TW574234B - Thermally cured underlayer for lithographic application - Google Patents

Description

574234 A7 ____________ B7 V. Description of the invention (1) Technical invention of the invention The invention relates to the deep ultraviolet lithography technology used in the manufacture of semiconductors, and more specifically to the primer coating for chemically amplified double-layer resist systems . BACKGROUND OF THE INVENTION The fabrication of integrated circuits relies on the use of photolithography to define active components and interconnect structures on microelectronic devices. Until recently, g-line (436 nm) and I-line (365 nm) light were used in most lithography applications. However, in order to achieve a smaller resolution, the wavelength of light in the microlithography technology used in semiconductor manufacturing has been reduced to the deep ultraviolet region of 254 nm and 193 nm. The problem with using deep UV wavelengths is that the resist used at higher wavelengths has too high light absorption and too low sensitivity. Therefore, in order to use a deep ultraviolet wavelength, a resist substance having low light absorption and improved sensitivity is required. Recently, chemically amplified resist substances have been developed through the use of acid-labile polymers to meet the aforementioned standards. These have shown great potential for increasing resolution. However, chemically amplified resist systems have many disadvantages. One of these problems is the standing wave effect, which occurs when monochromatic light is reflected from the surface of a green substrate during exposure. If a standing wave phenomenon is formed in the resist, the resolution will be reduced and the line width will be changed. For example, a standing wave in a positive resist has a tendency to form a foot (Fot) at the resist / substrate interface, and reduces the resolution of the resist. In addition, the characteristics and resolution of chemically amplified resists may change due to the toxic effects of the substrate. In more detail, the effect occurs when the substrate has a nitride layer. It is believed that the residual postal bonds in the nitride film will be located on this paper scale and apply the Chinese National Standard (CNS) A4 specification (21 × 297 mm) 4… see ... /-(Please read the precautions on the back before filling this page ), \ Swallow. 574234 V. Description of the invention (2 The acid of the nitride / resistor interface is deactivated. In the case of a positive resist, it causes an insoluble region, and it causes resistance at the nitride / resistor interface. Smearing or footing of the agent. Furthermore, the lithography chord ratio requires the use of a thin chemically amplified resist (eg, about 0.5 microns or less) to print a profile below 0.18 microns. It further requires the use of an excellent Resistant to plasma etching, which can transfer the resist pattern profile to the underlying substrate. However, in order to reduce the absorbance of chemically amplified resists, such aromatic groups as phenolic resins have been removed This further reduces the resistance to etching. Before applying the chemically amplified film, placing a primer or primer film on the substrate can reduce the above problems. The primer coating absorbs most of the deep ultraviolet light and weakens the Wave effect. Also, the bottom The coating prevents deactivation of the acid catalyst at the resist / substrate interface. Furthermore, the undercoat layer contains some aromatic groups to provide resistance to etching. In a typical two-layer resist method, the undercoat layer is It is applied on the substrate. Then, a chemically amplified resist is applied on the undercoat layer, which is exposed to deep ultraviolet light, and then developed to form a surface coating on the chemically amplified resist. Then a double-layered resist is formed. The chemically amplified resist in a two-layer system, which is placed in an oxygen plasma remaining environment and is engraved on the area where the chemically amplified resist has been removed by development, typically contains silicon, so it can be changed by Convert silicon into silicon dioxide to withstand oxygen plasma etching. Silicon dioxide can withstand the etching process. After the bottom layer is etched, the resist can be used for subsequent processing, such as for removing the bottom Chemical process for non-oxygen slurry etching of substrates. The available maps are based on the standard of Chinese paper (CNS) A4 (21〇297297). 574234 A7 _ B7 1 — -__— _ 5. Description of the invention (3) Although the bottom The layer can reduce the toxic effect of standing waves and the substrate, which also causes other problems. First, some primer coatings are soluble in the chemically amplified resist solvent group / [knife. There is a mutual interaction between the top coating and the base coating. The mixing phenomenon will damage the resolution and sensitivity of the surface resist layer. In addition, if the refractive index difference between the chemically amplified resist and the undercoat layer is large, light will reflect from the undercoat layer and cause standing waves in the resist. Therefore, the actual part of the refractive index of the two layers "n, must be substantially consistent, or the difference between them must be minimized; and the imaginary part of the refractive index of the two layers" k, It is optimized to reduce the reflection effect. Another problem of the undercoat layer is that it has an excessively high light absorption due to the inclusion of aromatic groups. Some deep ultraviolet exposure devices used in the manufacture of semiconductors are based on photoresist In the process of exposing and aligning the exposure mask to the layer under the photoresist, light of the same wavelength is used. If the light absorption of the undercoat layer is too high, the reflected light required for the alignment effect will be excessively weakened and cannot be applied. However, if the light absorption of the undercoat layer is insufficient, standing waves may occur. The formulator must strike a balance between these two competing goals. In addition, some primers are extremely poor in plasma etch resistance for etching chemical processes. The etch resistance of the undercoat layer should be comparable to that of the phenolic resin to be commercially applicable. Furthermore, some undercoats require UV exposure to form crosslinks before applying light-sensitive resist topcoats. The problem with the cross-linking green layer of the purple line is that it requires a long time exposure before it can form a paternal effect. Prolonged exposure will severely limit output and increase the cost of manufacturing integrated circuits. At the same time, UV appliances do not provide uniform paper sizes. Appropriate (⑽) A4 size (2K) X2J ^ J7 ---

f:-(Please read the notes on the back before filling this page). Order 丨 574234 A7 B7 V. Description of the invention (4) (Please read the notes on the back before filling this page) Part of the coating may have a higher degree of crosslinking than other areas of the basecoat. In addition, UV cross-linked exposure equipment is very expensive and is often not included in most photoresist coating equipment due to cost and space constraints. Some primer coatings are crosslinked by heating. However, the problem with these primer coatings is that they require high curing temperatures and long curing times before they can be applied to the top layer. For commercial applicability, the base coat should be cured at temperatures below 250 ° C, and the cure time should be less than 180 seconds. After curing, the base coat should have a high glass transition temperature to withstand subsequent high temperature processing and avoid blending with the photoresist layer. Therefore, it has recently been proposed to use a heat-curable undercoating in a deep ultraviolet lithography process, which uses a composition containing a specific hydroxyl-functional polymer, a thermal acid-generating compound, and an amine cross-linking agent. The hydroxy-functional polymers proposed for use in these heat-curable undercoating compositions are copolymers of biphenyl methacrylate (BPMA) and 2-hydroxyethyl methacrylate (hema). Used in combination with a hot acid generating compound (TAG) and a monoamine cross-linking agent. However, the proposed thermosetting undercoating (TCU) composition faces the following issues: (a) The current 248nm TCU generation is in common crystal edge removal (EBR) solvents such as propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), ethyl ethoxypropionic acid (EEP), etc.); (b) standing waves, which may be attributed to the base coating and the substrate and The light parameters (η and k) of the pattern layer (IL) do not have the best degree of correspondence; and (c) the stain on the TCU / pattern layer (IL) interface. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 public love) η 574234 A7 B7 V. Description of the invention (5) In the proposed thermosetting undercoating (TCU) composition, although the optical constant can be promoted to have Reasonable degree of conformity, but it can not completely eliminate the floating of the standing CU / pattern layer (IL) interface. In addition, although it has been proposed that methyl methoxypropionate (MMP) is suitable for dissolving TCU polymers and removing features based on crystal edges, MMP is not a generally acceptable lithographic solvent. Summary of fcg Therefore, it is an object of the present invention to provide a thermosetting polymer and a thermosetting polymer layer which are suitable as a primer coating composition and compatible with crystal edge scavenger (EBR), which can avoid or Reduce the aforementioned disadvantages. Another object of the present invention is to provide such a thermosetting polymer to provide an undercoat layer which cures at a temperature of less than 250 ° C in less than about 3 minutes. A further object of the present invention is to provide a primer coating, which is insoluble in a surface resist solvent system, which reduces the reflection effect 'and its etching rate is comparable to that of a phenolic resin. Other objects, advantages and features of the present invention will be understood from the following description. The present invention relates to a thermosetting polymer composition compatible with crystal edge scavenger (EBR), which includes a novel hydroxyl-containing polymer, an amine cross-linking agent, and a thermal acid generator. The heat-curable polymer composition is soluble in a solvent and is suitable as a primer layer in a deep ultraviolet lithography process. In addition, the present invention also relates to a photolithographic coating substrate comprising: a substrate, a thermosetting polymer composition on the substrate, and a radiation-sensitive resist on the thermosetting polymer composition. Agent surface coating. Furthermore, the present invention also relates to a method for coating the substrate using the photolithography in the manufacture of the relief structure. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) .....--(Please read the precautions on the back before filling this page)

