CN110041345B - Resist underlayer film monomer, resist underlayer film composition and pattern forming method - Google Patents
Resist underlayer film monomer, resist underlayer film composition and pattern forming method Download PDFInfo
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- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
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- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
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- C08G2261/10—Definition of the polymer structure
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Abstract
The invention belongs to the field of photoetching, and particularly relates to a resist lower layer film monomer, a composition and a pattern forming method. The resist underlayer film composition contains a resist underlayer film monomer represented by the formula (1), an aromatic polymer and a solvent, wherein in the formula (1), Ar is1Represents an arylene group having 6 to 30 carbon atoms, R1And R2Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 30 carbon atoms. The resist underlayer film composition provided by the invention has excellent etching resistance, heat resistance, solvent solubility, gap filling characteristics and planarization characteristics. In addition, the composition of the lower layer film of the resist provided by the invention can perform self-crosslinking reaction by heating without using a curing reaction additive, and gas is not generated during curing, so that the problems of pollution of the lower layer film of the resist and equipment can be effectively prevented.
Description
Technical Field
The invention belongs to the field of photoetching, and particularly relates to a resist lower layer film monomer, a composition and a pattern forming method.
Background
The photolithography process is one of the most important process steps in semiconductor manufacturing, and mainly functions to copy the pattern on the mask plate to the substrate through the photoresist and prepare for the next etching or ion implantation process. Typical lithographic processes include: the method includes forming a material layer on a semiconductor substrate, coating a photoresist on the material layer, exposing and developing the photoresist layer to provide a photoresist pattern, and etching the material layer using the photoresist pattern as a mask.
In recent years, with the high integration and high speed of semiconductor devices, the shorter wavelength of KrF excimer laser (248nm) has been advancing to ArF excimer laser (193nm) as a lithography light source used for forming a photoresist pattern. However, in the case of using short wavelength exposure light, problems of diffuse reflection and standing waves are often generated, affecting the resolution of the photoresist pattern. In order to solve this problem, a method of providing a bottom anti-reflection film (BARC) as a resist underlayer film between a photoresist and a material layer has been widely studied. On the other hand, as the demand for the refinement of the photoresist pattern increases, there arise problems of resolution and collapse of the photoresist pattern after development, and therefore, it is desired to make the photoresist layer thinner. Thus, it is difficult to obtain a sufficient resist pattern thickness for material layer processing, and therefore not only the photoresist layer but also the resist underlayer film provided between the photoresist layer and the material layer is required to have a mask function for material layer processing. As a resist underlayer film having the above function, a selection ratio of a dry etching rate close to that of a photoresist, a selection ratio of a dry etching rate smaller than that of a photoresist, and a selection ratio of a dry etching rate smaller than that of a semiconductor substrate are required. At the same time, such a resist underlayer film can also be imparted with an antireflection function.
On the other hand, it has recently been proposed to prepare a resist underlayer film by spin coating, not chemical vapor deposition. Spin coating requires the use of polymers that are sufficiently soluble in solvents; meanwhile, in order to secure good etching resistance, it is generally necessary to use a polymer having an extremely high carbon content, a crosslinking agent capable of reacting with the polymer, and an additive for performing a curing reaction (e.g., an acidic curing catalyst), however, in the high-temperature baking process, the additive generates gas due to thermal decomposition, and there is a concern of contaminating the resist underlayer film and equipment.
Disclosure of Invention
The present invention is directed to provide a novel resist underlayer film monomer and composition, and a pattern forming method, which not only have high etching resistance and heat resistance, and good solubility in conventional solvents, but also have both gap-filling characteristics and planarization characteristics, and at the same time, are capable of performing a self-crosslinking reaction by heating without using a curing reaction additive, and do not generate gas upon curing.
Specifically, the present invention provides a resist underlayer film monomer, wherein the resist underlayer film monomer has a structure represented by formula (1):
in the formula (1), Ar1Represents an arylene group having 6 to 30 carbon atoms, R1And R2Each independently represents a carbon atomAlkyl with a sub-number of 1-6 or aryl with a carbon number of 6-30.
