embodiments, the monomer D is
In some embodiments, the resin has a weight average molecular weight (Mw) of 5000 to 10000, e.g., 5600 to 9800.
In one embodiment of the invention, the resin has a molecular weight distribution coefficient (Mw/Mn) of from 1.0 to 2.0, for example from 1.2 to 2.0.
The molecular weight distribution coefficient refers to a ratio of the weight average molecular weight to the number average molecular weight of the resin.
In some embodiments, the portion of monomer A is from 40 to 47.5 (e.g., 41.5, 45, or 46), such as from 41.5 to 45.
In some embodiments, the portion of monomer B is from 2.5 to 4 parts.
In some embodiments, the fraction of monomer C is from 0.25 to 1.75 parts (e.g., 0.5, 0.75, 1.25, 1.5, or 1.75), such as from 0.5 to 1.25 parts.
In some embodiments, the portion of monomer D is from 0.5 to 1.75 parts (e.g., 0.75 or 1.25), such as from 0.5 to 1.25 parts.
In some embodiments, the portion of monomer a is from 40 to 47.5 parts;
the part of the monomer C is 0.25-1.75;
the part of the monomer D is 0.5-1.75;
R 2 is C 1-10 Alkyl groups of (a);
R 5 and R 6 Independently is C 1-5 Alkyl group of (1).
In some embodiments, the monomer A is
41.5-45 parts of the raw materials;
the part of the monomer B is 2.5-4 parts;
the monomer C is
The parts are 0.5 to 1.25;
the monomer D is
The parts are 0.5-1.25 parts.
In some embodiments, the resin is any one of resins 1 to 8 obtained by polymerizing the following monomers in parts by weight:
resin 1:41.5 parts of monomer A, 5 parts of monomer B, 1.25 parts of monomer C and 1.25 parts of monomer D; the weight average molecular weight is 7100, and the molecular weight distribution coefficient is 1.2;
resin 2:45 parts of monomer A, 4 parts of monomer B, 0.5 part of monomer C and 0.5 part of monomer D; the weight average molecular weight is 9800, and the molecular weight distribution coefficient is 1.3;
resin 3:45 parts of monomer A, 4 parts of monomer B, 0.25 part of monomer C and 0.75 part of monomer D; the weight average molecular weight is 8500, and the molecular weight distribution coefficient is 1.2;
resin 4:45 parts of monomer A, 2.5 parts of monomer B, 1.25 parts of monomer C and 1.25 parts of monomer D; the weight average molecular weight is 6400, the molecular weight distribution coefficient is 2;
resin 5:41.5 parts of monomer A, 4 parts of monomer B, 1.75 parts of monomer C and 1.75 parts of monomer D; the weight average molecular weight is 5600, the molecular weight distribution coefficient is 1.9;
resin 6:47.5 parts monomer A, 1 part monomer B, 0.75 part monomer C and 0.75 part monomer D; the weight average molecular weight is 8700, and the molecular weight distribution coefficient is 2;
resin 7:40 parts of monomer A, 7.5 parts of monomer B, 1.5 parts of monomer C and 1 part of monomer D; the weight average molecular weight is 9300, the molecular weight distribution coefficient is 1.6;
resin 8:46 parts of monomer A, 2.5 parts of monomer B, 0.75 part of monomer C and 0.75 part of monomer D; the weight average molecular weight is 8100, and the molecular weight distribution coefficient is 1.7;
in the resin 1-8, the monomer A is
The monomer C is->
The monomer D is->
The invention also provides a preparation method of the resin, which comprises the following steps: polymerizing 40-50 parts by weight of monomer A, 1-7.5 parts by weight of monomer B, 0.25-2.5 parts by weight of monomer C and 0.25-2.5 parts by weight of monomer D in an organic solvent to obtain the resin;
R 1 、R 2 、R 3 、R 4 、R 5 and R 6 The definitions of (A) and (B) are the same as those described above;
the parts and kinds of the monomers A, the parts and kinds of the monomers B, the parts and kinds of the monomers C and the parts and kinds of the monomers D are the same as those described above.
The conditions and operations of the polymerization reaction may be those conventional in the art for such reactions, with the following conditions and operations being particularly preferred in the present invention:
in the polymerization reaction, the weight ratio of the total weight of the monomer a, the monomer B, the monomer C, and the monomer D to the organic solvent is preferably 0.7 to 1.2, for example, 1.
In the polymerization reaction, the organic solvent is preferably one or more of an aromatic hydrocarbon solvent (e.g., toluene or benzene), an ether solvent (e.g., tetrahydrofuran (THF), diethyl ether or dioxane), methyl Ethyl Ketone (MEK), propylene Glycol Monomethyl Ether Acetate (PGMEA) and γ -butyrolactone, for example, propylene glycol monomethyl ether acetate.