η 574234 5. Description of the invention (6) Generally applicable to the polymer of the present invention, R will be hydrogen or methyl, and R2 is a substituted or unsubstituted C6_Ci4 aryl group having the following general chemical formula, OfR40tR5. Enoate or C6_CM aryl methacrylate, wherein the substituent may be phenyl, C! _4 alkyl or Cl_4 alkoxy; R3 is a hydroxy-functional alkyl acrylate, methacrylate Or C6_CM aryl; R4 is Ci-C1Q straight or branched alkylene; p is an integer from 1 to 5, provided that the number of carbon atoms in [β4〇-] P does not exceed 30; R5 is a Ci_Ci 〇 linear, branched, or cyclic alkyl, substituted or unsubstituted c6_Ci4 aryl, or substituted or unsubstituted CVC1S alicyclic hydrocarbon; and ⑺ is about 40 to 70, n is about 15 to 35, and 0 are about 15 to 25. The preferred mole percentage ranges are m = 60-68, n = 15-20, and 0 = 15-20. The aryl group in the above definition is preferably C6-C1G aromatic. It is more preferably a phenyl group. The molecular weight of the polymer of the present invention is generally about 8,000 to 100,000, preferably about 10,000 to 24,000. When applied as a heat-curing undercoat layer ( TCU) materials, the components m and 0 impart light absorption, solubility and cross-linking functions. Each monomer unit is focused on one of the three functions listed above, but may have an effect on more than one function. The effect is based on It depends on the specific monomer unit used. Changing the early body Xia 'represented by m in the chemical formula can change the engraving and absorbance of the anti-resistance device, the pot will significantly change the light parameter k, and its effect is due to the reflection of the TCU material The paper size is applicable to China National Standard (CNS) Α4 (210X297 mm)

(Please read the notes on the back before filling this page) 9 574234 A7 B7 V. Description of Invention (7) It is used for control. You can optimize the solubility and resistance to corrosion by choosing the appropriate monomers η and 〇. The crosslinking rate is determined by the amount of monomer represented by m in the chemical formula. In general, for a 248 nm micron lithography process, the optimal ranges of the refractive index (η) and the composite index (k) are about 1.56 to 1.76 and 0.125 ^ 0.275, respectively. The detailed description and specific examples of the invention Invented, we obtain these thermosetting polymers compatible with crystal edge scavenger (EBR) by providing monomer units in the polymer that are designed to improve solubility / absorbance characteristics. The monomer units provided in the polymer are selected from ethylene glycol dicyclopentenyl methacrylate (EGDCPMA) monomers, biphenyl methacrylate (BPMA) having the following three chemical formulas: Monomer unit and hydroxystyrene (HS): (Please read the notes on the back before filling this page)

In general, by using AcSt as the polymerization monomer in the polymerization reaction mixture,

OAc AcSt and after the polymerization reaction, the reaction mixture is diluted with methanol and sodium methoxide (such as 10% solution) in methanol to carry out methanol decomposition, and 10 paper sizes are applicable to Chinese National Standard (CNS) A4 specifications ( 210X297 mm) 574234 A7 ___ B7_ 5. Description of the invention (8) Hydroxystyrene (HS) unit. The phenolic hydroxyl group in PHS promotes the cross-linking reaction with melamine or urea-based cross-linking agents; and the ethylene glycol group in EGDCPMA and the phenolic functional group in phs can promote the Solubility in methyl ether acetate (PGMEA), ethyl lactate (EL), ethyl ethoxypropionate (EEP), etc. It is possible to control the absorbance at 248 nanometers by trimerization by adjusting the ratio between biphenyl methacrylate, acetophenone and ethylene glycol functional monomers. The thermosetting polymer composition includes a hydroxyl-containing monomer unit. Any hydroxy-containing polymer may be used, such as a polymer of monomer units including hydroxystyrene, hydroxyalkylacrylate, or hydroxyalkylmethacrylate. Examples of suitable hydroxyalkyl acrylate or fluorenyl acrylate monomer units are 2-hydroxyethyl acrylate or methacrylate, 3-hydroxypropyl acrylate or methacrylate, 4-hydroxybutyl acrylate Or methacrylate, 5-methylpentyl acrylate or fluorenyl acrylate and 6-hydroxyhexyl acrylate or methacrylic acid ester. Although it is also possible to use a secondary alcohol hydroxyl group and a tertiary alcohol hydroxyl group, a mixture of a primary alcohol hydroxyl group and a secondary alcohol hydroxyl group, or a mixture of a primary alcohol hydroxyl group, a secondary alcohol hydroxyl group, and a tertiary alcohol group, the trimethylpropionate or methacrylate monomer Monofluorene preferably contains a primary alcohol hydroxyl group. Suitable examples of secondary alcohols are 2-hydroxypropyl acrylate or methacrylate, 3-hydroxybutyl acrylate or fluorenyl acrylate, 4-hydroxypentyl acrylate or methacrylate, 5-hydroxyhexyl acrylate Esters or fluorenyl acrylates. The preferred hydroxyalkyl acrylate or fluorenyl acrylate is 2-hydroxyethyl acrylate or methacrylate. The hydroxyl-containing polymer should contain aromatic monomer units to balance the resist 2η standard (CNS) A4 specification (210X297 mm) ~ ΤΓZ- ------------------- ------- *-(Please read the precautions on the back before filling this page) Xu 丨 574234 A7 __________B7______ V. Description of the invention (9) and k 'The better is biphenyl acrylic acid vinegar or 曱Acrylic acid, naphthyl acrylic acid or methacrylate and anthracene acrylate or fluorenyl acrylate. In addition, the heat-curable polymer composition may further include an acrylate or methacrylate monomer unit of ethylene glycol to produce a polymer with higher solubility. Suitable examples of the monomer unit include ethylene glycol methyl ether acrylate and methacrylate, ethylene glycol phenyl ether acrylate and fluorenyl acrylate, monoethylene glycol fluorenyl propionate and fluorenyl propylene Esters and so on. The number average molecular weight of the polymer containing acrylstyrene, biphenyl methacrylate, and 2- (dicyclopentenyloxy) ether acrylic acid and methacrylate units is preferably about 8,000 to 40,000, more It is preferably ι〇, 000 to 24,000. Suitable solvents for undercoating include ketones, ethers and esters such as 2-heptanone, cyclohexanone, propylene glycol monoethyl ether acetate, propylene glycol methyl acetate, methyl lactate, lactic acid Ethyl ester, methyl 3-methoxypropionate, N-methyl-2-pyrrolidone, ethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and the like. The present invention relates to a heat-curable polymer composition compatible with crystal edge scavenger (EBR), which can be used to form a primer layer in a deep ultraviolet lithography process. The thermosetting polymer composition includes a hydroxyl-containing polymer, a amine-based cross-linking agent, a thermal acid generator, and a solvent. When the composition is heated, the thermal acid generator generates an acid, which protonates the polyfunctional amine cross-linking agent and generates a very strong electrophilic group. This group reacts with a hydroxyl group on the hydroxyl-containing polymer to form a cured crosslinked polymer matrix. The present invention can use any suitable amine-based cross-linking agent, such as methylated and / or methylolated and etherified melamine, methylolated and / or methylated paper. Applicable to Chinese countries Standard (CNS) A4 specification (210X297). 12 (Please read the precautions on the back before filling this page)

574234 A7 B7 V. Description of the invention (10) Dimerization and etherification of melamine and the like. A preferred amine-based crosslinking agent has the following general formula: R7 /

N, NγΝγΝ Υ / R8 where Υ is NR1% 11, or is a substituted or unsubstituted c6_c "aryl or C ^ -C: 8 alkyl group; R6 to R11 are independently a hydrogen or have a chemical formula _CH2〇H4 -CH2OR is one of the groups wherein R12 is an alkyl group having about 1 to & carbon atoms. An example of a suitable melamine crosslinker is methoxyalkyl melamine Donkey amines such as hexamethylol melamine, trimethoxymethyl melamine, hexamethyl ethyl melamine, tetramethyl ethyl melamine , Hexamethoxypropyl melamine, pentamethoxypropyl melamine, women's college. The preferred di-t-oxyamine conjugate parent agent is from Sanwa Chemical Company (Cymel 303, Kanazawa District, Japan) ) Of MW100LM melamine crosslinker, and Powderlink from Cytec Industries (Patterson, New Jersey, USA). The thermal acid generator of the present invention has the following general chemical formula ...

