CN101880352B - Copolymer for gap filling material composition, preparation method thereof and gap filling material composition for antireflective coating layer - Google Patents
Copolymer for gap filling material composition, preparation method thereof and gap filling material composition for antireflective coating layer Download PDFInfo
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- CN101880352B CN101880352B CN2010101247234A CN201010124723A CN101880352B CN 101880352 B CN101880352 B CN 101880352B CN 2010101247234 A CN2010101247234 A CN 2010101247234A CN 201010124723 A CN201010124723 A CN 201010124723A CN 101880352 B CN101880352 B CN 101880352B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/02—Homopolymers or copolymers of esters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Abstract
The present invention provides a copolymer for a gap filling material, as expressed in Chemical Formula 1 below, [Chemical Formula 1] wherein R1, R2, R3, R4, R5, R6, and R7 are independent from each other, R1 is hydrogen or a C1-10 alkyl group, each of R2, R3, and R4 indicates hydrogen, the C1-10 alkyl group, or a C1-20 arylalkyl group, each of R5, R6, and R7 indicates hydrogen or a methyl group, and each of a, b, c, and d is a number indicating a repeating unit in a main chain, where a+b+c+d = 1, 0.05 < a/(a+b+c+d) <0.95, 0.05 <b/(a+b+c+d) <0.95, 0.05 < c/(a+b+c+d) <0.95, and 0.05 <d/(a+b+c+d) <0.95.
Description
Technical field
The present invention relates to a kind of multipolymer be used to the gap filling material that can be used as antireflecting coating, make the method and the gap filling material composition that contains the multipolymer that is useful on gap filling material of the multipolymer that is used for gap filling material.
Background technology
Current, along with the Highgrade integration day by day of semiconductor devices, the manufacturing of ultra-large integrated (ULSI:ultra-Large ScaleIntegration) etc. need be used and is less than or equal to 0.10 micron ultra-fine figure.And, utilize than the lithography technology that has the littler wavelength of wavelength in g-ray and i-field of radiation now to be used.That is, two embedded (dualdamascene) are a kind of methods that forms fine-line, and are a kind of main stream approach that is used in for the manufacturing process of meticulous semiconductor integrated circuit equipment.Embedded technology forms the fine-line groove at the insulation layer of semiconducter substrate, on insulation layer and comprise the inside deposit layer of described circuit groove, use chemical mechanical milling method (CMP:chemicalmechanical polishing) to remove the metal level of described circuit groove outside then, to form the meticulous concealed wire of described circuit groove inside.And described embedded technology can be divided into single embedded and two embedded.
Two embedded technologies are formed for connecting the via (via hole) of bottom wiring (bottom-layered wiring) in the bottom that is formed at the circuit groove on the insulation layer, and metal level is embedded to forms circuit (wire) in described circuit groove and the via simultaneously, in order to reduce the technology number of times of handling.Single embedded technology is in advance at via inner formation metal insert (metal plug) and at the inner concealed wire that forms of described circuit groove.
According to described two embedded technologies, semiconductor devices is formed on the semiconducter substrate, and the bottom cloth line is formed on the top of described semiconductor devices.Insulation layer is deposited in the top of bottom wiring, antireflecting coating be formed on described insulation layer above, and photoresist layer (photoresist layer) is formed on the described antireflecting coating.Photomask (photomask) exposure that described photoresist layer has the via figure to form by use, and developed continuously, so the figure that the via zone is opened is transcribed described photoresist layer.Described antireflecting coating is formed to prevent the reduction of resolution and when described photoresist layer is exposed, prevention will be sent to described photoresist layer by the light that the surface of bottom wiring is reflected.The antireflecting coating that is formed on the bottom of photoresist layer is called as bottom antireflective coating (BARC:Bottom Anti ReflectiveCoating).Dry-etching carries out at described antireflecting coating and insulation layer, by with photoresist layer as mask to form via at insulation layer.Described photoresist layer and antireflecting coating are removed and the inside of via is filled gap filling material.Described gap filling material comprises almost and the identical dielectric composition of described anti-reflective coating composition of layer.In order to fill up the inside of via with gap filling material, on insulation layer and comprise that the inside of via piles up described gap filling material, and remove by eat-backing (etchback) process quilt at the gap filling material of via outside.When carrying out etch-back technics, the surface of filling the gap filling material of via becomes evenly, and surperficial height surperficial consistent with insulation layer almost.Second antireflecting coating forms at insulation layer, and second photoresist layer is formed on described second antireflecting coating.The photomask exposure that described second photoresist layer has circuit groove figure to form by use, and developed continuously, therefore there is the figure in via zone to be transcribed on described second photoresist layer.Carry out dry etching at described second antireflecting coating, and proceed to continuously in the inner layer dielectric (inter-layer dielectric), form the circuit groove with the top at via.Being removed back second anti-reflecting layer at second photoresist layer also is removed.When described second anti-reflecting layer was removed, the gap filling material of filling via also was removed, and the surface of base fabric line is exposed in the bottom of via.Copper conductor is formed at the inside of via and circuit groove.Form the copper layer by sputtering technology or craft of gilding at the insulation layer that contains via and circuit groove inside, and the copper layer of circuit groove outside is removed by CMP technology.
