TW502134B - Chemically amplified resist compositions and process for the formation of resist patterns - Google Patents

Abstract

Alkali-developable, chemically amplified resist composition which comprises an alkali-insoluble compound having a structural unit containing a protected alkali-soluble group in which unit a protective moiety of said protected alkali-soluble group contains an alicyclic hydrocarbon group having bonded to a carbon atom thereof a -CH2-R1 group wherein R1 is methyl, ethyl, propyl or isopropyl, and said alkali-soluble group is cleaved upon action of an acid generated from a photoacid generator used in combination with said compound, thereby releasing said protective moiety from the alkali-soluble group and j converting said compound to an alkali-soluble one, and a photoacid generator capable of being decomposed upon exposure to a patterning radiation to thereby produce an acid capable of causing cleavage of said protective moiety. The resist composition can exhibit a high sensitivity (not more than 5 mJ/cm<SP>2</SP>) and therefore is particularly suitable for ArF lithography and also can exhibit stable patterning properties.

Description

502134 A7 B7 V. Description of the invention (1) · Background of the present invention 1. Field of the present invention The present invention relates to a chemically amplified photoresist composition and a method for forming a photoresist pattern using the composition. More specifically, the present invention relates to a photoresist composition, which can exhibit higher resolution, higher sensitivity, and excellent resistance to dry etching. The photoresist composition of the present invention has high sensitivity and stable pattern formation properties which are particularly required in the field of ArF lithography technology. Therefore, the present invention can be effectively used to manufacture semiconductor elements such as LSIs, VLSIs, ULSIs, and other elements by a lithography technique. 2. Description of related technologies Recently, in the fabrication of semiconductor integrated circuits, the degree of integration has increased significantly, and accordingly LSIs and VLSIs have been manufactured on a commercial scale. The lowest line widths of circuit patterns on these components are on the order of sub-micron or quarter-micron. In other words, when manufacturing these high-performance components, it is necessary to provide a reliable microfabrication technology. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs in the field of lithography technology, to meet the above requirements, ultraviolet (UV) radiation as an exposure light source such as g-line (wavelength 436nm) and i-line (wavelength 365 nm), nm The method of shifting micrometers to shorter wavelengths in the far-ultraviolet or deep-ultraviolet region has been proposed, and a new type of exposure element equipped with a light source capable of emitting such a short-wavelength in the deep-ultraviolet region has also been studied. Recently, lithography technology using 248nm wavelength KirF excimer laser and 193nm argon fluoride (ArF) excimer laser as exposure light source has been valued as a newly developed exposure technology, and it is also a new development Is suitable for 4 (Please read the notes on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 502134 A7 B7 V. Description of the invention (2) Exposure to such a short wavelength Photoresist material, a chemical amplification system and a photoresist material, a chemical amplification photoresist composition based on this system, have been proposed by Ito et al. Of IBM Corporation for KrF lithography technology (see J.M. Proc. Microcircuit Eng., Firechet et al., 260 (1982); Digest of Technical Papers of 1982 Symposium on VLSI Technology, 86 (1983) by Ito et al .; "Polymers in Electronics" by H. Ito et al. "5 ACS Symposium Series 242, edited by T. Davidson, ACS 11 (1984); and U.S. Patent No. 4,491,628. Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Using this fine manufacturing technology, the fine photoresist pattern is generally formed, and can be selectively selected on its surface. A thin layer or coating to be manufactured, such as an etched thin layer, is coated with a chemically amplified photoresist substance, and the photoresist coating is exposed to image-forming radiation to form an image relative to the radiation Potential image. The potential image of this photoresist coating is then developed by a suitable developer. And get the desired photoresist pattern. This photoresist pattern can be effectively used as a masking tool for the subsequent etching steps to selectively etch the underlying thin layer. The pattern-forming radiation generally includes ultraviolet radiation such as g-line (wavelength 436nm) and i-line (wavelength 365nm). However, as briefly mentioned in the previous paragraph, it can also include other radiation with shorter wavelengths, such as deep ultraviolet radiation, Vacuum ultraviolet radiation, electron beam, X-rays, and excimer lasers such as KrF lasers at 248 nm and ArF lasers at 193 nm. Note that the word "radiation" is used here to mean all the radiations mentioned earlier. When the pattern-forming radiation used to form a submicron photoresist pattern is located in the far ultraviolet or vacuum ultraviolet range, a specific photoresist material must be used. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm). Excellent transparency for pattern-forming radiation, and high resistance to dry finishes. The inventor of this application has studied this property and found that the demand can be irradiated by &amp; a polymer or copolymer containing a dienoate and an I-substituted arsenic acid backbone with a diamond-based backbone at the base. Satisfied by inductive substances (see Japanese Emperor Guihuang Huang '39665). However, the photoresist material described by the inventor suffers from a serious problem. Because the photoresist material has strong hydrophobic properties, when the exposed photoresist material is to be revealed ... Phase agents cannot be used. This problem is thought to be due to the strong hydrophobic nature of the adamantyl skeleton in the photoresist structure, which inhibits the photoresist substance from dissolving in the alkaline phase developer. In order to solve this problem, due to enthusiastic research, the inventor discovered a new pattern formation method, which is described in the description of I &quot; June 5th M Application Day, Taibei Tufeng Liaoning AZ-162287 . This pattern generation method is characterized in that it contains an alicyclic hydrocarbon with adamantane or its derivative based on the ester-based site of the polymer or homopolymer that constitutes the radiation-sensitive photoresist substance, but this will inhibit the alkaline phase The alicyclic hydrocarbon group used in the agent is removed from the photoresist in the next step. In practice, using this pattern formation method can use an alkaline developer in the development process, and in addition, it can reduce other problems, such as the formation of cracks during the development process or the pattern falling off. In summary, the chemically amplified photoresist materials and methods of patterning invented by the present inventors recently provide satisfactory results, such as high transparency to various radiations, especially short-wavelength radiation including KrF and ArF excimer lasers, and Excellent resistance to dry etching. Furthermore, they are printed by 502134 A7 B7, the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (4) Use of general-purpose phase developer. However, these chemically amplified photoresist substances still have questions about sensitivity. That is, when the excimer laser is used as the exposure source of the photoresist process, especially when using ArF lithography technology, due to the durability of the lens material in the laser device, the photoresist material must have high sensitivity, in other words In other words, the threshold energy Eth of the exposure amount must be 5 mJ / cm2 or lower. Until now, no chemically amplified photoresist capable of meeting the aforementioned threshold energy Eth requirements has been proposed. SUMMARY OF THE INVENTION One object of the present invention is to provide a new type of chemically amplified photoresist composition, which has high transparency to various kinds of radiation including excimer laser light, and can form a fine photoresist with excellent resistance to dry etching. Patterns, and sensitivity of special rounds. Another object of the present invention is to provide an improved method for forming a photoresist pattern using the photoresist composition of the present invention ^ Other objects of the present invention can be recognized from the description related to the embodiments below. According to one of the features, the present invention provides a photoresist pattern that can be formed by using a chemically amplified photoresist composition with a visible phase, which comprises: I. An alkali-insoluble compound, which has a structural unit, this unit Contains-Protected and soluble in the test group. In this unit, the protected "soluble" group in the test group is produced by the photoacid generator used with the compound. The acid group will break off, so the protective "group," is released from the soluble group, (Please read the precautions on the back before filling this page).

