CN1267000A - Cyclic olefin polymer and additive photoetching resin composition - Google Patents

Cyclic olefin polymer and additive photoetching resin composition Download PDF

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Publication number
CN1267000A
CN1267000A CN 00101840 CN00101840A CN1267000A CN 1267000 A CN1267000 A CN 1267000A CN 00101840 CN00101840 CN 00101840 CN 00101840 A CN00101840 A CN 00101840A CN 1267000 A CN1267000 A CN 1267000A
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China
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cyclic olefin
olefin polymer
matrix
radiation
unit
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CN 00101840
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Chinese (zh)
Inventor
P·R·瓦拉纳希
J·F·马尼斯卡尔科
M·C·劳森
A·M·麦惠特
M·M·克霍扎斯特
G·M·乔德哈莫
R·D·阿兰
J·奥彼兹
伊藤洋
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国际商业机器公司
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Priority to US09/266,342 priority
Application filed by 国际商业机器公司 filed Critical 国际商业机器公司
Publication of CN1267000A publication Critical patent/CN1267000A/en

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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

The photoetching compositions of cyclic olefin polymer and adjuvant

With the application submits to simultaneously US patented claim series No.09/266 arranged, 343, name is called " photoetching compositions of cyclic olefin polymer and the alicyclic adjuvant of hydrophobic on-steroidal "; US patented claim series No.09/266,341, name is called " photoetching compositions of cyclic olefin polymer and hydrophobic-non-stero superfatted ring family adjuvant "; With US patented claim series No.09/266,304, name is called " photoetching compositions of cyclic olefin polymer and saturated steroid compound additive ".The disclosure of above-mentioned application is drawn in this article and is reference.

Comprise in the microstructure manufacturing (first-class) in microelectronics industry and other industry, all wish to reduce the size of structure member always such as, micromachine, magneto-resistor.In microelectronics industry, wish to reduce the size of microelectronic device and/or provide more circuit number for given chip size.

Making more, the ability of skinny device is subjected to the restriction that can photoetching technique reliably differentiate littler feature and gap ability.Camera lens character makes the ability of fine-resolution more of producing be subjected to forming the restriction of the used light wave of photoengraving pattern (or other radiation) wavelength on some degree.Therefore, the application of shorter optical wavelength always is the trend that is advancing in the photoetching process.Recently, trend has moved to the 248nm radiation from so-called I beta radiation (350nm).

In order further to reduce size, may need to adopt the radiation of 193nm.Unfortunately, the photoetching compositions that occupy current 248nm photoetching process core typically is not suitable for shorter wavelength.

Can resolution image under desired radiation wavelength though photoetching compositions must have desired optical characteristics, photoetching compositions also must have suitable chemistry and mechanical property so that on image can being delivered to basic unit under it from the patterning photoresist.Therefore, the positive photoresist of patterned exposure must have the ability dissolving is made correct response (that is the selective dissolution of exposure area) to form required photolithographic structures.According to for many years experience in adopting the technical field of lithography of alkaline developer solution, importantly in this type of developer solution commonly used, obtain suitable solubility behavior.

Patterning photolithographic structures (back of developing) must have enough resistibilitys so that pattern is delivered on the bottom.Typically, the transmission that realizes pattern by the wet-chemical chamber or the ion etching of certain form.The patterning photoresist layer is the important performance of photoetching compositions to the ability to bear (that is the anti-etching ability of photoresist layer) that pattern transmits etching technics.

Though designed some photoetching compositions for the 193nm radiation use, owing to do not possess the performance in above-mentioned one or more fields, the general embodiment of these compositions does not go out the more real advantage of short wavelength's imaging resolution.What therefore, need is and to have the photoetching compositions of excellent developing and etch resistance for (such as the UV radiation of 193nm) of shorter wavelength radiation imaging.

The invention provides the photoetching compositions that can provide the high resolution lithography performance by the 193nm image-forming radiation.Photoetching compositions of the present invention has the combination property of imaging, development and etch resistance, is to realize that very the high resolution design transmission is necessary, and suffered restriction just comes from the wavelength of image-forming radiation.Photoetching compositions of the present invention usually is characterized in that the existence of cyclic olefin polymer, and it contains the combination of acid labile functional group and polar acidic functional group.It preferably is further characterized in that the hydrophobic additive to 193nm radiation substantially transparent that contains a large amount of (bulky) photoetching compositions of the present invention.

