CN1756994A - Resist material for liquid immersion exposure process and method of forming resist pattern with the resist material - Google Patents
Resist material for liquid immersion exposure process and method of forming resist pattern with the resist material Download PDFInfo
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Abstract
The invention provides negative resist material including the a resin component and the cross linking agent component of the resin component and being used for the liquid immersion exposure process in which the cross linking agent component is hardly dissolved into the liquid immersion medium, and a method for forming the resist pattern adopting the negative resist material. In the liquid immersion exposure process, even if the light through the planography exposure reaches at least the resist film of the path of the resist film, the medium is exposed under the condition of the thick specified liquid with the refraction index of the thick specified liquid larger than the refraction index of air and lower than the refraction index of the negative resist film, to enhance the resolution factor of the resist pattern in the liquid immersion exposure process, and simultaneously to prevent the deterioration of the resist film in the liquid immersion exposure and the deterioration of the used liquid; thereby forming the resist pattern of high resolution factor through the liquid immersion exposure.
Description
Technical field
The present invention relates to the resist pattern formation method of anticorrosive additive material and this anticorrosive additive material of use, this material is suitable for obtaining the resist film that uses in the liquid for immersion exposure process of following formation, in immersion exposure (Liquid Immersion Lithography) technology, wherein arrive on the above-mentioned at least resist film in path of resist film at the light of offset printing exposure, Jie is under the state of the liquid of the low specific thickness of refractive index ratio air height and the above-mentioned resist film of refractive index ratio, to above-mentioned resist film exposure, improve the resolution of resist pattern.
Background technology
In the manufacturing of the fine structure of various electronic installations such as semiconductor device, liquid-crystal apparatus, usually use the offset printing method, but, the resist pattern in the offset printing operation is also required to become more meticulous along with the becoming more meticulous of apparatus structure.
At present, adopt the offset printing method,, can form the meticulous resist pattern of the about 90nm of live width, will require to form meticulousr pattern from now on for example in most advanced field.
In order to form the pattern meticulousr than this 90nm, the exploitation of exposure device and its corresponding resist becomes the 1st main points.In exposure device, F
2The increase of the short wavelengthization of optical source wavelengths such as laser, EUV (extreme ultraviolet light), electron ray, X ray and the pinhole number (NA) of lens etc. generally is the main points of exploitation.
But the short wavelengthization of optical source wavelength needs expensive novel exposure device, and in high NAization, because there are trade-off relation in the resolution and the depth of focus width of cloth, even improve resolution, the problem that also exists the depth of focus width of cloth to reduce.
Recently, as the lithographic printing that can address this problem, reported the such method of immersion exposure (Liquid Immersion Lithography) method (for example, non-patent literature 1 (J.Vac.Sci.Technol.B (1999) 17 (6) p3306-3309), non-patent literature 2 (J.Vac.Sci.Technol.B (2001) 19 (6) p2353-2356), non-patent literature 3 (Proceedings of SPIE Vol.4691 (2002) 4691p459-465)).This method is when exposure, and Jie is at aqueous index mediums (maceration extract) such as the pure water of specific thickness or fluorine-containing inert fluids on the above-mentioned at least resist film between the resist film on lens and the substrate.In the method, with the bigger liquid of refractive index (n), for example displacement such as pure water was the exposure light path space of inert gases such as air or nitrogen in the past, even use the light source of identical exposure wavelength, during also with the light source that uses short wavelength more or the same when using high NA lens, when reaching high resolution, the depth of focus width of cloth can not reduce.
If use this immersion exposure, use the lens of in existing device, installing, can realize forming the resist pattern that high resolution is better and the depth of focus is also good, thereby receive very big concern with low cost.