This paper size applies to Chinese National Standards (CNs) A4 specifications (210X297 mm) (Please read the precautions on the back before filling out this page) # 丨 ref-5. Description of the invention (11) where R13 is substituted or unsubstituted Alkyl, cycloalkyl or aromatic, wherein the substituents are functional groups, alkoxy groups, aromatic groups, stone groups or amine groups; and R to R are independently hydrogen, straight chain or branched to alkyl, Alkoxy, amine, alkylamino, aromatic, dilute, haloyl, alkoxy, cycloalkyl or cyclic cycloalkyl, aromatic or heterocyclic. The preferred thermal acid generators are cyclohexyl p-toluenesulfonate, methyl p-toluenesulfonate, norbornyl p-toluene% acid, cyclohexyl diisopropylbenzoate xanthate, cyclohexyl Methoxybenzenesulfonate. More preferred thermal acid generators are cyclohexyl p-toluenesulfonate, methyl p-toluenesulfonate, and cyclohexyl 2,4,6 • triisopropylbenzenesulfonate. Cyclized-withered refers to the ring, aromatic or heterocyclic system connected to the benzene ring of the thermal acid generator, such as the following cyclized aromatics:

Cyclic aromatics The above-mentioned thermal acid generators should not be regarded as photoacid generators. Thermal acid generators are very insensitive to ultraviolet light, and they cannot actually be used in photolithography processes as photoacid generators. The heat-curable polymer composition preferably contains 75 to 95% by weight (based on the total solids) of the hydroxyl-containing polymer, and more preferably about 82 to 95% by weight. The content of the amine-based crosslinking agent in the heat-curable polymer composition is preferably about 3 to 20% by weight, and more preferably about 3 to 6% by weight. The content of the thermal acid generator in the heat-curable polymer composition is preferably about 0.5 to 5% by weight, and more preferably about 2 to 4% by weight. The heat-curable polymer composition of the present invention reaches a temperature of about 50 ° C.

574234 A7 B7 V. Description of Invention (Π) ............. b ...: f: * · W (Please read the notes on the back before filling this page) Significant cross-linking effect. At 50. 〇 Cross-linking below may cause gel formation at room temperature, which will reduce shelf life. When the thermosetting polymer composition is used as an undercoating layer in the microlithography process, gel formation will cause uneven coating and line width variation of the entire substrate. The present invention also relates to a photolithographic coating substrate, which includes a substrate, a heat-curable undercoating composition on the substrate, and a radiation-sensitive resist on the heat-curing undercoating composition. Agent surface coating. The heat-curable undercoating composition includes a heat-curable polymer composition including a hydroxyl-containing polymer, an amine-based cross-linking agent, and a thermal acid generator which forms a cross-linked matrix upon heating. Any of the above polymers can be used as a hydroxyl-containing polymer. . Order_ The present invention further relates to a method for coating a substrate using the photolithography to manufacture a relief structure, the steps include: providing the photolithography coating substrate, and coating a radiation-sensitive resist surface Imagewise exposure to actinic radiation; and by developing the radiation-sensitive resist surface coating with a developer, forming an open area on the radiation-sensitive resist surface coating to form a Photoresist pattern. In addition, the heat-curable undercoating composition can be removed by any suitable method (such as an oxygen plasma epitaxy) in the open area of the developed radiation-sensitive resist surface coating, in order to The coating composition forms a pattern. One advantage of the heat-curable polymer composition is that it can be cured at a temperature of less than 250 ° C. in a time of less than about 80 fy. This advantage makes it particularly suitable for use as a primer for a resist system, where both temperature and time limitations are important for the commercial applicability of the resist system. The heat-curable polymer composition is preferably cured at a temperature between 150 and 250 C, and more preferably between 180 and 22 °.

5. Description of the invention (η) One of the temperatures of c. The curing time is preferably from about 30 to 180 seconds, and more preferably from about ⑼ to 120 seconds. Both the bottom main layer and the radiation-sensitive composition are uniformly applied to a substrate by a known coating method. The composition is dissolved in an organic solvent, and the coating can be applied by spin coating, dip coating, blade coating, lamination, brush coating, spray coating, and reverse roll coating. The coating thickness is generally from about 01 to 10 microns or more; in the case of a radiation-sensitive resist, it is more preferably about 01 to 15 microns; and in the case of an undercoating layer, it is more preferably about 03 to 30. Microns. After the coating operation, the solvent is generally removed by curing or drying. Solvents for radiation-sensitive compositions of the undercoat and surface layers, including ketones, ethers and esters, such as methyl ethyl ketone, methyl isopropyl ketone, 2-heptanone, cyclopentanone , Cyclohexanone, 2-methoxy-propionic acetate, 2-methoxyethanol, 2-ethoxyethanol, ammonium ethoxyacetate, ^ methoxy-2-propyl Acetate, ι, 2-dimethoxyethane ethyl acetate, acetic acid cellosolve, glycerol monoethyl ether acetate, propylene glycol methyl ether acetate, methyl lactate, ethyl lactate, Methyl pyruvate, ethyl pyruvate, ethyl 3-methoxypropionate, N-methyl-2-pyrrolidone, ι, 4-dioxane, ethylene glycol monoisopropyl ether, diethylene glycol Alcohol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl. The solvent used for the undercoat layer and the surface photoresist composition will be remotely selected with reference to the compatibility with the polymer resin of the undercoat layer and the surface photoresist composition. For example, the choice of the solvent used for the photoresist composition and its concentration is mainly determined by the type of functionality incorporated in the acid-labile polymer, the photoacid generator, and the coating method. The solvent should be inert, should be soluble in all components of the photoresist, should not undergo any chemical reaction with the component, and should be A4 size (210X297 mm). The paper size applies to Chinese National Standard (CNS) 574234 A7 I ---- B7____ 5. Description of the invention (14) It is removed again during the drying period after coating. The invention's radiation-sensitive resist surface coating can be any suitable sensitive resist. It is typically a chemically amplified resist that is sensitive to light in the deep ultraviolet region, such as discussed in U.S. Patent Nos. 5,492,793 and 5,747,622. As far as the double-layer resist system is concerned, stomach-type resists should contain tritium to protect them from oxygen and electricity. Radiation-sensitive resists also contain a photoacid-generating (pAG) compound. The PAG compound can be in any suitable form, such as iron sulfide or moth iron salt, stilbene group, imine compound, and the like. Typically, PAG will be present in an amount of 1 to 10% by weight of the polymer. Any appropriate photoacid generator compound can be used in the photoresist composition. Photoacid-generating compounds are well known and include phosphonium salts (such as diazonium, thiosulfurium, thiosulfurium oxide, and iodonium salts) and diphosphonium salts. Suitable photoacid generator compounds are disclosed, for example, in U.S. Patent Nos. 5,558,978 and 5,468,589 ', which are incorporated herein by reference. Examples of suitable photoacid generators are: benzamidine methyl p-toluenesulfonate, benzoin p-toluenesulfonate, α_ (p-toluenesulfonyloxy) methylbenzoin , 3- (p-_benzenebenzenesulfonyloxy) _2-hydroxy-benzyl_1βphenylpropyl ether, N- (p-dodecylbenzenesulfonyloxy) ^-naphthalenedimethylimide And ν_ (phenyl-sulfonyloxy) -1,8_naphthalenedimethylimide. /, Other suitable compounds are o-Cyclylbenzidine, which rearranges at the time of photochemical administration And o-nitrobenzoic acid, o-nitrobenzaldehyde such as 1-nitrobenzaldehyde and 2,6_nitrobenzaldehyde; halogenated fluorenyl benzophenone, such as α, α, ^^) M specifications (210X297 mm)-~ ΤΓΤ-