Further, in the formula (1), Ar1Represents naphthyl, binaphthyl, pyrenyl or benzoperylene, R1And R2Each independently represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, an anthryl group or a pyrenyl group.
Further, the resist underlayer film monomer is selected from at least one of the following chemical formulas 1-1 to 1-17:
the invention also provides a resist lower layer film composition, wherein the resist lower layer film composition contains the resist lower layer film monomer, the aromatic polymer and the solvent.
Further, the aromatic polymer is a phenol resin.
Further, the weight average molecular weight of the phenolic resin is 400-7000, and the polydispersity is 1.5-2.5.
Further, the weight ratio of the aromatic polymer to the resist underlayer film monomer is 9:1 to 1: 9.
Further, the total content of the aromatic polymer and the resist underlayer film monomer is 4 to 25 wt% based on the total weight of the resist underlayer film composition.
Further, the solvent is at least one selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, butyl lactate and cyclohexanone.
Further, the resist underlayer film composition further contains a surfactant.
Further, the surfactant is at least one selected from the group consisting of polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.
Further, the content of the surfactant is 0.01 to 0.8 wt% based on the total weight of the resist underlayer film composition.
In addition, the present invention also provides a pattern forming method including the steps of:
forming a material layer on a substrate;
applying the above-mentioned resist underlayer film composition on the material layer and performing heat treatment to form a resist underlayer film;
forming a thin layer containing silicon on the resist underlayer film;
forming a photoresist resist layer on the thin silicon-containing layer;
exposing and developing the photoresist resist layer to form a photoresist pattern;
selectively removing portions of the thin silicon-containing layer and the resist underlayer film using the photoresist pattern to expose a portion of the material layer;
the exposed portions of the material layer are etched.
Further, the manner of applying the resist underlayer film composition on the material layer is a spin coating method.
The invention has the following beneficial effects:
the resist underlayer film composition provided by the invention has excellent etching resistance, heat resistance, solvent solubility, gap filling characteristics and planarization characteristics. In addition, the composition of the lower layer film of the resist provided by the invention can perform self-crosslinking reaction by heating without using a curing reaction additive, and gas is not generated during curing, so that the problems of pollution of the lower layer film of the resist and equipment can be effectively prevented.
Detailed Description
The present invention is described in detail below.
Monomer
The resist underlayer film composition of the present invention contains a monomer. Wherein the monomer has a structure represented by formula (1):
in the formula (1), Ar1Represents an arylene group having 6 to 30 carbon atoms, R1And R2Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 30 carbon atoms.
From the viewpoint of etching resistance, Ar1Preferably a naphthyl group, a binaphthyl group, a pyrenyl group or a benzoperylene group.
As mentioned above, R1And R2Each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1, 2-dimethyl-cyclopropyl, 2, 3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-butyl, isobutyl, tert-butyl, 1-methyl-cyclopropyl, 2-methyl-n-propyl, 1-ethyl-cyclopropyl, 2-methyl-cyclobutyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1-dimethyl-n-butyl, 1, 2-dimethyl-n-butyl, 1, 3-dimethyl-n-butyl, 2, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1,2, 2-trimethyl-n-propyl, 1-methyl-1-ethyl-n-propyl, 1-ethyl-2-methyl-n-propyl, n-butyl, n-, Cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1, 2-dimethyl-cyclobutyl, 1, 3-dimethyl-cyclobutyl, 2, 2-dimethyl-cyclobutyl, 2, 3-dimethyl-cyclobutyl, 2, 4-dimethyl-cyclobutyl, 3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2, 2-trimethyl-cyclopropyl, 1,2, 3-trimethyl-cyclopropyl, 2, 3-methyl-cyclopropyl, 2-methyl-cyclobutyl, 2-methyl-cyclopentyl, 2, 3-methyl-cyclobutyl, 2-dimethyl-cyclobutyl, 2,3, 2,2, 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, and the like. Specific examples of the aryl group having 6 to 30 carbon atoms include, but are not limited toWithout limitation: phenyl, naphthyl, anthracenyl, pyrenyl, and the like.