The present invention also provides and has utilized photoetching compositions of the present invention to form the photoetching method of photolithographic structures and utilize photolithographic structures that pattern is delivered to method in the basic unit.Photoetching method of the present invention preferably is characterized in that having adopted the patterned exposure of UV radiation of 193nm.Method of the present invention preferably can be differentiated size less than about 150nm need not to use under the situation of transmitting mask mutually, more preferably size is less than the feature of about 120nm.

On the one hand, the present invention includes photoetching compositions, comprise: (a) a kind of cyclic olefin polymer comprises:

I) have the cycloolefin list that can promote the polar acidic functional group of in alkaline aqueous solution, dissolving

Unit and

Ii) have the cycloolefin that can be suppressed at the acid labile group that dissolves in the alkaline aqueous solution

The unit, (b) a kind of photolytic activity component and (c) a kind of a large amount of hydrophobic additive components to 193nm UV radiation substantially transparent.

Cyclic olefin polymer of the present invention preferably contains the unit i of the 5~40mol% that has an appointment).Cyclic olefin polymer of the present invention preferably mainly is made of the cyclic olefin monomers unit; More preferably mainly by unit i) and ii) constitute.A large amount of hydrophobic additive preferably comprises an alicyclic group.

On the other hand, the present invention includes a kind of method that on matrix, forms the patterning photolithographic structures, the method comprises: a kind of matrix that has photoetching compositions superficial layer of the present invention (a) is provided, (b) photoresist layer exposes through the radiation pattern formula, whereby with photoresist layer part through radiant exposure, and (c) photoresist layer contacts with alkaline developer solution, and the exposed portion of removing photoresist layer is to form the patterning photolithographic structures.

Preferably, the radiation of adopting in the said method step (b) is the UV radiation of 193nm.

The present invention also comprises the technology that adopts the patterning photolithographic structures that contains the present composition to make electric conductivity, semiconductive, magnetic or insulativity structure.

Below will do further specific descriptions with regard to these several and other characteristics of the present invention.

Photoetching compositions of the present invention usually is characterized in that having a kind of polymkeric substance, and it contains i) have the cycloalkene unit that can promote the polar acidic functional group of in alkaline aqueous solution, dissolving and ii) have the cycloalkene unit that can be suppressed at the acid labile group that dissolves in the alkaline aqueous solution.Cyclic olefin polymer preferably contains the cycloalkene unit i that is no more than 40mol%).It is further characterized in that this composition and contains a large amount of hydrophobic additive to 193nm radiation substantially transparent.These compositions can provide high-resolution photoengraving pattern by the radiation of 193nm, and are aided with good development and pattern transmission characteristic.

The present invention more comprises the patterning photolithographic structures that contains photoetching compositions of the present invention, and forms photolithographic structures and utilize photolithographic structures to form the technology of electric conductivity, semiconductive and/or insulativity structure.

Photoetching compositions of the present invention preferably comprises: (a) a kind of cyclic olefin polymer comprises:

I) have the cycloolefin list that can promote the polar acidic functional group of in alkaline aqueous solution, dissolving

Unit and

Ii) have the cycloolefin that can be suppressed at the acid labile group that dissolves in the alkaline aqueous solution

The unit, (b) a kind of photolytic activity component and (c) a kind of a large amount of hydrophobic additive components to 193nm radiation substantially transparent.

Cyclic olefin unit i) can be any cyclic olefin monomers unit that has the polar acidic functional group that can promote alkali dissolution.The example of cyclic olefin monomers comprises the monomer shown in the following structure (I), wherein R 1Represent the polar acidic group, and n is 0 or positive integer:

More preferably, cyclic olefin unit i) select certainly: R wherein 1Represent and to promote the polar acidic group that in alkaline aqueous solution, dissolves.Preferred its pK of polar acidic group aBe less than or equal to about 13.Preferred polar acidic group comprises the polar group of selection from carboxyl, sulfamoyl, fluorinated alcohols and other polar acidic group.Preferred polar acidic group is a carboxyl.As required, can adopt the cycloalkene unit i that has different polar acidic functional group) potpourri.