• 、 可 I (Please read the notes on the back before filling out this page) 15 ^, "," · Teclophenone: and o · 574234 V. Description of the Invention (α-Trichloroacetophenone) and _ Tetrabutyl hydroxy hydroxy benzophenone sulfonate, '^ ^ 夂 axis such as 2. hydroxybenzophenone mesylate and 2,4-hydroxybenzophenone bis (mesylate) ). Other examples of suitable photoacid generators are: desertified triphenylsulfide, vaporized triphenylsulfide, triphenylsulfide iodide, triphenylsulfide hexafluorophosphate, triphenyl Thiohexafluoroarsinate, triphenylthiosulfan triflate, vaporized diphenylethylsulfanium, vaporized benzamidinemethyldimethylsulfanil, vaporized benzamidinemethyl Tetrahydrothiophene fluorene, 4-nitrobenzyl chloromethyltetrahydrothiophene fluorene, and vaporized 4-acryl-2_fluorenylphenylhexahydrothiosulfuranil. Photoacid generation suitable for use in the present invention Other examples of the agent are: bis (p-toluene xanthanyl) diazomethane, methylcontinyl p-tolylite xanthenyldiazomethane, 1-cyclo · hexylsulfonyl-1- (1,1-dimethyl Ethyl sulfonyl) diazomethane, bis (1,1- Methyl ethyl stilbene) diazomethane, bis (丨 -fluorenylethyl stilbene) diazomethane, bis (cyclohexyl difluorenyl) diazomethane, 1_p-toluene stilbene-1_cyclo Hexyl-Weiyldiazopyrene, 2-methyl-2- (p-toluenesulfenyl) phenylpropanyl I, 2-methythanthenyl-2-fluorenyl-4-methylthiophenylpropionamidine, 2 , 4-methyl-2_ (p-toluene luteinyl) pentan-3-one, 2-diazo-1-fluorenyl luteinyl-4-phenyl-2-butanone, 2- (cyclohexylcarbonyl)- 2- (p-toluenesulfonyl) propane, 丨 -cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl 2-butanone, 1-diazo-1- (1,1-dimethylethylsulfonyl) -3,3-dimethyl-2-butanone, 1-ethanyl-1- (1-methylethylsulfonyl) diazonium, 1-diazo-1- (p-toluenesulfonyl) -3,3-difluorenyl-2-butanone, 1-diethyl Amino-1-benzenesulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1- (p-fluorenylbenzenesulfonyl) -3 · methyl-2-butanone 、 Cyclohexyl 2-diazo-based 2- (Applicable to Chinese paper (CNS) A4 specification (210X297 public love) for this paper size (Please read first Note the surface to fill out this page)

574234 V. Description of the invention (i6)-methylbenzyl fluorenyl acetate, t-butyl 2-diazo group, 2-benzenesulfonyl acetate, isopropyldiazo group, 2-methylsulfonium Methyl acetate, cyclohexyldiazomethanesulfonyl acetate, t-butyl 2-diazo-2- (p-toluenesulfonyl) ester, 2-nitrobenzyl p-toluene Sulfonic acid vinegar, 2,6-dinitrobenzyl p-toluene phyllate, 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate. Other suitable examples of the light generating agent are hexafluorotetrabromo_bisphenol A, ^, butris (3,5 · 5 dibromo_4_hydroxyphenyl) ethane and n_ (2,4,6-tribromobenzene ) -N '-(p-tosylsulfonyl) urea. The photoacid generator compound is typically used in an amount of about 0.0001 to 20% by weight of the polymer solids, preferably about 1% to 10% by weight of the polymer solids. In another specific example, a base additive may be added to the photoresist composition. The purpose of the alkali additive is to remove protons existing in the photoresist before irradiation with actinic radiation. Alkali can prevent the attack of undesired acids and cut the action of acid-labile groups, thereby improving the performance and stability of the resist. The percentage of the base in the composition should be significantly lower than the percentage of the photoacid generator, because after the photoresist composition is irradiated, the intervention of the base to cut the acid-labile groups is undesirable. When present, a preferred range for the car base is about 3% to 50% by weight of the photoacid generator. Suitable examples of test additives are 2-fluorenimidazole, triisopropylamine, 4-difluorenylamino, 0-pyridine, 4,4'-diaminophenyl ether, 2,4,5-triphenyl Imidazole and 丨, 5-diazobicyclo [4.3_0] non-5-ene. A dye may be added to the photoresist to increase the absorbance of the composition for the wavelength of actinic radiation. The dye must not be toxic to the composition and must be resistant to process conditions, including any heat treatment. Examples of suitable dyes are (please read the notes on the back before filling this page) Order 丨 • 磬 574234 A7

V. Description of the invention (π) Goubenone, I derivative Silk perylene derivatives. Other specific dyes suitable for use in photoresists are described in U.S. Patent No. 5,593,812. The photoresist composition may further include conventional additives such as a tackifier and a surface active agent. Skilled artisans will be able to select the appropriate additives and their concentrations as desired. The present invention also relates to a method for forming a pattern on a substrate, which comprises the following method steps: applying a photoresist coating comprising one of the above-mentioned compositions on the substrate; The coating was exposed to actinic radiation; the coating was treated with an alkaline aqueous developer until the exposed area of the coating of Kota Shot was dissolved from the substrate, and a patterned photoresist structure was left on the substrate Floor. In order to produce a relief structure, the radiation-sensitive agent is exposed to actinic radiation in an imagewise manner. '' Photographic exposure, '' the term, also refers to exposure through a mask containing a predetermined pattern; by any suitable source of actinic radiation, such as moving one on the surface of a coated substrate Computer controlled laser beam) exposure; computer controlled electron beam exposure; and X-ray or ultraviolet light exposure through a corresponding mask. ~ Exposure in the manner described above generates an acid in the exposed area of the resist, which cuts off non-sexual groups to produce a water-soluble polymer. Typically, the chemical amplification type resist is subjected to a post-exposure heat treatment after the exposure in the image forming mode, which completes the reaction between the photoacid generator and the acid-labile group. After the exposure of the material into an image and any heat treatment, the surface layer is typically radiation-sensitive by dissolving in an aqueous developer and exposed to a resistive acid image.

(Please read the notes on the back before filling out this page) Order | 18 V. Description of the invention = 剂 = Γ. The choice of a particular developer depends on the type of photoresist. Developer; properties of polymer resins or photolysis products, or mixtures thereof. Particularly preferred is a 2 denier aqueous solution to which organic solvents have been added, including aqueous alkaline solutions for gold testing. For example, the aqueous solution of Te + Gepai hydroxide and carbonate, the water ^ tetramethyl group (more preferably tetramethyl oxychloride (⑽ 网)) The right is what you want, but also in these Soluble wetting agents and / or organic solvents. Radiation-sensitive resists that are used by humans in the above-mentioned two-layer method, typically 2 have stone ^ or include stone eve in the resist after development. Sensitivity. After patterning, the substrate is placed in an oxygen-containing electric paddle environment to remove the primer coating on the unprotected area. When exposed to oxygen plasma, The stone of the people contained in the resist will form the stone of the dioxide, and the resist is protected from the engraving effect, thereby forming a relief structure in the undercoat layer. After the oxygen plasma, it has a double-layer relief structure. The substrate is usually subjected to y further processing steps, which change the substrate located in an area not covered by the double-layer coating. Typically, this step may be implanting a dopant and depositing another substance on the substrate Or etching the substrate. After this step, the resist coating is usually removed from the substrate by fluorine / oxygen electrocuting. The previously mentioned copolymers containing biphenyl methacrylate (BPMA) and 2-hydroxyethyl methylpropionate (HEMA) are insoluble in large compatible with crystal edge scavenger (EBR) Part of the solvents and lithographic solvents (such as propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), etc.). The warp system of HEMA is 574234 A7 B7 V. Description of the invention (19) As a cross-linking functional group In the preferred terpolymer of the present invention, that is, biphenyl methacrylate (BPMA) and acetyl styrene (AcSt) (which is further subjected to methanol decomposition to become p-hydroxystyrene (HS )) And a terpolymer of ethylene glycol dicyclopentenyl methacrylate (EGDCPMA). The BPMA unit in the polymer helps to optimize the η and k values of the undercoat layer. In addition to its role in absorbance and etch resistance, the PHS unit has two functions. It provides functionality for cross-linking, and its utility is better than the hydroxyl functionality in HEMA. Furthermore, because of PHS The ethoxylated acetophenone precursor was copolymerized with BPMA in a random manner, which changed the polymer microstructure. BPMA block properties in the structure and improve the solubility of the polymer. The third monomer-an ester with at least one ether bond, which enhances the solubility of the polymer and increases the polymer's resistance to etching. The polymer system is Compatible with crystal edge scavenger (EBR) solvent. The present invention relates to a polymer composition containing a thermal cross-linking group which is highly soluble in all solvents compatible with crystal edge scavenger (EBR). The present invention A heat-curable polymer composition is provided, which is suitable as an undercoat for deep ultraviolet lithography. The undercoat polymer can be cured at a temperature below 220 ° C in less than about 2 minutes. The primer system is insoluble in the surface resist solvent system, and its etching rate is equivalent to that of phenolic resin. The primer can be adjusted by optimizing the composition to reduce the reflection effect of the pattern layer / primer interface. The refractive index (η and k) of the polymer composition of the layer, and the stains and feet can be completely removed by adjusting the crosslinking amount in the formulation. The invention is illustrated by, but not limited to, the following examples, parts and percentages of which are based on weight unless otherwise specified. This paper size applies to China National Standard (CNS) Α4 specification (210X297 mm) 22 (Please read the precautions on the back before filling this page)