Summary of the invention
But, in aforesaid liquid for immersion exposure process, as the maceration extract that uses, inertia water such as pure water, deionized water have been proposed, and perfluor ether, wait from cost and processing easiness, think that inertia water is more promising, but during exposure, because of resist film directly contacts with maceration extract, resist film is subjected to the invasion and attack of maceration extract.Therefore, in order to make aforesaid novel flat-plate printing technology practicability, be necessary to provide to form the anticorrosive additive material that above-mentioned maceration extract is had the resist film of high patience.
The present invention In view of the foregoing makes, and its problem is to provide the material of the negative resist in the liquid for immersion exposure process that is applicable to the novel flat-plate printing technology, and the resist pattern formation method of using this negative resist material.
In order to solve above-mentioned problem, liquid for immersion exposure process of the present invention is characterised in that with the negative resist material, contains the crosslinking chemical composition of resinous principle and this resinous principle, and it is slightly solubility that above-mentioned crosslinking chemical composition soaks medium to liquid.
In addition, resist pattern formation method of the present invention is to use the resist pattern formation method of liquid for immersion exposure process, it is characterized in that, be included on the substrate, at least use above-mentioned anticorrosive additive material, form photoresist film, at lamination on the aforesaid substrate of above-mentioned resist film directly the configuration maceration extract, by above-mentioned maceration extract, pattern light to above-mentioned resist film irradiation regulation carries out heat treated as required, removes above-mentioned maceration extract from above-mentioned postradiation resist film, the resist film of having removed above-mentioned maceration extract is developed, obtain the resist pattern.
In addition, in the above-described configuration, the preferred such formation of liquid for immersion exposure process, promptly, wherein reach on the above-mentioned at least resist film in path of resist film at the light of offset printing exposure, Jie exposes under the state of the maceration extract of the low specific thickness of refractive index ratio air height and the above-mentioned resist film of refractive index ratio, improves the resolution of resist pattern.
In addition, the inventor etc. are doing when of the present invention, just are used for the adaptive evaluation method of the resist film of liquid for immersion exposure process, have carried out following analysis, based on its analysis result, estimated the resist pattern formation method of negative resist material and this negative resist material of use.
Promptly, when estimating the resist pattern formation performance that adopts immersion exposure, if can confirm the performance of the optical system of (i) immersion exposure method, (ii) resist film is for the influence of maceration extract, (iii) rotten this 3 point of the resist film that causes of maceration extract, it is fully necessary then being judged as.
Performance about the optical system of (i), if for example imagination sinks to the photo of surperficial water tolerance in the water with photographic plate, situation to its surface irradiation pattern light then can be clear and definite: if the optical transmission loss that does not reflect at the interface on the water surface and water and photographic plate surface etc., then problem does not take place in the back, and this does not have query on principle.Optical transmission loss under this situation can easily solve by suitableization of the incident angle of exposure light.Therefore, when the material as exposure object is resist film, be photo use light sensitive plate the time, or during the imaging silk screen, if they are inertia to maceration extract, if not influenced by maceration extract, do not influence maceration extract yet, can think that then the performance of optical system does not change.Therefore, about this point, needn't confirm experiment again.
Resist film (ii) specifically is composition stripping in liquid of resist film for the influence of maceration extract, and liquid refractive index is changed.If liquid refractive index changes, then the optics definition of pattern exposure is changed, and this need not experimentize, and promptly is definite theoretically.About this point, only resist film is immersed in the occasion in the liquid, if can confirm the composition stripping, the composition of maceration extract changes, perhaps variations in refractive index then is fully, does not in fact need irradiation pattern light, resolution is confirmed in video picture.
In contrast, resist film irradiation pattern light in liquid, video picture, the occasion of affirmation definition, enable promptly to confirm whether definition is good, whether whether rotten influential to definition, the going bad of anticorrosive additive material that can not distinguish maceration extract influence definition or this two aspect.