The polymerization is preferably initiated in the presence of a free-radical initiator or by means of heat, for example by means of heat.
When the polymerization is initiated in the presence of a radical initiator, the radical initiator is preferably one or more of 2,2 '-Azobisisobutyronitrile (AIBN), 2' -azobis (2, 4-dimethylvaleronitrile), 2-azobis (methyl 2-methylpropionate), benzoyl peroxide and lauroyl peroxide.
When the polymerization is initiated by heating, the polymerization temperature is preferably 50 to 150 deg.C, more preferably 60 to 100 deg.C, for example 70 deg.C.
In the polymerization, the time of the polymerization is preferably 2 to 6 hours, for example, 3 hours.
Preferably, the polymerization reaction comprises the following steps:
step 1: mixing the monomer A, the monomer B, the monomer C, the monomer D and propylene glycol monomethyl ether acetate to obtain a mixture;
the weight ratio of the total weight of monomer a, monomer B, monomer C, and monomer D to the propylene glycol monomethyl ether acetate is from 5 to 3 (e.g., 10;
step 2: carrying out polymerization reaction on the mixture obtained in the step 1 in propylene glycol monomethyl ether acetate to obtain the resin;
the ratio of the total weight of the monomer A, the monomer B, the monomer C and the monomer D to the total weight of the propylene glycol monomethyl ether acetate (i.e., the sum of the weight of the propylene glycol monomethyl ether acetate in step 1 and the weight of the propylene glycol monomethyl ether acetate in step 2) is from 0.7 to 1.2;
the polymerization temperature is 60-100 ℃.
In the polymerization reaction, any known chain transfer agent (e.g., dodecanethiol or 2-mercaptoethanol) may be added for the purpose of controlling the molecular weight. The amount of chain transfer agent added is preferably 0.01 to 10mol% (the amount of chain transfer agent may be based on the total moles of monomers to be polymerized).
After the polymerization reaction is finished, the post-treatment of the polymerization reaction is preferably as follows: cooling, precipitation of solid (e.g. addition of methanol to precipitate solid), filtration and drying (e.g. vacuum drying at 40 ℃ for 24 hours).
The invention also provides a resin prepared by the preparation method of the resin.
The invention also provides a photoresist composition, which is prepared from the following raw materials in parts by weight: 75-95 parts of resin, 1.0-10 parts of photoacid generator, 1000-2000 parts of solvent, 0.5-3.0 parts of quencher and surfactant;
the resin is the resin or the resin prepared by the preparation method of the resin.
In the photoresist composition, the resin is preferably used in an amount of 85 to 95 parts, for example, 90 parts.
In the photoresist composition, the photo-acid generator is preferably used in an amount of 3 to 10 parts, for example, 5 parts or 7 parts.
In the photoresist composition, the photoacid generator may be a photoacid generator conventional in the art, and preferably has a structure represented by formula (I):
X + Y -
(I)，
wherein, X + Is composed of
Y - Is composed of
/>
Further preferred is
One or more of (a).
In the photoresist composition, the solvent is preferably used in an amount of 1200 to 1600 parts, for example 1500 parts or 1600 parts.
In the photoresist composition, the solvent may be any well-known solvent conventionally used in photoresists, especially chemically amplified photoresist compositions. The solvent is preferably one or more of a ketone solvent (e.g., cyclohexanone and/or methyl-2-n-amyl ketone), a monohydric alcohol solvent (e.g., one or more of a monohydric alcohol solvent (e.g., 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol), a glycol solvent (e.g., diacetone alcohol), an ether solvent (e.g., one or more of propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether), and an ester solvent (e.g., one or more of Propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monoethyl ether acetate, methyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ -butyrolactone);
more preferably one or more of ketone solvents, ether solvents and ester solvents, for example one or more of cyclohexanone, ethylene glycol monoethyl ether and gamma-butyrolactone.
In the photoresist composition, the quencher is preferably used in an amount of 0.8 to 2 parts, for example 1.5 parts.
In the photoresist composition, the quencher may be a quencher conventional in the art, preferably one or more of amine-containing compounds (e.g., primary, secondary and tertiary amine compounds, specifically amine compounds having hydroxyl, ether, ester, lactone, cyano or sulfonate groups), sulfonates and carboxylates, more preferably sulfonates, and further preferably compounds of formula Q1 and/or compounds of formula Q2 as follows;
protection with amine-containing compounds is effective, particularly when the photoresist composition also includes a base labile component.