574234 A7 __ B7_ V. Description of the invention (20) The general synthetic procedure for preparing the polymer of the present invention by polymerization in tetrahydrofuran is described below. Under a stream of nitrogen, in a round bottom flask equipped with a reflux condenser and a gas inlet, a mixture of monomer, initiator and chain transfer agent was dissolved in 150 g of tetrahydrofuran. The mixture was heated to 65 ° C with stirring and maintained at the same temperature for 20 hours under nitrogen. After that, the reaction mixture was cooled to room temperature, and an entire portion was subjected to gel permeation chromatography (GPC). The reaction mixture was diluted with 60 ml of methanol, and sodium methoxide (10% solution) in methanol was added thereto for methanolysis. The mixture was refluxed and the by-product acetic acid acetate was continuously removed by performing an azeotropic distillation for 4 hours and using a Dean-Stark interceptor. After cooling to room temperature, 20 g of Amberlyst 15 resin (ion exchange resin available from Rohm & Haas) was added to the mixture for ion exchange of sodium and stirring for 3 hours. The resin was filtered, and the solution was slowly poured into 4 liters of distilled water. The solid polymer was separated by filtration and redissolved in 300 ml of tetrahydrofuran. The polymer was precipitated in 2 liters of isopropanol. After filtration, the solid was dried under vacuum at 60 ° C for 24 hours. The general analysis procedure used is as follows. The molecular weight and molecular weight distribution were measured using liquid chromatography (refractive index detection, GPC V software Millennium) from Waters, which was equipped with the following P-10, 7.8 x 250 mm column: 10-4A, 500A and 50A (from Phenomena Company) and Tetrahydrooran extract. Thermal Decomposition Measurement (TGA) is based on Perkin-Elmer pyrolysis. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 23 (Please read the precautions on the back before filling in this (Page). # 574234 A7 __ B7___ V. Description of the invention (21) The quantity analyzer performs it. The glass transition temperature (Tg) of the polymer was measured using a Perkin-Elmer Pyris 1 differential scanning calorimeter with a heating rate of 1 (TC / minute). A Bruker 400 MHz NMR-spectrometer was used The structure and composition of the polymer were analyzed by 13C NMR. The first example polymer was based on the general procedure described above. The monomers [4-biphenylfluorenyl acrylate (72.37 g, 0.303 mole), and acetoxyl were used. Styrene (10.56 g, 0.055 mol) and ethylene glycol dicyclopentenyl ether methacrylate (17.07 g, 0.065 mol)], initiator VAZO 67 (6.00 g, 6.0% by weight relative to monomer) and a chain transfer agent 1-dodecanethiol (1.80g, 30% by weight relative to initiator) were polymerized. Transesterification was performed using 4.0 g of sodium methoxide solution. Yield : 91.3 g, 94%. Mw4 14,666; MW / MJ 1.92. With 35% weight loss at 310 °. Glass transition temperature (Tg) is 128 ° C. Polymer composition (mol%): 69% biphenyl Methacrylic acid ester units; 6% acetylene units; and 15% ethylene glycol dicyclopentenyl ether fluorenyl acrylate units. Two polymers were prepared according to the general procedure described above. The monomers [4-biphenyl methacrylate (62.74 g, 0.263 moles), ethoxylated styrene (42.23 g, moles), and ethylene glycol were used. Alcohol dicyclopentenyl ether methacrylate (230.3 g, 0.0087 mol)], initiator 28067 (6.00 g, 0.0% by weight relative to monomer) and chain transfer agent 1- A mixture of dodecanethiol (1.80 g, 30% by weight relative to the initiator) was polymerized. Transesterification was performed using 5-0 g of sodium alkoxide solution. Yield: 91_5 g, 95%. M413,715; The paper is 197. Thermal decomposition measurement (TGA): 5% weight loss at 305 ° C, glass transition temperature (Tg) is 124 This paper is applicable to China National Standard (CNS) A4 specification (210X297 mm) 24 (Please Read the notes on the back before filling this page) • Order · 豢 | 574234 A7 __ B7_ V. Description of the invention (22) ° c. Polymer: Composition (mole%): 60% biphenyl methacrylate unit 19% hydroxystyrene units; and 21% ethylene glycol dicyclopentenyl ether methacrylate units. The third example polymer follows the general procedure described above The monomer [4-biphenyl methacrylate (54.09 g '0.227 mole), ethoxylated styrene (22.09 g, 0.136 mole) and ethylene glycol dicyclopentenyl ether methacrylate (23.82 g, 0.09 mole)], initiator \ ^ \ 20 67 (6.00 g, 6.0 weight 0 / 〇 relative to the monomer) and chain transfer agent 1-dodecanethiol (1.8 G, 30% by weight relative to the initiator) was polymerized. For transesterification, 6.0 g of sodium methoxide solution was used. Yield: 85.5 grams, 91%. 1 is 11,262 / 1.88; Mw / Mn is 1.88. Thermal decomposition test (TGA): 5% weight loss at 300 ° C, glass transition temperature (Tg) is 118 ° C. Polymer composition (Mole: 51% biphenylfluorenyl acrylate units; 28% warp-styrene units; and 21% ethylene glycol dicyclopentenyl ether methacrylate units. The fourth example polymer was Under a stream of nitrogen, in a 500 ml round bottom flask equipped with a reflux condenser and a gas inlet, the monomer [4-biphenylfluorenyl acrylate (BPMA) (37.74 g, 0.158 mol), acetamidine Styrene (8.54 g, 0.0527 mole) and ethylene glycol dicyclopentenyl ether methacrylate (1382 g, 0.0527 mole)] and chain transfer agent dodecanethiol (108 g , 30% by weight of the initiator) was dissolved in 836 g of propylene glycol monofluorenyl ether acetate (PGMEA) (40% solids). The mixture was heated to 70 π. Then, in 15 minutes Slowly add 6.4 grams of this paper to the reaction mixture. Applicable Chinese National Standard (CNS) A4 specification (210X297). -25-(Please read the precautions on the back before filling this page). Τ 574234 A7 ___B7 V. Description of the Invention (23) (Please read the notes on the back before filling this page) VAZ0 67® in PGMEA [ Based on the initiator, Dupont's product, 2,2-Azo- (2-methylbutane)] (3.6 grams, 6% by weight of the monomer used) 'and interference under nitrogen Stir for 24 hours. Use a UV detector set at 254 nm to detect the disappearance of BPMA by GPC. After 24 hours, the BPMA is less than 0.1%. The reaction mixture is cooled to room temperature. Then added to the flask 2.0 g of sodium methoxide (10% solution) in methanol and $ 0 ml of methanol. The reaction mixture was refluxed for 3 hours, and azeotropic using a Dean-Stark interceptor. About 25 ml of methanol was removed by distillation. The solution was cooled to room temperature 'and 10.0 g of Amberlyst 15 resin was added. The reaction mixture was stirred for 2 hours, and the resin was separated by filtration. Under vacuum and below 60 C At the temperature, the solution was distilled with half the volume left to remove methanol and propylene glycol methyl by-product. Finally, a 30% by weight solid solution was prepared by adding PGMEA to it. It was 15,700; Mw / Mn was 1.95 ; And polymer composition (mol%): 59% biphenyl methyl acrylate Units: 20% styrene-based units; and 21% ethylene glycol dicyclopentenyl ether fluorenyl acrylate units. Example 5: A polymer under a nitrogen stream is equipped with a reflux condenser and a gas inlet. In a 500-ml round-bottomed flask, the monomers [4-biphenylmethacrylate (BPMA) (37.74 g, 0.158 mol), ethoxylated styrene (8.54 g, 0.0527 mol), and ethylene glycol Dicyclopentenyl ether methacrylate (1382 g, 0.0527 mole)] and a chain transfer agent (dodecanethiol (2008 g, 30% by weight of initiator)), dissolved in 83.6 g of propylene glycol Monomethyl ether acetate (PGMEA) (40% solids). Heat the mixture to 7 (rc. Then, this paper size applies Chinese National Standard (CNS) A4 specifications) -26-574234 A7 ___B7_ V. Description of the invention (24) Add slowly to the reaction mixture in 15 minutes VAZ0 67® [Free radical initiator, Dupont's product '2, 2, Azobis (2-methylbutane)] in 6.4 grams of PGMEA (3.6 grams, 6 weight percent of monomer used) . Then, the temperature was gradually increased to 80 ° C and stirred under nitrogen for 4 hours. The UV detector set at 254 nm was used to detect the disappearance of BPMA by GPC. After 3 hours, the BPMA was less than 0.10 / 0. The mixture was cooled to room temperature. 