About because the resist film that (iii) maceration extract causes rotten makes the problem of definition deterioration, adopt following evaluation test promptly enough: ", checking the definition of resulting resist pattern " in the laggard processing of maceration extract shower on resist film of being about to that expose; video picture then.And, in this evaluation method,, soak more too harshness of condition as liquid to the direct spraying liquid of resist film.About this point, the occasion of the test that under the thorough impregnation state, exposes, whether have by the rotten influence that brings of maceration extract, resist composition by maceration extract cause rotten whether be reason or whether since both sides' influence to make that definition changes all indeterminate.
Above-mentioned phenomenon (ii) and (iii) is the phenomenon of one in the table, can hold by the metamorphic grade that is caused by liquid of confirming resist film.
Based on this analysis, by " resist erosion agent film after the exposure and apply the processing that maceration extract (pure water) is bathed; develop afterwards; check the resolving power of gained resist pattern " this evaluation test, confirm to be suitable for the immersion exposure adaptability of the resist film that the novel anticorrosive additive material of liquid for immersion exposure process forms.The maceration extract that uses in this affirmation is a pure water low from cost and that the processing easiness is expected.And, as other evaluation method, also adopt " the pattern light that the interference light replacement that produces with prism exposes makes sample place liquid to soak state, makes it exposure (two-beam interference exposure method) " of simulation to estimate actual manufacturing process.
The best mode that carries out an invention
Liquid for immersion exposure process of the present invention is characterized in that containing the crosslinking chemical composition of resinous principle and this resinous principle with anticorrosive additive material as previously mentioned, and it is slightly solubility that above-mentioned crosslinking chemical composition soaks medium to liquid.
In addition, as liquid for immersion exposure process of the present invention, preferred such formation, promptly reach on the above-mentioned at least resist film in path of resist film at the light of offset printing exposure, Jie is under the state of the maceration extract of the low specific thickness of refractive index ratio air height and the above-mentioned resist film of refractive index ratio, above-mentioned resist film is exposed, improve the resolution of resist pattern.
As above-mentioned resinous principle, so long as the resinous principle that uses in the negative resist composition of routine is unqualified, preferred following composition.Preferred use (A) becomes in the insoluble resinous principle of alkali by acid, in molecule, have 2 kinds of functional groups that can form ester by reacting to each other, the effect of the acid that it produces by the acid-producing agent that adds to simultaneously in the anticorrosive additive material, dehydration forms ester, becomes the insoluble resin of alkali.Wherein so-called can reacting to each other forms 2 kinds of functional groups of ester, is meant to be used to form for example hydroxyl of carboxylate and the functional group of carboxyl or this class of carboxylate.In other words, be 2 kinds of functional groups that are used to form ester.As this resin, preferably on the side chain of resin main framing, has resin at least a in hydroxyalkyl and carboxyl and the carboxylic acid ester groups.The resinous principle that further preferred (B) is made of the polymkeric substance with dicarboxylic acid monoesters unit.
The resinous principle of above-mentioned (A) in other words, is the resinous principle that has the monomeric unit of following general formula (2) expression at least.
(in the formula, R
2Be the alkyl of hydrogen atom, C1～C6, perhaps have the alkyl of polycycle ring skeletons such as bornyl, adamantyl, Fourth Ring dodecyl, three ring decyls)
As the example of this resin, preferably can enumerate (A-1) and be selected from least a kind of polymer of monomers (homopolymer or multipolymer) in α-(hydroxyalkyl) acrylic acid and α-(hydroxyalkyl) alkyl acrylate and (A-2) be selected from least a kind of monomer and the multipolymer that is selected from least a kind of monomer in other ethene unsaturated carboxylic acid and the ethene esters of unsaturated carboxylic acids etc. in α-(hydroxyalkyl) acrylic acid and α-(hydroxyalkyl) alkyl acrylate.
Polymkeric substance as above-mentioned (A-1), the multipolymer of preferred α-(hydroxyalkyl) acrylic acid and α-(hydroxyalkyl) alkyl acrylate, as the multipolymer of (A-2), preferred use be selected from acrylic acid, methacrylic acid, alkyl acrylate and the alkyl methacrylate at least a kind as above-mentioned other ethene unsaturated carboxylic acid or ethene esters of unsaturated carboxylic acids.
