TW500979B - Photoresist compositions with cyclic olefin polymers and additives, patterned photoresist structure, and the method of forming the same - Google Patents

Abstract

Acid-catalyzed positive photoresist compositions which are imageable with 193nm radiation and are developable to form photoresist structures of high resolution and high etch resistance are enabled by the use of a combination of cyclic olefin polymer, photosensitive acid generator and of a saturated steroid component, a hydrophobic non-steroidal alicyclic component, a hydrophobic non-steroidal multi-a licyclic component containing plural acid labile linking groups, or a bulky hydrophobic additive which is substantially transparent to 193 nm radiation. The cyclic olefin polymers contain (i) cyclic olefin units having polar functional moieties, and (ii) cyclic olefin units having acid labile moieties that inhibit solubility in aqueous alkaline solutions.

Description

^ 00979 V. Description of the invention (i) Background of the invention In the microelectronics industry ^ magnetoresistive head industry, other ancient industries include the construction of microstructures (such as micromechanics, microelectronics industry): I hope to reduce the structural part of the Size. Here we set the wafer size more: electrical: the size of the microelectronic components and / or provide special sum = ϊ 丄 ::: J force is the ability of the light receiving lithography technology to really resolve smaller parts ^ =. | Quality is limited by the finer resolution of the gain. Because: The tendency of the wave order of the light (or radiation) in the manufacture of lithographic patterns. Most recently, there has been a use of shorter light wavelengths for light lithographic meters.) The trend of moving to 248 nanoimitations has shifted from the so-called Bu-line radiation (350 nano-capillary water radiation. 'For husband inflammation P 2 requirements. Unfortunately, the two lowered, generating demand using 193 nm radiation is generally not suitable The main photoresist combination of the 1nm photolithography program is used when the photoresist group is ::, wavelength. When it is made long, it has the ideal lens characteristics after the shadow f to achieve the chemical and mechanical analysis of the desired radiation combination. , The photoresist composition must also have a suitable layer: after the light image ) Must be sufficient to prevent the graph == under_ from completing. ® 幸 彳 卜 ^ it #It can be patterned by chemical etching or ion etching to form a patterned first resist layer to resist the pattern transfer remaining process (such as the photoresist layer on the surface substrate layer. It can be imaged from the patterned photoresist Transfer to the lower response (that is, selective ha, the front photoresist of the exit pattern must be able to dissolve the aqueous test / Λ1 part appropriately) to produce the desired photoresist structure. Using the extensive experience provided by the universal use of Sii printing, here Species

Page 7 500979 V. Description of the invention (2) # The ability to engraved resistance is an important photoresistance feature. Some of the photoresist compositions have been designed to work with 193 nm radiation to make Ϊ 2 7 多个 one or more of the above parts ineffective. These groups of objects cannot generally show the trueness of shorter wavelength imaging. The advantages of resolution. = 2: Light: When the composition has better imaging ability and etching resistance, the light of the wavelength (such as 193 nm ultraviolet radiation) makes its invention summary-$: ί 1 has the performance of analytic lithography Λ, especially the use of 193 force, imaging ability and money resistance to provide extremely high ::: = transfer, because its resolution is limited only by the wavelength of the imaging radiation 4 4 The characteristics of bright photoresist compositions are generally (A) the presence of saturated steroid components of cycloolefin polymers, hydrophobic sterol polyalicyclic components (" HNMp ") or hydrophobic non-steroidal alicyclic rings containing t The presence of a cycloolefin polymer containing an acid-stabilizing functionality and an acid polar: S-energy composition, which is preferably additionally characterized by the presence of a super-aqueous additive, wherein the additive is substantially irradiated by 193 nm The above is transparent ^ The present invention also provides a photo-printing method using the photoresist composition of the present invention to create a photoresist structure and a method using the photoresist structure to transfer a pattern to the lower layer. The feature of this * lithography method is best to use 丨9 3 nm UV Radiation makes the map-and ode. The method of the present invention can resolve the size without using a phase shift mask. It is about 150 nm, preferably less than about 115 nm (using

5. Description of the invention ¢ 3) 0.68 digital aperture lens). In terms of features :: month includes: a photoresist composition, which includes: (a)-a cycloolefin polymer, which includes: υ ring dilute unit with a polar functional group portion, and π) μ The ring-shaped unit of the acidic indeterminate part, the acid indeterminate part can inhibit the solubility in alkaline aqueous solution, (b) — a kind of photoactive ingredient, and (:) J saturated t; sterol ingredient, hydrophobic Non-steroidal alicyclic ingredients or (,, read " ^ Non-Women's linker hydrophobic non-steroidal multi-alicyclic ingredients class ΐ group is preferably composed of cyclic dilute hydrazones. Units. Best two'men ^ The units on the eve of i) and _ 'blemishes contain the acidic polar portion of pKa $ 1 3. ϊ: Ϊί Most: = t sexual. The preferred saturated steroids are modified by Shishan acid of Beishan, and the water-based non-steroidal alicyclic component preferably contains ⑴ = a few more alicyclic parts. HNMp preferably contains at least two alicyclic moieties # or carbon f. The acid leaving of the ingredients is preferably caused to have a plurality of acidic = functional groups and / or a plurality of each having at least one acidic polar group: the formation of acidic compounds. α is contained in another feature. The present invention includes a photoresist composition comprising (a) a cycloolefin polymer) U〇979 5. Description of the invention (4) ii) a ring having an acid-labile portion A unit of thallium, the acid-labile part can inhibit the solubility in alkaline aqueous solution, (b) a photoactive component, and (c) a huge hydrophobic additive, the additive is irradiated at 1 93 nm The bottom is essentially transparent. ⑽ In this feature, the cycloolefin-based polymer of the present invention contains about 5 to 40 mol%, bit 1). The cycloolefin-based polymers of the present invention are basically composed of cycloolefin-based single sites; preferably, they are basically composed of units ^ and "). The huge hydrophobic additive preferably contains a The alicyclic part. In another feature, the present invention includes a method of photoresist structure, the method includes: Table 埏 patterning (a)-a surface with a photoresist composition of the present invention (b) pattern-like exposure The photoresist layer is a base material, a photoresist layer, and a layer under emission, so part of the photoresist layer is exposed to (C) a light-resistant developer solution contacting the light-exposed portion to create a patterned photoresist structure In addition, the radiation used in the step (hi age m) of the above method is preferably 193 nm. 疋 氅 micron ultraviolet radiation. The present invention also includes the use of fields to make conductive, semi-conductive, bright compositions. The photoresist method of the present invention and the method of generating or forming a marginal structure .... The structure ij is described in detail, and its characteristics will be discussed in further detail below. The photoresist composition of the present invention includes a n-position. , Where the

Page 10, 500979 V. Explanation of the invention (5) The solubility of the solution and ") have acid-unstable iid: position, which makes the acid-unstable portion can be inhibited in the cycloolefin unit υ% of the test water. In addition, there is a kind of huge = Sheng Mo Er Li II: feature 'where the additive is substantially i under 193 nm radiation :; cb) ---- Λ1Λ alicyclic component containing multiple acid labile links / Or exist. Xi 璟 suspected of taking people & soil 1 l water-based non-steroidal polyalicyclic components jn? Ene t compounds preferably contain i) have acidic polar functional beauty