20 g of sodium methoxide (10% solution) in methanol and 50 ml of methanol were then added to the flask. The reaction mixture was refluxed for 3 hours, and about 25 ml of methanol was removed by co-evaporation using a Dean-Stark interceptor. The solution was cooled to room temperature, and 100% was added. Grams of Amberlyst 15 resin. The reaction mixture was stirred for 2 hours, and the resin was separated by filtration. Under vacuum and below 60 ° C., the solution was distilled at half the volume to remove methanol and by-products. Propylene glycol fluorenyl ether. Finally, a 30% by weight solid matter solution was prepared by adding PGMEA to it .... 11,044; Mw / Mn was 2.11; and polymer composition (mole%): 60% Biphenyl methacrylate units; 19/0 hydroxystyrene units; and 21% ethylene glycol dicyclopentyl succinic acid methyl hydrazine units. In the following examples, the following polymers were prepared: Undercoating Formulation: The first undercoating layer is 14.02g of the first polymer, 4.0g] \ 4 \ ^ 1001 ^ (melamine conjugate parent agent 'from Sanwa Chemical Co., Ltd., Kanazawa, Japan) solution ( 20% by weight solution in propylene glycol monofluorenyl ether acetate (PGMEA) and 1 to 875 grams Hexyl benzene sulfonate thermal acid generator solution (20% by weight solution in PGMEA) was mixed and dissolved in 80. 丨 grams of propylene glycol monomethyl ether acetate. This paper applies Chinese National Standard (CNS) A4 specifications ( 21〇χ297mm) 27 (Please read the notes on the back before filling this page):? Τ— Mongolia, 574234 A7 ____B7_ 5. In the description of the invention (25) (PGMEA), 100 grams of undercoating was obtained. Solution (total 15% by weight solids). The mixture (Polymer / Crosslinker / TAG II 93.5 / 4.0 / 2.5%) was rolled overnight, and the basecoat solution was filtered through a 0.1 micron Teflon filter II Times 0 The second example of the undercoat layer is 14.02 grams of the second polymer, 4.0 grams of a MW100LM crosslinker solution (a 20% by weight solution in PGMEA) and 1.875 grams of a cyclohexyltoluene sulfonated thermal acid generator solution (located in PGMEA 20% by weight of the solution) was mixed and dissolved in 80.1 g of propylene glycol monofluorenyl ether acetate (PGMEA) to obtain 100 g of an undercoating solution (a total of 15% by weight of solids). This mixture (polymer /Crosslinker/TAG=93.5/4.0/2.5%) rolling overnight, and the base coating solution Filtered through a 0.1 micron Teflon filter twice. The third undercoat layer contained 14.02 grams of the third polymer, 4.0 grams of the MW100LM crosslinker solution (a 20% by weight solution in PGMEA), and 1.875 grams of cyclohexyl toluene. The sulfonated hot acid generator solution (20% by weight solution in PGMEA) was mixed and dissolved in 80.1 g of propylene glycol monofluorenyl ether acetate (PGMEA) to obtain 100 g of an undercoating solution (total .15 weight % Solids). The mixture (polymer / crosslinker / TAG 2 93.5 / 4.0 / 2.5%) was rolled overnight, and the undercoat solution was filtered through a 0.1 micron Teflon filter twice. The fourth example of the undercoat layer was 46.75 grams of the fourth polymer, 4.0 grams of a MW100LM crosslinker solution (a 20% by weight solution in PGMEA), and 1.875 grams of a cyclohexylmethanite yellowing thermal acid generator solution (in PGMEA). 20% by weight solution) The size of the mixed paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -28-(Please read the precautions on the back before filling this page)-· Order-574234 A7 B7 V. Description of the invention (26) is combined and dissolved in 47.4 g of propylene glycol monomethyl ether acetate (PGMEA) to obtain 100 g of an undercoating solution (15 wt% solids in total). The mixture (polymer / crosslinker / TAG = 93.5 / 4.0 / 2.5%) was rolled overnight, and the primer solution was filtered through a 0.1 micron Teflon filter twice. The fifth example of the undercoat layer was 46.75 grams of the fifth polymer, 4.0 grams of a MW100LM crosslinker solution (a 20% by weight solution in PGMEA), and 1.875 grams of a cyclohexyl toluene sulfonate thermal acid generator solution (in a PGMEA solution). 20 wt% solution) was mixed and dissolved in 47.4 g of propylene glycol monomethyl ether acetate (PGMEA) to obtain 100 g of an undercoating solution (total 15 wt% solids). The mixture (polymer / crosslinker / TAG = 93.5 / 4.0 / 2.5%) was rolled overnight, and the primer solution was filtered twice through a 0.1 micron Teflon filter. The sixth example of the undercoat layer is 14.33 g of the polymer of the first example, 2.0 g of 1 ^ 1001 ^^ 4 crosslinker solution (a 20% by weight solution in PGMEA), and 1.875 g of cyclohexyltoluene sulfonate thermal acid generator. The solution (a 20% by weight solution in PGMEA) was mixed and dissolved in 81.8 grams of propylene glycol monomethyl ether acetate (PGMEA) to obtain 100 grams of an undercoating solution (total, 15% by weight solids). The mixture (polymer / crosslinker / TAG = 95.5 / 2.0 / 2.5%) was rolled overnight, and the primer solution was filtered through a 0.1 micron Teflon filter twice. The seventh example of the undercoat layer is 14.18 g of the first example polymer, 3.0 g of a MW100LM crosslinker solution (a 20% by weight solution in PGMEA), and 1.875 g of a cyclohexyltoluene xanthate thermal acid generator solution (in PGMEA). 20% by weight solution) mixed 29 (please read the precautions on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) 574234 A7 __ B7_ V. Description of the invention (27) And dissolved in 81.0 g of propylene glycol monofluorenyl ether acetate (PGMEA) to obtain 100 g of an undercoating solution (15 wt% solids in total). The mixture (polymer / crosslinker / TAG = 94.5 / 3.0 / 2.5%) was rolled overnight, and the undercoat solution was filtered through a 0.1 micron Teflon filter twice. The 8th undercoat layer will be 13.83g of the polymer of the 1st example, 6.0g] \ 4 ~ 1001 ^] ^ crosslinker solution (20% by weight solution in PGMEA) and 1.875g of cyclohexyltoluene xanthophyll acid. The generator solution (20% by weight solution in PGMEA) was mixed and dissolved in 78.4 g of propylene glycol monomethyl ether acetate (PGMEA) to obtain 100 g of an undercoating solution (total 15 weight% solids). The mixture (polymer / crosslinker / TAG = 91.5 / 6.0 / 2.5%) was rolled overnight, and the undercoat solution was filtered through a 0.1 micron Teflon filter twice. The ninth example undercoat layer produced 13.13 g of the first example polymer, 10.0 g] ^ 11 ^ 1001 ^] ^ crosslinker solution (20% by weight solution in PGMEA) and 1.875 g of cyclohexyltoluene sulfonated hot acid to generate The solvent solution (a 20% by weight solution in PGMEA) was mixed and dissolved in 75.0 g of propylene glycol monomethyl ether acetate (PGMEA) to obtain 100 g of