As the example of the hydroxyalkyl in above-mentioned α-(hydroxyalkyl) acrylic acid and α-(hydroxyalkyl) alkyl acrylate, can enumerate rudimentary hydroxyalkyls such as methylol, hydroxyethyl, hydroxypropyl, hydroxyl butyl.Wherein from forming the complexity of ester, preferred hydroxyethyl and methylol.
In addition, as the example of the alkyl of the Arrcostab of α-(hydroxyalkyl) alkyl acrylate part, can enumerate low alkyl groups such as methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, amyl group; Two ring [2.2.1] heptyl, bornyl, adamantyl, Fourth Ring [4.4.0.1
2.5.1
7.10] dodecyl, three the ring [5.2.1.0
2.6] bridging type polycycle cyclic hydrocarbon group such as decyl etc.The alkyl of ester moiety is the polycycle cyclic hydrocarbon group, and is effective to improving anti-dry ecthing.In these alkyl, particularly,, preferably use low price and the easy alcohol that obtains as the pure composition that forms ester in the occasion of low alkyl groups such as methyl, ethyl, propyl group, butyl.
In the occasion of lower alkyl esters, the same with carboxyl, the esterification with hydroxyalkyl takes place, but in the occasion of the ester that forms with bridging type polycycle cyclic hydrocarbon, is difficult to take place this esterification.Therefore, in the occasion that will import to the ester that bridging type polycycle cyclic hydrocarbon forms in the resin, preferred have carboxyl at the resin side chain simultaneously.
On the other hand, as other ethene unsaturated carboxylic acid in the resin of above-mentioned (A-2) and the example of ethene esters of unsaturated carboxylic acids, can enumerate unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid; Arrcostabs such as the methyl esters of these unsaturated carboxylic acids, ethyl ester, propyl ester, isopropyl ester, positive butyl ester, isobutyl ester, just own ester, monooctyl ester etc.In addition, as the alkyl of ester moiety, also can use to have two ring [2.2.1] heptyl, bornyl, adamantyl, Fourth Ring [4.4.0.1
2.5.1
7.10] dodecyl, three the ring [5.2.1.0
2.6] ester of acrylic or methacrylic acid of bridging type polycycle cyclic hydrocarbon group such as decyl.Wherein, from low price and can obtaining easily, preferred acrylic acid and methacrylic acid, perhaps lower alkyl esters such as these sour methyl esters, ethyl ester, propyl ester, positive butyl ester.
In the resin of above-mentioned (A-2), be selected from least a kind of monomeric unit and the ratio that is selected from least a kind of monomeric unit in other ethene unsaturated carboxylic acid and the ethene esters of unsaturated carboxylic acids in α-(hydroxyalkyl) acrylic acid and α-(hydroxyalkyl) alkyl acrylate, with molar ratio computing, scope at 20: 80 to 95: 5 was particularly preferably in 50: 50 to 90: 10 scope.The ratio of Unit two is as long as in above-mentioned scope, in molecule or intermolecularly be easy to form ester, can obtain good resist pattern.
In addition, the resinous principle of above-mentioned (B) is the resinous principle that has the monomeric unit of following general formula (3) or (4) expression at least.
(in the formula, R
3And R
4The alkyl chain of expression carbon number 0～8, R
5The substituting group that expression has at least 2 above ester ring type structures, R
6And R
7The alkyl of expression hydrogen atom or carbon number 1～8.)
Use has the negative resist composition resolving power height of the resinous principle of this dicarboxylic acid monoesters monomeric unit, is preferred reducing aspect the line edge roughness.In addition, swelling patience height, in liquid for immersion exposure process more preferably.