Part of the cycloolefin unit, and in the ancient and lacking π AAA f 丨 Wang S guilty of violence P in the mouth X X —), a cycloolefin unit with acid and no son-in-law part, order f acid not son-in-law part It can suppress the dissolving sound in alkaline aqueous solution t. Eight

= Some of the compositions of the present invention can be particularly utilized 丨 93 milliseconds of imaging capabilities and pattern transfer characteristics to provide high-resolution light lithography / this hair month also includes the photoresist group containing the present invention = create a photoresist structure and use this Photoresistance Junction: First: Method of Electrical and / or Insulating Structure. / Wind power and photoconductor The photoresist composition of the present invention generally includes: U) a kind of cycloolefin polymer, which comprises: a total of 1i cycloolefin units with a polar functional group moiety, centered 嗲 shirt A; It is selected from the group that can help in the alkaline phase. It is possible to prevent the polar part, the polar part, and the acidic part and the non-acid part in Hakkei. Solubility in alkaline aqueous solution, the acid and non-sex part can be found on page 500500979. V. Description of the invention (6) (b)-a kind of pre-activated ingredient, and (c) a kind of saturated steroid ingredient, hydrophobic non-steroidal lipid Ring components. Hydrophobic non-steroidal alicyclic components containing multiple acid-labile linking groups or a huge hydrophobic additive, the additive is substantially transparent under 9 nm radiation. The cycloolefin unit i) may be any cycloolefin-based monomer unit having an acidic polar functional group, wherein the acidic polar functional group promotes alkali solubility or a cycloolefin-based monomer unit having a non-acidic polar group. Examples of cycloolefin monomers include the following monomers represented by the structure (ί), where d represents a (acid) polar moiety and ^ is zero or a positive integer: (1) · M cycloolefin unit i) Is selected from: a)

(Π) where R! Represents an acidic polar part or a non-acidic polar part which can help the solubility in an alkaline aqueous solution. The pKa of the acidic polar part is preferably

Page 12 500979 V. Description of the invention (7) About 13 or less. Preferred acidic polar moieties include polar groups selected from the group consisting of fluorenyl, #sulfofluorenyl, fluoroalcohol, and other acidic polar groups. Second, the sword is finished. The non-acidic polar part preferably has a team > 13 y-heteroatoms such as oxygen, nitrogen or sulfur. If necessary, a combination of cycloolefin units i) with t-functional groups can be used. Preferably at least some or two units i) have an acidic polar functionality. Acene cycloene units ii) can be any and ancient ~ significant, T ~ /, cycloenes with acid-free female sex part of the early position, the acid-labile part can suppress Qiu neck early Examples of acrocyclene-based monomers include the following solubility in a basic aqueous solution of Jf. μ represents a monomer of the protective acid-not i = conformation (III), where 其 and η are zero or a positive integer:

Ra (HI). Η cycloolefin unit i i) is preferably selected

Wherein h represents a protective acid ~ I & the fixed part is selected from the Γ fire part containing tertiary alkane. Better protected acid-unstable, methylcyclopentyl, methyl, di (/ cycloalkyl) acetic acid (such as tert-butyl | hexyl, methyl, adamantyl), ester 500979 V. Invention Explanation (8) ~ —---------— ^ a ^ ketal two: ί: carboxylic acid vinegar is the best protective acid-unstable part. ^ Group right combination is best Λ use Λ Cyclo-diluted units with different protective functionalities 1 functionality. yt or all mountene units 0 has acidic polarity = product = road structure and other microstructures used in the manufacture of light stone:,:, this: bright ring dilute polymers preferably contain about 5, mocarboxylic acid functional units Where it is composed, the cyclic olefin polymer 2 of the present invention preferably contains about 5-30 mole%, preferably about 10-25 mole. The women's unit U. Where the cyclic unit = = = unit is composed, the cyclic dilute polymer of the present invention preferably contains 10-80 mol%, and most preferably about 20-40 mol%. % ~ Halopoly sigma is preferably at least about 20-90 mol%, and Ringer is about 40-90 mol%. If carboxylic acid is used as an acidic group, it is preferably 1 乂 80-90 mol%, or If acid functionalized units are used, the most 60 to 80 mole%. The cycloolefin-based polymer of the present invention contains other monomer units in addition to units. The cycloolefin polymer of the present invention preferably contains other monomer units such as ^ > / 〇 or 祗, preferably about 20 mol. The cyclic cyclic polymer of the present invention is basically The inventive photoresist composition is additionally characterized by the presence of a saturated steroid q. The ss component can generally increase and / or increase the correction of 77? κ M Eight N W shellfish with aqueous SS; f agent; ability to resolve extremely fine lithographs in response. The special saturation: sterol (C17) alicyclic skeleton structure is: The saturated steric enzyme component may contain a kind of residues with multiple residues 500979, invention description (9)

The acid produced in the reaction part, because: after the species can promote the solubility test molecules, sterols or tri-steroids). The SS component preferably contains pendant groups of acid-labile parts (such as the part of the photolithography process, so the part is lysed to provide the molecule for verification). The preferred SS component y contains additional pendant groups such as those selected from the group consisting of formamyl, hydroxyl, or trifluoroacetamidine. If this acid-labile moiety is present, it can be separated by one or more spacers' as shown in the following structures SL-1 and SL-2. Generally speaking, the more hydrophobic SS component is preferred. If necessary, a composition containing SS ingredients may be used. Examples of preferred SS ingredients include cholic acid esters (such as tertiary-butyllithocholic acid ester, tertiary-butyl deoxycholate, tertiary-butyl cholate), ester modified Lithocholic acid esters (such as tert-butyl-3-trifluoroethylfluorenyllithocholic acid, tertiary-butyl-3-ethynylphosphocholic acid ester, tertiary-butyl-3-tetramethylenefluorite) Cholic acid esters), ester modified cholic acid esters (such as tertiary-butyl-3, 7, 12-trimethylamidinocholate, tertiary-butyl ginseng— (3, 7,12-tris) Fluoroacetamyl) cholic acid ester) and separated lithocholic acid esters have the following structures SL-1 and SL-2.