Cycloalkene unit ii) can be to have any cycloolefin monomers unit that can be suppressed at the acid labile group that dissolves in the alkaline aqueous solution.The example of cycloolefin monomers comprises the monomer shown in the following structure (III), wherein R 2Represent the acid labile blocking group, and n is 0 or positive integer:

More preferably, the cyclic olefin unit is ii) selected certainly: R wherein 2Represent the acid labile blocking group.The acid labile blocking group is preferably selected from thing tertiary alkyl (or naphthenic base) carboxylate (such as the tert-butyl group, methylcyclopentyl, methylcyclohexyl, methyl adamantane base), ketals and ester acetal.Tert-butyl group carboxylate is most preferred acid labile blocking group.As required, can adopt the cycloalkene unit potpourri ii) that has different protectiveness functional group.

To being used for the photolithography use of integrated circuit structure and other micromechanism manufacturing, cyclic olefin polymer of the present invention preferably contains the cyclic olefin unit i of the 5~80mol% that has an appointment).As cycloalkene unit i) when mainly being made of the carboxylic-acid functional unit, cyclic olefin polymer of the present invention preferably contains the 5~30mol% that has an appointment, more preferably from about 10~25mol%, most preferably from about 10~20mol%.As cycloalkene unit i) when mainly being made of other acid functional unit, cyclic olefin polymer of the present invention more preferably contains the 10~80mol% that has an appointment, most preferably from about 20~40mol%.Cyclic olefin polymer of the present invention preferably contains at least about the cycloalkene unit of 30mol% ii), 40~90mol% more preferably from about, if if with carboxylic acid as acidic-group 80~90mol% or adopted other acid functional unit then be about 60~80mol% most preferably from about.Cyclic olefin polymer of the present invention can contain except that unit i) and ii) other monomeric unit.Preferably, cyclic olefin polymer of the present invention contains other monomeric unit that is equal to or less than about 40mol%, more preferably from about 20mol% or lower.More preferably, cyclic olefin polymer of the present invention is mainly by cycloalkene unit i) and ii) constitute.

Except cyclic olefin polymer, photoetching compositions of the present invention contains the sour agent of a kind of photosensitive life (PAG).The present invention does not limit any specific PAG or the application of PAG potpourri, adopts the known sour agent of any photosensitive life of prior art can both embody advantage of the present invention.Preferred PAG has the aromatic group of reduction amount (or preferably not having).When employing had the PAG of aryl, PAG can limit the amount of the PAG that can contain in the prescription in the absorption characteristic of 193nm.

The example of the suitable sour agent of photosensitive life comprises that (but preferably replacing one or more in any listed aryl with alkyl) salt is such as the hexafluoro-antimonic acid triaryl matte; hexafluoro-antimonic acid diaryl iodine; the hexafluoro arsonate; triflate; perfluoroalkanesulfosalt salt is (such as perfluoromethane sulfonate; perfluorinated butane; perflexane sulfonate; perfluoro octane sulfonate etc.); the arylsulphonate that replaces is such as Pyrogallol class (such as three mesylates of Pyrogallol or the trisulfonate of Pyrogallol); the imido sulphonic acid ester of hydroxyl; N-sulfonyl oxygen base naphthalimide (N-camphoryl sulfonyl oxygen base naphthalimide; N-pentafluorophenyl group sulfonyl oxygen base naphthalimide); α, α '-two sulfonyl two azomethane classes; naphthoquinones-4-two nitrine classes; alkyl two sulfones etc.

It is further characterized in that photoetching compositions of the present invention and contains a kind of a large amount of hydrophobic additive to 193nm radiation substantially transparent (" BH " adjuvant).Be equipped with alkaline developer solution commonly used, the ability of the hyperfine lithographic features of resolution is generally given and/or strengthened to " BH " adjuvant.The BH adjuvant preferably is characterized in that containing the alicyclic structure of at least one.Preferably, the BH adjuvant contains at least about 10 carbon atoms, more preferably at least 14 carbon atoms, most preferably from about 14~60 carbon atoms.The BH adjuvant preferably contains one or more other groups, and such as the acid labile side group, it decomposes a kind of composition of generation under the situation that acid is arranged, and plays the effect that promotes photoresist radiant exposure district alkali dissolution.Preferred BH adjuvant is to select self-saturating steride, on-steroidal alicyclic compound and non-stero superfatted cyclic compound, and the latter exists a plurality of acid labile linking groups between at least two alicyclic group.Preferred BH adjuvant comprises lithocholate class such as the tert-butyl group-3-trifluoroacetyl group lithocholate, the two adamantyl tert-butyl esters of carboxylic acid tert-butyl group diamantane ester and carboxylic acid.As required, can adopt the potpourri of BH adjuvant.