Substituent R in above-mentioned general formula (3) and (4)
5Be the substituting group with at least 2 above ester ring type structures, it can have more than 2 independently alicyclic structure in substituting group, also can have with the form of condensed ring, volution.Adopting the big substituting group of this carbon density, is being preferred aspect the elching resistant that can improve polymkeric substance.
As this substituting group, specifically be preferably selected from least a kind in diamantane, tristane, isobornyl, norborene, adamantanol, the norborene lactone or derivatives thereof with at least 2 above ester ring type structures.
As this dicarboxylic acid monoesters compound, preferred especially fumaric monoalkylester, itaconic acid monoesters.Can enumerate fumaric acid list diamantane ester, fumaric acid monomethyl diamantane ester, fumaric acid list ethyl diamantane ester, fumaric acid list Isobornyl, fumaric acid list norborneol ester, fumaric acid two cyclopentene esters, fumaric acid two ring pentyl esters, itaconic acid list diamantane ester, itaconic acid monomethyl diamantane ester, itaconic acid list ethyl diamantane ester, itaconic acid list Isobornyl, itaconic acid list norborneol ester, itaconic acid two cyclopentene esters, itaconic acid two ring pentyl esters etc. particularly.
In addition, the dicarboxylic acid monoesters compound as in addition also can use the monoester compound that derives from mesaconic acid, glutaconic acid and traumatic acid.
Be further used as resin, preferably can enumerate (B-1) dicarboxylic acid monoesters polymer of monomers or multipolymer and (B-2) dicarboxylic acid monoesters monomer and the multipolymer etc. that is selected from least a kind of monomer in above-mentioned α-(hydroxyalkyl) acrylic acid, α-(hydroxyalkyl) alkyl acrylate, other ethene unsaturated carboxylic acid and the ethene esters of unsaturated carboxylic acids with above-mentioned dicarboxylic acid monoesters unit.
In the present invention, these resinous principles may be used alone, two or more kinds can also be used in combination.In addition, the weight-average molecular weight of resinous principle is 1000～50000, preferred 2000～30000.
As of the present invention be the crosslinking chemical composition that liquid soaks the medium indissoluble to liquid for immersion exposure process with the important composition key element of anticorrosive additive material, preferred use at least that each molecule has being cross-linked to form property functional group more than 3, and the being cross-linked to form property functional group with nitrogen-atoms is the crosslinking chemical below 1.Wherein, preferred glycoluril derivant, the structure of preferred especially following general formula (1) expression.
(in the formula, R
1Be the alkyl of carbon number 1～10, n is 1～5 alkyl chain)
As the glycoluril derivant (liquid is soaked the crosslinking chemical that medium is a slightly solubility) of above-mentioned general formula (1) expression, butoxymethyl glycoluril the best.
As the acid-producing agent that can be used for anticorrosive additive material of the present invention, promptly stand the light that exposes and acidic compound, select to use in the known acid-producing agent that can be suitably from the negative type photoresist of chemical amplifying type in the past, uses, especially preferably contain alkyl sulfonic acid ion that alkyl or halogen replace as anionic salt.As the kation of this salt, preferably enumerating can be by low alkyl groups such as methyl, ethyl, propyl group, normal-butyl, the tert-butyl groups; Or the phenyl-iodide that replaces such as lower alkoxies such as methoxyl, ethoxy and sulfonium etc., and dimethyl (4-hydroxyl naphthyl) sulfonium.
On the other hand, the fluoroalkyl azochlorosulfonate acid ion that part or all of the hydrogen atom of the alkyl of the preferred carbon number of negative ion about 1～10 replaced by fluorine atom, and, carbochain is long more, and it is more little to fluoridize rate (ratio of the fluorine atom in the alkyl), intensity as sulfonic acid will descend, the fluoroalkyl azochlorosulfonate acid ion that the hydrogen atom of the alkyl of therefore preferred carbon number 1～5 is all replaced by fluorine atom.