500979

❿, and tBu 疋 tertiary butyl. One of the best SS ingredients is Dibuthi-3-trifluoroacetamidite-depleted urethane monobutyl your stone cholate. ^ / v " ^ 1 denier compound additionally with a hydrophobic non-steroidal alicyclic ring (丨 丨 HNA ",

, The deposit * is special. The HNA component can generally reconcile / dissolve HNA ~ h with the ability to react with an aqueous alkali imaging agent. The HNA component is characterized by the presence of non-steroidal lipids, and the presence of 4 # condensed ring structures of HNA on the w side. Cn " h \), which does not contain steroids. The alicyclic structure preferably contains up to carbon atoms. The whole two A 1 ° ..., the best is about 1 " ο more preferably about 1 4-50 carbon atoms. ~ 2 contains at least about 14 carbon atoms' and contains more than one alicyclic moiety. / It is necessary that the ΗNA additives of the present invention are suitable. They are preferably separated from the lower H linking group by an example of an alicyclic compound comprising two alicyclic moieties. — So many

Page 500 500979

V. Description of the invention (π)

The ΗΝΑ preferably contains one or more pendant acid labile moieties (ie, a moiety that reacts with the acid produced by the lithographic process, so this moiety is cleaved to provide molecules that promote alkali solubility). The preferred acid labile moiety is selected from the group consisting of tertiary alkyl (or cycloalkyl) carboxylates (such as tertiary butyl, methylcyclopentyl, methylcyclohexyl, methyladamantyl), Ester acetals and ester acetals. Tertiary-butyl carboxylate is a preferred acid labile pendant group. The HNA component may also include pendant groups that increase molecular volume and / or increase molecular hydrophobicity in a manner that enhances the effectiveness of the photoresist composition. If necessary, the y-side acid labile moiety may be separated from one or more spacer groups from the alicyclic moiety. If necessary, HNA ingredient compositions can be used. Examples of your preferred HNA composition include adamantane and carboxylate esters of higher carbon fused alicyclic systems. An optimal HNA ingredient is adamantane tert-butyl elephantate.

The following structure illustrates some examples of HNA components:

Page 17

500979

Page 18 500979

The photoresist button compound of the present invention is further characterized by the presence of multiple acid-labile and water-soluble non-steroidal polyalicyclic components (" " NMP "). The components can generally and / or improve the resolution of the ultra-fine lithographed part to the aqueous alkali The developer's ability to react. The ΗNMP component is characterized by the presence of at least two different non-steroidal alicyclic structures (ie, k-condensed ring structure features that do not include steroid compounds). The alicyclic structures preferably each include at least 7 carbon atoms () 'are preferably about 10-30 carbon atoms, including pendant groups. The entire ηnMp component preferably contains about 20-60 carbon atoms. The ΗNMP broadly encompasses at least two acids The labile linker and at least two alicyclic moieties allow an acid labile linker to exist between the at least two alicyclic moieties. The ΗNMP compound comprises a plurality of acid labile linkers and a plurality of alicyclic moieties. The structure of this compound can be represented by the following formula: (X)

R X

Page 19 500979 V. Description of the invention (14) The bond between R and X is acid labile, so that at least one Xc-R1 derivative can be formed by cleaving the R-X bond with an acid, in which X. Is an acidic polar side-group extending from R '. η is at least two. If R contains an alicyclic moiety, then at least one R ' contains an alicyclic moiety. If R does not contain an alicyclic moiety, then at least two R 'groups each contain an alicyclic moiety. Wherein X is a carboxylic acid group, the structure is: (νι) Ο

R—-O——C—R1 L J η where the R—O bond is acid labile. After cleavage, a carboxylic acid group will remain on the flanking side. Where η is 2 and R ’contains an adamantane moiety, the structure may be

Among them, R is preferably an acid-labile ester group such as two third-butyl ester groups bonded together (in the following structure XI a, 1 refers to the position of the acid-labile linker) or some other acid-labile linker Of combination. As a result of cleavage, multiple

Page 20 500979 V. Description of the invention (15) parts of the compounds have side carboxylic acid groups

(Xla)

Alternatively, the HNMP compound may have a structure

R X1 R · (XII) where the bond between R 'and X' is acid-labile so that R- (Xe) n, a derivative can be formed by cleaving the R'-X 'bond with an acid, where Xc is an extension from R is an acidic polar pendant group. η 'is at least two. At least one QT has an alicyclic moiety and at least one R or the remaining R 'moiety contains an alicyclic moiety. In either case, the final result after cleavage will create two smaller molecules each with an alicyclic moiety and make multiple polar functionalities extending from R. Where X is a traitor, the structure is: 0

R

C Ο (XIII) η

500979 Page 21

500979 Page 22

In the HNMP compound used in the present invention, the acid-labile linker preferably reacts with the acid generated in the light lithography process. Therefore, this part can provide molecules or substantially reduce the molecular weight through dream interpretation, and then promote photoresistance. Alkali solubility of the radioactive part. The most unstable linker moiety contains at least _'s selected from the group consisting of tertiary alkyl (or cycloalkyl) carboxylates (such as tertiary butyl, methylcyclopentyl, methylcyclohexyl, methyladamantine Alkyl), esters, and aldehydes. The HNMP component may also include pendant groups that increase molecular volume and / or increase molecular hydrophobicity in a manner that enhances the effectiveness of the photoresist composition. If _% is desired, HNMP ingredient composition can be used.

Examples of preferred HNMP ingredients include adamantane and bis-carboxy esters of salicyclic systems of higher carbon numbers. One of the best HNMP ingredients is bis-adamantine ^^-butyl carboxylate. In addition to the cycloaliphatic polymer, the photoresist composition of the present invention contains a light-sensitive acid generator (PAG). The invention is not limited to the use of any particular

P.23 500979 V. Description of the invention (18)

Or the P A G composition ', the benefits of the present invention, can be obtained by using various light-sensitive acid generators well known in the art. The preferred PAGs are those PAGs containing low (or preferably no) aryl moieties. Where pAG containing aryl groups is used, the absorption characteristics of PAG at 193 nm may limit the amount of pAG contained in the formulation.

Examples of acid generators suitable for photosensitivity include (but preferably substituted one or more of any specified aryl moieties with alkyl groups) gun salts such as triaryl hexafluoroantimonate, diaryl iodohexafluoro antimonate Esters, hexafluoroquinates, trilates, perfluoroalkane% esters (such as perfluoromethanesulfonate, perfluorobutane, perfluorohexanesulfonate, perfluorooctanesulfonate, etc.), Substituted aryl sulfonates such as trisphenol f (such as pyromellitic esters of pyrogallol or ginseng (sulfonate)), sulfonates of hydroxyimine, N-perfluoro Benzyloxynaphthalenedimethylamine, α ^ α'bis-maplediazomethane, naphthoquinone diazide, alkyl dibasic acid ester, and others. The transparent giant BH additive of the present invention contains carbon atoms in the alkali developer part. The BH fixed side group is selected from the group consisting of a photoresist group and a large hydrophobic group through radiation. Generally, it is particularly preferable to be added. The agent is in the acid-emitting part and is saturated.