According to a preferred embodiment of the present invention, the resist underlayer film monomer is selected from at least one of the following chemical formulae 1-1 to 1-17:
the monomer of the resist underlayer film provided by the invention contains a benzoxazine structural unit, and can generate ring-opening polymerization reaction like reaction formula A under the heating action to generate a network structure containing nitrogen and similar to phenolic resin, so that no small molecules are released in the curing process, the volume shrinkage rate is approximately zero, and the worry of polluting the resist underlayer film and equipment is avoided.
When the resist underlayer film monomer is used as a monomer component of the resist underlayer film composition, the low viscosity of the resist underlayer film composition containing the monomer is ensured due to the low molecular weight and good solubility of the monomer having the structure represented by formula (1) during the spin coating of the resist underlayer film composition, and the resist underlayer film composition can be easily and uniformly filled into each corner of a height difference even if applied to a substrate having the height difference, ensuring excellent gap-filling property and planarization property; in addition, in the process of heating the resist lower layer film composition to form a film, the monomer molecules are subjected to ring opening and crosslinking reaction to form a polymer with high crosslinking density, so that the heat resistance and the etching resistance of the resist lower layer film composition are ensured.
Polymer and method of making same
The resist underlayer film composition contains a polymer. The polymer is preferably a phenolic resin. The weight average molecular weight of the phenolic resin is preferably 400-7000, and the polydispersity is preferably 1.5-2.5.
The phenol resin may be obtained commercially, or may be obtained by subjecting a compound containing an aromatic ring to a polycondensation reaction with an aldehyde or ketone in the presence of an acid catalyst. Specific examples of the aromatic-containing compound include, but are not limited to: benzene, phenol, naphthalene, hydroxynaphthalene, fluorene, carbazole, diphenylamine, triphenylamine, anthracene, pyrene, hydroxypyrene, and the like. Specific examples of the aldehyde include, but are not limited to: formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde and corresponding isomers, butyraldehyde and corresponding isomers, valeraldehyde and corresponding isomers, hexanal and corresponding isomers, benzaldehyde, naphthaldehyde, anthracenealdehyde, pyreneformaldehyde, salicylaldehyde and the like. Specific examples of the ketone include, but are not limited to: diaryl ketones such as diphenyl ketone, phenyl, naphthyl ketone, dinaphthyl ketone, and 9-fluorenone. In the polycondensation reaction for forming the phenol resin, when the aromatic ring-containing compound is 1 equivalent, the aldehyde or ketone is used in an amount of generally 0.1 to 10 equivalents. The acid catalyst may be an inorganic acid such as sulfuric acid, phosphoric acid, perchloric acid, or an organic acid such as p-toluenesulfonic acid, formic acid, oxalic acid. The acid catalyst may be used in an amount of 0.1 to 100 parts by mass when the aromatic ring-containing compound is used in an amount of 100 parts by mass. The above polycondensation reaction is usually carried out in a solvent. The solvent may be any of various inert liquid substances existing as long as it does not hinder the reaction, and specific examples thereof include, but are not limited to, tetrahydrofuran, propylene glycol monomethyl ether, and the like. In addition, if the acid catalyst used is a liquid such as formic acid, it may also serve as a solvent. The temperature of the polycondensation reaction is usually 40-200 ℃, and the reaction time is selected according to the requirements of the reaction temperature and the molecular weight, and is usually about 30 minutes to 50 hours.
In the present invention, the weight ratio of the polymer to the monomer is preferably 9:1 to 1:9, more preferably 3:7 to 7: 3. Further, the total content of the polymer and the monomer is preferably 4 to 25 wt%, more preferably 8 to 20 wt%, based on the total weight of the resist underlayer film composition.
Solvent(s)
The solvent in the resist underlayer film composition may be any substance sufficient to dissolve or disperse the monomer and the polymer, and may be selected from, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl ethoxypropionate, and mixtures thereof, At least one of ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate and butyl lactate. Among these solvents, at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, butyl lactate and cyclohexanone is preferable. Further, a high boiling point solvent such as propylene glycol monobutyl ether, propylene glycol monobutyl ether acetate, or the like may be used in combination.