, 1T

502134 A7 V. Description of the invention (shown to become soluble in alkali, the alkali-soluble group is protected by an alicyclic hydrocarbon "group" containing the following chemical formula. (Please read the precautions on the back before reading (Fill in this page) The "alicyclic hydrocarbon group" group is represented by the following formula ⑴ ... Z where I may be substituted or unsubstituted methyl, ethyl, propyl or isopropyl, and z represents Together with the carbon atom bonded to _CH2_Ri, the atom required to complete the alicyclic hydrocarbon group; and

The 1T II · mono photoacid generator can decompose when exposed to pattern-forming radiation, and generates an acid that can break the protective group. According to another feature of the present invention, the present invention provides a method for forming a photoresist pattern, which comprises these steps. The chemically amplified photoresist composition of the present invention is coated on a substrate to be manufactured to form thereon. Photoresist coating; selectively exposing the photoresist coating to radiation that causes the photoacid generator to produce an acid pattern; printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs; heating the exposed photoresist coating To the temperature at which the protective "group" can break; and the use of a basic phase developer to reveal a latent image on the exposed and heated photoresist coating. According to the present invention, since the The chemically amplified photoresist composition of the "group" represented by) becomes Arp

5. Description of the invention (6) High sensitivity (less than 5niJ / Cm2) required for lithography technology and stable pattern formation properties. In addition to these advantages, according to the present invention, if the photoresist composition is combined with a specific photophase solution, such as an aqueous solution or an alcohol solution of a specific ammonium or morphine compound, the compatibility of the photophase composition with the photoresist composition can be controlled. And the solubility of the composition in the phase developer, and alleviate the stress generated in the photoresist composition during the development process, thereby reducing cracks and peeling of the photoresist pattern. Furthermore, since the exposed edges can expand, a fine photoresist pattern can be formed stably. Brief description of the graphs. The first graph is an infrared absorption spectrum showing the change of the chemical photoresist composition according to the present invention with the exposure; and the second graph is a graph showing various 2-alkyl-2-AdMA homopolymers with different ArF. Shrinkage of exposure. DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a chemically amplified photoresist composition. As described above, it includes:

Employees 'Cooperative Cooperative Seal II of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) I. An acid-sensing compound with a structural unit containing an alkali-soluble group' This group is a The former chemical formula is protected by a group containing an alicyclic carbofluorenyl group. The base-soluble group in this structural unit is cut off when subjected to an acid, thereby making the compound soluble in the test; and II A photoacid generator (PAG) can generate acid after pattern formation exposure. In the aforementioned chemical formula (I), K must be methyl, ethyl, propyl, or isopropyl, and a substituted group may be used if desired. When 1 in the chemical formula ⑴ is a hydrogen atom, the ideal high sensitivity cannot be obtained, although other properties of this paper are applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 502134 A7 B7 V. Description of the invention (may Satisfactory results were obtained. As will be further clarified in the following explanation, the present invention is particularly complete due to the improvement of the 1 substituent of the protecting group in the group containing an alicyclic hydrocarbon group. In the photoresist composition according to the present invention, as the main component of the acid-sensing and film-forming compound, the protected soluble group is located in its structural unit, preferably on the side sister. It can be thrown if appropriate. Examples of soluble test groups that form protected test groups include ortho groups, acid groups, amino groups, amino groups, and imino groups, but they are not limited to the above examples. The alkali-soluble group needs to be protected at first to prevent the film-forming compound from dissolving in the alkaline phase developer, and as the protective "group" of the test group, it is preferable to contain an alicyclic group. Hydrocarbon-based " The most protected, base-soluble groups are the carboxylic acid groups represented by the following chemical formula (11). Ϋ tm ....... I I ...... ........ I ......... 1 ....... `` in (Please read the notes on the back and fill in this page)

Order I I 0 Λ ch 2 -r%… (2) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Its center and Z are as defined above. The alicyclic hydrocarbon group to be contained in the soluble base group contains many groups that are familiar in the field of chemistry, and may be substituted if desired. Preferably, these alicyclic hydrocarbons, which will be described in detail later, can have two or more cyclic structures or concentrated rings. More preferably, the alicyclic hydrocarbon group is adamantane and its derivatives. This paper size applies to China National Standard (CNS) A4 specification (21 Ox297 mm) 10 34 1X 02 5 X-printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A 7 _L ___ ^ B7__Invention description (8) Furthermore, the alkali-insoluble film-forming compound is sensitive to the acid produced by the photoacid generator used with the film-forming compound. The compound includes a wide range of compounds from low molecular weight to high molecular weight, as long as it satisfies The foregoing requirements, and they can be used alone or as a mixture of two or more compounds. Generally speaking, the film-forming compounds can be divided into two categories: (1) polymers or homopolymers containing the structural unit as a repeating unit, and (2) with one or more alkali-soluble polymers. Non-polymeric compounds used with polymers or homopolymers. The film-forming compound may be in the form of a polymer or a copolymer and has a wide molecular weight range from low to high. The polymer may be a homopolymer containing a single monomer, or a polymer having two or more monomers, such as a copolymer, a trimer, and the like. Appropriate polymers or copolymer monomers, not limited to the following, include acrylates containing methylpropionic acid and its derivatives; methylene succinate and its derivatives; transbutene Diacids and their derivatives' and styrene substitutes and their derivatives. When the film is formed as a non-polymer compound, to obtain the desired photoresistive properties, an alkali-soluble polymer or copolymer must be used in combination with the compound. In reference to the aforementioned patent application, the present inventors revealed their findings as follows: 'It is (1) In a chemically amplified photoresist composition, if an alicyclic carbophenyl group is contained in a photoresist structure, the exposed film is Dissolution in the aqueous solution may be suppressed due to the strong hydrophobicity of the hydrocarbon group during the phase revealing of the film in the alkaline solution. (2) Due to this fact, it is best to introduce a lipid The ring group is a protecting group, (the size of the protected soluble paper is subject to the Chinese National Standard (CNS) A4 specification (210X297 mm)

II (Please read the precautions on the back before filling out this page) Qin 502134 Printed by A7 B7, Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) The base group will be removed from the photoresist composition when subjected to acid action Upper cut) in the photoresist structure and remove the alicyclic group from the exposed area after exposure and post-exposure baking: and (3) in order to facilitate the cleavage reaction of the alicyclic group, it is best to introduce a "group" Contains an alicyclic group, in which a carbon atom constituting the ring backbone in the alicyclic group is suitably substituted with a lower alkyl group as a "group" of a protecting group. However, when the previous application was archived, the invented photoresist composition was insufficient to provide the sensitivity required in ArF lithography technology. The present inventors continued their research to completely solve the aforementioned problem of high sensitivity, and they have now found that significantly increased sensitivity can be obtained by using -CH2-R, one of the protecting groups in the photoresist structure, Where &amp; is methyl, ethyl, propyl, or isopropyl. As mentioned above, the chemically amplified photoresist composition according to the present invention is a chemically amplified photoresist composition which includes a compound as an acid sensor and a photoacid generator. This chemically amplified photoresist composition and its formulation, and the use of this photoresist composition to form a photoresist pattern will be described below with reference to examples. However, the invention should not be limited to the described embodiments. The protected soluble test group in the acid-sensing compound is cleaved together with the acid to make the compound soluble, preferably a polymer or a homopolymer where "copolymers," including terpolymers or other A copolymer of one or more components, or a non-polymeric compound. In the chemically amplified photoresist composition according to the present invention, the main component contained in the composition, the protected structure of the acid-sensitive compound is soluble in the test The group is preferably one of a carboxylic acid group, a continuous acid group, a fluorenyl group, a fluorenimine group, and a fluorenyl group, and more preferably a carboxylic acid group of the aforementioned chemical formula (II). Applicable to China National Standard (CNS) Α4 specification (210 × 297 mm) 12 (Please read the precautions on the back before filling this page)

1T 502134 A7 B7 V. Description of the invention (10) The fluorenimine group of the formula (V), or the phenol group of the following formula (VI) ...

〇 II C CHr R ″ 0 C ·… (V)

0 11 C 0 • Z (VI) (Please read the notes on the back before filling out this page. J Pack-some of them are as defined previously. For example, as a carboxylic acid group that is soluble in a base group, The action causes the protective group to break, which is a unit that can generate carboxylic acid, and it contains secondary carbon esters such as t-butyl ester, amyl ester, and α, α-dimethylbenzyl, such as Acetal esters of tetrahydroalanyl esters, such as the cold-oxy-esters of cyclooxycyclohexyl, such as mevalonyl lactone esters, and others. Furthermore, the chemically amplified photoresist used in the present invention The acid-sensing compound in the composition preferably contains esters derived from trimethylmethanol, acetal, stone oxyketone, cold-oxygen smoker, α-oxocyclic hydrocarbon, and others. Structural unit. Further, the alicyclic hydrocarbon group contained in the base group includes many kinds of groups that are familiar in the field of chemically amplified photogroups. The appropriate alicyclic hydrazone group is not limited thereto. Contains the following compounds as the backbone. The paper ruler ^. (2iQX 297 mm) • Order 'Staff of the Central Bureau of Standards of the Ministry of Economic Affairs 13 502134 Μ B7 printed by Feihe Co. 5. Description of the invention (11) (1) Adamantane and its derivatives; (2) Norbornane and its derivatives; (3) Perhydroanthracene and its derivatives; (4) ) Perhydronaphthalene and its derivatives; (5) Tricyclo [5 · 2 · 1 · 02 6] decane and its derivatives; (6) Dicyclohexane and its derivatives; (7) Spiro [4 · 4] nonane and its derivatives; and (8) spiro [4 · 5] decane and its derivatives. These compounds have the following structure: (Please read the notes on the back before filling this page) Central Bureau of Standards, Ministry of Economic Affairs Printed by Employee Consumer Cooperative