The amount of the surfactant in the photoresist composition may be that which is conventional in the art for such photoresists, and is preferably 0.1 to 0.2 parts, for example 0.15 parts, by weight.
In the photoresist composition, the surfactant may be a surfactant conventional in the art (a surfactant insoluble or substantially insoluble in water and soluble in an alkaline developer, and/or a surfactant insoluble or substantially insoluble in water and an alkaline developer), preferably one or more of FC-4430 (from 3M), S-381 (from AGC Seimi chemical), E1004 (from Air Products), KH-20 and KH-30 (from Asahi Glass), more preferably KH-20 and/or KH-30.
In some embodiments, the photoacid generator is
One or more of (a);
the solvent is one or more of cyclohexanone (S1), ethylene glycol monoethyl ether (S2) and gamma-butyrolactone (S3);
the quenching agent is
The surfactant is KH-20 and/or KH-30.
In some embodiments, the photoresist is prepared from the following raw materials in parts by weight: the resin as described above (including the kind and part of the resin), the photoacid generator as described above (including the kind and part of the photoacid generator), the solvent as described above (including the kind and part of the solvent), the quencher as described above (including the kind and part of the quencher), and the surfactant as described above (including the kind and part of the surfactant).
In some embodiments, the photoresist composition is any one of the following photoresist compositions prepared from the following raw materials in parts by weight:
photoresist composition 1:85 parts of resin 1, 7 parts of compound shown as a formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 2:75 parts of the resin 1,1 part of the compound shown in the formula X1Y1, 1000 parts of cyclohexanone (S1), 0.5 part of the compound shown in the formula Q1 and 0.1 part of KH-30;
photoresist composition 3:80 parts of resin 1,3 parts of compound shown as a formula X1Y1, 1200 parts of cyclohexanone (S1), 0.8 part of compound shown as a formula Q1 and 0.12 part of KH-30;
photoresist composition 4:90 parts of the resin 1, 5 parts of the compound shown in the formula X1Y1, 1600 parts of cyclohexanone (S1), 1.5 parts of the compound shown in the formula Q1 and 0.16 part of KH-30;
photoresist composition 5:95 parts of the resin 1, 10 parts of the compound shown in the formula X1Y1, 2000 parts of cyclohexanone, 3 parts of the compound shown in the formula Q1 and 0.2 part of KH-30;
photoresist composition 6:85 parts of resin 1, 7 parts of compound shown as formula X1Y3, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as formula Q1 and 0.15 part of KH-30;
photoresist composition 7:85 parts of resin 1, 7 parts of compound shown as formula X2Y5, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as formula Q1 and 0.15 part of KH-30;
photoresist composition 8:85 parts of resin 1, 7 parts of compound shown as formula X3Y6, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as formula Q1 and 0.15 part of KH-30;
photoresist composition 9:85 parts of resin 1, 7 parts of compound shown as a formula X4Y4, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 10:85 parts of resin 1, 7 parts of compound shown as a formula X5Y8, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 11:85 parts of resin 1, 7 parts of compound shown as formula X1Y8, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as formula Q1 and 0.15 part of KH-30;
photoresist composition 12:85 parts of resin 1, 7 parts of compound shown as formula X2Y7, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as formula Q1 and 0.15 part of KH-30;
photoresist composition 13:85 parts of the resin 1, 7 parts of the compound shown in the formula X1Y1, 1500 parts of ethylene glycol monoethyl ether (S2), 2 parts of the compound shown in the formula Q1 and 0.15 part of KH-30;
photoresist composition 14:85 parts of the resin 1, 7 parts of the compound shown in the formula X1Y1, 1500 parts of gamma-butyrolactone (S3), 2 parts of the compound shown in the formula Q1 and 0.15 part of KH-30;
photoresist composition 15:85 parts of resin 1, 7 parts of compound shown as formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as formula Q2 and 0.15 part of KH-30;
photoresist composition 16:85 parts of the resin 1, 7 parts of the compound shown in the formula X1Y1, 1500 parts of gamma-butyrolactone (S3), 2 parts of the compound shown in the formula Q1 and 0.15 part of KH-20;
photoresist composition 17:85 parts of resin 2, 7 parts of compound shown as formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as formula Q1 and 0.15 part of KH-30;
photoresist composition 18:85 parts of resin 3, 7 parts of compound shown as formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as formula Q1 and 0.15 part of KH-30;
photoresist composition 19:85 parts of the resin 4, 7 parts of the compound shown in the formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of the compound shown in the formula Q1 and 0.15 part of KH-30;
photoresist composition 20:85 parts of resin 5, 7 parts of compound shown as formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as formula Q1 and 0.15 part of KH-30;
photoresist composition 21:85 parts of resin 6, 7 parts of compound shown as formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as formula Q1 and 0.15 part of KH-30;
photoresist composition 22:85 parts of the resin 7, 7 parts of the compound shown in the formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of the compound shown in the formula Q1 and 0.15 part of KH-30;
photoresist composition 23:85 parts of resin 8, 7 parts of compound shown as formula X1Y1, 1500 parts of cyclohexanone (S1), 2 parts of compound shown as formula Q1 and 0.15 part of KH-30.