Surface active agent
In the resist underlayer film composition provided by the present invention, a surfactant may be used in combination in order to prevent occurrence of pinholes, streaks, and the like and to further improve the film formation quality of the resist underlayer film. Specific examples of the surfactant include, but are not limited to: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, and sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monoleate, sorbitan monolaurate and sorbitan tristearate, at least one polyoxyethylene sorbitan fatty acid ester such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monolaurate, and polyoxyethylene sorbitan tristearate. Further, the content of the surfactant is 0.01 to 0.8 wt% based on the total weight of the resist underlayer film composition.
Pattern forming method
The pattern forming method provided by the invention comprises the following steps: forming a material layer on a substrate; applying the above-mentioned resist underlayer film composition on the material layer and performing heat treatment to form a resist underlayer film; forming a thin layer containing silicon on the resist underlayer film; forming a photoresist resist layer on the thin silicon-containing layer; exposing and developing the photoresist resist layer to form a photoresist pattern; selectively removing portions of the thin silicon-containing layer and the resist underlayer film using the photoresist pattern to expose a portion of the material layer; the exposed portions of the material layer are etched.
The substrate may be a silicon wafer, a glass substrate, or a polymer substrate.
The material layer is a material to be finally patterned, and may be, for example, a metal layer such as an aluminum layer or a copper layer, a semiconductor layer such as a silicon layer, or an insulating layer such as silicon dioxide or silicon nitride.
The resist underlayer film composition is coated on the material layer in the form of a solution and preferably by a spin coating method. Here, the thickness of the resist underlayer film composition is not particularly limited, and may be, for example, 100-10000 angstrom. In addition, the heat treatment conditions may include a temperature of 200 ℃ to 500 ℃ and a time of 10 seconds to 10 minutes.
The thin layer containing silicon may be formed of, for example, silicon nitride, silicon oxide, or silicon oxynitride.
The photoresist resist layer may be formed of, for example, ArF type, KrF type, or EUV type photoresist.
The method of exposing the photoresist resist layer may be ArF, KrF, or EUV, for example.
The main improvement of the pattern forming method provided by the present invention is to use a new resist underlayer film composition to form a resist underlayer film, and the manner of selectively removing a portion of the silicon-containing thin layer and the exposed portions of the resist underlayer film and the etching material layer can be the same as the prior art, which will be known to those skilled in the art and will not be described herein again.
The present invention will be described in more detail with reference to examples and comparative examples. However, these examples are merely illustrative, and the present invention is not limited thereto.
Synthesis of monomers and polymers
Monomer Synthesis example 1
At normal temperature, 50ml of toluene, 4.0g (25mmol) of 2, 6-naphthalenediol, 3.15g (105mmol) of paraformaldehyde and 4.65g (50mmol) of aniline are added into a 250ml three-neck flask provided with a stirrer and a reflux condenser, the temperature is raised to 120 ℃ under the protection of nitrogen, the mixture reacts for 5h at the temperature, the mixture is cooled to room temperature, n-hexane is added, precipitates are separated out, the mixture is filtered, and a filter cake is dried for 24h at the temperature of 60 ℃ to obtain a product monomer 1-1 a. Wherein the specific reaction process is shown in the following reaction formula (1).
Reaction formula (1)
Monomer Synthesis example 2
The synthesis of monomer 1-1a was repeated except that 4.0g (25mmol) of 1, 5-naphthalenediol was used instead of 4.0g (25mmol) of 2, 6-naphthalenediol to give the product monomer 1-9 a. The specific reaction process is shown in the following reaction formula (2).
Reaction type (2)
Monomer Synthesis example 3
The synthesis of monomer 1-1a was repeated except that 5.85g (25mmol) of 1, 8-dihydroxypyrene was used instead of 4.0g (25mmol) of 2, 6-naphthalenediol to give the product monomer 1-16 a. The specific reaction process is shown in the following reaction formula (3).