an undercoating solution (total .15% by weight solids). The mixture (polymer / crosslinker / TAG = 87.5 / 10.0 / 2.5%) was rolled overnight, and the base coating solution was filtered through a 0.1 micron Teflon filter twice. In the tenth base coat, 14.02 g of the first polymer, 4.0 g of a Powderlink crosslinker solution (a 20% by weight solution in PGMEA), and 1.875 g of a cyclohexyl toluene sulfonate thermal acid generator solution (in a PGMEA) 20% by weight solution) The paper size of this paper applies Chinese National Standard (CNS) A4 specification (210X297 mm) 30 (Please read the precautions on the back before filling this page)-Order-, 0m, 574234 A7 _ B7___ V. Invention Explanation (28), and dissolving in 80_1 g of propylene glycol monomethyl ether acetate (PGMEA) to obtain 100 g of the undercoating solution (a total of 15% by weight of solids). The mixture (polymer / crosslinker / TAG = 93.5 / 4.0 / 2.5%) was rolled overnight, and the primer solution was filtered through a 0.1 micron Teflon filter twice. The 11th undercoat layer produced 14.10 g of the first polymer, 4.0 g of 4 ^^ 1001 ^ 1 ^ crosslinking agent solution (a 20% by weight solution in PGMEA), and 1.5 g of cyclohexyltoluene sulfonated hot acid. The agent solution (a 20% by weight solution in PGMEA) was mixed and dissolved in 80.4 g of propylene glycol monomethyl ether acetate (PGMEA) to obtain 100 g of an undercoating solution (a total of 15 weight% solids). The mixture (polymer / crosslinker / TAG = 94.0 / 4.0 / 2.0%) was rolled overnight, and the undercoat solution was filtered twice through a 0.1 micron Teflon filter. The twelfth example of the undercoat layer was 13.95 grams of the first example polymer, 4.0 grams of the MW100LM crosslinker solution (a 20% by weight solution in PGMEA) and 2.25 grams of a cyclohexyl toluene sulfonate thermal acid generator solution (located in PGMEA 20% by weight of the solution) were mixed and dissolved in 79.8 g of propylene glycol monofluorenyl ether acetate (PGMEA) to obtain 100 g of an undercoating solution (a total of 15% by weight of solids). The mixture (polymer / crosslinker / TAG = 93.0 / 4.0 / 3.0%) was rolled overnight, and the undercoat solution was filtered through a 0.1 micron Teflon filter twice. The thirteenth undercoat layer was 13.80 g of the first polymer, 4.0 g of a MW100LM crosslinker solution (a 20 wt.% Solution in PGMEA) and 3.0 g of a cyclohexyltoluene xanthate thermal acid generator solution (located 20% by weight solution in PGMEA), this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -31-(Please read the precautions on the back before filling this page) · Order — 574234 A7 B7 5 2. Description of the invention (29) and dissolving in 79_2 g of propylene glycol monomethyl ether acetate (PGMEA) to obtain 100 g of an undercoating solution (a total of 15% by weight of solids). The mixture (polymer / crosslinker / TAG = 93.0 / 4.0 / 4.0%) was rolled overnight, and the undercoat solution was filtered twice through a 0.1 micron Teflon filter. In the 14th undercoat layer, 13.65 g of the polymer of the 1st example, 4.0 g of the polymer solution (20% by weight of the solution in PGMEA), and 3.75 g of the cyclohexyltoluene sulfonated hot acid generator solution (20 wt% solution in PGMEA) was mixed and dissolved in 78.6 g of propylene glycol monofluorenyl ether acetate (PGMEA) to obtain 100 g of a base coat solution (total 15 wt% solids). The mixture (polymer / crosslinker / TAG = 91.0 / 4.0 / 5.0%) was rolled overnight, and the undercoat solution was filtered twice through a 0.1 micron Teflon filter. The general procedure for lithographic test primer coating formulations is as follows. An undercoat layer from an undercoating formulation was spin-coated on a stone wafer and baked at 205 ° C for 90 seconds to obtain a thin film of 0.50 micron thickness. A pattern layer (TIS2000, a chemically amplified double-layer resist from Arch Chemical Corporation (Norwalk, Connecticut, USA)) was spin-coated on the undercoat layer, and baked at 135 ° C for 1 minute, and A 0.25 micron thick film was obtained. The coated wafer is then imaged using an Ultratech 248 nm stepper. After exposure, the wafer was baked at 125 ° C for 1 minute and mixed and developed in 0.262 N aqueous tetramethylammonium hydroxide (TMAH) for 60 seconds. Wash the wafer with deionized water and spin dry. The pattern was analyzed by scanning electron microscopy (SEM). Images from the SEM show that the bilayer resist can resolve profiles as small as 0.13 microns. This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 32 (Please read the notes on the back before filling out this page)-, τ 574234 A7B7 V. Description of the invention (3Q) Composition of the invention 妁 TIS-2000 General lithographic properties of objects are: light speed range: 30 to 40 (mJ / cm2); resolution range: 0.120 to 0.130 (micrometers); and focal depth: 0.70 to 1.0 (0.130 micrometer contour). The lithography test results of this composition are shown in Table 1 below. Table 1: Summary of formula and pattern quality evaluation examples of basecoat formulations Polymer polymer (g) Crosslinking agent Crosslinking agent (g) 20wt ° / 〇 Solids Thermal acid generator (g) 20wt% solids PGMEA (g) Resolution separation line (0.13 microns) Photoresist / undercoating (DL / UL) Interface quality 1 Polymer 1 14.02 MW100 LM 4.0 1.875 80.1 No footing at the IL / UL interface 2 Polymer 2 14.02 MW100 LM 4.0 1.875 80.1 No feet on the IL / UL interface 3 polymer 3 14.02 MW100 LM 4.0 1.875 80.1 Fouling on the EL / UL interface 4 polymer 4 14.02 MW100 LM 4.0 1.875 80.1 No feet on the EL / UL interface 5 polymer 5 14.02 MW100 LM 4.0 1.875 80.1 No feet on IL / UL interface 6 Polymer 1 14.3 MW100 LM 2.0 1.875 81.8 Line pattern collapse 7 Polymer 1 14.18 MW100 LM 3.0 1.875 81.0 Foot 8 Polymer 1 13.83 MW100 · LM 6.0 1.875 78.4 No feet on IL / UL interface 9 Polymer 1 13.13 MW100 LM 10.0 1.875 75.0 Feet 10 polymer 1 14.02 Powder-link 4.0 1.875 80.1 No feet on IL / UL interface 11 Polymer 1 14.10 MW 100 LM 4.0 1.5 80.4 No footing on the IL / UL interface 12 Aggregation 1 13.95 MW 100 LM 4.0 2.5 79.8 No feet on the IL / UL interface 13 Polymer 1 13.80 MW100 LM 4.0 3.0 79.2 No feet on the IL / UL interface 14 Polymer 1 13.65 MW 100 LM 4.0 3.75 78.6 T-top 33 ( Please read the notes on the back before filling this page.) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 574234 A7 ____B7 _ V. Description of the invention (31) Scanning electron microscopy (SEM) The results show that the photoresist / primer interface of the formulation with a high cross-linking site (hydroxystyrene) polymer has stains or feet. Similarly, SEM results show that in the case of a low concentration of melamine crosslinker, the line pattern collapses, which may be due to the insufficient curing effect of the undercoat layer, which may result in the photoresist / undercoat layer interface. Blending phenomenon. With a high concentration of the cross-linking agent, the formation of floating stains and the outline of the feet were observed. Although the present invention is described herein with reference to specific examples, it should be understood that modifications, improvements, and changes can be made without departing from the spirit and scope of the inventive concept disclosed herein. Therefore, it is intended to cover all such modifications, improvements and changes which fall within the spirit and scope of the scope of the appended patent applications. Track (Please read the notes on the back before filling this page), \ 二 口 ^ 0

