HK1069440B - Chemically-amplified resist compositions - Google Patents
Chemically-amplified resist compositions Download PDFInfo
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- HK1069440B HK1069440B HK05101872.6A HK05101872A HK1069440B HK 1069440 B HK1069440 B HK 1069440B HK 05101872 A HK05101872 A HK 05101872A HK 1069440 B HK1069440 B HK 1069440B
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Description
Technical Field
The present invention relates to a photoresist composition, and more particularly to a chemically amplified photoresist composition containing a novel high molecular polymer.
Background
With the rapid increase of the integration level of semiconductor integrated circuits, the line width required by the photolithography technology is also smaller and smaller. In theory, to achieve better pattern resolution in the photolithography process, short wavelength light sources or optical systems with larger numerical apertures may be used. Therefore, in order to adapt to the Design rule of integrated circuit (Design rule) and facilitate the mass production of 1G byte DRAM, it is necessary to push the line width of the photolithography process to be less than 0.13 μm, but the KrF (248nm) Excimer laser (eximer laser) is not sufficient for the device process of less than 0.13 μm, so the process of less than 0.13 μm is performed by ArF (193nm) Excimer laser lithography.
ArF lithography using chemically amplified resist is currently the most promising technology to push process line widths below 0.09 microns (90 nm). However, good 193nm photoresist properties require high resolution (below 0.13 μm), large depth of focus (DOF) and process width, good thermal stability and adhesion, high sensitivity (< 5mj/cm2), good plasma etch stop capability, adequate dissolution rate, and compatibility with standard chemicals used in the IC industry (e.g., 2.38% TMAH developer), which are all necessary for developing 193nm photoresists.
In the early development of 193nm photoresist, acrylic was the major polymer, but in order to improve the etching resistance and etching resistance of acrylic polymerThe lack of hydrophilicity, derived from many high molecular polymers with cyclic structures, e.g. cycloolefin-maleic anhydride copolymers (Cyclo-Olefin-co-Maleic A(ii) nhydide; COMA, hereinafter referred to as COMA), polycycloolefin high molecular weight polymer (C)Cyclo- Olefin CAn optomer; COC, hereinafter referred to as COC), cyclic Olefin-maleic anhydride-acrylic copolymer (Cyclo-Olefin-co-maleic anhydride-co-acrylate), and the like. However, these high molecular polymers have several disadvantages, such as difficult catalytic synthesis using a special transition metal catalyst, difficult removal of metal ions after synthesis, too high absorption, and poor hydrophilicity. In order to overcome the above-mentioned drawbacks of the high molecular weight polymer, it is necessary to develop a new high molecular weight polymer structure.
Vinyl ether-maleic anhydride Polymer (C:)Vinyl Ether- Maleic AAn nhydide copolymer; VEMA, the following documents will be referred to as VEMA) can ameliorate the disadvantages of the above copolymers, for example: the polymer can be synthesized by a convenient and simple free radical polymerization method, and the photoresist prepared by the polymer has the advantages of excellent adhesion with a substrate, better etching resistance than acrylic polymer, lower absorptivity than Norbornene (Norbornene), and the like.
Recently, VEMA-related documents have been published, and the structures of VEMA high-molecular polymers were originally proposed by Sang-Jun Choi et al in Proceedings of SPIE, 3999, 54-61(2000) and J.Photopolym.Sci.Technol., 13, 419-426 (2000). Wherein, the vinyl ether compound with linear alkyl substituted vinyl ether monomer or naphthenic substituent on the main chain is selected, such as: 3, 4-dihydro-2H-pyran (3, 4-dihydro-2H-pyran; DHP) and 3, 4-dihydro-2-ethoxy-2H-pyran (3, 4-dihydro-2-ethoxy-2H-pyran; DHEP), and maleic anhydride and an acid-sensitive acrylic monomer are matched to form a copolymer.
Georoge G.Barclay et al also disclose a high molecular polymer with similar structure composition, wherein a Norbornene (Norbornene) structural monomer is further added to the high molecular polymer composition to adjust the properties of the high molecular polymer, and the Vinyl Ether (Vinyl Ether; VE) disclosed in the patent, in addition to the above DHEP, is a Vinyl Ether with 3, 4-dihydro-2-methoxy-2H-pyran (3, 4-dihydro-2-mthoxy-2H-pyran (DHMP) and other naphthenic substituents on the main chain, and the high molecular polymer preferably has a weight average molecular weight (Mw) of 2,000 to 20,000, and a preferable polydispersity result of about 2 or less, and the synthesis example of the high molecular polymer composition disclosed therein has a higher proportion of acid-sensitive pressure-sensitive monomer, up to 40 to 60%.