When via and groove position (trench) when semiconducter substrate is carried out graphicprocessing, the gap filling material that is applied in the embedded technology does not possess anti-reflection function, fills function and only possess the gap.Conventionally, the material with high light intensity has been used in two embedded technologies and has been used for imbedding via and contact hole.Yet sometimes, though gap filling material has been filled described via and contact hole, the filling of gap filling material is also insufficient or have the space to produce.And, when the component of gap filling material does not have light absorptive, antireflecting coating need be inserted or before the resist coating layer, antireflecting coating need be coated on the gap filling material composition individually in the slot type pattern treatment procedure, thereby produces unnecessary high manufacturing cost loss.So far, the material that possesses anti-reflection function and can fill via equably also is not developed.
Summary of the invention
One aspect of the present invention provides a kind of gap filling material composition, and it can be filled inhomogeneous substrate and not produce the space and can improve homogeneity, therefore increases processing procedure scope (process margin) when carrying out the photoetching process of photoresist material.
Another aspect of the present invention also provides a kind of multipolymer for the gap filling material that is included in gap filling material composition and preparation method thereof.
According to the present invention, provide a kind of and represented as following Chemical formula 1 for the multipolymer as the gap filling material of antireflecting coating,
[Chemical formula 1]
Wherein, R1, R2, R3, R4, R5, R6 and R7 are independent each other, R1 is hydrogen atom or C1-10 alkyl, each R2, R3 and R4 represent hydrogen atom, C1-10 alkyl or C1-20 aralkyl, each R5, R6 and R7 represent hydrogen atom or methyl, and each a, b, c and d are number of repeating units on the expression main chain, a+b+c+d=1 wherein, 0.05＜a/ (a+b+c+d)＜0.95,0.05＜b/ (a+b+c+d)＜0.95,0.05＜c/ (a+b+c+d)＜0.95 and 0.05＜d/ (a+b+c+d)＜0.95.
According to the present invention, a kind of method of multipolymer of the gap filling material for the preparation of Chemical formula 1 is provided, described method comprises the polymerization of carrying out maleic anhydride and acrylic compound, to generate the polymkeric substance of being represented by following Chemical formula 2; With the described polymkeric substance of Chemical formula 2 and multipolymer and C1-10 Fatty Alcohol(C12-C14 and C12-C18) are reacted,
[Chemical formula 2]
Wherein, R1, R2, R3, R4, R5, R6 and R7 are independent each other, R1 is hydrogen atom or C1-10 alkyl, each R2, R3 and R4 represent hydrogen atom, C1-10 alkyl or C1-20 aralkyl, each R5, R6 and R7 represent hydrogen atom or methyl, and each a, b, c and d are number of repeating units on the expression main chain, a+b+c+d=1 wherein, 0.05＜a/ (a+b+c+d)＜0.95,0.05＜b/ (a+b+c+d)＜0.95,0.05＜c/ (a+b+c+d)＜0.95 and 0.05＜d/ (a+b+c+d)＜0.95.
Described polyreaction is at least a in mass polymerization, solution polymerization, suspension polymerization, body-suspension polymerization, letex polymerization and the radical polymerization.
Described gap filling material composition is deployed in the top of coating with etched, and the composition of described expansion hardens by curing to handle, and gap filling material is piled up.And, photoresist material is formed on the top of gap filling material, the photoresist material that forms is exposed and is developed to form the photoresist material figure, and described gap filling material is etched by using as the photoresist material figure of etching mask, and coating is etched to form the figure of coating.
Other aspects of the present invention, feature and/or advantage will be set forth in the following description, and part will obviously maybe can be grasped from implementing the present invention from specification sheets.
Description of drawings
By in conjunction with the following drawings, above-mentioned and otherwise feature and advantage of the present invention will become apparent from the detailed description of following concrete exemplary embodiment of the present invention and understand easily, wherein:
Fig. 1 is the scanning electron microscope image of the gap filling material composition of the example 1 launched at substrate.
Embodiment
Following will being described in detail exemplary embodiment of the present invention, its example will be described by reference to the accompanying drawings, and wherein identical reference number is represented identical element.Below by the present invention being described with reference to described diagram since exemplary embodiment is described.