This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 14 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 502134 A7 ~ I ..._ 87 __ V. Description of the invention (12) Practical application of the invention Among them, alicyclic hydrocarbon groups having two or more ring structures or concentrated rings can be effectively used, because if the alicyclic group has only one ring, such as cyclohexane, it cannot provide satisfactory resistance to dry etching. . Furthermore, in the above-mentioned examples of appropriate alicyclic nitrogen-breaking groups, if it is desired to obtain the same or higher barrier properties with respect to the dry type of the conventional novolak photoresist, it is best to use a compound containing adamantane or the like. Alicyclic hydrocarbon group with concentrated ring. In the chemically amplified photoresist composition according to the present invention, the acid-sensing, film-forming compound contained therein is preferably in the form of a polymer or a copolymer. This film-forming polymer or copolymer can be selected from many kinds of polymers or copolymers satisfying the foregoing requirements based on various factors such as the photoresist pattern property. Appropriate film-forming polymers or copolymers, although not limited to the ones mentioned below, which include repeating units of methacrylate and its derivatives, methylene succinate and its derivatives, butane Alkenyl esters and their derivatives, styrene substitutes and their derivatives, and others. These repeating units can be used individually or in combination. The inventors have found that if the previously listed repeating units are incorporated into a polymer or copolymer, the formulation of the photoresist composition coating and polymer or copolymer can provide significant benefits compared to other general polymers or copolymers. The advantages. In addition, if desired, the film-forming copolymer of the present invention can link this repeating unit with one or more other repeating units such as acrylonitrile, olefin, diene, and derivatives thereof, although The invention is not limited to these repeating units. In the film-forming polymer or copolymer used in the present invention, in order to obtain the paper size, the Chinese National Standard (CNS) A4 specification is applied ((Please read the precautions on the back before filling this page), 1T 502134 A7 B7 V. Description of the invention (13) The photoresist has good adsorption between the underlying substrate or the thin layer. It is best that the polymerized polymer contains repeating units with strong polarity. Especially if they are in addition to I, the components are soluble in the test group. In addition, it contains repeating units that are soluble in the test solution. Combining such repeating units in the polymer or silk makes the resulting photoresist composition visible in the test solution, as if protected by The function of a small amount of carboxylic acid produced in a base-soluble group is the same. According to a feature of the present invention, it provides a photoresist composition in which the film-forming compound, which is one of the main wounds, is in the form of a copolymer, and the Among the repeating units of the copolymer, in addition to the repeating units containing alicyclic hydrocarbon groups mentioned above, at least one repeating unit is selected from repeating units having a base group soluble in the side chain, and this Repeat unit Its side chain has another protected soluble base group, which will be cut off by the action of the acid generated by the photoacid generator (PGA). It is best to form a copolymer for the film used in the photoresist composition of the present invention The material has the following structural units represented by chemical formulas (III) and (IV): (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

(1) This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) -16 502134 A7 _________ B7 V. Description of invention (l4)

R R

The R printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs can be the same or different, and each ruler represents a hydrogen atom, a halo atom, or one to four carbon atoms, which are substituted or unsubstituted. Chain or fork alkyl. A represents that a protecting group will be cleaved when subjected to an acid action, and heart and Z are as previously defined. The structural unit represented by the above formula (III) shows that it introduces into the copolymer a protective group containing an alicyclic backbone such as adamantane or norbornane, and it will be generated when the light &amp; L product produces an acid. Is cleaved 'to produce a soluble carboxylic acid group. After the photoresist film is exposed, the exposed area of the photoresist film is soluble in an alkaline solution as a phase developer, because the copolymer has an acid group in the structure. Furthermore, by controlling the content of carboxylic acid groups in the photoresist copolymer, the exposed photoresist film can be displayed with a current standard alkaline developer such as a 2.38% aqueous solution of tetramethylammonium nitroxide (TMAΜ). image. In this example, the amount of the acid-containing unit in the photoresist copolymer is preferably not lower than 5 mole percentages or higher than 50 mole percentages. Furthermore, the structural unit represented by the above formula (IV) shows that it is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) on the paper size of the copolymer. (Please read the precautions on the back before filling this page) _ Equipment-Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs W2134 A7 ～ 一 __E_ V. Description of the Invention (15) A protective group containing an alicyclic backbone such as adamantane or norbornane was introduced into the structure. Acid is cut off from the photoacid generator; a general protecting group different from the alicyclic backbone-containing protecting group is cut off when it encounters an acid generated from the photoacid generator; and A base-soluble carboxylic acid group. If the photoresist composition containing the aforementioned copolymer is to be used in an ArF lithography technology using an ArF excimer laser light having a wavelength of 193 nm (亳 micron) as the exposure source, the aromatic ring is most excluded from the protective group. Using the structural unit, a flat developer can be obtained on the exposed photoresist film by using an alkaline developer, even if the desired protective group cannot be cut off due to some problems. In the structural units of the foregoing formulae (III) and (IV), the substituent 1 may be a methyl group, an ethyl group, and compounds thereof such as chlorides and bromides. Substituent A can be a general protecting group such as a four-carbon group like t-butyl or t-pentyl, or a non-oxyketone group like 3-oxocyclohexyl, mevalonyl lactone and the like . Furthermore, the alicyclic hydrocarbon group composed of the atom Z may be adamantyl and its derivative, norbornane and its derivative, perhydronaphthalene and its derivative, and tricyclic [5 · 2. 1 · 〇 2 6] Decane and its derivatives, spiro [4 · 4] nonane and its derivatives, and spiro [4. 5] decane and its derivatives. The film-forming polymer or copolymer used in the present invention, which has a carboxyl group, will be further described. It is better that the polymer formed by this film is a polymer of methacrylates represented by the chemical formula (νπ) ·· This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) · ^! (Please first (Read the notes on the back and fill out this page) Order 18

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

502134 A7 __B7 V. Description of the invention (16) f

^ CH /%

0 0 — A The center represents a proton (hydrogen), a halogen atom or a substituted or unsubstituted alkyl group such as methyl, ethyl, or methylol. A is the "group" (I) mentioned above, and represents a protecting group, preferably a protected group of an alicyclic hydrocarbon group, which contains a group having an ester bond as a ring structure and is compared by a Ethyl is substituted by a higher alkyl group. This alkyl group is preferably adamantyl, norbornyl, cyclohexyl, tricyclo [5 · 2 · 1 · 02.6] decane, and others are tetrahexyl or not- The oxyalkyl group is an alicyclic group protected by t-butyl, t-fluorenyl, 3-murylcyclohexyl and the like, and η is any positive integer. The film-forming copolymer is preferably a methacrylate copolymer represented by the formulae (VIII) and (IX). Although not shown, the methacrylate trimer can be represented in a similar structure except that a third repeating unit is added. … (逦) This paper size applies to China National Standard (CNS) Α4 size (210 × 297 mm) (Please read the precautions on the back before filling this page}

502134 A7 __ · — __B7 Five 'Explanation of invention (1?)

Among them, Ri, A and η are individually defined before. γ represents any substituent 'preferably an alkyl group such as butyl or the like' such as an ether of phenoxy and the like; such as adamantyl, norbornyl, cyclohexyl, tricyclic [5 · 2 · 1 · 〇2.6] Alicyclic hydrocarbon group of decane and the like, or the base represented by the following chemical formula: (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm> -20-502134 A7 B7 V. Description of the invention (18) where R1, R2 and R3 represent argon, substituted or unsubstituted alkyl radical Or alkenyl, such as methyl, ethyl or methylene, etc. B represents any substituent, preferably a carboxyl group or a radical represented by the following formula:

(Please read the note on the back first. • D is printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, where D represents -OR4, -COOR4, or -OCO-R4, where R4 in the substitute D represents hydrogen or is substituted or not Substituted alkyl groups, such as methyl or ethyl, etc., and m and η are any positive integers. In addition, if desired, the aforementioned film-forming polymers or copolymers may include alkali-soluble polymerization Materials or copolymers such as novolac resins, phenol resins, ammonium resins, carboxylic acid-containing resins, and the like. Furthermore, in the practice of the present invention, any unpolymerized compound having a relatively low molecular weight (hereinafter referred to as "Unpolymerized compounds") can be used for the same purpose to replace the previously described films to form polymers or copolymers. The unpolymerized compounds used herein, as described above, include any alkali-soluble and acid-sensitive compounds, It can show good solubility in basic phase developer, if it is protected and soluble in base, it will be cut off by the acid produced by the photoacid used in combination with the non-polymeric compound. The non-polymeric compound The substance should not be limited to the compound containing an alicyclic ring backbone, such as an aromatic ring backbone of an benzene ring, or an alkyl backbone, and one of the groups of the backbone is replaced by a group containing the formula (I). Appropriate film formation Typical examples of non-polymeric compounds — —, write this page) The size of the paper used in the edition is in accordance with the Chinese National Standard (CNS) A4 (210 × 297 mm) 21 502134 A7 B7 V. Description of the invention (19 contains the following compounds, although this The invention should not be limited to these compounds. In the general formulae below, Ri * z is as defined above

Ri%

Q

0 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs

C Η 2-R Ηά '€ * \% In addition to containing the group represented by formula (i), these non-polymeric compounds, if desired, may contain any other protected groups or units, where the protecting group may be Acidic cleavage to produce carboxylic acids or other soluble base compounds, such as tertiary carbon esters such as t-butyl ester, t-pentyl ester, α, α-bismethyl g, and the like, acetates Such as tetrahydrosulfanyl esters and the like, and oxone esters such as 3-oxocyclohexyl esters and the like. Since they do not exhibit the desired photoresistive properties when used alone, the aforementioned non-polymeric compounds must be used in combination with any soluble polymer and copolymer. Typical examples of suitable soluble polymers or copolymers include novolac resins, phenol resins, amine resins, carboxylic acid-containing resins, and the like, although the present invention should not be limited to these resins. The mixing ratio of the non-polymeric compound and the alkali-soluble polymer or copolymer can be based on various factors, such as the non-polymeric compound used, the desired photoresistance properties, and other factors. 〉 A4 specification (210 X 297 mm) 502134 A7 __ ^ _ B7 _ V. Description of the invention (20) Changes. In the chemically amplified photoresist composition according to the present invention, a photoacid generator will be exposed to radiation after pattern formation on the pattern. Decomposes to produce an acid that can cleave a protected "group" protected from soluble bases. The photoacid generator reacts with the previously described film-forming compounds, such as film-forming polymers or copolymers and non-polymeric compounds Combined use. The photoacid generator used for this can be a general reagent, which is a well-known photoacid generator (PAG) in photoresist chemistry. These compounds are exposed to a pattern on the photoresist composition coating to form radiation such as Proton acids can be produced after ultraviolet radiation, extreme ultraviolet radiation, vacuum ultraviolet radiation, electron beam, X-rays, and laser light. Typical examples of photoacid generators suitable for the present invention Contains various compounds described below, although the present invention should not be limited to these compounds. (1) Diazonium salt represented by the following formula: -Ar-N2 + X- Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (Please Read the notes on the back before filling this page) Where Ar represents a substituted or unsubstituted aromatic group, such as benzyl or a substituted phenyl group, and the substituents of these phenyl groups include elements such as chlorine and bromine , Iodine or fluorine, alkyl groups such as methyl, t-butyl, aromatic or other substituents, or substituted unsubstituted alicyclic hydrocarbons, and X represents halogen, BF4, BF6, AsF6, SbF6 , CF3S03, C104, or an anion of an organic continuous acid. (2) A phosphonium salt represented by the following formula:

This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) Age 23 502134 A7 B7 V. Description of invention (21) or A r '

CF3 CCKT A r where Ar and X are as previously defined. (3) phosphonium salt represented by the following formula: R2 — ^: S &quot; X &quot; R3 Ο

Ar-CH2 Sf HX-

R (Please read the notes on the back before filling this page)

, 1T

R Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs

R

S + X

Rj This paper size applies to Chinese National Standard (CNS) A4 specification (21 OX 297 mm) 24 502134 A7 B7

R1 V. Description of the invention (22 χ-r where R, R, R2, R3, ^, and χ are as defined above, such as R is methyl, R1, R2, R3 are each phenyl, and ^^ is ^ Butyl. (4) A sulfonic acid ester represented by the following formula:

Ar-C0CH2S02-Ar or (Please read the notes on the back before filling this page)

NO, CH2 S〇2

Order printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs where Ar and R are as defined previously. (5) oxazepine pentacyclic derivative represented by the following formula

Xi C N CX where X is as defined above and at least one of the substituents -Cl is substituted or unsubstituted aromatic or olefinic. (6) s_triazine derivative represented by the following formula: 297 mm in the paper size) 0

NX &quot; 〇 〇 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 502134 A7 B7 V. Description of the invention (23) M --- N H Λ x3 ce c-cx3 ▽ where X is as defined above and replaces at least -CX3 One is a substituted or unsubstituted aromatic or alkenyl group. (7) A difluorene derivative represented by the following formula:

Ar-S 〇2_ S 〇2_ Ar where Ar is as previously defined. (8) Amidimine compound represented by the following formula:

Or true

N where x is as previously defined. (9) Others such as sulfonic oxime. More specifically, some of the previously described compounds can be expressed by the following formula: The paper size applies the Chinese National Standard (CNS) A4 specification (21 Ox 297 mm) (Please read the precautions on the back before filling this page)

502134 A7 B7 V. Description of the invention (24)

• S * S b Fr

* S + P F

: · Ί + P F 丨

f Please read the notes on the back before filling in this page. j-Order the content of the PAG compound printed in the photoresist composition by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs based on a number of factors, such as the ability of the PAG compound to release acid and the pattern forming radiation And so on, and can vary considerably. The content of the PAG compound in the photoresist composition is preferably 0.1 to 50% by weight based on the total weight of the film-forming compound. Contents exceeding 50% by weight should be avoided, as excessive absorption of pattern-forming radiation does not result in a satisfactory pattern. The content of the PAG compound in the photoresist composition is calculated based on the total weight of the film-forming compound, and is preferably from 1 to 30 weights. Paper size Laijia County (CNS) A4 specification (210X297 mm) 27 502134 Α7 -^ __ · _W1_ V. Description of the invention (25) ~~ The amount percentage is preferably between 1 and 15 weight percentage. Using the previously described film-forming compound as the main component, plus the aforementioned photoacid generator (PAG), the photoresist composition according to the present invention can be manufactured by a general method familiar in photoresist chemistry. The photoresist solution is preferably provided as a solution. For example, if the film-forming compound constituting the photoresist composition is the aforementioned polymer or copolymer, the monomers used to form the polymer or copolymer are polymerized in the presence of a suitable polymerization initiator, and then a photoacid is added. The resultant is in the polymer or copolymer produced, and a photoresist solution is provided. The state of the polymerization reaction and the initiator used can be freely selected from a wide range of familiar states and initiators. Typical examples of suitable polymerization initiators include the following compounds, for example, AiBN (azoisobutyl residual): MAIB (bismethyl-2,2-azoisodibutyl vinegar) fH3 CH3 fj H 3 C-C ~ N di N-CH, H3 COCO 0 G oc c H 3 When preparing the photoresist solution, any organic solvent can be used to dissolve the film-forming compound and photoacid generator. The organic solvent used varies considerably depending on various factors, such as the photoresist composition and coating conditions used, and the typical examples of suitable organic solvents are not limited to the ones described below. The size of the coated paper Gu Gu 21GX 297 Li) ~ ------- (Please read the notes on the back before filling this page)