The invention provides a preparation method of the photoresist composition, which comprises the following steps: and (3) uniformly mixing all the components in the photoresist composition.
In the method for preparing the photoresist composition, after the mixing, a filtering step can be further included. The filtration may be performed in a manner conventional in the art, and is preferably performed using a filter. The filter membrane pore size of the filter is preferably 0.2 μm.
The invention provides a method for forming a photoetching pattern, which comprises the following steps:
s1: coating the photoresist composition on the surface of a base material, and baking to form a photoresist layer;
s2: exposing the photoresist layer formed in the step S1;
s3: baking the photoresist layer exposed in the step S2;
s4: and developing the photoresist layer baked in the step S3.
In S1, the substrate can be a substrate used for integrated circuit manufacturing (e.g., si, siO) 2 One or more of SiN, siON, tiN, WSi, BPSG, SOG, and organic antireflection film) or a base material for mask circuit fabrication (e.g., cr, crO, crON, moSi) 2 And SiO 2 One or more of the above).
In S1, the coating method may be a conventional coating method used in the art for forming a photolithographic pattern, such as spin coating.
In S1, the baking temperature may be a conventional baking temperature used in the art for forming a photolithographic pattern, for example, 60 to 200 ℃.
In S1, the baking time may be a conventional baking time used in the art for forming a photolithographic pattern, such as 1-10 minutes, and further such as 1 minute.
In S1, the photoresist layer may have a thickness of 0.05 to 2 μm, for example, 100nm.
In S2, the exposure is performed under conventional procedures used in the art for forming photolithographic patterns, such as high-energy radiation (e.g., krF excimer laser, arF excimer laser, or EUV), wherein the exposure dose may be in the range of 1-200mJ/cm 2 (e.g., 10-100mJ/cm 2 ) (ii) a Further, for example, electron beam exposure is used, wherein the exposure dose may be 0.1 to 100. Mu.C/cm 2 (e.g., 0.5-50. Mu.C/cm) 2 ) (ii) a Exposure is also accomplished, for example, by an immersion lithography method in which a liquid having a refractive index of at least 1.0 (e.g., water) is provided between the projection lens and the photoresist layer. In the case of immersion lithography, a protective film insoluble in water may be formed on the photoresist layer.
Among them, when a water-insoluble protective film used in the immersion lithography is used to prevent any component from leaching out of a photoresist layer and improve water slipperiness (water slippage) at the surface of the photoresist layer, the protective film is generally classified into two types. The first type is an organic solvent strippable protective film, which must be stripped with an organic solvent that does not dissolve the photoresist layer prior to alkaline development. The second type is an alkali-soluble protective film that is soluble in an alkali developer so that it can be removed simultaneously with the removal of the dissolved regions of the photoresist layer. The second type of protective film preferably contains a resin having 1,1,1,3,3,3-hexafluoro-2-propanol residues, which are insoluble in water and soluble in an alkaline developer, as a base material, in an alcohol solvent of at least 4 carbon atoms, an ether solvent of 8 to 12 carbon atoms, or a mixture thereof. Alternatively, the aforementioned surfactant that is insoluble in water and soluble in an alkaline developer may be soluble in an alcohol solvent of at least 4 carbon atoms, an ether solvent of 8 to 12 carbon atoms, or a mixture thereof, to form a material from which the second type of protective film is formed.
In S3, the baking temperature may be a conventional baking temperature used in the art for forming a photolithographic pattern, such as 60-150 ℃, such as 80-140 ℃, and further such as 95 ℃.
In S3, the baking time may be a conventional baking time used in the art for forming a photolithographic pattern, such as 1-5 minutes, and further such as 1 minute.
In S4, the developing method may be a conventional developing method used in the art for forming a photolithographic pattern, and is preferably one or more of dipping, spin immersion, and spraying, for example, spin immersion.
In S4, the developing developer may be a conventional developer used in the art for forming a photolithographic pattern, such as an aqueous alkaline solution and/or an organic solvent.
The concentration of the alkaline aqueous solution may be 0.1 to 5wt%, preferably 2 to 3wt% of tetramethylammonium hydroxide (TMAH) aqueous solution.
The organic solvent is preferably one or more of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butenyl acetate, phenyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, benzyl acetate, methyl phenylacetate, benzyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and 2-phenylethyl acetate.