Reaction type (3)
Monomer Synthesis example 4
The synthesis of monomer 1-1a was repeated except that 7.16g (25mmol) of 2,2 '-dihydroxy-1, 1' -binaphthyl was used instead of 4.0g (25mmol) of 2, 6-naphthalenediol to give the product monomer 1-17 a. The specific reaction process is shown in the following reaction formula (4).
Reaction type (4)
Comparative monomer Synthesis example 1
14.1g (0.1mol) of benzoyl chloride, 11.71g (0.05mol) of 1, 8-dihydroxypyrene and 120ml of 1, 2-dichloroethane were charged into a 250ml three-necked flask, after which 16.00g (0.12mol) of aluminum trichloride was slowly added to the reaction solution at room temperature, and the reaction mixture was heated to 60 ℃ under a nitrogen blanket to react for 8 hours. After the reaction was completed, the reactant was slowly poured into methanol, and then the precipitate generated therein was filtered to obtain dibenzoyl 1, 8-dihydroxypyrene.
8.93(0.02mol) dibenzoyl 1, 8-dihydroxypyrene and 70ml tetrahydrofuran are added into a 250ml three-neck flask, then an aqueous solution of sodium borohydride (the proportion of the aqueous solution is 7.566g (0.2mol) sodium borohydride is dissolved in 40ml water) is slowly dripped at 0-5 ℃, the aqueous solution is slowly dripped into a reaction bottle at 0-5 ℃, and the reaction is carried out for 24 hours at room temperature after the dripping is finished. After the completion of the reaction, the pH of the reaction mixture system was adjusted to about 7 with a 5% aqueous hydrogen chloride solution, followed by extraction with ethyl acetate to obtain a monomer represented by chemical formula 2-1.
Chemical formula 2-1
Polymer Synthesis example 1
28.83g (0.2mol) of 1-naphthol, 30.5g (0.14mol) of 1-hydroxypyrene, 12.0g (0.34mol) of paraformaldehyde and 500ml of propylene glycol monomethyl ether acetate were put into a 1000ml three-necked flask, and after mixing uniformly, 0.38g (0.002mol) of p-toluenesulfonic acid was added and reacted at 70 ℃ for 10 hours under nitrogen protection. After the reaction was completed, the reaction solution was cooled, then poured into methanol to remove unreacted monomers and low molecular weight polymers, the mixed solution was filtered, the filter cake was further washed with methanol 2 times, and then dried in a vacuum oven at 50 ℃ for 12 hours to obtain a polymer represented by chemical formula 3-1, which had a weight average molecular weight of 3600 and a polydispersity of 2.10.
Chemical formula 3-1
Examples and comparative examples
The monomer, polymer, solvent and surfactant were mixed uniformly in the proportions shown in table 1 to obtain a resist underlayer film composition. Wherein the solvent is Propylene Glycol Monomethyl Ether Acetate (PGMEA), and the surfactant is polyoxyethylene lauryl ether.
TABLE 1 (wt%)
Test example
(1) Evaluation of solubility
Adding the synthesized monomer 1-1a, monomer 1-9a, monomer 1-16a, monomer 1-17a and polymer 3-1 to PGMEA at a mass ratio of 20%, respectively, heating and stirring at 50 deg.C for 1 hr, and confirming the dissolved state; then cooling to 25 ℃, and immediately confirming the dissolution state; finally, the mixture was allowed to stand at 25 ℃ for 6 hours to confirm the dissolution state, and the results are shown in Table 2.
Solubility determination criteria:
◎, standing at 25 deg.C for 6h, and no undissolved substance is observed with naked eyes;
○ no insoluble matter was visually observed in the heated state and the immediately cooled state, but a small amount of insoluble matter was visually observed after standing at 25 ℃ for 6 hours;
△ in which no insoluble matter was visually observed in the heated state, but in the immediately cooled state and after standing at 25 ℃ for 6 hours, no insoluble matter was visually observed;
× insoluble matter was visually observed in the heated state.