Before being applied to required matrix, photoetching compositions of the present invention typically contains solvent.Solvent can be acid catalyzed photoresist any solvent commonly used, in others the performance of photoetching compositions is not had too many adverse effect.Preferred solvent is glycol monoethyl ether acetate, cyclohexanone and ethyl acetic acid cellosolve.

Composition of the present invention can further contain a spot of auxiliary components such as dyestuff/sensitizer, alkalinity additive etc., and these all are that prior art is known.Preferred alkalinity additive is the weak base that can catch acid traces, but the performance of photoresist is not but had too many influence.Preferred alkalinity additive is that (fat or alicyclic) alkyl amine or tertiary alkyl ammonium hydroxide are such as tert-butyl group ammonium hydroxide (TBAH).

Photoetching compositions of the present invention preferably contains the 0.5~20wt% that has an appointment, and (more preferably from about 3~15wt%) the sour agent of photosensitive life is based on the total amount of cyclic olefin polymer in the composition.Under the situation that solvent exists, Overall Group's compound preferably contains the solvent of the 50~90wt% that has an appointment.Composition preferably contains have an appointment 1wt% or described alkalinity additive still less, based on the total amount of acid-sensitive polymkeric substance.Photoetching compositions of the present invention preferably contains the BH additive component at least about 5wt%, based on the total amount of cyclic olefin polymer in the composition, and more preferably from about 10~25wt%, most preferably from about 10~20wt%.

To the synthetic method of the used cyclic olefin polymer of the present invention, the present invention does not have any special restriction.Preferably, cyclic olefin polymer forms by polyaddition reaction.Suitable method example is seen the U.S.Pat.No.5 that assigns to B.F.Goodrich Company, 468,818 and 5,705,503, and its disclosed method is quoted as a reference at this.

It is about 5,000~100,000 that cyclic olefin polymer of the present invention preferably has, more preferably from about 10,000~50,000 weight-average molecular weight.

Cyclic olefin polymer, PAG, BH adjuvant and any other required composition can be mixed with method commonly used, prepare photoetching compositions of the present invention.The photoetching compositions that is used for photoetching process generally can contain the solvent of significant quantity.

The photoetching process that is adopted in the manufacturing of photoetching compositions of the present invention to integrated circuit on the semiconductor substrate is particularly useful.This composition is particularly useful to the photoetching process that adopts the 193nm UV radiation.If require to adopt other radiation (such as medium ultraviolet, 248nm extreme ultraviolet, X-ray or electron beam), can be by in composition, adding to come the present composition is regulated (being necessary) with suitable dyestuff or sensitizer.Below just the generality of photoetching compositions of the present invention in the optical semiconductor lithography use and be described.

The semiconductor lithography The Application of Technology generally comprises pattern is passed to the material layer that is positioned on the semiconductor substrate.The material layer of semiconductor substrate can be metal conductor layer, ceramic insulating layer, semiconductor layer or with the production technology situation fixed other material and final products specific material.In many cases, before using photoresist layer, on material layer, impose anti-reflection coating (ARC).The ARC layer can be any common ARC compatible with acid catalyzed photoresist.

Typically, adopt spin-coating method or other technology that solvent-laden photoetching compositions is administered on the required semiconductor substrate.The matrix preferably heating subsequently (roasting before the exposure) that is loaded with photoresist coating is to remove the cohesiveness of desolvating and improving photoresist layer.The thickness of applied layer is preferably as far as possible thin, and prerequisite is that the preferred evenly basic and photoresist layer of thickness is enough to hold out against following process (typical reactive ion etching) photoengraving pattern is delivered on the base matter layer under it.Calcination steps before the exposure preferably continues about 10 seconds~15 minutes, more preferably from about 15 seconds~1 minute.According to the difference of photoresist glass transition temperature, the sintering temperature before the exposure also can be different.Preferably, the roasting before the exposure is carried out under the temperature than low at least 20 ℃ of Tg.