In S4, the developing temperature may be a conventional developing temperature used in the art for forming a photolithographic pattern, preferably 10 to 30 ℃, for example, room temperature.
In S4, the developing time may be a conventional developing time used in the art for forming a photolithographic pattern, for example, 0.1 to 3 minutes, for example, 0.5 to 2 minutes.
Any desired step may be added to the pattern forming method. For example, after the photoresist layer is formed, a step of rinsing with pure water (post-soaking) may be introduced to extract an acid generator or the like from the film surface or wash off particles. After exposure, a rinse (after soaking) step may be introduced to remove any water remaining on the film after exposure.
The above preferred conditions may be combined arbitrarily to obtain preferred embodiments of the present invention without departing from the general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the photoresist containing the resin of the invention has at least the following advantages: excellent photosensitivity, good depth of focus (DOF) and good line width uniformity (CDU).
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
In the following examples, the specific operation temperature is not limited, and all the operations are carried out at room temperature. The room temperature is 10-30 ℃.
Examples 1-8 and comparative examples 1-8 resins 1-8 and comparative resins 1-8 preparation
A solution was prepared by dissolving the following monomer A, monomer B, monomer C, monomer D in the following weight parts (g) of Table 1 in 70g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) under a nitrogen atmosphere. The solution was added dropwise to 30g of Propylene Glycol Monomethyl Ether Acetate (PGMEA) over 5 hours under a nitrogen atmosphere while stirring at 70 ℃. After completion of the dropwise addition, stirring was continued at 70 ℃ for 3 hours. The reaction solution was cooled to room temperature and added dropwise to 1000g of methanol. The solid thus precipitated was collected by filtration and dried under vacuum at 40 ℃ for 24 hours to obtain resins 1 to 8 and comparative resins 1 to 8 as powder solids.
TABLE 1
Preparation of photoresists 1-23 of examples 9-32 and comparative photoresists 1-23
The materials for photoresists 1-23 of the invention and comparative photoresists are listed in table 2.
According to the formulation shown in Table 3, solid components were added to the liquid components, and stirred uniformly, and the photoresists of examples 1 to 23 and comparative examples 1 to 23 were prepared in the form of solutions by filtering through a filter having a pore size of 0.2 μm.
TABLE 2
TABLE 3
Application and effects embodiments
ArF immersion lithography patterning test (hole pattern test)
1. Hole pattern formation:
on a substrate (silicon wafer), a spin-on carbon film ODL-70 (carbon content: 65wt%, shin-Etsu Chemical co., ltd.) was deposited to a thickness of 200nm and a spin-on hard mask SHB-a940 (silicon content: 43 wt%; shin-Etsu Chemical co., ltd.) containing silicon was deposited thereon to a thickness of 35 nm. Then, a photoresist composition was spin-coated thereon, and then baked on a hot plate at 200 ℃ for 60 seconds to form a photoresist layer 100nm thick.
The resist film was exposed to varying doses through a 6% halftone phase shift mask using immersion lithography using an ArF excimer laser immersion scanner NSR-S610C (Nikon corp., NA1.30, σ 0.9/0.72, 35 ° crossed polar aperture, azimuthally polarized illumination). The photoresist layer was baked (PEB) at a temperature of 95 ℃ for 60 seconds. After PEB, the developer in table 4 was injected from the developing nozzle while the wafer was spun at 30rpm for 3 seconds, which was followed by static immersion development for 27 seconds. Hole patterns with a pitch of 100nm were formed.
2. Evaluation of photosensitivity:
the hole pattern formed above was observed under TD-SEM (CG-4000, high-Technologies Corp.). The optimum dose (Eop) is an exposure dose (mJ/cm 2) providing a hole diameter of 50nm at a pitch of 100nm, and is used as an index of photosensitivity.
3. Evaluation depth of focus (DOF) margin:
the pore size at the optimal dose was measured under TD-SEM (CG-4000) from which the DOF margin providing a size of 50nm + -5 nm was determined. Larger values indicate smaller changes in pattern size as the DOF changes and thus better DOF margins.
4. Evaluation of CDU:
the hole pattern formed above was observed under TD-SEM (CG-4000) and the diameter of 125 holes was measured. From this, a triple value (3 σ) of the standard deviation (σ) was calculated and recorded as CDU. A smaller value of 3 σ indicates a smaller deviation of the pores.
5. Evaluation of PPD:
immediately after PEB (no retardation, PPD =0 h), the wafer was immersion in suspension in developer for 30 seconds to form a hole pattern having a diameter of 50nm and a pitch of 100nm. In another run, the wafer was held for 6 hours after PEB (PPD =6 h) and then developed similarly to form a pattern.