TABLE 2
| Item | Solubility in water |
| Monomer 1-1a | ◎ |
| Monomers 1 to 9a | ◎ |
| Monomers 1 to 16a | ○ |
| Monomers 1 to 17a | ○ |
| Polymer 3-1 | × |
As can be seen from the results of Table 2, the monomers 1 to 1a, 1 to 9a, 1 to 16a and 1 to 17a exhibited good solubility; the polymer 3-1 has poor solubility due to high molecular weight and high molecular rigidity.
(2) Void fill and planarization characteristics
The resist underlayer film compositions of examples and comparative examples in table 1 were each spin-coated on a silicon substrate coated with silicon oxide having a line/space width of 120nm/120nm and a height of 300nm, and fired at 350 ℃ for 180 seconds to form resist underlayer films. Observing the section of the formed resist underlayer film by using a field emission scanning electron microscope, and determining whether a gap exists or not to evaluate the gap filling characteristic; the planarization characteristics were determined by the difference between the high thickness portion (line portion) and the low thickness portion (space portion) of the spin-on resist underlayer film, wherein the difference between the two was less than 5nm, which was determined as "excellent" in the planarization characteristics, between 5nm and 10nm, which was determined as "excellent" in the case of more than 10nm, which was determined as "poor", and the results are shown in table 3.
(3) Evaluation of Heat resistance
The resist underlayer film composition solutions of examples and comparative examples were each coated on a silicon wafer using a spin coater and fired at 350 ℃ for 180 seconds to form a resist underlayer film. These resist underlayer films were scraped off from a silicon wafer to obtain a powder. The weight loss of each powder was measured by using a thermogravimetric analyzer (TGA) and raising the temperature from 40 ℃ to 400 ℃ under a nitrogen atmosphere, and the weight ratio was calculated according to the following calculation formula 1, and the obtained results are shown in table 3.
Calculation of equation 1
The mass loss rate was × 100% (initial mass-400 ℃ mass)/initial mass) and
evaluation criteria:
○, the mass loss rate A is more than or equal to 10 percent and less than 15 percent;
△, the mass loss rate A is more than or equal to 15 percent and less than or equal to 25 percent;
×, the mass loss rate A is more than 25 percent.
(4) Evaluation of etching resistance
The resist underlayer film compositions of examples and comparative examples in table 1 were coated on a silicon wafer using a spin coater, and fired at 350 ℃ for 120 seconds to form resist underlayer films, and the film thicknesses were measured by a film thickness measuring instrument manufactured by K-MAC. Then, CHF was used3/CF4The mixed gas was subjected to dry etching for 60 seconds, the film thickness was measured again after the etching was completed, and the etching rate was calculated using the calculation result of calculation formula 2, and the obtained results are shown in table 3.
Calculation formula 2
Etch rate (initial thickness of resist underlayer film-resist underlayer film thickness after etching)/etch time
And (3) judging the etching resistance:
○ etch Rate B of
△ etch Rate B of
× etch Rate B greater than
TABLE 3
| Item | Void fill characteristics | Planarization characteristic | Heat resistance | Resistance to etching |
| Example 1 | Without voids | Is very good | ○ | ○ |
| Example 2 | Without voids | Is excellent in | ○ | ○ |
| Example 3 | Without voids | Is excellent in | ○ | ○ |
| Example 4 | Without voids | Is excellent in | ○ | ○ |
| Example 5 | Without voids | Is very good | ○ | ○ |
| Comparative example 1 | Without voids | Is excellent in | △ | △ |
| Comparative example 2 | With a gap | Failure of the product | × | × |
As can be seen from the test results of table 3, the resist underlayer film composition provided by the present invention has excellent etch resistance, heat resistance, gap-fill characteristics, and planarization characteristics in combination. In addition, examples 1 to 5, at high temperature and in the absence of a catalyst, a polymer network having a cross-linked structure was obtained by a ring-opening reaction of benzoxazine, ensuring an improvement in heat resistance and etching resistance of the resist underlayer film; comparative example 1 contains a monomer having a benzyl hydroxyl group-active crosslinking site, but has low reactivity due to the absence of a catalyst, and cannot effectively form a crosslinked network, and thus has insufficient heat resistance and etching resistance as compared with examples 1 to 4.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (10)
1. A resist underlayer film composition is characterized by comprising a resist underlayer film monomer, an aromatic polymer and a solvent; the resist underlayer film monomer has a structure represented by formula (1):
in the formula (1), Ar1Represents a naphthyl group, a binaphthyl group or a pyrenyl group, R1And R2Each independently represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, an anthryl group or a pyrenyl group; the aromatic polymer is phenolic resin.