As the example of this salt, can enumerate the fluoroform sulphonate of the fluoroform sulphonate of the fluoroform sulphonate of the fluoroform sulphonate of the fluoroform sulphonate of diphenyl iodine or nine fluorine fourth sulfonate, two (4-tert-butyl-phenyl) iodine or nine fluorine fourth sulfonate, triphenylsulfonium or nine fluorine fourth sulfonate, three (4-aminomethyl phenyl) sulfonium or nine fluorine fourth sulfonate, dimethyl (4-hydroxyl naphthyl) sulfonium or nine fluorine fourth sulfonate etc.In the present invention, the acid-producing agent that is somebody's turn to do (A) composition can use a kind, also can be used in combination more than 2 kinds.
In anticorrosive additive material of the present invention, can further add as required to contain and have blended adjuvant, for example be used to improve the habitual adjuvants such as additional resin, plastifier, stabilizing agent, colorant, surfactant, amine of resist film performance.
Anticorrosive additive material of the present invention preferably when it uses, uses with the solution form of above-mentioned each composition of dissolving in solvent.As the example of this solvent, can enumerate ketones such as acetone, MEK, cyclohexanone, methyl isoamyl ketone, 2-heptane; Polyalcohols and derivants thereof such as ethylene glycol, ethylene glycol monoacetate, diglycol, diglycol monotertiary acetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate or their monomethyl ether, single ethylether, single propyl ether, single-butyl ether or single phenyl ether; Ring type ethers such as dioxane; And ester class such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate; N, amide solvents such as dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-etc.These may be used alone, can also be two or more kinds in combination.
As the maceration extract that in using the liquid for immersion exposure process of anticorrosive additive material of the present invention, uses, can enumerate the water that pure water or deionized water constitute, and by containing liquid that fluorous solvent constitutes etc.
Below, just use the resist pattern formation method of the immersion exposure method of maceration extract of the present invention to describe.
At first, on substrates such as silicon wafer, behind the above-mentioned anticorrosive additive materials of coating such as spinner, carry out prebake (PAB processing).
In addition, also can be 2 layers of layered product that organic class or mineral-type antireflection film are set between the coating layer of substrate and resist composition.
Operation so far can be carried out with known method.Operating conditionss etc. are preferably suitably set according to the composition and the characteristic of employed resist composition.
Then, the substrate that has formed resist film is immersed in the maceration extract of " inertia water such as pure water or deionized water, and perfluor ether, perfluoroalkyl amine etc. contain fluorous solvent " etc.
Resist film to the substrate of this impregnation state by desirable mask pattern, optionally exposes.Therefore, the light of exposure this moment will reach resist film by maceration extract.
At this moment, resist film directly contacts with maceration extract, and resist film is made of anticorrosive additive material of the present invention, to patience height with the maceration extract headed by the water, therefore resist film can not go bad, and maceration extract can be not rotten because of resist film yet, and optical characteristics such as its refractive index also undergo no deterioration.
The wavelength of the usefulness of exposing this moment, there is no particular limitation, can use ArF excimer laser, KrF excimer laser, F
2Laser, EUV (Extreme Ultraviolet), VUV (vacuum ultraviolet), electron ray, X ray, grenz ray isoradial carry out.Negative resist material of the present invention is using ArF excimer laser preferred especially as the light time of exposure.
After the liquid of stating maceration extract in the use soaks and finishes exposure process under the state, take out substrate, remove maceration extract from substrate from maceration extract.
Then, the resist film after the exposure is carried out PEB (heating of exposure back), then, use the alkaline-based developer that constitutes by alkaline aqueous solution to carry out development treatment.In addition, after development treatment, cure after also can carrying out.In addition, preferably use pure water to carry out rinsing.This water rinse Yi Bian for example make substrate rotation, drips on substrate surface on one side or sprays the resist composition of the developer solution on the flush away substrate and this developing solution dissolution.In addition, carry out drying, the resist film composition becomes the shape corresponding to mask pattern, obtains the resist pattern.