The hole patterns at PPD =0h and 6h were observed under TD-SEM (CG-4000) and the diameter of 125 holes was measured. The average thereof was taken as the pore size (CD), and the CDU was calculated by the same method as above. The difference between CD at PPD 0h and CD at PPD6h was taken as the CD shrinkage due to PPD (. DELTA.PPD CD).
The effects of photoresists P1-P23 prepared from examples 9-32 and photoresists CP1-CP23 prepared from comparative photoresists 9-23 are shown in Table 4.
The developers used in Table 4 were n-butyl acetate (D1), 2-heptanone (D2) and methyl benzoate (D3).
TABLE 4
As can be seen from the above table, the photoresist composition within the scope of the present invention shows improved DOF and CDU and reduced CD shrinkage (less CD change) due to PPD, as compared to the photoresist composition of the comparative example.
Claims (10)
1. A resin is obtained by polymerizing the following monomers in parts by weight: 40-50 parts of monomer A, 1-7.5 parts of monomer B, 0.25-2.5 parts of monomer C and 0.25-2.5 parts of monomer D;
wherein R is 1 Is C 1-10 Alkyl groups of (a);
R 2 is H or C 1-10 Alkyl groups of (a);
R 3 is C 1-10 Alkyl groups of (a);
R 4 is C 2-4 Alkenyl of (a);
R 5 and R 6 Independently is H or C 1-5 Alkyl group of (1).
2. The resin of claim 1, wherein the resin satisfies one or more of the following conditions:
(1)R 1 in (b), the C 1-10 Alkyl of (A) is C 1-5 Preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl;
(2)R 2 in (b), the C 1-10 Alkyl of (A) is C 1-5 Preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl;
(3)R 3 in (b), the C 1-10 Alkyl of (A) is C 1-5 Preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl;
(4)R 4 in (b), the C 2-4 Alkenyl of (A) is C 2-3 Alkenyl of (a), preferably vinyl or isopropenyl;
(5)R 5 in (b), the C 1-5 The alkyl group of (A) is preferably a methyl group,Ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
3. The resin of claim 1, wherein the resin satisfies one or more of the following conditions:
(1) The monomer A is
(2) The monomer C is
(3) The monomer D is
(4) The part of the monomer A is 40 to 47.5 parts, such as 41.5 to 45 parts;
(5) The part of the monomer B is 2.5-4 parts;
(6) The part of the monomer C is 0.25 to 1.75 parts, for example, 0.5 to 1.25 parts;
(7) The part of the monomer D is 0.5 to 1.75 parts, for example, 0.5 to 1.25 parts;
(8) The weight average molecular weight of the resin is 5000-10000, such as 5600-9800;
(9) The resin has a molecular weight distribution coefficient of 1.0 to 2.0, for example 1.2 to 2.0.
4. The resin of claim 1, wherein the monomer A is
The part of the monomer A is 41.5-45 parts;
the part of the monomer B is 2.5-4 parts;
the monomer C is
The part of the monomer C is 0.5-1.25;
the monomer D is
The part of the monomer D is 0.5-1.25 parts.
5. The resin according to claim 1, wherein the resin is any one of resins 1 to 8 obtained by polymerizing the following monomers in parts by weight:
resin 1:41.5 parts of monomer A, 5 parts of monomer B, 1.25 parts of monomer C and 1.25 parts of monomer D; the weight average molecular weight is 7100, and the molecular weight distribution coefficient is 1.2;
resin 2:45 parts of monomer A, 4 parts of monomer B, 0.5 part of monomer C and 0.5 part of monomer D; the weight average molecular weight is 9800, and the molecular weight distribution coefficient is 1.3;
resin 3:45 parts of monomer A, 4 parts of monomer B, 0.25 part of monomer C and 0.75 part of monomer D; the weight average molecular weight is 8500, and the molecular weight distribution coefficient is 1.2;
resin 4:45 parts of monomer A, 2.5 parts of monomer B, 1.25 parts of monomer C and 1.25 parts of monomer D; the weight average molecular weight is 6400, and the molecular weight distribution coefficient is 2;
resin 5:41.5 parts of monomer A, 4 parts of monomer B, 1.75 parts of monomer C and 1.75 parts of monomer D; the weight average molecular weight is 5600, and the molecular weight distribution coefficient is 1.9;
resin 6:47.5 parts monomer A, 1 part monomer B, 0.75 part monomer C and 0.75 part monomer D; the weight average molecular weight is 8700, and the molecular weight distribution coefficient is 2;
resin 7:40 parts of monomer A, 7.5 parts of monomer B, 1.5 parts of monomer C and 1 part of monomer D; the weight average molecular weight is 9300, the molecular weight distribution coefficient is 1.6;
resin 8:46 parts of monomer A, 2.5 parts of monomer B, 0.75 part of monomer C and 0.75 part of monomer D; the weight average molecular weight is 8100, and the molecular weight distribution coefficient is 1.7;
in the resin 1-8, the monomer A is
Said monomer C is->
The monomer D is->
6. The resin of claim 1, wherein the resin is prepared by a process comprising: polymerizing 40-50 parts by weight of monomer A, 1-7.5 parts by weight of monomer B, 0.25-2.5 parts by weight of monomer C and 0.25-2.5 parts by weight of monomer D in an organic solvent to obtain the resin;
R 1 、R 2 、R 3 、R 4 、R 5 and R 6 Are as defined in any one of claims 1 to 5;
the part and kind of the monomer A, the part and kind of the monomer B, the part and kind of the monomer C and the part and kind of the monomer D are as defined in any one of claims 1 to 5.