The compound is further characterized by the presence of substantially additive (" BH " additive) under 193 nm radiation. t and / or improve the ability to resolve the very fine lithographs' response to water usage. The BH component is preferably characterized by at least one lipid. The M additive preferably contains at least about 14 to 60 carbon atoms and at least 14 carbon atoms, most preferably about 14 to 60 carbon atoms. 3 Most preferably contains one or more additional moieties such as cleavage in the presence of acidic uneasiness to provide A composition that can promote light twist = solubility. Preferred paste additives: Steroids, non-steroidal alicyclic compounds, at least

Page 24 500979 V. Description of the invention (19) A non-steroidal polyalicyclic compound having multiple acid-labile linkers between alicyclic moieties. Preferred BH additives include lithocholic acid esters such as tertiary-butyl-3-trifluoroacetamidinocholate, tertiary-butadiene alloy carboxylic acid esters, and bis-adamantyl-butylcarboxylic acid esters. If necessary, M additive fat compositions can be used. This hair = The photoresist composition will generally contain a solvent before it is applied to the target substrate. The solvent can be any solvent that is customarily used with an acid-catalyzed photoresist, and in addition, it does not have any excessively negative effects on the effectiveness of the photoresist composition. Preferred solvents are propylene glycol monomethyl ether acetate and cyclohexanone ethyl acetate cellosolve. The composition of the present invention may further contain minor amounts of auxiliary ingredients such as dyes / sensitizers, alkali additives and the like known in the art. The preferred base additive is a weak base that removes a small amount of acid without having much effect on the photoresist effectiveness. Preferred base additives are (al iphat i c or alicyclic) tertiary alkylamines or tertiary alkylammonium compounds such as tertiary-butylammonium hydroxide (TBAH). The photoresist composition of the present invention preferably contains about 0.5-20% by weight (preferably 3-15% by weight) of a light-sensitive acid generator, based on the total amount of the composition of the composition. Fine in solvent, most of the entire composition: $ 50-90% by weight solvent. The composition preferably contains the alkali additive in weight percent or less. Based on the total weight of the acid-sensitive polymer, the compound preferably contains at least about 54% by weight of Lang, ss, and H_. It is about 10-25% by weight, and most preferably about OM_2%, based on the total amount of the cycloolefin-based polymer in the composition. The invention is not limited to any particular method for synthesizing too polymers. The material polymer is preferably formed by adding a cycloolefin compound used. Suitable for

Page 25 5. The technical example of the description of the invention (20) is disclosed in B.F Gcmrit ^ · k, 5,468,8 1 9 ^ 5,705,503 " This disclosure is incorporated herein as a reference-5, 000-1 0, 0, 00, preferably about 10, 000-50, ㈣❹. ss%: a means: use this method to remove the cycloolefin polymer, PAG, βΗ, and invent the cycloolefin polymer. It can be used for photo-acquisition and wound-acquisition. 'The photoresist composition of the sequence is generally = bright ring type polymers are particularly useful in photolithography processes for semiconductor circuits. In particular, the composition can be a light lithographic process for millimeters of radiation. If other radiations are to be used: for example, micron deep, νν, χ ′ rays, or e-beams), the composition of the present invention can be adjusted by adding appropriate wood chips or crackers to the composition. : General use of the resist composition in semiconductor light lithography technology

Semiconductor light lithography applications generally involve transferring a pattern to a material layer on a semiconductor substrate. The material layer of the semiconductor substrate can be a metal conductive layer, a ceramic insulation layer: a semiconductor layer, or other materials depending on the target material set by the manufacturing process steps and the final product. In many instances, an anti-reflective coating (ARC) is applied to the material layer before the photoresist layer is applied. The ARC layer is any conventional ARC that is compatible with acid-catalyzed photoresist. In general, a solvent-containing photoresist composition is coated on a target semiconductor substrate by spin coating or other techniques. After that, it is best to heat the photoresist coating

Page 26 500979 V. Description of the invention (21) layer substrate (baking before exposure) to remove the solvent and improve the cohesion of the photoresist layer. The thickness of the coating layer is preferably as thin as possible, but the condition is that the thickness is-most preferably substantially uniform and the photoresist layer is sufficient to withstand subsequent processing (generally reactive ion etching) to transfer the lithographic pattern to On the underlying material layer. The pre-exposure baking step is preferably performed for about 10 seconds to 15 minutes, and more preferably about 15 seconds to 1 minute. The pre-exposure bake temperature can be changed depending on the glass transition temperature of the photoresist. The pre-exposure bake is preferably performed at a temperature lower than at least 20 ° C. After removing the solvent ’, the photoresist layer is then pattern-wise exposed to the target radiation (eg, 193 nm ultraviolet radiation). Use a scanning particle beam such as an electron beam 'to sweep the substrate through the beam and selectively apply the beam to a target pattern to achieve pattern-like exposure. More generally, wave-like radiation is formed like a pattern of external radiation at 193 nanometers1. The exposure is performed through a mask placed on the photoresist layer. For 193 nm UV radiation, the total illumination energy is preferably about 100 mJ / cm2 or less, preferably about 50 mJ / cm2 or less (such as 15-30 mJ / cm2). . After the desired pattern is exposed, the photoresist layer is generally baked to further form an acid-catalyzed reaction and the contrast of the exposed pattern is raised—the exposure and co-baking are preferably at about 100-175 ° C, preferably at about 1 2 5-1 60 ° c. After ~ exposure baking is best performed for about 30 seconds to 5 minutes.

After the post-exposure baking, a photoresist structure having a target pattern can be obtained (developed) by contacting the photoresist layer with an alkaline solution, wherein the alkaline solution can selectively dissolve the photoresist that has been exposed to radiation. Part. The preferred test solution (developing agent) is an aqueous solution of tetramethylammonium hydroxide. It is better to use the usual 26N

Page 27 ^ uuy / 9 V. Explanation of the invention (22) ~~~-@ # 〖生生 水 的 Development of the photoresist composition of the present invention. The photoresist 1 and the compound of the present invention can also be developed using 0. 1 4N or 0.21 N or other alkaline aqueous solution. Generally, the photoresist structure obtained on the substrate is then dried to remove any residual developer solvent. The photoresist composition of the present invention is generally characterized in that the photoresist structure of the product has high resistance to etching. In some examples, the etch resistance of the photoresist structure can be further improved by using a method known in the art-a sintering technique. The composition of the present invention can reproduce the lithograph portion. The pattern from the photoresist structure is then transferred to the underlying substrate material (such as ceramic, metal or semiconductor). Typically, this transfer can be achieved by reactive etching or some other etching technique. In the reactive ion etching environment, the photoresist's etch resistance is particularly important. Therefore, the composition of the present invention and the resulting photoresist structure can be used to create a patterned material layer structure such as a metal wiring, a contact or a hole of a through hole in a design of an integrated circuit element. Or shallow trench isolation), trench # of capacitor structure. The procedure used to make these (ceramic, metal or semiconductor) parts is to change the material layer or part of the substrate, coating-photoresist layer on the material layer or. The photoresist is exposed to radiation, pattern-likely exposed to radiation, and sincerely! Solvent contact to develop the pattern, etch the two layers of the photoresist layer below the photoresist layer, and form a patterned material layer or substrate. And remove any remaining photoresist from the substrate. In some examples, a hard mask is used under the photoresist layer to help transfer the pattern to the underlying layer or portion. An example of this program is disclosed in US Patent 4, π 5, 〇 丨 7;

P.28 500979 V. Description of the invention (23) 5,362,663 429,710; 5,562,801; 5,618,751; 5 744, 376 ;; 5, 801, 〇94 and 5, 821, 46 9, the content of this patent is hereby incorporated by Reference. Other examples of pattern transfer procedures are in chapters 2 and 3 of the ffayne Mow " semiconductor lithography, principle, implementation, and materials " issued by Plenum Press in 1988. Incorporated for reference. It should be understood that the present invention is not limited by any fixed lithographic technique or component structure. Example 1 (control)