However, the above-disclosed high molecular weight polymers are still unsatisfactory. The vinyl ether monomers used in the VEMA high molecular polymer are vinyl ethers with naphthenic substituent groups on the main chain, the reactivity of the vinyl ether monomers is poorer than that of vinyl ethers with naphthenic substituent groups on the side chains, and the reactivity of the vinyl ether monomers is greatly different from that of other monomers when polymerization reaction occurs. Therefore, the structural composition of the polymer chain has high heterogeneity, and the yield and weight average molecular weight of the synthesis are low, and the polydispersity is high, resulting in complexity of the synthesis reaction. Especially, the introduction of another Norbornene (Norbornene) monomer is more complicated, which increases the difficulty and difficulty of polymerization reaction. On the other hand, vinyl ethers have a linear side chain substituent, and the resulting polymer has high uniformity of the composition of the polymer chain, high yield and weight average molecular weight, and narrow polydispersity, but the etch resistance of the polymer is weak. The present invention discloses vinyl ethers with cycloalkane substituents on the side chains, which have excellent reactivity and etching resistance, and the invention develops a high molecular polymer with excellent reactivity and etching resistance by matching with maleic anhydride and a proper acid-sensitive acrylic monomer.
The synthesis of vinyl ether monomers was first prepared by Reppe et al in 1956 using alcohols and acetylene. The reaction must be carried out under high pressure (20-50 atm) and high temperature (180-: y. okimoto et al j.am.chem.soc., 124, 1590 (2002). Thus limiting the development space of the VEMA high molecular polymer. More recently, however, it has been proposed in Synthesis, 11, 1521(2000) by b.a. trofimov et al that under milder conditions, various vinyl ether compounds can be synthesized from the reaction of appropriate alcohols and potassium hydroxide with acetylene in DMSO as solvent.
In addition, the present invention also discloses a composition of VEMA high molecular polymer, which breaks through the situation that the ratio of acid sensitive acrylic monomer in the main high molecular polymer composition is higher than 40 mol ratio to have good effect in the above documents, and adjusts the hydrophilicity, adhesion, dry etching resistance, thermal property, penetration and other properties of the high molecular polymer by adjusting the ratio of acid sensitive acrylic monomer in the high molecular polymer composition, so that the application of the photoresist is more flexible.
The present invention also discloses another high molecular polymer, which is the above high molecular polymer, and then introduces an acryl monomer with cyclic alkyl to solve the complexity problem of the synthesis reaction caused by introducing the Norbornene (norborn) structure monomer into the VEMA high molecular polymer, so as to improve the simplicity and the easy control of the polymerization reaction. The acrylic monomer with cyclic alkyl group also has the function of adjusting the property of high molecular polymer in the photoresist, and the hydrophilicity, the adhesive property, the dry etching resistance, the thermal property, the penetration degree and other properties of the high molecular polymer are adjusted by adjusting the proportion of the acrylic monomer with cyclic alkyl group in the high molecular polymer and the acid-sensitive acrylic monomer, so that the modification technology of the property of the photoresist high molecular polymer has elasticity and diversity, the applicability of the photoresist high molecular polymer in the 193nm lithography imaging process is enhanced, and the photoresist high molecular polymer has better resolution, profile and sensitivity.
The novel photoresist composition disclosed by the invention has excellent hydrophilicity, adhesiveness, dry etching resistance and other excellent performances, the excellent performances can increase the adhesiveness between the photoresist composition and a substrate, the film forming property of the photoresist is improved, and a developed photoresist pattern is not easy to topple. In addition, because of good hydrophilicity, the developing solution can be uniformly distributed on the surface of the photoresist, and the uniformity and the precise resolution of the surface of the photoresist pattern are improved.
Disclosure of Invention
The present invention provides a chemically amplified photoresist composition having excellent resolution, profile and sensitivity, which can be applied to a photolithography process.
The chemical amplification photoresist has excellent resolution, profile and light sensitivity, and is suitable for 193nm or 157nm lithography manufacturing method.