Η 3 GH j Η CIClc J Ν 'II .3. + .N. Η1 Ν c [c ——c * 印 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 502134 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 5 Description of the invention (%) Contains cyclohexanone, methyl ether propylene glycol (PGMEA), ethyl lactate, methylpentyl ketone, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diacetone alcohol , Ethyl pyruvate and the like, these organic solvents may be used alone, or if desired, as a mixture of two or more solvents. The amount of the organic solvent used is not limited, however, it is preferable that the amount of the solvent is sufficient to provide the photoresist coating with a desired thin layer thickness and the viscosity required for coating such as spin coating. In preparing the photoresist solution, if desired, in addition to the organic solvents described above (hereinafter referred to as "main solvents"), auxiliary solvents can be used. If the photoresist component is easy to dissolve in the main solvent, the auxiliary solvent is not needed. However, if the photoresist component is difficult to dissolve in the main solvent, the auxiliary solvent will help the solvent photoresist component in the main solvent. Useful auxiliary solvents, although not limited to the following, include butyl acetate, r • butyrolactone, propylene glycol, methyl ether, and similar solvents. Generally speaking, these auxiliary solvents are preferably used in an amount of 1 to 30% by weight, and more preferably 10 to 20% by weight relative to the main solvent. Another feature of the present invention is to provide a method for forming a photoresist pattern on a substrate to be manufactured, especially a positive photoresist pattern. The method includes these steps: applying a chemically amplified photoresist composition according to the present invention on a substrate; selectively exposing the photoresist coating produced in the previous coating step to exposing the photoresist composition The photoacid generator of the material produces an acid pattern that forms radiation; heating or baking the exposed photoresist coating to a temperature such that the film of the photoresist composition is protected and soluble in base groups in the compound, where The paper size is based on family standards () (Please read the precautions on the back before filling this page)

29 502134 A 7 ________- B7 V. The protection "group" of invention description (27) is cut off; and (please read the precautions on the back before filling this page) Use alkali in exposure and heating photoresist coating Sexual phase display agent, showing potential images. Preferably, in the aforementioned photoresist pattern forming method, in addition to the post-exposure baking (PEB) after the photoresist coating pattern is exposed, the photoresist coating can be subjected to another heating or baking process, namely, In other words, the pattern forming method of the present invention preferably further includes a step of heating the photoresist coating before exposing to pattern-forming radiation. According to the pattern forming method of the present invention, the general lithography method can be used. A series of practical process steps that can be effectively used in the present invention will be described below. However, the present invention should not be limited to the described steps. Therefore, any modification or change is within the scope and spirit of the present invention. Applicable to the method described in the present invention. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. First, a photoresist composition is coated on a substrate to be manufactured to form a photoresist coating having a predetermined thickness The substrate used for this can be any general substrate used in the field of semiconductor components or other components, and typical examples of suitable substrates include silicon substrates, glass substrates, SOS substrates, non-magnetic substrates such as ceramic substrates, etc. This substrate can be additionally covered with one or more cover layers, such as polycrystalline silicon layers; oxide layers such as silicon oxide layers; nitride layers such as silicon, if desired A nitride layer; a metal layer such as an aluminum layer; an intermediate insulating layer; a magnetization layer and the like. In addition, the substrate and / or the cover layer may include any component such as a wiring or a circuit manufactured therein. In order to increase the adsorption strength of the photoresist coating on the substrate, the surface of the substrate can be subjected to a general hydrophobic treatment. Typical examples of chemicals used in this treatment are 1, 1, 1, 3, 3, 3- 30 paper Standards are applicable to Chinese national standards. (CNS) A4 (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 502134 A7 _ B7 ------; --------- 5. Description of the invention (28) Hexamethyldicarboxylate, etc. The coating of the photoresist composition can be made of a photoresist solution with the same composition as described in the previous paragraph. The photoresist solution is preferably applied to the surface of the substrate by spin coating. Although other general coating methods such as roller coating and dip coating, It can also be used if desired. The thickness of the photoresist coating is generally in the range of 0.001 to 200 microns, and preferably between 0.1 and 2.0 microns. However, the thickness of the photoresist coating can be based on Different factors, such as the use of the photoresist pattern generated, etc. The photoresist coating formed on the substrate is preferably at a temperature between 60 ° C and 200 ° C before being selectively exposed to the pattern to form radiation. It is better to pre-bake at 60 ° C to 150 C for 60 to 180 seconds. Pre-baking can be implemented by any heating device commonly used in the photoresist process. Suitable heating devices include heating plates, infrared light (IR) Heating furnaces, microwave heating furnaces and the like. In addition, if a pre-coating or protective layer is to be added to the photoresist coating, it is generally a spin coating solution of an olefinic resin on the photoresist coating. Then, the olefinic coating is baked at about 100 ° C. Secondly, the optionally pre-baked photoresist coating is selectively exposed to patterning radiation in an exposure element or aligner. Appropriate exposure elements include commercially available elements such as ultraviolet (far ultraviolet, deep ultraviolet, or vacuum ultraviolet) exposure elements, X-ray exposure elements, electron beam exposure systems, and excimer laser steppers. The conditions of the exposure can vary and the best conditions can be selected in each process based on various considerations. It can be known from the foregoing description that in the practice of the present invention, the pattern-forming exposure can effectively use excimer lasers such as KrF laser (wavelength 248nm) and ArF (argon fluoride) laser (wavelength 193nm) as the exposure source. This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 31 (Please read the precautions on the back before filling this page)

502134 A7 B7 V. Description of the invention (29) Due to selective exposure, the photoacid generator in the exposed area of the photoresist coating is dissociated, so the exposed photoresist coating can be tested during the subsequent phase development. The phase-improving agent is dissolved and detached from the substrate. After the selective exposure is completed, the exposed photoresist coating is heated on a heating device such as a hot plate. As mentioned earlier, this heating is called post-exposure baking (PEB), and PEB is preferably implemented at a temperature that is sufficient to allow the film in the photoresist coating to form a compound that is protected and soluble in the base group The protective group is cleaved in the presence of a catalytic acid produced by a photoacid generator. PEB can be performed in a similar manner to the aforementioned pre-baking, and is generally performed at a temperature of 60 to 150 ° C, preferably 100 to 150 ° C, for 30 to 240 seconds. Furthermore, when using a photoresist coating with a precoat, it is best to separate and remove the top coating after PEB and before development by any suitable means such as organic solvents. In the last step of the present invention, the heated photoresist coating is phase-developed in a basic aqueous solution or an alcohol solution using a phase-developing agent according to any general method. Appropriate devices for the imaging step include well-known display cameras such as rotary display cameras, immersion display cameras, and spray display cameras. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Alkaline solution suitable as a phase developer contains water containing hydroxides of Group 1 or Group 2 metals of the periodic table. Or an alcohol solution, such as potassium hydroxide; or a metal or ion-free organic base in water or an alcohol solution, such as tetraalkylammonium hydroxide, a typical example will be described hereinafter with reference to its chemical formula. Furthermore, if desired, the alkaline solution as a phase-improving agent may additionally contain additives such as a surfactant to improve the phase-improving effect produced. Furthermore, if appropriate, as invented by the Japanese Unexamined Patent Publication, this paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -32-502134 A7 B7 V. Description of the Invention (30) (Kokai) No. 7_23053 It is suggested that the phase-improving agent used for this may be-an aqueous or alcoholic solution containing an ammonium compound represented by the following formula as a phase-improving agent

Ri I-R2 -N + -R, I · Ri OH; where Ri, R2,: ^ and d can be the same or different, and each represents a substituted or unsubstituted alkyl group containing 1 to 6 carbon atoms , A morphine compound represented by the following formula. 0 (Please read the notes on the back before filling in this page. J Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs or a mixture thereof. Ammonium compounds that can be used as a phase substance, although not limited to the following, they include: hydrogen Tetramethylammonium oxide (TMAH) Tetraethylammonium hydroxide (TEAH) Tetrapropylammonium hydroxide (TPAH) Tetrabutylammonium hydroxide (TBAH) etc. It is preferable that tetramethylammonium hydroxide is used as a visible phase. This visible phase Dissolve substances in water or alcohols such as methanol, ethanol, isopropanol, etc. to obtain a phase solution. The phase concentration of the phase solution in the phase solution can vary greatly, but it is generally between 0J to 15 weight percent Time, the maximum range is 0.1 to 10 weight percent. The appearance time is also greatly changed.