Below the multipolymer as the gap filling material of antireflecting coating is described.
The described multipolymer that is used for gap filling material with anti-reflective coating layer function is represented by following Chemical formula 1:
[Chemical formula 1]
Wherein, R1, R2, R3, R4, R5, R6 and R7 are independent each other, R1 is hydrogen atom or C1-10 alkyl, each R2, R3 and R4 represent hydrogen atom, C1-10 alkyl or C1-20 aralkyl, each R5, R6 and R7 represent hydrogen atom or methyl, and each a, b, c and d are number of repeating units on the expression main chain, a+b+c+d=1 wherein, 0.05＜a/ (a+b+c+d)＜0.95,0.05＜b/ (a+b+c+d)＜0.95,0.05＜c/ (a+b+c+d)＜0.95, and 0.05＜d/ (a+b+c+d)＜0.95.
The structure of described gap filling material can have different designs.The firstth, molecular-weight average is turned down to strengthen filling capacity, the secondth, the main chain and the 3rd that the light absorbing material of photoabsorption chemicals is offered polymkeric substance is to use light absorbing material and not light absorbing stiffening agent polymkeric substance respectively.Usually, use described light absorbing material to adjust the consumption of described photoabsorption chemicals individually.And hydroxy functional group, glycidyl (glycidyl) functional group or ethanoyl functional group are mainly as described stiffening agent polymkeric substance.
The gap filling material multipolymer as antireflecting coating that above-mentioned Chemical formula 1 is represented has been introduced carboxyl to realize photoabsorption and heat embrittlement (themosetting), and comprise maleic anhydride (maleic acid anhydride), maleic anhydride has good etching speed.
Below, elaborate preparation as the method for the gap filling material multipolymer of antireflecting coating by embodiment.
Chemical formula 1 represent as the gap filling material multipolymer of antireflecting coating by following preparation: at first carry out the polymkeric substance that polyreaction generates Chemical formula 2 by described maleic anhydride and acrylic compound, the reaction intermediates of Chemical formula 2 and Fatty Alcohol(C12-C14 and C12-C18) react then.
[Chemical formula 2]
Wherein, R2, R3, R4, R5, R6 and R7 are independent each other, each R2, R3 and R4 represent hydrogen atom, C1-10 alkyl or C1-20 aralkyl, each R5, R6 and R7 represent hydrogen atom or methyl, and each a, b, c and d are number of repeating units, wherein a+b+c+d=1 on the expression main chain, 0.05＜a/ (a+b+c+d)＜0.95,0.05＜b/ (a+b+c+d)＜0.95,0.05＜c/ (a+b+c+d)＜0.95, and 0.05＜d/ (a+b+c+d)＜0.95.
In this case, described acrylic compound is select from comprise following group at least a: methyl acrylate (methyl acrylate), ethyl propenoate (ethyl acrylate), isopropyl acrylate (isopropyl acrylate), vinylformic acid n-propyl (n-propyl acrylate), n-butyl acrylate (n-butyl acrylate), isobornyl acrylate (isobornylacrylate), 2-ethylhexyl acrylate (2-ethylhexyl acrylate), methyl methacrylate (methylmethacrylate), Jia Jibingxisuanyizhi (ethyl methacrylate), isopropyl methacrylate (isopropylmethacrylate), n propyl methacrylate (n-propyl methacrylate), methacrylic tert-butyl acrylate (tert-butylmethacrylate), n-BMA (n-butyl methacrylate), Propenoic acid, 2-methyl, isobutyl ester (isobutylmethacrylate), cyclohexyl methacrylate (cyclohexyl methacrylate), isobornyl methacrylate (isobornyl methacrylate), methacrylic acid diethylene glycol methyl ether ester (diethylene glycol monomethyl ethermethacrylate), methacrylic acid 2-ethylhexyl (2-ethylhexyl methacrylate), methacrylic acid benzene methyl (benzyl methacrylate), methacrylic acid 1-naphthyl methyl esters (1-naphthylmethyl methacrylate), methacrylic acid 2-naphthyl methyl esters (2-naphthylmethyl methacrylate), methacrylic acid 9-anthryl methyl esters (9-anthrylmethylmethacrylate), methacrylic acid 1-anthryl methyl esters (1-anthrylmethyl methacrylate) and methacrylic acid 2-anthryl methyl esters (2-anthrylmethyl methacrylate).