The invention relates to a chemical amplification photoresist composition, which is characterized in that the chemical amplification photoresist composition is a high molecular polymer containing a structural unit shown as the following formula (I)
Wherein R is1Is hydrogen, C1-C4Alkyl, trifluoromethyl; q is C4-C12A cyclic alkyl group of (a); r2Comprises the following steps: hydrogen, C1-C4Alkyl, trifluoromethyl; r3Is C4-C12Acid sensitive groups of branched or cyclic alkanes; and x + y + z is 1, wherein x/(x + y + z) is 0.1 to 0.45; y/(x + y + z) ═ 0.1 to 0.45; z/(x + y + z) ═ 0.1 to 0.8.
Wherein Q is selected from the group consisting of: cyclohexane group, isobornyl alkyl group, adamantyl group, and tricyclo [5.2.1.02，6]Decan-8-yl and tetracyclic [6.2.1.13，6.02，7]Dodecyl-9-yl.
Wherein R is3Is tert-butyl, 1-methyl-1-cyclohexyl, 1-ethyl-1-cyclohexyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 8-methyltricyclo [5.2.1.02，6]Deca-8-yl, 8-ethyl-tricyclo [5.2.1.02，6]Decan-8-yl, 9-methyltetracyclo [6.2.1.13，6.02，7]Dodecyl-9-yl,9-Ethyltetracyclo [6.2.1.1 ] -3，6.02，7]Dodecyl-9-yl.
Wherein the glass transition temperature of the high molecular polymer is between 50 and 350 ℃, the weight average molecular weight is between 1,000 and 300,000, the polydispersity is between 1 and 3, and the thermal cracking temperature is more than 80 ℃.
Wherein the structural unit of formula (I) is represented by formula (I-1), (I-2), (I-3), (I-4), (I-5), (I-6), (I-7), or (I-8)
Of the above-mentioned group.
The chemically amplified photoresist composition of the present invention can be used in general lithography process, especially 193nm lithography process, and has excellent resolution, profile and sensitivity. Lithographic manufacturing methods are well known to those skilled in the art and will not be described in detail herein.
The invention also relates to the application of the chemical amplification photoresist composition in the lithography manufacturing method of semiconductor devices, in particular to an exposure process using a light source with the wavelength of 193nm in the lithography manufacturing method. The method for manufacturing the micro-image has excellent resolution, profile and light sensitivity.
The novel photoresist composition disclosed by the invention has excellent hydrophilicity, adhesiveness, dry etching resistance and other excellent performances, the excellent performances can increase the adhesiveness between the photoresist composition and a substrate, the film forming property of the photoresist is improved, and a developed photoresist pattern is not easy to topple. In addition, because of good hydrophilicity, the developing solution can be uniformly distributed on the surface of the photoresist, and the uniformity and the precise resolution of the surface of the photoresist pattern are improved.
Detailed Description
The chemical amplification photoresist composition of the invention is prepared, wherein the high molecular polymer containing the structural unit of the formula (I) or the formula (II) contains the structural repeating unit of the compound of the formula (III)
R1＝CnH2n+1(n＝0～4)，CF3Q＝Alicyclic group
(III)
Wherein R is1Is H or C1-C4Alkyl or trifluoromethyl (CF)3) (ii) a Q is C4-C12A cyclic alkane substituent of (3). The compound of the formula (III) is ethylene with naphthenic substituent on side chainThe vinyl ether monomer is a vinyl ether monomer with a non-vinyl functional group on a naphthenic substituent, namely a vinyl ether monomer with a non-naphthenic substituent on a main chain, and a vinyl ether monomer with a side chain substituent in a straight chain structure. The compound of formula (III) can form a homopolymer (homopolymer) if it undergoes a self-addition reaction under appropriate conditions, and can prepare a structural configuration in which the high-molecular polymer is an alternating copolymer (alternating copolymer) if it undergoes a copolymerization reaction with maleic anhydride.
The high molecular polymer containing the structural unit of formula (I) or formula (II) is prepared by copolymerizing a compound of formula (III) with maleic anhydride, and other different types of acrylic monomers having a protecting group or other different types of acrylic monomers having a cyclic alkyl group introduced thereto.
With respect to the preparation of the compound of formula (III), it can be synthesized using, but is not limited to, the following method:
the appropriate alcohol was bubbled with acetylene in a KOH/DMSO system and stirring was continued for one hour at sufficient pressure and temperature. And after the solution is cooled, adding water for dilution, extracting, drying and concentrating to obtain the light yellow naphthenic substituent vinyl ether compound.