Claims (1)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 574234-- I m 4 ^ 25 Supplement No. VI. Patent Application No. 9H04609 Patent Application Application No. Patent Scope Amendment April 25, 1992 1. A hydroxyl-containing polymer including units 111, 11, and 0 having the following chemical formula: R 'R · 〇 十 R4〇4rR: where R1 is selected from the group consisting of hydrogen or fluorenyl; 112 is a monovalent group such that the monomer unit with the subscript m is selected from substituted or unsubstituted CVCu aryl A group consisting of an acrylate group and a (: 6 _ (: 14arylmethylpropionate) group, wherein the substituent is selected from the group consisting of phenyl, Cl_4 alkyl, or ^^ alkyl; R3 is a Monovalent groups such that the monomer units with the subscript η are selected from the group consisting of: CrCs alkyl acrylates functionalized with fluorenyl groups, fluorenyl acrylates, and c6_Cl4 aryl groups; R4 is a CVCio straight chain or branched alkylene group; p is an integer of 1 to 5, the limitation is: the number of carbon atoms in [-R40-] p does not exceed 30; R5 is selected from the group consisting of: Ci -Cio linear, branched or cyclic fluorenyl, substituted or unsubstituted <: 6-(: 14 aryl and substituted or unsubstituted (: 7-(: 15 alicyclic hydrocarbons); and m It is 40 to 70, η is 15 to 35, and 0 is 15 to 25. 2. The polymer according to item 丨 of the patent application range, wherein the monomer unit having the subscript m is biphenyl acrylate or fluorenyl C The acrylate unit, R5 is dicyclopentenyl. And the note for reading Ιΐ • Order # This paper size is applicable to China National Standard (CNS) A4 specification (21 × 297 mm) 35 574234, applying for patent scope 3. The polymer according to item 丨 of the patent application, wherein the monomer unit having the subscript n is a hydroxystyrene unit, and R5 is a dicyclopentenyl group. 4. The polymer according to the oldest application of the patent application. ^ The monomer unit with the subscript 系 is an otor phenyl acrylate or methacrylic acid vinegar unit; the monomer unit with the subscript η is a hydroxystyrene unit; and the monomer with the subscript 0 Single 7L is ethylene glycol dicyclopentenyl acrylate or fluorenyl acrylate unit. 5. The polymer of item 4 of the patent application, wherein the monomer unit with a subscript 0 is ethylene glycol di Cyclopentenyl methacrylate unit, the monomer unit with the subscript m is a biphenyl methacrylate unit. • Order 6. If the polymer of item 4 of the patent application scope, it has from 10,000 to 24 , 〇〇〇 number average molecular weight. 7 · — A thermosetting polymer composition comprising a hydroxyl-containing polymer, an amine-based cross-linking agent, and a thermal acid generator, wherein the hydroxyl-containing polymer comprises one of m, η, and 0 units having the following chemical formula: ··· R · R * R1 OtR O ^ rR 'Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs where R1 is selected from the group consisting of hydrogen or methyl; R2 is a monovalent group, and the monomer unit with the subscript m is selected from the substituted Or an unsubstituted C6-Cu aryl acrylate group and (: 6- (: 14 aryl methacrylate group), wherein the substituent is selected from phenyl, Ch4 alkyl, or Cl- 4 This paper size is applicable to China National Standard (CNS) A4 (21 × 297 mm) 574234 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs R3 group-monovalent group with subscript 仏 monomer unit is selected from the group consisting of: Ci_c8 alkyl acrylate functionalized with hydroxy, methacrylate and C6_Cm aryl ; R4 is always ^ or branched alkylene; p is an integer of 1 to 5, the restrictions are: the number of carbon atoms in [-ν〇-] ρ does not exceed 30; R5 is selected from the group consisting of the following groups Group ·· Linear, branched or cyclic alkyl, substituted or unsubstituted CO-CM aryl, and substituted or unsubstituted alicyclic smoke; and m is 40 to 70, and η is 15 To 35, and 0 to 15 to 25. 8. The composition according to item 7 of the scope of patent application, wherein the monomer unit having a subscript is a biphenylacrylate or methacrylate unit, and R5 is a dicyclopentenyl group. 9. The composition according to item 7 in the scope of the patent application, wherein the monomer unit having the subscript n is a phenylethene unit and R5 is a dicyclopentyl group. 10. The composition according to item 9 in the scope of the patent application, wherein the monomer unit with a subscript claw is a biphenyl acrylate or methacrylate unit; the early body unit with a "η" Diluted units; and monomer units with a subscript 0 are ethylene glycol dicyclopentenyl acrylate or methacrylate units. 11 · The composition according to item 9 of the scope of patent application, wherein the subunit with a subscript 0 The monomer unit is an ethylene glycol dicyclopentyl methacrylate unit, and the monomer unit having the subscript m is a biphenylmethylpropionate unit. 12. As described in item 5 of the scope of patent application The composition, wherein the warp-containing polymer has a molecular weight from 10,000 to 24,000. 13. —A kind of coated substrate with photolithographic sensitivity, including: The paper size is applicable to Chinese National Standard (CNS) A4 specifications (2〗 0 X 297 mm) 574234 A8 B8 C8 Scope of patent application: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (a)-substrate; (b) a heat-curing primer coating on the substrate; and (c) a mold coating on the primer coating Radiation-sensitive resist surface coating 'wherein the heat-curing primer layer includes a heat-curing composition, which includes a hydroxyl-containing polymer, an amine-based crosslinking agent, and a thermal acid generator, and the hydroxyl-containing The polymer system includes a polymer having one of m, η, and 0 units of the following chemical formula: Wherein R1 is selected from the group consisting of hydrogen or methyl; r2 is a monovalent group 'monomer unit with a subscript m is selected from substituted or unsubstituted aryl acrylate and c6-C14 aromatic A group consisting of a methyl acrylate group, wherein the substituent is selected from the group consisting of phenyl, Cl_4 alkyl, or Cl_4 alkoxy; R3 is a monovalent group, and the monomer unit having the subscript n is selected from the following Groups composed of groups · · hydroxyl-functionalized (^-(: 8 alkyl acrylate, methacrylate and c6_Cl4 aryl groups; R4 is a Ci-Cio linear or branched alkylene group; p is an integer from 1 to 5, and its limiting conditions are: [-R40-] p * has a carbon number of not more than 30; R5 is selected from the group consisting of Ci-Cio straight bonds, branches, or rings Lithium group, substituted or unsubstituted C ^ -Ci4 aryl group, and substituted or unsubstituted c7_c15 alicyclic hydrocarbon; and m is 40 to 70, η is 15 to 35, and 0 is 15 to 25. The scale is applicable to the Zhongguanjia Standard (CNS) A4 specification ⑵G χ 297 public love) —: ---: -------- install --------- T --- τ I-- --- (Please read the notes on the back before filling out this page) 38 574234 Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau & 8 C8 ~ ^ ----D8____, the scope of application for patents 14. If coated substrates for the scope of the patent application No. 13, among which the single unit with subscript melon It is biphenylpropionic acid or methyl-acid acetate 70, and R5 is dicyclopentenyl. 15. The coated substrate according to item 13 of the patent application scope, wherein the The monomer unit is a monohydroxystyrene unit, and R5 is a dicyclopentenyl group. 16. The coated substrate according to item 13 of the application, wherein the monomer unit having the subscript 111 is biphenylacrylic acid An ester or methacrylate unit; the monomer unit having a subscript η is a hydroxystyrene unit; and the monomer unit having a subscript 0 is an ethylene glycol dicyclopentenyl acrylate or a fluorenyl acrylate unit. 17. The coated substrate according to item 16 of the application, wherein the monomer unit with a subscript 0 is a glycol dicyclopentenyl methacrylate unit, and the monomer with a subscript m The unit is a biphenyl methacrylate unit. A coated substrate, wherein the hydroxyl-containing polymer has a number average molecular weight from 10,000 to 24,000. 19. A method of manufacturing a relief structure, the steps comprising: (a) forming a coated substrate, wherein the coated substrate The cover substrate includes: (1) a substrate, (2) a thermally-cured primer coating on the substrate, and (3) a radiation-sensitive resist surface coating on the primer. The heat-curing primer layer includes a heat-curing composition including a hydroxyl-containing polymer, an amine-based cross-linking agent, and a thermal acid generator, and the hydroxyl-containing polymer includes m having the following chemical formula: One of the units of η and 〇 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 public love) 39 „-------- ^ --- 7 —----- (please first Read the notes on the back and fill out this page) -A. 574234 A8 B8 C8 D8 Printed and patented by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Polymers: R, R * R 丨 Where R1 is selected from the group consisting of hydrogen or methyl; R2 is a monovalent group, and the monomer unit with the subscript m is selected from substituted or unsubstituted C6-C14 aryl acrylate groups and C6 -A group consisting of -C14 arylfluorenyl acrylate, wherein the substituent is selected from phenyl, Cm alkyl or Cm alkoxy; R3 is a monovalent group, a monomer unit having a subscript η Selected from the group consisting of: hydroxyl-functionalized (^-(: 8 alkyl acrylate, methacrylate, and C6-C14 aryl groups; R4 is a Cl_Cl〇 linear or branched alkylene P is an integer from 1 to 5, with the following restrictions: [-R40-] pt The number of carbon atoms does not exceed 30; R5 is selected from the group consisting of: CrCio linear, branched or cyclic Group, substituted or unsubstituted C6_Ci4 square group, and substituted or unsubstituted c7_c 1 $ alicyclic hydrocarbon; and m is 40 to 70, η is 15 to 35, and 0 is 15 to 25. (b) The radiation-sensitive topcoat is imagewise exposed to actinic radiation; and (c) a resist pattern is formed by developing the radiation-sensitive topcoat with a developer 20. The method according to item 19 of the scope of patent application, wherein the monomer unit with a subscript claw is a biphenyl acrylate or a fluorenyl acrylate unit, and the r5 ^ paper size applies the Chinese National Standard (CNS) A4 specification (21〇X 297 male • — " --- ^ ---------------- Order --- Γ ------ (Please read the precautions on the back before (Fill in this page) The C8 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ ---- D8__, the scope of patent application ~~ ^ --- is a dicyclopentenyl. Wherein, the monomer unit with subscript n-dibenzylene m5 is dicyclopentenyl. 仏 For example, the method in the scope of patent application No. 19, wherein the monomer unit with subscript m is biphenyl. Cyl ^ allyl units; the monomer units with subscript η are hydroxystyrene units; and the monomer units with subscript 0 are ethylene glycol dicyclopentenyl acrylate or methacrylate units 23. The method according to item 22 of the scope of patent application, wherein the monomer unit with a subscript 0 is a monoethylene glycol dicyclopentenyl methacrylate monoester The subscript m has the biphenyl-based monomer units of acrylic ester units Yue-yl. ί — L -------, ¾ (Please read the notes on the back before filling out this page) Order —— 24 · If the method of applying for the scope of patent No. 22, the hydroxyl-containing polymer has from 10,000 to Number average molecular weight of 24,000. -«^ 1 ϋ 1 ^^ — This paper size applies to China National Standard (CNS) A4 (2〗 〇 χ 297 mm)