Carboxyl reacts to generate crosslinking structure with the stiffening agent with functional group such as acetal for example, and described carboxyl prepares by the reaction intermediates of Chemical formula 2 and the open loop of Fatty Alcohol(C12-C14 and C12-C18) (ring-opening).Use is hardened the therefore decomposition that can resist solvent according to the gap filling material of the multipolymer of embodiment preparation in substrate (substrate) expansion and by curing to handle.That is to say, gap filling material filling contact hole and via, and after photoresist material is unfolded, become and be insoluble to photoresist solvent, therefore have stability.So, can be for the stiffening agent multipolymer of described gap filling material composition according to the described multipolymer of embodiments of the invention preparation.
When preparing the polymkeric substance of Chemical formula 2, carry out conventional polyreaction, for example: mass polymerization (bulkpolymerization), solution polymerization (solution polymerization), suspension polymerization (suspension polymerization), body-suspension polymerization (bulk-suspension polymerization), letex polymerization (emulsion polymerization) etc., and preferably use radical polymerization (radical polymerization).Unrestrictedly use a kind of common radical polymerization initiator as the initiator of described radical polymerization, common radical polymerization initiator can be: Diisopropyl azodicarboxylate (azobisisobutyronitrile), benzoyl peroxide (benzoyl peroxide), lauroyl peroxide (lauryl peroxide), azo two isocapronitriles (azobisiso capronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile) (azobisisovaleronitrile) and tertbutyl peroxide (t-butyl hydroperoxide) etc.
Polymer solvent is choose from benzene (benzene), toluene (toluene), dimethylbenzene (xylene), halogeno-benzene (halogenatedbenzene), ether (diethyl ether), tetrahydrofuran (THF) (tetrahydrofuran), ester class (esters), ethers (ethers), lactone (lactones), ketone (ketones) and amides (amides) at least a.Polymerization temperature is suitably selected according to the type of initiator.The molecular weight distribution of polymkeric substance is carried out suitable must the adjustment by the amount and the reaction times that change polymerization starter.After polymerization was finished, by product and the unreacted monomer that remains in the compound of reaction used solvent to remove by extraction or precipitation.When containing the maleic anhydride of open loop in the compound of reaction, because the carboxylic acid (carboxylic acid) that generates is difficult to obtain required molecular weight by conventional gel permeation chromatography (gel permission chromatography).Therefore, when adjusting molecular weight, the molecular weight of the polymkeric substance of Chemical formula 2 is with for referencial use, and the polymkeric substance of Chemical formula 2 is and C1-10 alcohol open loop polymkeric substance before.That is to say, be 1,000 to 100,000 by gel permeation chromatography by the weight average molecular weight of the polymkeric substance of polystyrene conversion (in terms of polystyrene) Chemical formula 2.At this, the polymkeric substance of Chemical formula 2 is the polymkeric substance before open loop.And, consider the solvability, propagation characteristic of solvent and enough crosslinked, the weight average molecular weight of the polymkeric substance of Chemical formula 2 is preferably 5,000 to 10,000.And the molecular weight distribution of polymkeric substance (PDI) is preferably 1.0 to 5.0, is particularly preferably 1.5 to 5.0.
Be the detailed example of the polymkeric substance represented of Chemical formula 1 by the polymkeric substance of chemical formula 3 to 6 expression.Yet described example is not limited to this.
[chemical formula 3]
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
At this, each a, b, c and d are number of repeating units, wherein a+b+c+d=1 on the expression main chain, 0.05＜a/ (a+b+c+d)＜0.95,0.05＜b/ (a+b+c+d)＜0.95,0.05＜c/ (a+b+c+d)＜0.95 and 0.05＜d/ (a+b+c+d)＜0.95.
Below, will elaborate the embodiment that is used for the gap filling material composition of antireflecting coating according to the present invention.
According to the gap filling material composition of the embodiment of the invention except the multipolymer of the Chemical formula 1 that is used for gap filling material, also comprise for the performance and the indurative additive (additive) that improve polymkeric substance and light absorbing material, and described additive comprises linking agent (crosslinking agent) and the living sour agent (thermal acid generator) of heat.Gap filling material according to the embodiment of the invention comprises the compound that contains light absorbing material or comprises the light absorbing material that separates with the polymer phase of non-photoabsorption.Usually, the amount of control photoabsorption chemicals since light absorbing material uses individually.Described light absorbing material is to contain the polymkeric substance of cross-linking set (crosslinking site) at an end of side chain or straight chain, and comprises the haplotype light absorbing material by chemical formula 7 and 8 expressions.
[chemical formula 7]
Wherein, R8 be-O-,
R9 represents hydrogen atom, C1-10 alkyl or C1-10 alkoxyl group independently.