After removing solvent, photoresist layer is with required radiation pattern formula exposure (such as the UV radiation of 193nm).If what adopt is that the scanning particle beams is such as electron beam, according to realizing patterned exposure with bunch transversal scanning matrix and according to the mode that required pattern applies bunch selectively.More typically, form UV radiation such as 193nm for the radiation of class ripple, patterned exposure is to see through the mask that is positioned on the photoresist layer to carry out.For the UV radiation of 193nm, the total exposure energy preferably is about 100mJ/cm 2Or still less, 50mJ/cm more preferably from about 2Or still less (such as 15~30mJ/cm 2).

After the required patterned exposure, typically the roasting photoresist layer is further to finish acid catalyzed reaction and to strengthen the contrast of exposing patterns.Roasting after the exposure is preferably at about 100~175 ℃, more preferably from about carries out under 125~160 ℃.Roasting after the exposure preferably continues about 30 seconds~5 minutes.

After exposure back roasting finished, photoresist layer contacted with the alkaline solution in each radiant exposure district of energy selective dissolution photoresist, has just obtained having the photolithographic structures (development) of required pattern.Preferred alkaline solution (developer) is a tetramethylammonium hydroxide aqueous solution.Preferably, photoetching compositions of the present invention can develop with common 0.26N alkaline aqueous solution.Photoetching compositions of the present invention also can develop with the alkaline aqueous solution of 0.14N or 0.21N etc.The photolithographic structures that obtains on matrix is typically dry subsequently to remove residual any developer.It is characterised in that generally the photolithographic structures of formation has high etch resistance energy photoetching compositions of the present invention.In some cases, utilize the known method of prior art can further strengthen the etch resistance energy of photolithographic structures by silylated aftertreatment means.The present composition makes duplicating of lithographic features become possibility.

The photolithographic structures pattern can be delivered on the material (such as pottery, metal or semiconductor) of lower floor's matrix subsequently.Typically, realize transmitting by reactive ion etching or some other lithographic technique.To reactive ion etching, the etch resistance of photoresist layer can be a particular importance.Therefore, composition of the present invention and resulting photolithographic structures can be used in and form patterning material layer structure, such as slot of metal wiring circuit, contact hole or passage, insulation layer (such as damascene groove or shallow isolation trench), capacitive element etc., in the design of integrated circuit (IC) apparatus, may meet these.

The manufacturing process of these (pottery, metal or semiconductor) parts generally comprises, the material layer or the zone for the treatment of the patterning matrix are provided, photoresist layer is administered on material layer or the zone, with radiation pattern formula exposed photoresist, the photoresist that exposed contacts so that pattern development with a kind of solvent, be positioned at material layer or the matrix region that layer under the photoresist layer has just formed patterning so see through space etching in the pattern, and remove any remaining photoresist from matrix.In some cases, using hardmask may help pattern is delivered on the more following material layer or zone under the photoresist layer.The example of this type of technology is disclosed in U.S.Pat.No.4, and 855,017; 5,362,663; 5,429,710; 5,562,801; 5,618,751; 5,744,376; 5,801,094; With 5,821, in 469, the disclosed content of these patents is quoted as a reference at this.The example of other pattern crimping and transfer processes is seen " Semiconductor Lithography, Principles, Practices; and Materials ", Wayne Moreau, in the 12nd and the 13rd chapter of PlenumPress (1998), its disclosed content is quoted as a reference at this.Should be appreciated that the present invention is not limited to any specific photoetching technique or device construction.

Embodiment 1 (relatively using)

For carrying out the photoetching test, by the mixing of following material, prepared the photoresist prescription that contains the norbornene copolymer that (NB-CA) constitutes by the 85% norborene tert-butyl ester (NB-t-BE) and 15% norborene-carboxylic acid (as side group), represent with weight portion.