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 502134 A7 ___ B7 V. The description of the invention (31), however, it is generally about 1 to 5 minutes, preferably about 丨 3 minutes. The exposed area of the photoresist coating is dissolved and removed from the surface of the substrate due to the effect of the photophase, thereby forming a desired positive photoresist pattern relative to the exposure pattern. The resulting photoresist pattern is washed with deionized water and dried in a general method. As can be known from the foregoing and the examples of the present invention, since the chemically amplified photoresist composition has a protecting group represented by the foregoing formula (I), the protecting group contains an alicyclic group, and one The ring-shaped backbone of an ester bond formed by one atom can reduce or relax the hardness of the composition because it contains an alicyclic hydrocarbon gene, thereby obtaining stable pattern-forming properties. The protective group used in the present invention can particularly show its superior efficiency when used in a chemically amplified photoresist composition having an alicyclic unit as a protection unit, but it is also considered to be applicable to other types of photoresist compositions. Can provide satisfactory results. As mentioned earlier, if this protective group is used for a photoresist resin, and this resin contains adamantane and its derivatives, norbornane and its derivatives, tricyclic [5. 2. · 1. 0] decane and its The most significant effect is obtained with alicyclic hydrocarbon groups derived from derivatives and the like. Examples The present invention will be further described with reference to related examples. However, the examples included here are for illustrative purposes only, and they are not a limitation of the present invention. Example 1 2-butyl-2-adamantyl methacrylate and mevalonate methacrylate as starting monomers are added to the polymerization container at a ratio of 1: 1. This paper is in accordance with Chinese national standards (CNS) A4 specification (210X 297mm) -34-(Please read the precautions on the back before filling this page)

502134 A7 B7 V. Description of the invention (32) Formulated as a 1,4-bisoxane solution containing 3mole / L monomer. After adding 15 mol% of 2,2'-azobisisobutyl residual (AIBN) to a 1,4-bisoxane solution as a polymerization initiator, the monomers were polymerized at 80 ° C for about 9 hours. When the polymerization reaction was completed, the polymerization product was purified using methanol as a precipitate. A copolymer consisting of 2-butyl-2-adamantyl methacrylate and mevalonyl methacrylate represented by the following formula was obtained. CH: I —. C Η 2 — C I. • CH: CH; I C I (Please read the notes on the back before filling this page) _ 装-

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, the resulting copolymer has a composition ratio (m: n) of 54:46, a weight average molecular weight (Mw) of 7,540 (standard polystyrene equivalent), and polydispersity (Mw / Mn) 1.8 〇 Example 2 Triphenylsulfonium trifluoromethanesulfonate as photoacid was added in an amount of 2% by weight relative to the copolymer to 2-methyl-2-adamantyl methacrylate prepared in Example 1. Ester and mevalonate methacrylate, and this mixture was dissolved in cyclohexanone to make a photoresist solution containing 14% by weight of copolymer. This photoresist solution was spin-coated on a silicon substrate treated with HMDS, and prebaked at 100 ° C for 60 seconds on a hot plate to form a 0.4 micron-thick photoresist coating. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 35 • A7 __E_____ V. Description of the invention (33) After pre-baking, this photoresist coating is selectively exposed to ArF excimer laser exposure system (Nikon, NA = 0.55) Laser light pattern with a wavelength of I93nm (亳 microns). The exposed photoresist coating was then accepted on a hot plate at 1000 and exposed to baking (PEB) for 60 seconds. The post-baked photoresist coating is developed with a 2.38% (0.27N) tetramethylammonium hydroxide aqueous solution (TMAH), NMD_3 (trade name, available from Tokyo Ohka Co.) for 60 seconds, and in pure water Wash for 30 seconds. Therefore, the resist pattern relative to the laser light pattern as the exposure source is obtained. In this example, the threshold energy Eth of the exposure amount is 3 mJ / cm2, and the pattern resolution is 0.17 micrometers L / S (line and pitch). Example 3 This example is for comparison. The procedure in Example 2 was repeated, however, for the purpose of comparison in this example, the copolymer used as the photoresist substance was 2-methyl-imadamantine and mevalonyl methacrylate. Copolymer composed of acrylate based on the following formula: (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

The copolymer of V0 above was made according to a method similar to Example 1, and had a composition ratio (111: 11) of 51:49 and a weight average molecular weight (1 ^^) of 8,900. 36 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm). Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 502134 A7 B7. 5. Description of the Invention (M) Using this copolymer, the photoresist process is described in the example Perform the same method in 2. The photoacid generator TPSS03CF3 in an amount of 2% by weight relative to the copolymer is added to a copolymer consisting of 2-methyl-2-adamantyl methacrylate and mevalonate methacrylate, and this The mixture was dissolved in cyclohexanone to form a photoresist solution containing 14% by weight of the copolymer. This photoresist solution was spin-coated on a silicon substrate treated with HMDS, and prebaked at 100 ° C for 60 seconds on a hot plate to form a 0.4 micron thick photoresist coating. After pre-baking, the photoresist coating was selectively exposed to a laser light pattern at a wavelength of 193 nm in an AirF excimer laser exposure system (Nikon, NA = 0.55). The exposed photoresist coating was then exposed to hot baking (PEB) for 60 seconds at 100 ° C. The post-baked photoresist coating was made visible in a 2.38% (0.27N) aqueous solution of tetramethylammonium hydroxide (NMD-3) for 60 seconds, and washed in pure water for 30 seconds. Thus, a positive photoresist pattern is obtained with respect to the laser light pattern as an exposure source. In this example, the threshold energy Eth of the exposure amount was 8 mJ / cm2, but the resolution was poor. The 0.2 micron L / S pattern could not be obtained due to the drop of the pattern. Example 4 This example is used to consider why the photoresist produced by Example 2 (containing 2-butyl substitution) and Example 3 (2-methyl substitution; comparative example) is different due to a difference in the substitution. Patterns make a significant difference. The procedures of Examples 2 and 3 were repeated and the amount of the photoacid generator TPSS03CF3 was increased to 5 weight percent relative to the copolymer. A 0.4 micron thick photoresist coating was thus formed. The photoresist coating is selectively exposed to an ArF excimer laser exposure system (Nikon, NA = 0.55) under a laser light pattern with a wavelength of 193 nm. In order to evaluate the paper size, the Chinese National Standard (CNS) A4 specification (210X 297 mm) is applicable. -37-(Please read the notes on the back before filling this page) Order 502134 A7 B7 V. Description of the invention (35) The relationship between the exposure amount and the photoresist coating is estimated, and the exposure energy is changed as shown in the curve shown in Figure 1. When the selective exposure is completed, the photoresist coating is placed on a hot plate at 100%. Bake for 60 seconds after applying force, develop phase for 60 seconds with phase-improving agent (NMD-3), and wash the button with pure water. Therefore, to obtain a positive photoresistance pattern relative to the laser light pattern as an exposure source As for the relationship between the exposure amount, each of the obtained photoresist patterns is subjected to infrared (IR) spectral analysis. The infrared absorption spectrum plotted in Figure 1 is obtained. The obtained infrared spectrum shows that the height of the carboxyl peak due to the presence of -COOH groups varies with the The increase in exposure energy increases, and it reaches saturation when the exposure energy increases to a certain degree. However, the curve of Comparative Example 2 (the present invention; butyl substitution) and the curve of Example 3 (Comparative Example; methyl substitution) Can send Now, the curve of Example 2 rises faster than that of Example 3. Therefore, it can be imagined from this result that the butyl substitution ensures effective and equivalent release of the carboxylic acid, thereby increasing the sensitivity, exposure gap, and environmental resistance. The previous steps were repeated to obtain a graph showing the shrinkage of various 2-alkyl-2-AdMA (adamantyl methacrylate) homopolymers with different ArF exposures, and the amount of photoacid generator TPSS03CF3 was determined by 5 weight percent becomes 2 weight percent ^ Shrinkage (reduced thickness after PEB) Shrinkage calculated from the following equation = Saturation shrinkage The results plotted in Figure 2 show that for 2-butyl and 2-ethyl substitution The shrinkage degree is highly saturated when the exposure is about 2mJ / cm2, while the 2-methyl substitution is highly saturated when the exposure is 1 OmJ / cm2. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 Mm) 38 (Please read the notes on the back before filling in this page}

View 134 A7 B7 V. Description of the invention (36)

Ml Repeat the procedure of Example 2. However, the copolymer used as the photoresist in this example is a copolymer composed of 2-ethyladamantine methacrylate and mevalonate methacrylic acid vinegar prepared according to a method similar to Example 1. It is represented by the following formula and has a composition ratio (m: n) of 53:47, a weight average molecular weight (Mw) of 9,200, and a polydispersity (Mw / Mn) of 2.0.