The compound of formula (III) can be copolymerized with maleic anhydride to obtain alternating copolymer (IV)
R1＝CnH2n+1(n＝0～4)，CF3Q＝Alicyclic group
(IV)
Wherein R is1Is H or C1-C4Alkyl or trifluoromethyl (CF)3) (ii) a Q is C4-C12A cyclic alkane substituent of (3).
The high molecular polymer containing the structural units of the formula (I) and the formula (II) is prepared by copolymerizing a compound of the formula (III) and maleic anhydride with other different types of acrylic monomers with protective groups or other different types of acrylic monomers with cyclic alkyl groups. The vinyl functional group of the key compound shown in the formula (III) is not positioned on the naphthenic substituent, so that the reaction difference between the vinyl ether monomer and other monomers is reduced; the vinyl ether monomer developed by the invention has the naphthenic substituent, so the vinyl ether monomer also has good etching resistance, and can obtain the photoresist high polymer with excellent properties by utilizing the high polarity of the vinyl ether monomer. In addition to the reactivity, etching resistance and polarity, the absorption at 193nm, good adhesion to the substrate and material cost of the compound of formula (III) are important references. The structural classes of the compounds of formula (III) are listed below: (wherein R is1Is H or C1-C4Alkyl or CF of3Fluoromethyl group)
The selection of the acrylic monomers with different protecting groups in the high molecular polymer structure composition containing the structural units of the formula (I) and the formula (II) is not particularly limited; certainly, the acrylic monomer with a protecting group and low absorbance under 193nm light source is selected, so that the prepared high molecular polymer has better penetration characteristic when applied to the 193nm light source lithography process. Factors other than degree of absorptionIn addition, the polymer is further selected according to the characteristics such as polarity and adhesion to the base material, and a suitable polymer is obtained. The acrylic monomer having a protecting group is listed as follows: (wherein R is2Is H or C1-C4Alkyl or trifluoromethyl (CF)3))
The present invention also discloses another high molecular polymer as formula (II), which is obtained by introducing an acryl monomer having a cyclic alkyl group into the high molecular polymer as formula (I). The other different types of acryl monomers with cyclic alkyl groups in the composition of the high molecular polymer structure of formula (II) improve the ease and controllability of the polymerization reaction compared to introducing a Norbornene (Norbornene) monomer, and the properties of the high molecular polymer in the photoresist are adjusted by adjusting the ratio of the acryl monomer with cyclic alkyl groups to the acid-sensitive acryl monomer in the composition of the high molecular polymer. The selection may be adjusted according to the properties of polarity, adhesion, etch resistance, thermal properties, and penetration. Suitable acrylic monomers having a cyclic alkyl group are listed below: (wherein R is4Is hydrogen, C1-C4Alkyl or trifluoromethyl (CF)3))
The acrylic monomer with cyclic alkyl group has more flexibility and diversity in the modification technology of the properties of the photoresist high polymer, so that the acrylic monomer has enhanced applicability in 193nm lithography process and has better resolution, profile and sensitivity.
As mentioned above, the compound of formula (III) and maleic anhydride are combined with other different acrylic monomers with protecting groups or introduced with other different acrylic monomers with cyclic alkyl groups for copolymerization to prepare various kinds of high molecular polymers. The present invention selects different vinyl ether monomers with different vinyl functional groups not located on naphthenic substituent groups and acrylic monomers with protective groups, or introduces different acrylic monomers with cyclic alkyl groups, and substitutes the vinyl ether monomers and the acrylic monomers with the protective groups into the macromolecular polymer structures in the formula (I) and the formula (II) to prepare various copolymers with different types and construct various VEMA high molecular polymers with excellent performance. The following will discuss the monomer composition ratio of the synthesized VEMA high molecular polymer, the polymerization reaction related technique, the physical properties of the high molecular polymer, and the like.
The high molecular polymer of the invention can be used alone or in combination of two or more kinds as a composition of a chemically amplified photoresist.