Propylene glycol monomethyl ether acetate 37

NB-t-BE and NB-CA multipolymer (85/15) 4

Perfluorooctane sulfonates di-tert-butyl-phenyl iodine 0.16

TBAH 0.008

This photoresist is filled a prescription spin coating (30 seconds) to the anti-reflective material (ArX that is stated from silicon chip , Shipley Company) and on the layer.Photoresist layer prepared the thick film body of about 0.4 μ m in 60 seconds with 130 ℃ of slight roastings on vacuum heat dish.Then with the radiant exposure (0.6NAArF, ISI stepper) of silicon chip with 193nm.Exposing patterns is the line of little different size to 0.1 μ m and the array in space.The silicon chip that exposed is coiling with 150 ℃ of roastings 90 seconds in vacuum heat after the exposure.Subsequently the photoresist of exposing patternsization is utilized the Tetramethylammonium hydroxide developer development (paste is smeared) of 0.263N.Then observe pattern with scanning electron microscope (SEM).The SEM cross-sectional view shows L/S less than 200nm (line-space to) because intersected with each other the passing through of circuit and can't differentiating.Because too much residue/residue between circuit, in addition greater than line-space of 200nm to all not distinguishing fully.Embodiment 2

Present embodiment shows the advantage of the present composition that contains the saturated steroid compound additive.By following material be mixed with the photoresist prescription, represent with weight portion.

Propylene glycol monomethyl ether acetate 38

The polynorbornene 4 that has t-BE and CA group

(t-BE/CA:85/15)

Perfluorooctane sulfonate di-tert-butyl-phenyl iodine 0.16

The tert-butyl group-3-trifluoroacetyl group lithocholate 0.4

TBAH 0.008

This photoresist prescription is spun to the anti-reflective material (ArX of silicon chip , ShipleyCompany) on the layer, patterned exposure (193nm radiation) and the mode identical with embodiment 1 are developed.The pattern that obtains is observed with scanning electron microscope (SEM) subsequently.Greater than good to differentiating with the line-space that equals 140nm, clear-cut.The required exposure energy of this prescription is 25~35mJ7cm 2Synthesizing of embodiment 3 diamantane-1-carboxylic acid tert-butyl ester

In the 600ml methylene chloride suspended matter that contains 25.34g (0.342mol) tert-butyl alcohol, add the triethylamine of 38.07g (0.3815mol) under the room temperature.The suspended matter of gained becomes clear solution in stirring at room until it.Diamantane-1-acyl chlorides with 74.75g (0.3762mol) under 0 ℃ adds in the above-mentioned solution.Add finish after, reaction mixture then refluxes and stirred 2 hours in stirring at room 12 hours.Reaction mixture filters to remove the triethylamine hydrochloride that generates in the course of reaction.Mother liquor with water (* 500ml) washing repeatedly with anhydrous sodium sulfate drying, and under reduced pressure concentrates.Raffinate is with column chromatography (silica gel; Hexanes/ch: 9: 1) purifying obtains the white solid of 48.4g (~60%), turns out to be diamantane-1-carboxylic acid tert-butyl ester through the NMR spectrum.Embodiment 4

Present embodiment shows the advantage of the present composition that contains diamantane-1-carboxylic acid tert-butyl ester.By following material be mixed with the photoresist prescription, represent with weight portion.

Propylene glycol monomethyl ether acetate 38

The polynorbornene 4 that has t-BE and CA group

(t-BE/CA:85/15)

Perfluorooctane sulfonates di-tert-butyl-phenyl iodine 0.16

Diamantane-1-carboxylic acid tert-butyl ester (embodiment 3) 0.4

TBAH 0.008

This photoresist prescription is spun to the anti-reflective material (ArX of silicon chip , ShipleyCompany) on the layer, patterned exposure (193nm radiation) and the mode identical with embodiment 1 are developed.The pattern that obtains is observed with scanning electron microscope (SEM) subsequently.Greater than good to differentiating with the line-space that equals 140nm, clear-cut.The required exposure energy of this prescription is 20~30mJ/cm 2Embodiment 52, two (adamantyls-1-carboxyl oxygen)-2 of 5-, 5-dimethylhexane synthetic