7. The resin of claim 6, wherein the resin satisfies one or more of the following conditions:
(1) In the polymerization reaction, the weight ratio of the total weight of the monomer a, the monomer B, the monomer C and the monomer D to the organic solvent is 0.7 to 1.2, for example 1
(2) In the polymerization reaction, the organic solvent is one or more of aromatic hydrocarbon solvents, ether solvents, methyl ethyl ketone, propylene glycol monomethyl ether acetate and gamma-butyrolactone, such as propylene glycol monomethyl ether acetate;
(3) The polymerization reaction is initiated in the presence of a free radical initiator or by means of heating; when the polymerization is initiated by heating, the polymerization temperature is preferably 50 to 150 ℃, more preferably 60 to 100 ℃, for example 70 ℃ in the polymerization.
8. The photoresist composition is characterized by being prepared from the following raw materials in parts by weight: 75-95 parts of resin, 1.0-10 parts of photoacid generator, 1000-2000 parts of solvent, 0.5-3.0 parts of quencher and surfactant;
the resin is as defined in any one of claims 1 to 7.
9. The photoresist composition of claim 8, wherein the photoresist composition satisfies one or more of the following conditions:
(1) In the photoresist composition, the resin is 85-95 parts, such as 90 parts;
(2) In the photoresist composition, the parts of the photoacid generator are 3-10 parts, such as 5 parts or 7 parts;
(3) In the photoresist composition, the photoacid generator is a compound having a structure represented by formula (I):
X + Y -
(I)，
wherein, X + Is composed of
Y - Is composed of
Preferably, it is
/>
One or more of;
(4) In the photoresist composition, the solvent is 1200-1600 parts, such as 1500 parts or 1600 parts;
(5) In the photoresist composition, the solvent is one or more of a ketone solvent, a monohydric alcohol solvent, a dihydric alcohol solvent, an ether solvent and an ester solvent, and is further preferably one or more of cyclohexanone, ethylene glycol monoethyl ether and gamma-butyrolactone;
(6) In the photoresist composition, the part of the quenching agent is 0.8-2 parts, such as 1.5 parts;
(7) In the photoresist composition, the quencher is one or more of amine-containing compound, sulfonate and carboxylate, preferably sulfonate, and further preferably a compound of formula Q1 and/or a compound of formula Q2;
(8) In the photoresist composition, the surfactant is 0.1-0.2 part, such as 0.15 part by weight;
(9) The surfactant is one or more of FC-4430, S-381, E1004, KH-20 and KH-30, and is more preferably KH-20 and/or KH-30.