The polymerization of the polymer used in the present invention is not limited to a specific process, and the polymerization can be performed by mixing the above-mentioned polymer monomers to be reacted and performing the polymerization in the presence of a catalyst initiator and at a suitable reaction temperature and a suitable feed composition ratio. The catalyst initiator may be a catalyst initiator as is conventional to those skilled in the art. Preferred catalytic starters are the generally known free radical starters of the type azonitriles, alkyl peroxides, acyl peroxides, organic peroxides and ketone peroxides, peroxyesters and peroxycarbonates, suitable and preferred free radical starters being listed below: tertiary-Butyl Peroxide (BPO), acetyl peroxide (acetyl peroxide), 2, 2 '-azobisisobutyronitrile (2, 2' -azo-bis-isobutronitril; AIBN), 2, 2 '-azobismethylnitrile (2, 2' -azo-bis-2-methylisobutyronitrile; AMBN), dimethyl 2, 2 '-azobisisobutyl ester radical initiator (dimethyl-2, 2' -azo-bis-isobutryate radial initiator; V-601), and the like. In the presence of nitrogen, proper reaction temperature and proper reaction solvent are selected according to the thermal cracking property of the free radical initiator, and other proper reaction conditions are matched to perform polymerization reaction, so that the free radical initiator has better reaction efficiency, the reaction yield is improved, the applicability of the performed polymerization reaction technology is improved, and the preparation of the excellent VEMA high molecular polymer is completed.
The VEMA high molecular polymer of the invention is soluble in a photoresist solvent. The high molecular polymer has physical properties that the glass transition temperature (Tg) is between 50 and 250 ℃, the weight average molecular weight (Mw) is between 1,000 and 300,000, the Polydispersity (PDI) is between 1 and 3, and the thermal cracking temperature (Td) is more than 80 ℃. The preferred polymer has physical properties of a glass transition temperature Tg of 60 to 210 ℃, a weight average molecular weight of 3,000 to 50,000, a polydispersity of 1 to 3, and a decomposition temperature Td of greater than 80 ℃. A suitable method for measuring the weight average molecular weight and polydispersity of the high molecular weight polymer is gel permeation chromatography (gel permeation chromatography).
The chemical amplification photoresist composition of the invention mainly comprises a high molecular polymer of a structural unit of a formula (I) or a formula (II), and can also comprise other components according to the actual application requirement: Photo-Acid generator (PAG), Acid scavenger (Acid queue), additive (additive) and solvent (solvent).
The photoacid generator used in the present invention is not particularly limited as long as it can generate an acid upon irradiation with radiation such as ultraviolet rays, and other basic requirements are that it has a low absorbance under 193nm light source and a certain degree of stability before exposure to avoid affecting the reliability of the process. Preferred photoacid generators can be: (C in the following structural formulanF2n+1Wherein n is an integer of 1-12; knotC in the formulamH2m+1Wherein m is an integer of 1 to 12)
The photoacid generators described above may be used singly, in admixture of two or more. The photoacid generator may be added in an amount of 0.1 to 20 parts, preferably 0.5 to 7 parts, based on 100 parts of the resin (all proportions herein being by weight).
The acid scavenger of the present invention is to adjust the diffusion characteristic of acidic ions generated by PAG in the photoresist, so as to improve the characteristics of the photoresist. Preferred acid scavengers suitable for use in the present invention are:
tetrabutylammonium hydroxide (tetrabutylammonium hydroxide), tetrabutylammonium lactate (tetrabutylammonium lactate), tributylamine (tributylamine), trioctylamine (trioctylamine), triethanolamine (triethanolamine), tris [2- (2-methoxyethoxy) ethyl ] amine (tris [2- (2-methoxyethoxy) ethyl ] amine), N- (2, 3-dihydroxypropyl) piperidine (N- (2, 3-dihydroxypropyl) piperidine), N- (2-hydroxyethyl) piperidine (N- (2-hydroxyethyl) piperidine), morpholine (morpholine), N- (2-hydroxyethyl) morpholine (N- (2-hydroxyethyl) morpholine), N- (2-hydroxyethyl) pyrrolidine (N- (2-hydroxyethyl) pyrrolidine), or N- (2-hydroxyethyl) pyrrolidine (N- (2-hydroxyethyl) pyrrolidine), etc. The acid scavenger may be added in an amount of 0.1 to 50 mole% of the photoacid generator, and preferably in an amount of 1 to 25 mole% of the photoacid generator.
The additive of the present invention is not particularly limited, and according to the application requirements of the photoresist, a proper amount of sensitizers (sensitizers), dissolution inhibitors (dissolution inhibitors), surfactants (surfactants), stabilizers (stabilzers), dyes (dies) and other high molecular polymers can be selectively added, so that the photoresist can meet the required requirements and standards.