2. The composition for a resist underlayer film according to claim 1, wherein the resist underlayer film monomer is selected from at least one of the following chemical formulae 1-1 to 1-17:
3. the resist underlayer film composition as claimed in claim 1, wherein the weight average molecular weight of the phenolic resin is 400-7000 and the polydispersity is 1.5-2.5.
4. The resist underlayer film composition of any one of claims 1 to 3, wherein a weight ratio of the aromatic polymer to the resist underlayer film monomer is 9:1 to 1: 9; the total content of the aromatic polymer and the resist underlayer film monomer is 4 to 25 wt% based on the total weight of the resist underlayer film composition.
5. The resist underlayer film composition of any one of claims 1 to 3, wherein the solvent is at least one selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, butyl lactate, and cyclohexanone.
6. The resist underlayer film composition of any one of claims 1 to 3, further comprising a surfactant.
7. The composition for an underlayer film of a resist according to claim 6, wherein the surfactant is at least one selected from the group consisting of polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.
8. The resist underlayer film composition of claim 6, wherein the surfactant is contained in an amount of 0.01 to 0.8 wt% based on the total weight of the resist underlayer film composition.
9. A pattern forming method, characterized by comprising the steps of:
forming a material layer on a substrate;
applying the resist underlayer film composition of any one of claims 1 to 8 on the material layer and performing heat treatment to form a resist underlayer film;
forming a thin layer containing silicon on the resist underlayer film;
forming a photoresist resist layer on the thin silicon-containing layer;
exposing and developing the photoresist resist layer to form a photoresist pattern;
selectively removing portions of the thin silicon-containing layer and the resist underlayer film using the photoresist pattern to expose a portion of the material layer;
the exposed portions of the material layer are etched.
10. The pattern forming method according to claim 9, wherein a manner of applying the resist underlayer film composition on the material layer is a spin coating method.
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| CN111240153B (en) * | 2020-02-12 | 2022-05-20 | 厦门恒坤新材料科技股份有限公司 | Hard mask composition, hard mask and method for forming pattern |
| CN111290216B (en) * | 2020-02-12 | 2022-05-20 | 厦门恒坤新材料科技股份有限公司 | Hard mask composition, hard mask and method for forming pattern |
| WO2023189799A1 (en) * | 2022-03-28 | 2023-10-05 | 日産化学株式会社 | Self cross-linkable polymer and resist underlayer film-forming composition |
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| US5152939A (en) * | 1991-03-12 | 1992-10-06 | Edison Polymer Innovation Corp. | Composite densification with benzoxazines |
| JP4145640B2 (en) * | 2002-11-28 | 2008-09-03 | 新日鐵化学株式会社 | Heat resistant adhesive film for printed circuit board and method for producing the same |
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| CN102649838B (en) * | 2011-02-25 | 2014-01-01 | 华东理工大学 | Bisphenol benzoxazine modified silicon-contained aryne resin and preparation method thereof |
| CN106280449B (en) * | 2016-08-19 | 2019-08-20 | 大连理工大学 | A kind of high tenacity, benzoxazine/diallyl diphenol/bismaleimide blending resin of low viscosity and preparation method thereof |
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| CN108997574A (en) * | 2018-08-22 | 2018-12-14 | 西南石油大学 | A method of polyamide-based derivative is prepared by benzoxazine and isonitrile copolymerization |
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