CH CH; I C-C Η CH:! C-

H3d 0

C 0

H3C

V ο Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Using this copolymer, the photoresist process was performed as described in Example 2. Copolymer of 2% by weight of the photoacid generator TPSSC ^ CF3 added to the copolymer added to 2-ethyl-2-manganyl methacrylate and mevalonate methacrylate The mixture was dissolved in cyclohexanone to form a photoresist solution containing 14 weight percent copolymer. This photoresist solution was spin-coated on a silicon substrate treated with HMDS, and prebaked at 100eC for 60 seconds on a hot plate to form a 0.4 micron-thick photoresist coating. After pre-baking, this photoresist coating was selectively exposed to an ArF excimer laser exposure system (Nikon, NA = 0.55) under a laser light pattern with a wavelength of I93nm. The exposed photoresist coating was then applied on a hot plate at 100 ° C. (3 After acceptance, exposure baking (PEB) 60 seconds. Post-baking photoresist coating with alkaline phase developer, (Please read the precautions on the back before filling in this page)

This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 39 502134 A7 B7 i. Description of the invention (37) NMD-3 (brand name 'available from Tokyo Ohka Co.) showing 60 seconds And rinse with pure water for 30 seconds. Thus, a positive photoresist pattern is obtained with respect to the laser light pattern as an exposure source. In this example, the threshold energy of the exposure is 4mJ / cm2, and the resolution of the pattern is 0.18 micron L / S. Example 6 The procedure of Example 2 was repeated. However, in this example, the copolymer used as a photoresist is a copolymer composed of 2-ethyladamantyl methacrylate and methacrylic acid prepared according to a method similar to Example 1, which is represented by the following formula and It has a composition ratio (m: n) of 65:35, a weight average molecular weight (Mw) of 3,900, and a polydispersity (Mw / Mn) of 2.5. (Please read the notes on the back before filling this page)

CH: I C one

• CH G Η1 C-Order Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Ο Ο η-Β Using this copolymer, the photoresist process was carried out according to the method of Example 2. Two weight percent of the photoacid generator TPSS03CF3 relative to the copolymer was added to a copolymer consisting of 2-butyl-2-adamantane methacrylate and methacrylic acid. And the mixture was dissolved in cyclohexanone to form a photoresist solution containing 14% by weight of a copolymer. The photoresist solution was spin-coated on a silicon substrate treated with HMDS, and pre-treated on a hot plate at 100 ° C. Bake for 60 seconds to form a 0.4 micron thick photoresist coating. After pre-baking, this photoresist coating is selectively applied to the ArF excimer laser system.

〇

G Ο Η

40 This paper size applies Chinese National Standard (CNS) A4 specification (21 × 297 mm) 5. A7 B7 Description of Invention (38) system (Nikon, NA = 0.55), exposed to laser light with a wavelength of 193nm (亳 microns) Under the pattern. The exposed photoresist coating was then exposed to baking on a hot plate at 130 ° C for 60 seconds. The post-baked photoresist coating was developed with NMD-3 (trade name, available from Tokyo Ohka Co.) diluted 20 times as a basic phase developer for 60 seconds, and washed with pure water for 30 seconds. Thus, a positive resist pattern is obtained with respect to the laser light pattern as an exposure source. In this example, the threshold energy Eth of the exposure amount is 2 mJ / cm2, and the resolution of the pattern is 0.7 μL / S. . m Repeat the procedure in Example 2. However, in this example, the copolymer as a photoresist was a copolymer prepared in a similar manner to Example 1 and consisting of 2-butyl-2-adamantyl methacrylate and anhydrous methylene succinic acid. It is represented by the following chemical formula and has a composition ratio (m: n) of 58:42, a weight average molecular weight (Mw) of 6,500, and a polydispersity (Mw / Mn) of 1.8. C Η 3 c Η 2 — C-~ c

= C I 0, &gt; Printed by the Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs. Using this copolymer, the photoresist process was performed in the same way as in Example 2. 2 weight percent of the photoacid generator tpss〇3CF3 relative to the copolymer was added to a copolymer composed of 2-butyl-2-adamantyl methacrylate and anhydrous butylene butyrate, and the mixture was dissolved in the ring Hexanone to form a photoresist solution containing several weight percent copolymer. This photoresist solution is spin-coated on a silicon substrate treated with HMDS, and it is pre-baked at 100 on a hot plate. This paper size applies Chinese national standards ^ Γ) A4 size () (please first (Read the notes on the back and fill out this page)

41 502134 A7 B7 V. Description of the invention (39) seconds to form a 0.4 micron thick photoresist coating. After pre-baking, the photoresist coating is selectively exposed to an ArF excimer laser system (Nikon, NA = 0.55) under a laser light pattern with a wavelength of 193 亳 micrometers (nm). The exposed photoresist was then placed on a hot plate at 100 ° C. (: Post-exposure bake for 60 seconds after acceptance. Post-bake photoresist coatings are developed with a basic developer nmD-3 (trade name, available from Tokyo Ohka Co.) for 60 seconds, and in pure water Wash for 30 seconds. Thus, a positive resist pattern is obtained relative to the laser light pattern as an exposure source. In this example, the threshold energy Eth of the exposure amount is 5 mJ / cm2, and the resolution of the pattern is 0.20 micrometer L / S. Example 8 This example is a comparative example. Repeat the procedure of Example 7. However, in this example, for comparison, the copolymer used as a photoresist was prepared according to a similar method in Example 1, and was made from methacrylic acid. Copolymer composed of 2-methyl-2-adamantyl ester and anhydrous methylene succinic acid. It can be represented by the chemical formula and has a composition ratio (m: ti) 55:45, weight average molecular weight] ^^ 8 , 500, and polydispersity () ^ ~] ^ 11) 19 (Please read the precautions on the back before filling in this page)

Order

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs CH: ί C Bt — Q-:

C

Io——e 'Using this copolymer, photoresist manufacturing is carried out according to the same method as in Example 2. This paper size is applicable to Chinese national standard (2Η) × 2 · worry 42 502134 A7 B7 V. Description of the invention (40). 2 weight percent of the photoacid generator TPSS03CF3 relative to the copolymer was added to a copolymer consisting of 2-methyl-2-adamantyl methacrylate and anhydrous butylene succinic acid, and the mixture was dissolved in cyclohexane Ketone to form a photoresist solution containing 14 weight percent copolymer. This photoresist solution was spin-coated on a silicon substrate treated with HMDS, and prebaked at 100 ° C for 60 seconds on a hot plate to form a 0.4 micron photoresist coating. After pre-baking, the photoresist coating is selectively exposed to an AirF excimer laser. Exposure system (Nikon, NA = 0.55) and exposed to a laser light pattern with a wavelength of 193 亳 microns (nm). The exposed photoresist coating was then subjected to post-exposure bake at 100 ° C on a hot plate for 60 seconds. After baking the photoresist coating, a basic developer, NMD_3 (trade name, available from Tokyo Ohka Co.) was developed for 60 seconds, and washed in pure water for 30 seconds. No photoresist pattern was formed because of light. The resist coating dissolves and is removed from the silicon substrate. In this example, the threshold energy Eth of the exposure amount is 15 mJ / cm2, which is a very low sensitivity. Example 9: The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed the procedure of Example 2 in the same manner. In the phase display step, the same concentration (2.38%; 0.27N) of tetrabutylammonium hydroxide (TBAH) in water was used as the phase developer. Replaces 0.27N tetramethylammonium hydroxide (NMD-3). A satisfactory positive photoresist pattern corresponding to that in Example 2 was obtained. The threshold energy Eth is 5mJ / cm2 and the resolution is 0.16 micrometers L / S. Example 10 The procedure in Example 2 was repeated. However, in this example, the copolymer used as a photoresist was prepared in a similar manner as in Example 1, and was 2-butyl-2-adamantyl methacrylate, t-butyl methacrylate, and methacrylic acid. Composition of 43 (Please read the notes on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) ^ 134 A7 ----B7 V. Description of Invention (41) Dimerization Compounds, which can be represented by the following chemical formulas, and have a composition ratio (1: m: n) 58:22:20, a weight average molecular weight of 12,000, and a polydispersity (Mw / Mn) of 2.6 〇Ο;- € CHa —G 4 Μ Μ c—β