Containing 50g (0.342mol) 2 under the room temperature, 6-dimethyl-2 adds the triethylamine of 76.14g (0.762mol) in the 600ml methylene chloride suspended matter of 5-hexanediol.The suspended matter of gained becomes clear solution in stirring at room until it.Diamantane-1-acyl chlorides with 149.5g (0.7524mol) under 0 ℃ adds in the above-mentioned solution.Add finish after, reaction mixture then refluxes and stirred 2 hours in stirring at room 12 hours.Reaction mixture filters to remove the triethylamine hydrochloride that generates in the course of reaction.Mother liquor with water (* 500ml) washing repeatedly with anhydrous sodium sulfate drying, and under reduced pressure concentrates.Raffinate is with column chromatography (silica gel; Hexanes/ch: 9: 1) purifying obtains the white solid of 128g (~80%), turns out to be 2 through the NMR spectrum, two (adamantyls-1-carboxyl oxygen)-2 of 5-, 5-dimethylhexane.Embodiment 6

Present embodiment shows and contains 2, two (adamantyls-1-carboxyl oxygen)-2 of 5-, the advantage of the present composition of 5-dimethylhexane.By following material be mixed with the photoresist prescription, represent with weight portion.

Propylene glycol monomethyl ether acetate 38

The polynorbornene 4 that has t-BE and CA group

(t-BE/CA:85/15)

Perfluorooctane sulfonates di-tert-butyl-phenyl iodine 0.16

2, two (adamantyls-1-carboxyl oxygen)-2 of 5-, oneself 0.4 alkane (embodiment 5) of 5-dimethyl

TBAH 0.008

This photoresist prescription is spun to the anti-reflective material (ArX of silicon chip , ShipleyCompany) on the layer, patterned exposure (193nm radiation) and the mode identical with embodiment 1 are developed.The pattern that obtains is observed with scanning electron microscope (SEM) subsequently.Greater than good to differentiating with the line-space that equals 140nm, clear-cut.The required exposure energy of this prescription is 20~30mJ/cm 2

Claims (20)