[chemical formula 8]
Described linking agent is the compound that contains at least two kinds of crosslinking functionalities, and the example of described linking agent comprises aminoplast compounds, polyfunctional epoxy resin, dianhydride mixture.And described linking agent is from least a by what choose oxa-cyclobutyl (oxetanyl), oxazoline (oxazolin), cyclic carbonate ester (cyclocarbonate), ethanol silyl (alcohol silyl), amino methylol (aminomethylol), alkoxy methyl (alkoxymethyl), '-aziridino (aziridinyl), methylol (methylol), isocyanic ester (isocyanate), (alkoxymethyl)-2 amino (alkoxymethylamino) and multifunctional fundamental mode Resins, epoxy (multifunctional epoxy) the formation group.
Described aminoplast compounds comprises dimethoxy-methyl glycoluril (dimethoxymethylglycouril), diethoxymethyl glycoluril (diethoxymethylglycouril), the mixture of dimethoxy-methyl glycoluril and diethoxymethyl glycoluril, diethyl-dimethyl glycoluril (diethyldimethylmethylglycouril), tetramethoxymethylglycoluril (tetramethoxymethylglycouril) and hexamethoxymethyl melamine resin etc. (hexamethoxymethyl melamineresin) etc.And, MY720, CY179MA, DENACOL etc. also can be used as described polyfunctional epoxy resin.
Preferably use described thermal acid generator to accelerate sclerous reaction as catalyzer.For example, to give birth to sour agent be choose from the group that the pyridinium salt by the amine salt of the pyridinium salt of the amine salt of toluenesulphonic acids (toluenesulfonic acid), toluenesulphonic acids, toluenesulphonic acids, alkylsulphonic acid (alkylsulfonic acid), alkylsulphonic acid and alkylsulphonic acid constitutes at least a for described heat.
The organic solvent that is used for gap filling material composition is from by propylene glycol monomethyl ether (propylene glycol monomethylether, PGME), 1-Methoxy-2-propyl acetate (propylene glycol monomethyl ether acetate, PGMEA), pimelinketone, ethyl lactate, propylene glycol positive propyl ether (propylene glycol n-propyl ether), dimethyl formamide (dimethylformamide, DMF), gamma-butyrolactone, ethoxy ethanol, methoxyethanol, 3-methoxypropionic acid methyl esters (methyl 3-methoxy propionate, MMP) and the 3-ethoxyl ethyl propionate (ethyl 3-ethoxtypropionate, what EEP) choose in the group of Gou Chenging is at least a.
Comprise according to the gap filling material composition of the embodiment of the invention accounting for total composition 0.1w% to the light absorbing material of 40w%, and preferably include and account for total composition 0.01w% to the light absorbing material of 15w%.And, described clearance material composition preferably includes and accounts for total composition 0.1w% to the polymkeric substance of 20w%, comprise accounting for total composition 0.01w% to the linking agent of 15w% and comprising and account for total composition 0.01w% to the heat life sour agent (thermal generator) of 20w%, and preferably include and account for total composition 0.01w% to the thermal acid generator of 15w%.
According to embodiments of the invention, gap filling material composition is deployed in wafer (wafer) and upward heat-treats afterwards, as: when curing etc., the thermal acid generator will generate acid, light absorbing material, polymkeric substance and be used as the hot acid that the crosslinking reaction between the linking agent of additive produced and accelerate have generated the gap filling material that is insoluble to organic solvent like this.Described gap filling material is filled via and contact hole, thereby forms meticulous circuit by two embedded technologies.
Below, elaborate use forms semiconductor devices according to the gap filling material composition of the embodiment of the invention method of patterning.Described method is included in the coating top and launches organic gap filling material with etched, handle the composition that sclerosis is unfolded by curing, form crosslinked so that the accumulation of described gap filling material, photoresist material is launched at top at gap filling material, exposure and develop to form the photoresist material figure has come the pattern of formation figure layer since the described gap filling material of etching and the described coating of etching by making figure with photoresist as etching mask.
Said curing handled the time of carrying out under the temperature that is preferably in 150 ℃ to 250 ℃ 30 seconds to 5 minutes.And, after hard mask (hard mask) is unfolded, before or after stacked organic/inorganic gap filling material composition on the top of the Spun-on carbon hard films (spin-on carbon hard mask) that forms, also must cure processing in addition, and described cure to handle under the temperature be preferably in 70 ℃ to 200 ℃ carry out.
Below, introduce some embodiment in detail.