The solvent used for producing the chemically amplified resist composition of the present invention is also not particularly limited, and the species are listed as follows: higher alcohols (e.g., n-octanol), ester derivatives of ethylene glycol acid (e.g., methyl lactate, ethyl lactate, or ethyl glycolate), ester derivatives of ethylene glycol ethers (e.g., ethylene glycol ethyl ether acetate, ethylene glycol methyl ether acetate, or propylene glycol monomethyl ether acetate), ketone esters (e.g., methyl pyruvate, or ethyl pyruvate), alkoxycarboxylates (e.g., ethyl 2-ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, or methyl ethoxypropionate), ketone derivatives (e.g., methyl ethyl ketone, methyl amyl ketone, acetylacetone, cyclopentanone, cyclohexanone, or 2-heptanone), ketone ether derivatives (e.g., diacetone alcohol methyl ether), ketone alcohol derivatives (e.g., acetol or diacetone), alcohol ether derivatives (e.g., ethylene glycol butyl ether or propylene glycol ethyl ether), Amide derivatives (e.g., dimethylacetamide or dimethylformamide), ether derivatives (e.g., anisole or diglyme), or mixtures thereof. Among them, n-octanol, propylene glycol monomethyl ether acetate, ethyl 2-ethoxyacetate, methyl 3-methoxypropionate, methyl ethoxypropionate, methyl ethyl ketone, methyl amyl ketone, cyclopentanone, methyl lactate, ethyl lactate, ethylene glycol butyl ether, propylene glycol ethyl ether or a mixture thereof is preferable as the solvent for the main component.
The solvent is suitably added in an amount of 200 to 2000 parts by weight, preferably 400 to 1000 parts by weight, per 100 parts by weight of the high molecular polymer (all proportions herein being by weight).
The chemically amplified resist composition of the present invention is obtained by mixing the above-mentioned components. The polymer may be dissolved in a solvent and then mixed with other components. Or mixing the other components except the high molecular polymer and dissolving the mixture in the solvent, and then mixing the mixture into the high molecular polymer.
The amount of impurities (e.g., trace amounts of metals and halogens) contained in the chemically amplified resist composition should be minimized, and the components may be purified prior to mixing to produce the chemically amplified resist composition. Alternatively, the components may be mixed to produce a chemically amplified photoresist composition, which is then subjected to purification techniques prior to use.
The chemical amplification light resistance agent composition of the invention can be used in general micro-image forming process, especially, the chemical amplification light resistance agent composition of the invention can be used in the micro-image forming process of the light with the conventional wavelength, and is more suitable for the micro-image forming process of the light with the wavelength of 193 nm.
The chemically amplified photoresist composition of the present invention can be patterned by the presently known photolithography process. Such as coating the chemically amplified photoresist composition on a substrate, and then performing the photolithography process steps of baking, exposing, developing, etc.
The substrate may be a silicon wafer or have a variety of materials and the coating may be performed by methods such as spin coating, spray coating, or roll coating. After coating, the substrate is typically heated on a hot plate to remove the solvent, and then exposed through a photomask to form the desired pattern on the substrate.
The developer can be selected from alkaline aqueous solutions such as ammonia, triethylamine, dimethylamine methanol, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or trimethylhydroxyethylammonium hydroxide.
The chemically amplified photoresist composition of the present invention has excellent resolution, profile and sensitivity, and is excellent in depth of focus, exposure margin and removal margin.
Detailed description of the preferred embodiments
To better understand the technical content of the present invention, a preferred embodiment is described below.
Preparation example 1
Synthesis of high molecular Polymer formula (I-1a)
In a reactor, 30 ml of Tetrahydrofuran (THF), 2.84 g of t-butyl methacrylate (t-butyl methacrylate), 3.92 g of maleic anhydride, 5.04 g of cyclohexyl vinyl ether (cyclohexyl vinyl ether), 4.6 g of 2, 2' -Azobisisobutyl (AIBN) as a starter, was added, the temperature was raised to about 50 ℃ and 50 ml of tetrahydrofuran was added after completion of the reaction, and the product obtained by the reaction was poured into a vessel containing 1 liter of isopropanol to precipitate a white solid, followed by drying by filtration to obtain 9.43 g of a white powder of the polymer of the formula (I-1a) in a yield of 80% as measured by GPC, a weight average molecular weight of 13,100 and a glass transition temperature Tg of 146 ℃.