For the purpose of lithographic experiments, a photoresist formulation containing an original norbornene copolymer was prepared by mixing the materials listed below in parts by weight, wherein the original norbornene copolymer contained 85% orthobornene tertiary-butyl Esters and 15% orbornene-carboxylic acid (as a side group) (NB-CA). 37 4 0. 16 0. 008 Copolymer of propylene glycol monomethyl ether acetate NB-ΐ-BE and NB-CA (85/15) Di-tertiary-butylphenyl iodogun perfluorooctane sulfonate Tetrabutylammonium phosphonium oxide The photoresist formulation was spin-coated (30 seconds) on an anti-reflective material (Ur, Shipley, Inc.) coated on a silicon film. The photoresist layer was soft-baked for 60 seconds on a vacuum hot plate at 30 ° C to soften to produce a thin film of about 0.4 microns. The film was then exposed to 193 nm radiation (0.6 NA ArF, ISI stepper camera). The exposed pattern is an array of lines and spaces of different sizes, wherein the size of the spaces can be reduced to 0.1 micron. Let illuminated film

Page 29 500979 V. Description of the invention (24) Post-exposure baking at 150 ° C on vacuum heating plate for 90 seconds. Then use 0 · 2 6 3 N tetramethylammonium hydroxide developer to develop the photoresist (stirring) of the exposed pattern. The pattern was then determined by scanning electron microscopy (SEM). The cross section of the S EM pattern indicates that it cannot resolve below 200 μm L / S (line-spaced pair) due to overlapping lines. Even line-spaced pairs larger than 200 nm cannot be fully resolved because of excessive residue / residues between the lines. Example 2 This example illustrates the benefits of a composition of the invention containing a saturated steroid additive. Photoresist formulations can be prepared by mixing the materials listed below in parts by weight in propylene glycol monomethyl ether acetate g | 38 Poly (orthobornene) with t-BE and CA groups (t-BE / CA: 85 / 15) 4 bis-tertiary-butylphenyl iodonium perfluorooctane sulfonate 0.16 tertiary-butyl-3-trifluoroethylfluorenyllithocholic acid-0.4 tetrabutylammonium hydroxide. 008 The photoresist formulation is applied by spinner; Μ ΓΑγχ®, the chamber is placed on the anti-reflection material coated by silicon film, αγα slave (bhipley company), Tuzhong M η know luxury you μ know η ^ 1 was illuminated as a national beam (193 nm) and developed in the same manner as in Example 1. Ran Hu

(SEM) measured the obtained figure 荦. The 14 micromolds of the microscopic electron microscopy clearly knows that the 庑 u card and the line-space pairs above can be completely resolved by 4 m. This blend 4 ranges from 25-35 mJ / cm2. The energy needed for lighting is

500979 V. Description of the invention (25) Example 3 Synthesis of adamantane-1-carboxylic acid third-butyl ester

To a suspension of 25.34 g (0.332 mol) of tertiary-butyl alcohol in 600 liters of methane at room temperature was added 3807 g (0.315 mol) of tris-butyl alcohol. Ethylamine. The resulting suspension was stirred at room temperature until it became a clear solution. At (TC, 74.75 g (0.3762 mol) of King Kong & -1 -carbonyl chloride was added to the above solution. After the addition was completed, the reaction mixture was stirred at room temperature for 12 hours, then under reflux conditions Heated for 2 hours. The reaction mixture was filtered to remove triethylamine gaseous hydrogen formed during the reaction. The mash was washed several times with water (500 ml), dried over anhydrous sodium sulfate, and under reduced pressure. Concentrated. Purified residue by column chromatography (Shi Xijiao; hexane / dichloromethane: 9: 1) to obtain 48.4 g (~ 60%) of a white solid, identified by NMR spectroscopy This is the third-butyl ester of adamantane-1-carboxylic acid. Example 4 This example illustrates the benefits of the composition of the present invention containing the third-butyl ester of adamantane-1-carboxylic acid. The photoresist formulation can be mixed Made from the materials listed below in parts.

P.31 500979 V. Description of the invention (26) Propylene glycol monomethyl ether acetate poly (orthobornene) having fluorene-BE and CA groups 4 (t-BE / CA: 85/15) 'Second-third- Butylphenyl iodonium perfluorooctane acid

Amantadine-1-carboxylic acid tertiary-butyl ester (Example 4 Tetrabutylammonium hydroxide 〇 * 〇〇8

This photoresist formulation was spin-coated on an anti-reflective material (Alphax'Shipley Company) on a silicon film, pattern-like light (193 nm), and developed in the same manner as in Example i. The resulting pattern was then measured by scanning electron microscopy (SEM). Line-space pairs of 140 nm and above can be clearly resolved with clear contours. The light energy required for this formulation is in the range of 20-30 millijoules per square centimeter. Example 5 Synthesis of 2,5 -bis (adamantane-1-carboxyoxy) -2,5-dimethylhexane At room temperature, a compound containing 50 g (0.342 mol) of 2,6 -A suspension of dimethyl-2,5-hexanedionate in 600 ml of dioxane was added with 76.14 g (0.762 mol) of triethylamine. The resulting suspension was stirred at room temperature until it became a clear solution. At TC, 149.5 g (0.7524 mol) of rimana-1-carbonyl gaseous substance was added to the above solution. After the addition was completed, the reaction mixture was stirred at room temperature for 12 hours, and then refluxed. It was heated under conditions for 2 hours. The reaction mixture was filtered to remove triethylamine gaseous hydrogen formed during the reaction. The filtrate was washed several times with water (500 ml), dried over anhydrous sodium sulfate, and then Concentrated at low pressure. Purification of the residue by column chromatography (silica gel; hexane / digas methane: 9: 1) yields 1 2 8 g

P.32 500979 V. Description of the invention (27) (~ 80%) A white solid identified by NMR spectroscopy means that it is 2,5-bis (adamantyl ~ fluorenyloxy) -2,5-dimethyl Hexane. Example 6 This example illustrates the benefits of a composition of the present invention containing 2,5-bis (adamantyloxy) -2,5-dimethylhexane. Photoresist formulations can be prepared by mixing the materials listed below in parts by weight to produce propylene glycol monomethyl ether acetate 38 poly (orthobornene) with t-BE and CA groups 4 (t-BE / CA: 85 / 15) Mono-tertiary-butylphenyl iron hindering perfluorooctanoate 0.16 2,5 ~ bis (adamantane-1-carboxyoxy) -2,5-dimethylhexane 0.4 (Example 5) Tetrabutylammonium hydroxide 0.008 The photoresist formulation was spin-coated on an anti-reflection material (AΓχ® 'Shipley Company) on a silicon film, pattern-like light (93 nm), and an example was used. 1 in the same way. The scanning pattern was then determined by scanning electron microscopy (SEM). Line-space pairs of i 30nm and above can be clearly resolved with clear contours. The light energy required for this formulation is in the range of 20-30 mJ / cm2. Example 6 (Control) For the purpose of lithographic experiments, a photoresist formulation containing an original norbornene copolymer was prepared by mixing the materials indicated in parts listed below in weight, where the