10. The photoresist composition of claim 8 or 9, wherein the photoresist is prepared from the following raw materials: said resin, said photoacid generator, said solvent, said quencher, and said surfactant;
preferably, the photoresist composition is any one prepared from the following components in parts by weight:
photoresist composition 1:85 parts of resin 1, 7 parts of a compound shown as a formula X1Y1, 1500 parts of cyclohexanone, 2 parts of a compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 2:75 parts of the resin 1,1 part of the compound shown in the formula X1Y1, 1000 parts of cyclohexanone, 0.5 part of the compound shown in the formula Q1 and 0.1 part of KH-30;
photoresist composition 3:80 parts of resin 1,3 parts of compound shown as formula X1Y1, 1200 parts of cyclohexanone, 0.8 part of compound shown as formula Q1 and 0.12 part of KH-30;
photoresist composition 4:90 parts of resin 1, 5 parts of compound shown as a formula X1Y1, 1600 parts of cyclohexanone, 1.5 parts of compound shown as a formula Q1 and 0.16 part of KH-30;
photoresist composition 5:95 parts of the resin 1, 10 parts of the compound shown in the formula X1Y1, 2000 parts of cyclohexanone, 3 parts of the compound shown in the formula Q1 and 0.2 part of KH-30;
photoresist composition 6:85 parts of resin 1, 7 parts of a compound shown as a formula X1Y3, 1500 parts of cyclohexanone, 2 parts of a compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 7:85 parts of resin 1, 7 parts of a compound shown as a formula X2Y5, 1500 parts of cyclohexanone, 2 parts of a compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 8:85 parts of resin 1, 7 parts of a compound shown as a formula X3Y6, 1500 parts of cyclohexanone, 2 parts of a compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 9:85 parts of resin 1, 7 parts of a compound shown as a formula X4Y4, 1500 parts of cyclohexanone, 2 parts of a compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 10:85 parts of resin 1, 7 parts of a compound shown as a formula X5Y8, 1500 parts of cyclohexanone, 2 parts of a compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 11:85 parts of resin 1, 7 parts of a compound shown as a formula X1Y8, 1500 parts of cyclohexanone, 2 parts of a compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 12:85 parts of resin 1, 7 parts of a compound shown as a formula X2Y7, 1500 parts of cyclohexanone, 2 parts of a compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 13:85 parts of the resin 1, 7 parts of the compound shown in the formula X1Y1, 1500 parts of ethylene glycol monoethyl ether, 2 parts of the compound shown in the formula Q1 and 0.15 part of KH-30;
photoresist composition 14:85 parts of resin 1, 7 parts of compound shown as a formula X1Y1, 1500 parts of gamma-butyrolactone, 2 parts of compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 15:85 parts of resin 1, 7 parts of compound shown as formula X1Y1, 1500 parts of cyclohexanone, 2 parts of compound shown as formula Q2 and 0.15 part of KH-30;
photoresist composition 16:85 parts of resin 1, 7 parts of compound shown as a formula X1Y1, 1500 parts of gamma-butyrolactone, 2 parts of compound shown as a formula Q1 and 0.15 part of KH-20;
photoresist composition 17:85 parts of resin 2, 7 parts of compound shown as formula X1Y1, 1500 parts of cyclohexanone, 2 parts of compound shown as formula Q1 and 0.15 part of KH-30;
photoresist composition 18:85 parts of resin 3, 7 parts of compound shown as formula X1Y1, 1500 parts of cyclohexanone, 2 parts of compound shown as formula Q1 and 0.15 part of KH-30;
photoresist composition 19:85 parts of resin 4, 7 parts of compound shown as formula X1Y1, 1500 parts of cyclohexanone, 2 parts of compound shown as formula Q1 and 0.15 part of KH-30;
photoresist composition 20:85 parts of resin 5, 7 parts of a compound shown as a formula X1Y1, 1500 parts of cyclohexanone, 2 parts of a compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 21:85 parts of resin 6, 7 parts of a compound shown as a formula X1Y1, 1500 parts of cyclohexanone, 2 parts of a compound shown as a formula Q1 and 0.15 part of KH-30;
photoresist composition 22:85 parts of the resin 7, 7 parts of the compound shown in the formula X1Y1, 1500 parts of cyclohexanone, 2 parts of the compound shown in the formula Q1 and 0.15 part of KH-30;
photoresist composition 23:85 parts of resin 8, 7 parts of a compound shown as a formula X1Y1, 1500 parts of cyclohexanone, 2 parts of a compound shown as a formula Q1 and 0.15 part of KH-30.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1135522A (en) * | 1997-05-23 | 1999-02-09 | Daicel Chem Ind Ltd | Polymerizable adamantane derivative and its production |
| US20050074690A1 (en) * | 2003-10-01 | 2005-04-07 | Shenggao Liu | Photoresist compositions comprising diamondoid derivatives |
| US20200218154A1 (en) * | 2019-01-08 | 2020-07-09 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
-
2021
- 2021-10-08 CN CN202111172218.1A patent/CN115947885A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1135522A (en) * | 1997-05-23 | 1999-02-09 | Daicel Chem Ind Ltd | Polymerizable adamantane derivative and its production |
| US20050074690A1 (en) * | 2003-10-01 | 2005-04-07 | Shenggao Liu | Photoresist compositions comprising diamondoid derivatives |
| US20200218154A1 (en) * | 2019-01-08 | 2020-07-09 | Shin-Etsu Chemical Co., Ltd. | Resist composition and patterning process |
Non-Patent Citations (1)
| Title |
|---|
| 李虎: "光刻胶用成膜树脂的合成及性能研究", 《中国博士学位论文全文数据库 工程科技I辑》, no. 1, pages 016 - 40 * |
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