1. a photoetching compositions comprises (a) cyclic olefin polymer, (b) the sour agent of photosensitive life and (c) to a large amount of hydrophobic additive of 193nm radiation substantially transparent, and described cyclic olefin polymer comprises:
I) have the cycloolefin list that can promote the polar acidic functional group of in alkaline aqueous solution, dissolving
Unit and
Ii) have the cycloolefin list that can be suppressed at the acid labile group that dissolves in the alkaline aqueous solution
Unit.
2. the composition of claim 1, wherein said cyclic olefin polymer contains the cycloalkene unit i of the 5~40mol% that has an appointment).
3. the composition of claim 1, wherein said cyclic olefin polymer is mainly by cycloalkene unit i) and cycloalkene unit ii) constitute.
4. the composition of claim 1, wherein said cycloalkene unit i) contain a kind of polar acidic functional group, it comprises the acidic-group of a selection from carboxyl, sulfonamido, fluorinated alcohols and other polar acidic group.
5. the composition of claim 4, wherein said acidic-group is a carboxyl.
6. the composition of claim 1, wherein said cycloalkene unit ii) contains a kind of acid labile blocking group, and it comprises the group of a selection from tertiary alkyl carboxylate, uncle's naphthenic base carboxyl, ketals and ester acetal.
7. the composition of claim 1, wherein said a large amount of hydrophobic additive comprise a kind of compound, and it contains at least 10 carbon atoms and has an alicyclic group.
8. the composition of claim 7, wherein said a large amount of hydrophobic additive comprises a kind of compound, selects self-saturating steride, on-steroidal alicyclic compound and exist the non-stero superfatted cyclic compound of a plurality of acid labile linking groups between at least two alicyclic group.
9. the composition of claim 1, wherein said composition comprises described a large amount of hydrophobic additive components of about 5~25wt%, based on the amount of described cyclic olefin polymer.
10. the composition of claim 1, wherein said cyclic olefin polymer contains the cycloalkene unit i of the 10~20mol% that has an appointment) and the cycloalkene unit of about 40~90mol% is ii).
11. a kind of patterning photolithographic structures on the matrix, described photoresist comprises (a) cyclic olefin polymer, (b) the sour agent of photosensitive life and (c) to a large amount of hydrophobic additive of 193nm radiation substantially transparent, and described cyclic olefin polymer comprises:
I) have the cycloolefin list that can promote the polar acidic functional group of in alkaline aqueous solution, dissolving
Unit and
Ii) have the cycloolefin list that can be suppressed at the acid labile group that dissolves in the alkaline aqueous solution
Unit.
12. a method that forms the patterning photolithographic structures on matrix, described method comprises:
(A) photoetching compositions is administered in the described matrix on described matrix, to form photoresist layer, described photoetching compositions comprises (a) cyclic olefin polymer, (b) the sour agent of photosensitive life and (c) to a large amount of hydrophobic additive of 193nm radiation substantially transparent, described cyclic olefin polymer comprises:
I) have the cycloolefin that can promote the polar acidic functional group of in alkaline aqueous solution, dissolving
The unit and
Ii) have the cyclenes that can be suppressed at the acid labile group that dissolves in the alkaline aqueous solution
The hydrocarbon unit,
(B) described matrix exposes through the radiation pattern formula, thereby utilizes described radiation to produce acid by the sour agent of described photosensitive life in the exposure region of described photoresist layer, and
(C) described matrix contacts with alkaline developer solution, thereby the described exposure region of described photoresist layer is that the dissolving of the selected property of described developer solution is to present described patterning photolithographic structures on described matrix.
13. the method for claim 12, wherein the described radiation of adopting in the step (B) is the UV radiation of 193nm.
14. the method for claim 12, wherein said matrix are in step (B) with roasting (C).
15. a method that forms the patterning structure of matter on matrix, described material is selected from semiconductor, pottery and metal, and described method comprises:
(A) provide a kind of matrix that has described material layer,
(B) photoetching compositions is administered in the described matrix on described matrix, to form photoresist layer, described photoetching compositions comprises (a) cyclic olefin polymer, (b) the sour agent of photosensitive life and (c) to a large amount of hydrophobic additive of 193nm radiation substantially transparent, described cyclic olefin polymer comprises:
I) have the cycloolefin that can promote the polar acidic functional group of in alkaline aqueous solution, dissolving
The unit and
Ii) have the cyclenes that can be suppressed at the acid labile group that dissolves in the alkaline aqueous solution
The hydrocarbon unit,
(C) described matrix exposes through the radiation pattern formula, thereby utilizes described radiation at described photoresist layer
Exposure region produce acid by the sour agent of described photosensitive life,
(D) described matrix contacts with alkaline developer solution, thereby the described of described photoresist layer exposed to the sun
The light district is that the dissolving of the selected property of described developer solution is to present the photoetching knot of patterning
Structure, and
(E) the photolithographic structures pattern is delivered to described material layer, method is to see through described photolithographic structures figure
The space of case is etched into described material layer.
16. the method for claim 15, wherein said material is a metal.
17. the method for claim 15, wherein said etching comprises reactive ion etching.
18. the method for claim 15 wherein provides the middle layer with at least one between described material layer and described photoresist layer, and step (E) comprises through carrying out etching in described middle layer.
19. the method for claim 15, wherein said radiation has the wavelength of about 193nm.
20. the method for claim 15, wherein said matrix are in step (C) with roasting (D).
CN 00101840 1999-03-11 2000-02-02 Cyclic olefin polymer and additive photoetching resin composition CN1267000A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101300317B (en) * 2005-11-21 2012-02-01 国际商业机器公司 Water castable - water strippable top coats for 193 nm immersion lithography

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
US5863699A (en) * 1995-10-12 1999-01-26 Kabushiki Kaisha Toshiba Photo-sensitive composition
AT297562T (en) * 1996-03-07 2005-06-15 Sumitomo Bakelite Co Photoresis compositions with polycly polymers with saverelabilen groups at the end
US5879857A (en) * 1997-02-21 1999-03-09 Lucent Technologies Inc. Energy-sensitive resist material and a process for device fabrication using an energy-sensitive resist material
US6146810A (en) * 1998-09-23 2000-11-14 Korea Kumho Petrochemical Co., Ltd. Resist polymer and chemical amplified resist composition containing the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101300317B (en) * 2005-11-21 2012-02-01 国际商业机器公司 Water castable - water strippable top coats for 193 nm immersion lithography

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