P.33 500979 V. Description of the invention (28) The original norbornene copolymer contains 85% orthobornene tertiary-butyl ester (Kwanichi t-gg) and 1 5% orthobornene-carboxylic acid (as a side group) . Propylene Glycol Monomethyl Ether Acetate 37 Copolymer of NB-1-BE and NB-CA (85/15) 4 Di-Second-Butylbenzyl Perfluorooctanesulfonate 0.1% Tetrabutylammonium Hydroxide 0008 The photoresist formulation was spin-coated (30 seconds) on an anti-reflective material (Ar) (Shipley Corporation) coated on a silicon film. Baking on a vacuum hot plate at 13 ° C. for 60 seconds to soften the photoresist layer to produce a thin film of about 0.4 microns. The film was then exposed to 193 nm radiation (0.6 NA ArF, I SI step camera). The exposed pattern is an arrangement of lines and spaces of different sizes, where the size of the spaces can be reduced to 0.1 micron. The illuminated film was post-exposed and baked on a vacuum hot plate at 150 ° C for 9 q seconds. Then, the photoresist (stirring) of the exposed pattern was developed using a 0. 263N tetramethylammonium hydroxide developer. The pattern was then measured by scanning electron microscopy (SEM). The cross section of the SEM pattern indicates that it is impossible to resolve below 200 micrometers L / S (line-space pair) due to the overlapping lines. Even line-space pairs larger than 200 nm cannot be fully resolved because of excessive residue / residues between the lines. Example 7 A 12-liter four-necked round bottom flask was charged with 500 g (1.328 mol) of cholestyronic acid and 4 liters of dry THF, wherein the round-bottomed flask was equipped with a head shaker,

Page 34

Dvvy / y V. Description of the invention (29) Thermocouple temperature monitor and 1 liter of nitrogen inlet:. J ”1 920 ml (13.6 mol) trifluoroacetic acid in a second funnel. Cool the flask in ice and add trishydride to a dilute stream of water. Heat the mixture to room temperature and stir with a funnel. After that, the solvent and acid anhydride were removed in a rotary evaporator. The thick and viscous intermediate was transferred to another refilling tank; the liter was a liter flask. 740 g (10 mol) of the third-butyl (explained as (To prevent solidification) into the addition funnel.-^ Amount F dilute * 々 独 才 T. Dandu in an ice bottle and the third -butyl alcohol was added to keep the temperature below 10% to reach room temperature. Then Add nearly 200 g of solid NaHC03 and continue to bleed for another 2 hours. Then remove the solvent and excess tertiary butyl alcohol in the spin. And mix • Mainly 3x800 ml of saturated NaHC03 in ether, then Take 2χΐ〇〇〇〇 liter ^: heart wash it. # With stirring, dry the solvent by heart for about ^ hours, filter it and evaporate it in a rotary evaporator. _ Slowly extract the thick and viscous residue Matter, by a big official to slow silicon haze? # 占 | 物。 The column contains 80 0g 'yuan. In a rotary evaporator发 所 人 |, and under vacuum and 40. (: next to the suspected animal continued :; the product of the depleted and unincorporated into a wound to obtain 620 g (88%) mesh = :::: to the remaining solvent to-fixed In the Chinese Academy of Sciences, the date can be successfully settled: ；: ;; 'colored white syrup. A low melting point white wax was obtained from Example 8 from the negative load. This example illustrates the composition of the present invention expressed in parts by weight. Materials can be borrowed " combined

P.35 500979 V. Description of the invention (30) Propylene glycol monomethyl ether acetate 38 Poly (orthobornene) having fluorene-ΒΕ and CA groups 4 (t-BE / CA: 85/15) Second-third- Butylphenyl iodine gun perfluorooctane sulfonate 0.16 second-butyl-3-digas ethyl alcohol lithocholic acid ester (Example 2) 0.4 tetrabutylammonium hydroxide 0.008

The photoresist formulation was spin-coated on an anti-reflective material (Ari®, Shipley, Inc.) coated with a silicon film, pattern-like light (193 nm), and developed in the same manner as in Example 6. The resulting pattern was then measured by scanning electron microscopy (SEM). Line-space pairs of 140 nm and above clearly show that the contours are fully resolved. The light energy required for this formulation is in the range of 25-35 mJ / cm2. Example 9

To a suspension of 25.34 g (.342 mol) of tertiary-butyl alcohol in 600 ml of dichloromethane was added 38.Q7 g (0.315 mol) at room temperature. Triethylamine ◎ The resulting suspension was stirred at room temperature until it became a clear solution. At 0 ° C, 74.75 grams (0.3762 moles) of diamond-fired 1-carbonyl gas was added to the above solution. After the addition was completed, the reaction mixture was stirred at room temperature for 12 hours, and then heated under reflux for 2 hours. The reaction mixture was filtered to remove triethylamine hydrogen chloride formed during the reaction. The filtrate was washed several times with water (500 ml), dried over anhydrous sodium sulfate and concentrated under reduced pressure. Via column chromatography (silicon

P.36 500979 V. Description of the invention (31) Gum 'Hotong / Digasaki: 9: 1) Purified residue can obtain 48.4 g (~ 60%) of white beetle. Spectral identification indicates that it is diamond. Alkane- 丨 -carboxy # acid third-butyl ester. Example 10 For the purpose of lithographic inspection, a photoresist formulation containing an original norbornene copolymer was prepared by mixing the materials listed below in parts by weight, wherein the original norbornene copolymer contained 85% of the original norbornene copolymer. Tri-butyl ester be) and 15% orbornene-carboxylic acid (as a side group) (NB-CA). Propylene glycol monomethyl ether acetate 3 7 Copolymer of NB-1-BE and NB-CA (85/15) 4 Di-tertiary-butylphenyliodine tweezers perfluorooctane sulfonate ^ i 0.08

The cross section of the SEM pattern indicates the photoresist of the tetrabutylammonium hydroxide due to the lines overlapping each other. The pattern was measured. Cannot parse out below 500979 V. Description of the invention (32) 2 0 0 Wei L / S (line-space pair). Pairs cannot be fully resolved. Object 0 Even lines larger than 200 nm. Line spacing because of excessive residue / residue between lines. Example 11 Photoresist formulations can be mixed. This example illustrates the benefits of the composition of the present invention. Made from the materials listed below in parts. 38 4 0. 16 0.4 0. 008

Propylene glycol monomethyl ether acetate Poly (original borneol) with fluorene-BE and CA groups (t-BE / CA: 85/15) Di-tertiary-butylphenyl iodogun perfluorooctane sulfonate Adamantane-1 -carboxylic acid third-butyl ester (Example 3) The tetrabutylammonium argon oxide barrier formulation was spin-coated on an anti-reflective material (ArP, Shipley Co.) Light was patterned (193 nm) and developed in the same manner as in Example 10. The resulting pattern was then measured by scanning electron microscopy (SEM). Line-spaced pairs of 14 nm and above can

The clear outline is fully resolved. The light energy required for this formulation is in the range of 20-30 mJ / cm2. Example 1 2 At room temperature, 7β was added to a suspension containing 50 g (.342 mol) of 2, 6-dimethyl-2,5-hexanediol in 600 ml of digasmethane. 14 grams (0.762 moles) of triethylamine. Stir the resulting suspension at room temperature