Η C

Η CMC

0 \ € ο s Η 3c3 Η I Η clcic Η ο (Please read the notes on the back before filling out this page) The Central Consumers Bureau of the Ministry of Economic Affairs's Consumer Cooperatives printed and used this trimer. The photoresistance process is in accordance with Example 2. Method implementation. 2% by weight of the photo-acid generator tPSS〇3CF3m with respect to the trimer is composed of 2-butyl-2-adamantyl methacrylate, t-butyl methacrylate, and methacrylic acid Terpolymer, and the mixture is dissolved in cyclohexanone to form a photoresist solution containing 14% by weight of the terpolymer β This photoresist solution is spin-coated on a silicon substrate treated with HMDS, The plate was pre-baked at 100 ° C for 60 seconds to form a 0.4 micron thick photoresist coating. After pre-baking, the photoresist coating was selectively exposed to an ArF excimer laser exposure system (Nikon, NA = 0.55) and exposed to a laser light pattern with a wavelength of 193 μm. The exposed photoresist coating was then exposed on a hot plate at 100 ° C and exposed to baking (PEB) for 60 seconds. The post-baked photoresist coating was developed with NMD-3 (trade name, commercially available from Tokyo Ohka Co.) diluted 10 times in a alkaline developer for 60 seconds, and washed in pure water for 30 seconds. . Thus, a positive resist pattern is obtained with respect to the laser light pattern as an exposure source. In this example, the threshold energy Eth of the exposure amount is 3 mJ / cm2, and the resolution of the pattern is 0.8 μm / s. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 44 Sichuan 2134 A7 B7 V. Description of the invention (42) Example 11 This example is a comparative example. Repeat the procedure of Example 10. However, in this example, the third compound I, which is a photoresist material, was prepared according to a method similar to that in Example 1. A polymer 'can be represented by the following chemical formula and has a composition ratio (l: m: n) 53:27:20' a weight average molecular weight (mw) of 16.0,00, and a polydispersity (Mw / Mn) of 1.6.

ml nn nn 1 = 1- ^ sue —ϋ ml 1, Jw (please read the precautions on the back before filling this page) Order the Central Consumer Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives to print and use this dimer 'photoresistance process according to The method in Example 2 was implemented. 2 weight percent of the photoacid generator relative to the trimer is incorporated into a terpolymer composed of 2-methyl-2-adamantyl methacrylate, t-butyl methacrylate and methacrylic acid, and This mixture dissolved cyclohexanone to form a photoresist solution containing 14 weight percent of a trimer. This photoresist solution was spin-coated on a silicon substrate treated with HMDS, and prebaked on a hot plate at 100 ° C for 60 seconds to form a 0.4 micron thick photoresist coating. After pre-baking, the photoresist coating was selectively exposed to an ArF excimer laser exposure system (Nikon, NA = 0.55) to a laser light pattern with a wavelength of 193 nm. The exposed photoresist coating was then accepted on a hot plate at 100 ° C.

This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) 45 502134 A7 B7 V. Description of the invention (43) _ Exposure baking 60 seconds. The post-baked photoresist coating was developed with NMD-3 (trade name, available from Tokyo Ohka Co.) diluted with a 10-fold solution of alkaline developer for 60 seconds, and washed in pure water for 30 seconds. Thus, a positive photoresist pattern with respect to the laser light pattern as an exposure source is obtained. In this example, the threshold energy Eth of the exposure amount is 4 mJ / cm2, but the resolution is poor. It is obvious that the pattern of 0.19 μm L / S has dropped and broken. (Please read the precautions on the back before filling out this page) Printed by the Consumers' Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs 46 This paper is sized for China National Standard (CNS) A4 (210X297 mm)

Claims (1)

502134 Patent Application No. 86117963 Patent Application Patent Application Amendment Amendment Date: 01/91/01 · An alkali-reproducible chemically amplified photoresist composition for forming a photoresist pattern, comprising: I. An alkali-insoluble copolymer having a structural unit as a repeating unit, the structural unit containing a protected alkali-soluble group, the repeating unit of the copolymer is one of the following groups, this group contains acrylic acid Esters and their derivatives, methylene succinates and their derivatives, fumarate and its derivatives, and styrene substitutes and their derivatives, in which the protected base may be The protective part of the soluble group will be cut off by the acid generated by the photoacid generator used with the copolymer, so the protective part will be released from the alkali-soluble group '' and The copolymer becomes soluble, and the soluble group is a member selected from the group consisting of carboxylic acid group, acid group, amido group, imino group, and phenol group and contains an alicyclic ring represented by the following chemical formula ⑴ Protected by a hydrocarbon moiety (Please read the notes on the back before filling this page) 2 * Η \ · c1c ': \ R where 1 can be substituted or unsubstituted methyl, ethyl, propyl or isopropyl, and Z stands for Together with a carbon atom bonded to -CH ^ Ri to complete all the atoms required to complete an alicyclic hydrocarbon group; and Π.—photoacid generator, which will be applicable to the paper size when exposed to pattern-forming radiation China National Standard (CNS) A4 (210 X 297 mm) 47 The scope of the patent application CH 丨 X C. R (I) Decomposes to produce an acid that can break the protected part. For example, the photoresist composition of claim 1 in the patent scope, wherein the protected soluble group is a fluorenic acid group represented by the following chemical formula (II): 〇 1 and Z are individually defined previously. 3. The photoresist composition according to item 1 of the application, wherein the alicyclic hydrocarbon group in the alicyclic hydrocarbon group-containing portion contains one or more ring structures or condensed rings. 4. The photoresist composition according to item 3 of the application, wherein the alicyclic hydrocarbon group is one of the following groups: (1) adamantane and its derivatives; (2) norbornene and its derivatives (3) perhydroanthracene and its derivatives; (4) perhydronaphthalene and its derivatives; (5) tricyclic [5 · 2 · 1. 〇2.6] decane and its derivatives; (6) two Cyclohexane and its derivatives; (7) Spiro [4 · 4] nonan and its derivatives; and (8) Spiro [4 · 5] decane and its derivatives. 5. The photoresist composition according to item 1 of the application, wherein the alkali-insoluble copolymer is a copolymer containing the repeating unit as the first repeating unit, and the copolymer is not the first repeating unit Other repeating units of this paper are in accordance with the Chinese National Standard (CNS) A4 specification (21〇 &gt; &lt; 297 mm) for this paper size ................. ：… ： —— Order ： …… ............. f (Please read the notes on the back before filling this page) -48 502134 A8 Β8 C8 ______ D8 VI. The scope of patent application includes one A repeating unit with an unprotected alkali-soluble group on its side chain, and / or a repeating unit with another protected alkali-soluble group on its side chain, the group being subjected to photoacid The acid produced by the product will be cut off. 6 · If the photoresist composition of item 5 of the patent is declared, the copolymer has a structural unit represented by the following chemical formula (III) or (IV): Wherein R may be the same or different, and each represents a hydrogen atom, a halogen atom, or a named or unsubstituted, straight or branched chain containing 1 to 4 carbon atoms, and the tomb is represented by Α is a protecting group , The acid will be released when this paper is used. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ........ (Please read first Note on the back then fill out this page). Order 丨 -49 A8 B8 C8 D8 The scope of patent application comes as defined above. 7. The photoresist composition according to item 1 of the patent application, wherein the alkali-insoluble copolymer is used together with one or more alkali-soluble polymers or copolymers. 8 · A method for forming a photoresist pattern The method comprises the steps of: coating a chemically amplified photoresist composition on a substrate to be manufactured to form a photoresist coating thereon, the photoresist composition comprising: I · an alkali-insoluble copolymer, which It has a structural unit as a repeating unit. The structural unit contains a protected alkali-soluble group. The repeating unit of the copolymer is one of the following groups. This group contains acrylate and its derivatives, Methyl succinate and its derivatives, fumarate and its derivatives, and styrene substitutes and their derivatives, in which the protected portion of the protected alkali-soluble group is in this unit , Will be cut off by the acid generated by the photoacid generator used with the copolymer, so the protective part is released from the soluble group, and the copolymer becomes alkali-soluble, The alkali-soluble group is optional One of the carboxylic acid group, sulfonic acid group, amido group, amido group and phenol group and is protected by the part containing alicyclic hydrocarbon group represented by the following chemical formula ⑴: This paper size is applicable to Chinese National Standard (CNS ) A4 size (210 × 297 male Chu) (Please read the precautions on the back before filling this page) Wherein 1 may be substituted or unsubstituted methyl, ethylpropyl or isopropyl, and 50 502134 A8 B8 C8 D8 patent application scope z represents together with a carbon atom bonded to -CHrl to complete a All the atoms required for the alicyclic hydrocarbon group; and II · a photoacid generator, which will decompose when exposed to the picture, resulting in Ά'Ι: which can cause the protective portion to break; selectively coating the photoresist The layer is exposed to a pattern of biologically-produced acid to form a car beam; the light film is heated to expose the photoresist coating to a temperature that can cause the part to be cut off; and the use of an alkaline phase The photoresist causes the exposed and heated photoresist layer to show a latent pattern. This paper size applies to China National Standard (CNS) A4 (210X 297mm) 51