Preparation examples 2 to 27
Synthesis of high molecular weight polymers of formulae (I-2a) to (I-9a), formulae (I-1b) to (I-9b), and formulae (I-1c) to (I-9c)
The procedure of preparation example 1 was repeated, and polymerization was carried out using different monomers or compositions to obtain high molecular weight polymers of different structures, such as formula (I-2a) to formula (I-9a), formula (I-1b) to formula (I-9b), and formula (I-1c) to formula (I-9c), all as white powders. The results of the synthesis are shown in the following table.
For the purpose of describing the technology of the invention, the polymer platform (polymer platform) mainly used in the preparation examples of the polymer is shown in formulas (I-1) to (I-9) and (II-1) to (II-8). The polymer platform item columns in the following tables show the above formulas (I-1) to (I-9), and formulas (II-1) to (II-8):
wherein the symbols a, b, c in the formulae (I-1) to (I-9) represent the respective different compositions, and the symbols a, b in the formulae (II-1) to (II-8) represent the respective different compositions. The following examples (examples 1 to 43) of the polymer preparations are illustrative of the above-described various preparations and synthesis results, and the structural compositions and synthesis results of the polymer preparations in examples 1 to 43 are shown in the following tables:
example 1
Photoresist composition formulation
After mixing uniformly 4 g of the polymer of the formula ((I-1a) obtained in preparation example 1, 0.08 g of triphenylsulfonium perfluoro-1-butanesulfonate (TPS-PFBS), 0.80 g of tert-butyl cholate (TBC), 35 g of Propylene Glycol Monomethyl Ether Acetate (PGMEA), and 20 mg of tetrabutylammonium hydroxide (tetrabutylammonium hydroxide), the solution was filtered through a 0.45 μm filter, coated on a silicon wafer, and spin-coated at 3000rpm for 20 seconds, a uniform film was obtained.
The film was then dried at 130 ℃ for 60 seconds to give a film having a thickness of 290.2 nm. Irradiating the film with a Deep Ultraviolet (DUV) ray having an irradiation energy of 10 to 30mj/cm2 at 193nm, heating the film on a hot plate at 130 ℃ for 90 seconds, and baking the film after exposure.
The irradiated film was developed with 2.38 aqueous tetramethylammonium hydroxide (TMAH) solution, washed with deionized water, spin-dried, and the microstructure pattern of the photoresist was analyzed by scanning with an electron microscope, showing a structure with a resolution of 0.13 μm.
Examples 2 to 11 formulations of Photoresist compositions
The procedure of example 1 was repeated, and the polymer obtained in the other preparation example was substituted for the polymer of example 1, and the results are shown in the following table:
| high molecular polymer | Film thickness (nm) | Resolution (μm) | |
| Example 1 | (I-1a) | 290.2 | 0.13 |
| Example 2 | (I-4b) | 296.5 | 0.15 |
| Example 3 | (I-4c) | 288.3 | 0.15 |
| Example 4 | (I-5b) | 278.3 | 0.15 |
in031249
| Example 5 | (I-6c) | 269.8 | 0.18 |
| Example 6 | (I-8a) | 267.1 | 0.14 |
| Example 7 | (II-1a) | 262.9 | 0.15 |
| Example 8 | (II-4a) | 316.4 | 0.15 |
| Example 9 | (II-5a) | 309.7 | 0.14 |
| Example 10 | (II-6a) | 309.7 | 0.13 |
| Example 11 | (II-7a) | 309.7 | 0.14 |
The chemically amplified photoresist composition of the present invention can be used in general lithography process, especially 193nm lithography process, and has excellent resolution, profile and sensitivity.
Comparative example of the invention
In order to illustrate the novelty and advancement of the present invention, the polymer platform (polymer platform) of formula (IV) is specifically mentioned in the comparative example for the purpose of illustration. Formula (IV) below is shown in the following table in the macromolecule platform item column:
the structural composition conditions of formula (IV) and the polymer formula (I-10) prepared by the published technique of the present invention are compared, and the structural composition and synthesis results of the polymer cited in the comparison example are shown in the following table:
comparative example 1
Synthesis of high molecular Polymer formula (IV)
Tetrahydrofuran 30 ml and 8-methyl tricyclo [5.2.1.0 ] are added into the reactor2，6]Deca-8-ylmethyl propenyl ester (8-methylcyclo [ 5.2.1.0)2，6]dec-8-ylmethylcrylate) 4.68 g, maleic anhydride 3.92 g, 3, 4-dihydro-2H-pyran (3, 4-dihydro-2H-pyran)3.36 g, and then 0.65 g of 2, 2' -Azobisisobutyl (AIBN) as a starting material were added, the temperature was raised to about 70 ℃, tetrahydrofuran 20 ml was added after completion of the reaction, and the product obtained by the reaction was poured into a container containing 1 l of isopropyl alcohol to precipitate a white solid, which was then dried by filtration to obtain 5.69 g of a white powder of the polymer of the formula (IV), which was 47.63% in yield and had a weight average molecular weight of 12,600 as measured by GPC and a glass transition temperature Tg of 145.45 ℃. Due to 8-methyltricyclo [5.2.1.02，6]The deca-8-yl methacrylate has a much faster reaction rate than maleic anhydride and 3, 4-dihydro-2H-pyran, and the yield is derived from 8-methyltricyclo [5.2.1.0 ]2，6]The high molecular polymer obtained by self-polymerizing the deca-8-yl methacrylate has poor compositional uniformity and, of course, the yield is also lowered.