[synthesis example]
Synthesis example 1: polymer A synthetic that is used for gap filling material
20 gram maleic anhydrides, 20.42 gram methyl methacrylates, 34.31 gram cyclohexyl methacrylates (cyclohexylmetacrylate), 29 gram methacrylic tert-butyl acrylates and 10.37 gram AIBN are dissolved in 342 grams, 1, the 4-dioxane and carried out polyreaction 4 hours under 80 ℃ of temperature.After described polyreaction is finished, reaction soln is splashed in the methyl alcohol to leach the throw out of generation, with washed with methanol final vacuum drying (molecular weight: 7800, PDI:2.84, output: 60%) repeatedly.Mix mutually with 342 gram methyl alcohol with 1.03 gram toluenesulphonic acids monohydrates (toluenesulfonic acid monohydrate) 62.23 restrain vacuum drying polymkeric substance, reaction is 20 hours under 80 ℃ of temperature.When reaction finished, reaction soln splashed in the distilled water to leach the throw out of generation, with distilled water cleaning final vacuum drying (output: 58%).
Synthesis example 2: polymer B synthetic that is used for gap filling material
20 gram maleic anhydrides, 20.42 gram methyl methacrylates, 34.31 gram cyclohexyl methacrylates, 35.93 gram methacrylic acid benzene methyls (benzyl methacrylate) and 11.06 gram AIBN are dissolved in 365 grams, 1, the 4-dioxane and carried out polyreaction 4 hours under 80 ℃ of temperature.After described polyreaction is finished, reaction soln is splashed in the methyl alcohol to leach the throw out of generation, with washed with methanol final vacuum drying (molecular weight: 7800, PDI:2.79, output: 59%) repeatedly.Mix mutually with 365 gram methyl alcohol with 1.1 gram toluenesulphonic acids monohydrates (toluenesulfonic acid monohydrate) 65.28 restrain vacuum drying polymkeric substance, reaction is 20 hours under 80 ℃ of temperature.When reaction finished, reaction soln splashed in the distilled water to leach the throw out of generation, with distilled water cleaning final vacuum drying (output: 59%).
Synthesis example 3: polymkeric substance C synthetic that is used for gap filling material
20 gram maleic anhydrides, 20.42 gram methyl methacrylates, 35.93 gram methacrylic acid benzene methyls, 29 gram methacrylic tert-butyl acrylates and 10.53 gram AIBN are dissolved in 347 grams, 1, the 4-dioxane and carried out polyreaction 4 hours under 80 ℃ of temperature.After described polyreaction is finished, reaction soln is splashed in the methyl alcohol to leach the throw out of generation, with washed with methanol final vacuum drying (molecular weight: 7800, PDI:2.82, output: 58%) repeatedly.Mix mutually with 347 gram methyl alcohol with 1 gram toluenesulphonic acids monohydrate (toluenesulfonic acid monohydrate) 60.1 restrain vacuum drying polymkeric substance, reaction is 20 hours under 80 ℃ of temperature.When reaction finished, reaction soln splashed in the distilled water to leach the throw out of generation, with distilled water cleaning final vacuum drying (output: 59%).
Synthesis example 4: polymkeric substance D synthetic that is used for gap filling material
20 gram maleic anhydrides, 20.42 gram methyl methacrylates, 35.93 gram methacrylic acid benzene methyls, 38.38 gram methacrylic acid diethylene glycol methyl ether esters (diethylene glycol methylether methacrylate) and 11.47 gram AIBN are dissolved in 378 grams, 1, the 4-dioxane and carried out polyreaction 4 hours under 80 ℃ of temperature.After described polyreaction was finished, reaction soln splashed in the methyl alcohol to leach the throw out of generation, with washed with methanol final vacuum drying (molecular weight: 7800, PDI:2.94, output: 62%) repeatedly.Mix mutually with 378 gram methyl alcohol with 1.1 gram toluenesulphonic acids monohydrates (toluenesulfonicacid monohydrate) 71.1 restrain vacuum drying polymkeric substance, reaction is 20 hours under 80 ℃ of temperature.When reaction finished, reaction soln splashed in the distilled water to leach the throw out of generation, with distilled water cleaning final vacuum drying (output: 60%).
Embodiment
Embodiment 1: the preparation of gap filling material composition A
1.90 gram is by the polymkeric substance that is used for gap filling material of synthesis example 1 preparation, 2.85 gram light absorbing material, 1.43 gram tetramethoxymethylglycoluril (tetramethoxymethylglycouril) and 0.10 gram thermogenesis agent are dissolved among the 93.73 gram acetic acid propylene glycol monomethyl ether ester propylene glycol monomethyl ether acetate (PGMEA), and described solution is that the filtering membrane of 0.2 μ m filters by having diameter, thereby prepares described gap filling material composition A.