Page 38 ^ uuy / 9 V. Issue ⑶) ~ " — until it becomes a clear solution. At 0 t: 149.5 g (0.7524 mol) of adamane-1 -carbonyl chloride was added to the above solution. After the addition was completed, the reaction mixture was stirred at room temperature for 12 hours, and then heated under reflux for 2 hours. The reaction mixture was filtered to remove triethylamine gaseous hydrogen formed during the reaction. The filtrate was washed several times with water (x500 ml), dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. Purify the residue by column chromatography (silica gel; hexane / dichloromethane: 9: 1) to obtain j 2 8 g (~ 80%) of a white solid, which is identified by NMR spectroscopy as 2, 5-Bis (Diamond Diamond-1, Carboxyloxy) -2,5-dimethylhexane. Example 13 (Comparison) For the purpose of lithographic experiments, a photoresist formulation containing an original norbornene copolymer was prepared by mixing the materials expressed in parts listed below in parts by weight, wherein the original norbornene copolymer contained g5% of original norbornene Tertiary-butyl ester (Long Yibu Yi) and 15% orthobornene-carboxylic acid (as a side group). 37 4 0. 16 0. 008 Copolymer of propylene glycol monomethyl ether acetate NB-1-BE and NB-CA (85/15) Di-tertiary-butylphenyl iodogun perfluorooctane sulfonate Tetrabutylammonium hydroxide The photoresist formulation was spin-coated (30 seconds) on an anti-reflective material (Arf, Shipley) coated on a silicon film. Baking on a vacuum hot plate at 13 ° C. for 60 seconds to soften the photoresist layer to produce a thin film of about 0.4 micron thickness and then exposing the film to 193 nm radiation (0 m ArF,

Page 39 500979 V. Description of the invention (34) ^ _ ISI stepper camera). The exposed pattern is a line and a different arrangement in which the size of the spaces can be reduced to 0.1 micron. After the "Zhao" and "f" flakes were performed on a vacuum hot plate at 150t—exposure bake 90, Wako glue was exposed with a 0.263N tetramethylammonium hydroxide developer to expose pixels = ,. Then (refined) development. Then, scanning electron microscopy (SEM) was used to measure the photoresistance. The cross-section of the SEM pattern indicated that lines could not be resolved due to overlapping lines. , 200 microns L / S (line-spaced pair). Even pairs larger than 200 nm cannot be fully resolved because there are too many artifacts between the lines. Example 1 4 This example illustrates the benefits of this sun and moon composition. Photoresist formulation can be blended with the materials listed below in parts by weight to obtain 38 4 0. 16 0 · 4 0. 008 Propylene glycol monomethyl ether acetate Poly (original borneol) with t-BE and CA groups Ethylene) (t-BE / CA: 85/15) Di-tert-butylphenyliodonium perfluorooctane oxalate 2,5-bis (adamantane-1-carboxyoxy) -2, Bu Dimethyl hexane (Example 5) Tetrabutylammonium hydroxide The photoresist formulation was spin-coated on an anti-reflective material (ArX, Shipley, Inc.) coated with silicon film, and patterned to illuminate 093 nm. ) And developed it in the same manner as in Example 13. Scanning electron microscopy

40th stomach 500979 V. Description of the invention (35) (SEM) Measurement of the obtained pattern. 1 Line-space pairs of 30 nm and above can be clearly resolved with clear contours. The light energy required for this formulation is in the range of 20-30 mJ / cm2. 500979

O: \ 62 \ 62934.ptc Page 42

Claims (1)