If the monomer feeding manner in the polymer synthesis procedure of formula (IV) is changed, the problems of too low yield and uneven reaction can be slightly improved. However, the feeding method is not easy to control the reaction, and the properties of the finished products in different batches are different.
However, taking the polymer synthesis procedure of formula (I-10) prepared by the present invention as an example, compared with the polymer synthesis procedure of formula (IV), the polymer synthesis procedure of formula (I-10) is simple and easy to control, the synthesis yield is high (80.65%), and the composition uniformity of the prepared polymer is good, and meanwhile, the polymer can be uniformly reacted with acrylic monomer to form a four-component polymer platform, so as to flexibly adjust the properties of the polymer. This demonstrates that the polymer platform with good reactivity and economic benefit, which is the actively developed object of the present invention, has excellent extension modification potential, and the prepared chemically amplified photoresist composition has excellent lithography performance.
In summary, the present invention shows features different from those of the prior art in terms of purpose, technique and effect, or in terms of technical level and research and development design. It should be noted that the above-mentioned embodiments are only for illustrative purposes, and the claimed invention should be subject to the claims rather than the embodiments described above.
Claims (5)
1. A chemically amplified resist composition characterized in that it is a high molecular polymer containing a structural unit of the following formula (I)
Wherein R is1Is hydrogen, C1-C4Alkyl, trifluoromethyl; q is C4-C12A cyclic alkyl group of (a); r2Comprises the following steps: hydrogen, C1-C4Alkyl, trifluoromethyl; r3Is C4-C12Acid sensitive groups of branched or cyclic alkanes; and x + y + z is 1, wherein x/(x + y + z) is 0.1 to 0.45; y/(x + y + z) ═ 0.1 to 0.45; z/(x + y + z) ═ 0.1 to 0.8.
2. The chemically amplified photoresist composition of claim 1, wherein Q is selected from the group consisting of: cyclohexane group, isobornyl alkyl group, adamantyl group, and tricyclo [5.2.1.02，6]Decan-8-yl and tetracyclic [6.2.1.13，6.02，7]Dodecyl-9-yl.
3. The chemically amplified photoresist composition of claim 1, wherein R is3Is tert-butyl, 1-methyl-1-cyclohexyl, 1-ethyl-1-cyclohexyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 8-methyltricyclo [5.2.1.02，6]Deca-8-yl, 8-ethyl-tricyclo [5.2.1.02，6]Decan-8-yl, 9-methyltetracyclo [6.2.1.13，6.02，7]Dodecan-9-yl, 9-ethyltetracyclo [6.2.1.13，6.02，7]Dodecyl-9-yl.
4. The chemically amplified photoresist composition of claim 1, wherein the high molecular weight polymer has a glass transition temperature of 50 to 350 ℃, a weight average molecular weight of 1,000 to 300,000, a polydispersity of 1 to 3, and a thermal cracking temperature of more than 80 ℃.
5. The chemically amplified photoresist composition of claim 1, wherein the structural unit of formula (I) is represented by formula (I-1), (I-2), (I-3), (I-4), (I-5), (I-6), (I-7), or (I-8)
Of the above-mentioned group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HK05101872.6A HK1069440B (en) | 2005-03-03 | Chemically-amplified resist compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HK05101872.6A HK1069440B (en) | 2005-03-03 | Chemically-amplified resist compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1069440A1 HK1069440A1 (en) | 2005-05-20 |
| HK1069440B true HK1069440B (en) | 2006-04-07 |
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