Embodiment 2: the preparation of gap filling material composition B
1.90 gram is by the polymkeric substance that is used for gap filling material of synthesis example 2 preparations, 2.85 gram light absorbing material, 1.43 gram tetramethoxymethylglycoluril (tetramethoxymethylglycouril) and 0.10 gram thermogenesis agent are dissolved among the 93.73 gram PGMEA, and described solution is that the filtering membrane of 0.2 μ m filters by having diameter, thereby prepares described gap filling material composition B.
Embodiment 3: the preparation of gap filling material composition C
1.90 gram is by the polymkeric substance that is used for gap filling material of synthesis example 3 preparations, 2.85 gram light absorbing material, 1.43 gram tetramethoxymethylglycoluril (tetramethoxymethylglycouril) and 0.10 gram thermogenesis agent are dissolved among the 93.73 gram PGMEA, and described solution is that the filtering membrane of 0.2 μ m filters by having diameter, thereby prepares described gap filling material composition C.
Embodiment 4: the preparation of gap filling material composition D
1.90 gram is by the polymkeric substance that is used for gap filling material of synthesis example 4 preparations, 2.85 gram light absorbing material, 1.43 gram tetramethoxymethylglycoluril (tetramethoxymethylglycouril) and 0.10 gram thermogenesis agent are dissolved among the 93.73 gram PGMEA, and described solution is that the filtering membrane of 0.2 μ m filters by having diameter, thereby prepares described gap filling material composition D.
Test case
Test case 1: demoulding test (stripping test)
Gap filling material composition launches in silicon wafer (wafer) spin, cures 1 minute at the dish that is heated to 230 ℃, thereby forms the coating that one deck is used for gap filling material.In this case, gap filling material can be by embodiment 1 to 4 preparation.After crosslinked, measure to be used for the thickness of the coating of gap filling material, the wafer that will scribble the gap filling material coating immerses solvent, in the ethyl lactate (ethyl lactate) 1 minute.After removing ethyl lactate fully, wafer was cured 1 minute at the dish that is heated to 100 ℃, measure the thickness of the coating that is used for gap filling material again.The result who measures is for all gap filling material compositions by embodiment 1-4 preparation, before handling ethyl lactate and to handle the thickness of the coating after the ethyl lactate as broad as long.Therefore, owing to hardened fully through the gap filling material composition of embodiment preparation, when carrying out photoetching process, gap filling material composition can not mix mutually with photoresist material.
Test case 2: check is used for the filling characteristic of gap filling material
Gap filling material composition fill contact hole in two embedded technologies and via and on substrate spin coating, cure 1 minute at the dish that is heated to 230 ℃, thereby obtain the coating for gap filling material.In this case, described gap filling material can be by embodiment 1 to 4 preparation.Identify the coating of described gap filling material with scanning electronic microscope (scanning electronmicroscope).
Fig. 1 is the scanning electron microscope image after substrate launches of the gap filling material composition of embodiment 1 preparation.As Fig. 1, in handling, the filling of two embedded technologies do not produce the space.And described gap filling material composition has and surpasses 95% abundant filling characteristic and have the surface of good homogeneity after filling.
The present invention is not limited to described embodiment.Do not break away from by claim of the present invention and be equal to the principle of defined scope and the situation of spirit under, those skilled in the art can carry out various changes to it, its scope is limited by described claim and its condition of equivalent.
According to described embodiment, the gap filling material composition that can obtain not mixing mutually with photoresist material, have good filling characteristic, have good bonding characteristic and protectiveness and have quick dry etching rate.
According to described embodiment, in handling, the filling of two embedded technologies can not produce the space; And described gap filling material composition can fully be filled, and has to surpass 95% homogeneity.
And according to described embodiment, in the photoetching process, when gap filling material composition was exposed, gap filling material composition can absorb the reflected light that takes place fully after filling.
And gap filling material composition can not mix mutually with photoresist material, antireflecting coating, insulating material etc., and has high etching selectivity between gap filling material composition and photoresist material, gap filling material composition and bottom antireflective coating.Therefore, described gap filling material mixture can be simplified technology, omits unnecessary technology to prevent cost waste.
Claims (6)
1. gap filling material composition, described composition comprises light absorbing material, the living sour agent of heat, linking agent, with the multipolymer that is used for described gap filling material composition by each expression in the following Chemical formula 1-4, described light absorbing material comprises the haplotype light absorbing material by following chemical formula 5 and 6 expressions
[Chemical formula 1]
[Chemical formula 2]
[chemical formula 3]
[chemical formula 4]
Wherein, each a, b, c and d are number of repeating units on the expression main chain, a+b+c+d=1 wherein, 0.05＜a/ (a+b+c+d)＜0.95,0.05＜b/ (a+b+c+d)＜0.95,0.05＜c/ (a+b+c+d)＜0.95 and 0.05＜d/ (a+b+c+d)＜0.95;
[chemical formula 5]
Wherein, R
8Be-O-,
Or
R
9Represent independently hydrogen atom, C1-10 alkyl or C1-10 alkoxyl group and
[chemical formula 6]
Wherein, R
10Be-O-,
Or
R
11Represent hydrogen atom, C1-10 alkyl or C1-10 alkoxyl group independently.