500979 > Annual Report This Amendment No. 89104Π2 VI. Patent Application Scope 1. A photoresist composition comprising (a) a cycloolefin polymer, (b) a light-sensitive acid generator, and (c) saturation Steroid component, hydrophobic non-steroidal alicyclic component or hydrophobic non-steroidal polyalicyclic component containing multiple acid-labile linkers, wherein the composition contains 0.5-20% by weight (b) and 5-25% by weight i % (c), based on the total amount of cycloolefin-based polymer (a), wherein the cycloolefin-based polymer contains: i) 10-80 mole% of cycloolefin units having polar functional groups, and ii) 20 -90 mole% of a cycloolefin unit having an acid-labile portion, which can inhibit the solubility in an alkaline aqueous solution. 2. The composition according to item 1 of the scope of patent application, wherein the cycloolefin polymer is basically composed of a cycloolefin unit i) and a cyclofluorene unit ii). 3. The composition according to item 1 of the scope of patent application, wherein the polar functional group portion is selected from the group consisting of an acidic polar functional group portion having a pKa of about 13 or less and a non-acidic polar functional group portion having a pKa of greater than 13 Servings or combinations thereof. 4. The composition according to item 3 of the scope of patent application, wherein the cyclic olefin unit i) comprises an acidic polar functional group moiety which has a member selected from the group consisting of a carboxyl group, an aminofluorenyl group, a fluoroalcohol and other acidic polar groups. The acidic polar group. 5. The composition according to item 4 of the patent application, wherein the acidic polar group is a carboxyl group. 6. The composition according to item 1 of the scope of patent application, wherein the cycloolefin unit ii) comprises an acid-labile protecting group having a member selected from the group consisting of a tertiary alkyl carboxylate, a tertiary cycloalkyl carboxyl group Ester, ester ketal and ester acetic acid. O: \ 62 \ 62934.ptc Page 43 500979 Case No. 89104172 _ Amendment VI. Patent application scope f Where the saturated solid, the skeleton has at least * where the saturated solid is selected from the group containing hydroxyl, Wherein the saturated steroid 7. The composition alcohol according to item 1 of the scope of patent application contains at least one saturated C17 steroid alicyclic skeleton with one acid-labile protecting group on one side. 8. The composition according to item 7 of the patent application. The alcohol compound further contains an additional side moiety, a methyl group, a methyl group, an ethyl group and a fluoroethyl group. 9. The alcohol component of the composition according to item 1 of the patent application scope comprises a steroid compound selected from the group consisting of phosphonates, ester-modified lithocholic acid esters, ester-modified cholic acid esters, and spacers. The stone cholic acid meets each other. 10. The composition according to item 9 of the scope of patent application, wherein the saturated steroid component is selected from the group consisting of tertiary-butyllithium cholate, tertiary-butyldeoxycholate, tertiary-butylcholic acid Esters, tertiary-butyl-3 -trifluoroacetamidinocholate, tertiary-butyl-3-ethynylcholate, tertiary-butyl-3-pentylfluorenylcholate, Tertiary-butyl-3, 7, 12-trimethylfluorenylcholate, tertiary-butyl-huang- (3,7,12-trifluoroethylfluorenyl) cholate, and separated stone gallbladder Ester structure: m O: \ 62 \ 62934.ptc Page 44 500979 Amendment No. 89104172 Appeal March: f F. Scope of Patent Application ❿ O-fBu where tBu is a tertiary butyl. 11. The composition according to item 10 of the scope of patent application, wherein the saturated steroid component is tertiary-butyl-3-trifluoroacetamidinocholate. ί I Ϊ O: \ 62 \ 62934.ptc Page 45 500979 Amendment_Case No. 89104172 VI. Patent Application Range 12. The composition according to item 1 of the patent application range, wherein the hydrophobic non-steroidal alicyclic component contains at least one Non-steroid C6 or higher alicyclic parts. 13. The composition according to item 1 of the patent application scope, wherein the hydrophobic non-steroidal alicyclic compound has at least one side acid labile protecting group. 14. The composition according to item 12 of the scope of patent application, wherein the hydrophobic non-steroidal alicyclic component comprises an acid labile protective group selected from the group consisting of tertiary alkyl carboxylate, tertiary cycloalkyl carboxyl, Ester ketals and ester acetals. 15. The composition according to item 14 of the scope of patent application, wherein the hydrophobic non-steroidal alicyclic component comprises at least one non-steroidal C1Q-C3Q alicyclic component. 16. A composition according to item 14 of the patent application, wherein the hydrophobic non-steroidal alicyclic component comprises a tertiary alkyl carboxylate. 17. The composition according to item 1 of the patent application scope, wherein the hydrophobic non-steroidal polyalicyclic component comprises at least two non-steroidal or alicyclic moieties having a higher carbon number. 18. The composition according to item 17 of the application, wherein the hydrophobic non-steroidal polyalicyclic component comprises two acid-labile linking moieties. 19. The composition according to item 18 of the scope of patent application, wherein the hydrophobic non-steroidal alicyclic component comprises an acid-labile linking moiety selected from the group consisting of a tertiary alkyl carboxylate, a tertiary cycloalkyl carboxyl, Ester ketals and ester acetals. 20. The composition according to item 17 of the scope of patent application, wherein the hydrophobic non-steroidal alicyclic component comprises at least two non-steroidal C1Q-C3Q alicyclic portions O: \ 62 \ 62934.ptc Page 46 500979 Case No. 89104172 Amendment 6. Scope of patent application. 21. Linking esters according to instability 02. 2. According to a composition comprising 5 to 25-requested patents in the scope of item 18, wherein the two acid moieties are two tertiary alkyl radicals which are bonded to each other. The composition of claim 1 in the patent application range, wherein the hydrophobic non-steroidal alicyclic component in the composition% is based on the weight of the cycloolefin polymer. A method for forming a patterned photoresist structure on a substrate, the method 23 includes forming a photosensitive sterol multi-sensitive photoresist to expose 24 parts. A kind of (A) photo-resistive acid alicyclic ring becomes an alicyclic ring. (B) The acid-generating (C) layer is exposed to the substrate. According to the following: i) ii) inhibiting the coating of the photo-generating agent or the component, the base photoresist combination is placed on the substrate to The steric hindrance composition on the substrate comprises (a) a cycloolefin polymer, (b) pairs, and (c) a saturated steroid component, and a hydrophobic non-hydrophobic non-steroid having multiple acid-labile linkers. The material is exposed to radiation as a pattern, so that the photosensitizer generates an acid in the area where the photoresist layer is exposed to the radiation, and contacts the substrate with an aqueous alkaline developer solution, so the area of light is selectively Dissolved by the developer solution to develop the patterned photoresist structure. The method of claim 23, wherein the cycloolefin is a cycloolefin unit having a polar functional group portion, and the cycloolefin unit having an acid-labile portion, and the acid-labile portion is soluble in an alkaline aqueous solution. O: \ 62 \ 62934.ptc P.47 500979 Case No. 89104Π2 6. Scope of patent application 2 5. According to the radiation used in the application 2 6. According to 27 (B) and (C) of the application.-Kind of correction in θ It is selected from the group consisting of a pair of photosensitive steroid sterol-sensitive acid photoresist layers to expose the photoresist 28. The compound inclusions can suppress the acid alicyclic ring containing half (A) and (B) photoresist layer coating Alicyclic (C) The generator (D) is exposed to a pattern (E) 4k structure drawing according to the application: 1) ii) Manufactured in the method of examination patent scope is 1M ^ 23 method Feces / meter UV radiation. Β Weiwei method 23 is baked. Method of forming a method of forming a conductor structure on a substrate, and forming a material structure on the substrate. The material is provided for one and two metals. The method includes: A with the material layer, a photoresist, and a slippery one. Storm material, the photoresist group iff on the substrate to generate an agent on the material layer, and f L contains (a) cycloolefin-based polymer, (b) parts or contains multiple c and steroid components, hydrophobic non- Part, the hydrophobicity of the k labile linker is not similar to the substrate as shown in Figure &# under the radiation of the photoresist layer, so the photosensitivity-type visual inspection; aquatic acid ,; also by the developer The solution dissolved by the solution to show the photoresist structure pattern is transferred to the material. 处: Ice into the material layer in the white part will ask for the method in the scope of patent No. 27, in which the% ethylene of long methyl group has a polar functional group. Solubility in this acidic aqueous solution, and cycloolefin units with acid labile parts. The unwritten part where step (B) where the substrate is in step 500979, _Case No. 89104172, _ _ must be said in the month of January __ Sixth, the scope of patent application 29. The method according to item 27 of the scope of patent application, where the material is metal. 30. The method according to item 27 of the patent application scope, wherein the etching includes reactive ion instrumentation. 31. The method according to item 27 of the scope of patent application, wherein at least one intermediate layer is provided between the material layer and the photoresist layer, and step (E) includes etching through the intermediate layer. 32. The method according to item 27 of the scope of patent application, wherein the wavelength of the radiation is about 193 nm. 3 3. The method according to item 27 of the scope of patent application, wherein the substrate is baked between steps (C) and (D). 3 4 · A photoresist composition comprising (a) a cycloolefin polymer, (b) a light-sensitive acid generator, and (c) a substantially transparent giant under radiation of 193 nm A hydrophobic additive, wherein the composition comprises 0.5 to 20 weight (b) and 5 to 25 weight (c), based on the total amount of the cycloolefin polymer (a), wherein the cycloolefin polymer Containing: i) 5 to 40 mole% of a cycloolefin unit having an acidic polar functional moiety, the acidic polar functional moiety can promote solubility in an alkaline aqueous solution, and ii) an acidic unstable moiety Cycloalkene units, this acid-labile portion can inhibit solubility in aqueous solutions. 35. The composition according to item 34 of the scope of the patent application, wherein the cycloolefin polymer is basically composed of a cycloolefin unit i) and a cycloolefin unit ii). 36. The composition according to item 34 of the claims, wherein the cycloolefin O: \ 62 \ 62934.ptc Page 49 500979 Amendment_ Case No. 89104172 VI. Patent application scope bit i) Contains an acidic polar functional group moiety, which has a member selected from the group consisting of carboxyl, sulfamoyl, and fluorine An acidic group of alcohols and other acidic polar groups. 37. The composition according to item 36 of the application, wherein the acidic polar group is a carboxyl group. 38. The composition according to item 34 of the scope of patent application, wherein the cycloolefin unit ii) comprises an acid-labile protecting group having a member selected from the group consisting of a tertiary alkyl carboxylate, a tertiary cycloalkyl carboxyl group Part of esters, ketals and acetals. O: \ 62 \ 62934.ptc Page 50