2. gap filling material composition as claimed in claim 1, wherein, described linking agent is the compound that contains at least 2 crosslinked functional groups, and is choose from the group that is made of aminoplast compounds, polyfunctional epoxy resin, acid anhydrides and composition thereof at least a.
3. gap filling material composition as claimed in claim 1, wherein, described linking agent is choose from the group that is made of oxa-cyclobutyl, oxazoline, cyclic carbonate ester, ethanol silyl, amino methylol, alkoxy methyl, '-aziridino, methylol, isocyanic ester, alkoxy methyl amino and multifunctional fundamental mode Resins, epoxy at least a.
4. gap filling material composition as claimed in claim 2, wherein, described aminoplast compounds is choose from the group that is made of dimethoxy-methyl glycoluril, diethoxymethyl glycoluril, dimethoxy-methyl glycoluril and diethoxymethyl glycoluril mixture, diethyl-dimethyl glycoluril, tetramethoxymethylglycoluril and hexamethoxymethyl melamine resin at least a.
5. gap filling material composition as claimed in claim 1, wherein, to give birth to sour agent be choose from the group that the pyridinium salt by the amine salt of the pyridinium salt of the amine salt of toluenesulphonic acids, toluenesulphonic acids, toluenesulphonic acids, alkylsulphonic acid, alkylsulphonic acid and alkylsulphonic acid constitutes at least a for described heat.
6. gap filling material composition as claimed in claim 1, wherein, described gap filling material composition comprises:
0.1w% is to the described multipolymer that is used for described gap filling material composition of 30w%;
15w% is to the described light absorbing material of 50w%;
0.01w% gives birth to sour agent to the described heat of 30w%; With
0.01w% is to the described linking agent of 25w%.
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| KR10-2009-0039809 | 2009-05-07 | ||
| KR1020090039809A KR20100120930A (en) | 2009-05-07 | 2009-05-07 | Copolymer for gap filling material composition, preparation method thereof and gap filling material composition for antireflective coating layer |
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| CN101880352A CN101880352A (en) | 2010-11-10 |
| CN101880352B true CN101880352B (en) | 2013-10-02 |
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| KR (1) | KR20100120930A (en) |
| CN (1) | CN101880352B (en) |
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| EP2886620B1 (en) | 2013-12-18 | 2019-11-27 | 3M Innovative Properties Company | Post-curable pressure-sensitive adhesive |
| US9761449B2 (en) | 2013-12-30 | 2017-09-12 | Taiwan Semiconductor Manufacturing Company, Ltd. | Gap filling materials and methods |
| EP3020755B1 (en) | 2014-11-14 | 2018-01-10 | 3M Innovative Properties Company | Post-curable rubber-based pressure-sensitive adhesive |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6037416A (en) * | 1995-08-10 | 2000-03-14 | Mitsubishi Rayon Co., Ltd. | Thermosetting coating composition |
| CN101100496A (en) * | 2006-07-07 | 2008-01-09 | 戈尔德施米特股份公司 | Maleic anhydride copolymer containing amine oxide group and use thereof |
| CN101230179A (en) * | 2007-01-26 | 2008-07-30 | 罗门哈斯公司 | Light-scattering compositions |
-
2009
- 2009-05-07 KR KR1020090039809A patent/KR20100120930A/en not_active Application Discontinuation
- 2009-11-05 SG SG200907426-1A patent/SG166040A1/en unknown
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2010
- 2010-02-05 CN CN2010101247234A patent/CN101880352B/en not_active Expired - Fee Related
- 2010-02-10 TW TW099101358A patent/TW201040205A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6037416A (en) * | 1995-08-10 | 2000-03-14 | Mitsubishi Rayon Co., Ltd. | Thermosetting coating composition |
| CN101100496A (en) * | 2006-07-07 | 2008-01-09 | 戈尔德施米特股份公司 | Maleic anhydride copolymer containing amine oxide group and use thereof |
| CN101230179A (en) * | 2007-01-26 | 2008-07-30 | 罗门哈斯公司 | Light-scattering compositions |
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| TW201040205A (en) | 2010-11-16 |
| CN101880352A (en) | 2010-11-10 |
| SG166040A1 (en) | 2010-11-29 |
| KR20100120930A (en) | 2010-11-17 |
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