By such formation resist pattern, can make the resist pattern of fine linewidth, particularly closely spaced lines and intermittent pattern with fine resolution.
In addition, wherein the spacing in lines and the intermittent pattern is meant the wide and wide at interval total distance of resist pattern on the live width direction of pattern.
Embodiment
Below, embodiments of the invention are described, but these embodiment only are suitable for describing example of the present invention, the present invention are not done any qualification.In addition, in the following description and embodiment put down in writing comparative example together.
(embodiment 1)
In propylene glycol monomethyl ether, dissolve resinous principle as the repetitive of the following chemical formula of having of resinous principle (5) expression,
(in the formula, m: n is 84: 16 (mole %))
And with respect to this resinous principle, the amine component that the acid-producing agent of the slightly water-soluble crosslinking chemical that the four butoxymethyl glycolurils of 10 quality % constitute, the triphenylsulfonium nine fluorine fourth sulfonate of 1 quality % formation and the 4-phenylpyridine of 0.6 quality % constitute, preparation solid content weight is the negative resist material of 8.1 quality %.
In addition, use spinner on silicon wafer substrate, be coated with organic class antireflection film " AR-19 " (trade name, Shipley society system), made it dry in 60 seconds, organic class antireflection film of formation thickness 82nm under 215 ℃, firing on the electric hot plate.On this antireflection film, be coated with above-mentioned negative resist material with spinner, at 110 ℃, it is dry that prebake made it in 60 seconds, forms the resist film of thickness 250nm on above-mentioned antireflection film.
Use " by prism irradiation two-beam interference light; the two-beam interference exposure device (experimental provision of ニ コ Application society of Co., Ltd. system) of the light of simulation pattern exposure ", making maceration extract is pure water, and light source uses the ArF excimer laser of wavelength 193nm, and aforesaid substrate is carried out impregnated exposure.In addition, the prism of the device of use contacts with resist film below by pure water.
After the above-mentioned exposure, under 110 ℃, 60 seconds condition, carry out PEB and handle, further developed 40 seconds with alkaline-based developer at 23 ℃.As alkaline-based developer, use the 2.38wt% tetramethylammonium hydroxide aqueous solution.
Observe the lines of the 90nm obtain like this and be spaced apart 1: 1 resist pattern with scanning electron microscope (SEM), the profile of this pattern is good, does not see that pattern such as swelling is bad.
(embodiment 2)
Adopt above-mentioned " resist erosion agent film after the exposure and apply the processing that maceration extract (pure water) is bathed; develop afterwards; check the resolving power of gained resist pattern " this evaluation test, to the foregoing description 1 same substrate that constitutes, with and embodiment 1 in the identical light source of use, expose, carry out pure water and bathed 120 seconds, afterwards, the same with embodiment 1, carry out PEB and handle and development treatment, obtain the resist pattern.
Observe the 160nm lines obtain like this and be spaced apart 1: 1 resist pattern with scanning electron microscope (SEM), the profile of this pattern is good, does not see that pattern such as swelling is bad.In addition, obtain the susceptibility of this moment, be 30.7mJ/cm
2On the other hand, use the anticorrosive additive material of present embodiment 2, do not carry out above-mentioned bath and handle, and adopt formation method in the past to form the resist pattern, susceptibility is 30.1mJ/cm
2Obtaining the ratio of the sensitivity of immersion exposure processing to the susceptibility of usual method, is 101.9.
(embodiment 3)
In propylene glycol monomethyl ether, dissolve resinous principle as the repetitive of the following chemical formula of having of resinous principle (6) expression,
(in the formula, 1: m: n is 12: 44: 44 (mole %).)
And with respect to this resinous principle, the amine component that the acid-producing agent of the slightly water-soluble crosslinking chemical that the four butoxymethyl glycolurils of 10 quality % constitute, the triphenylsulfonium perfluor fourth sulfonate of 1.5 quality % formation and the triethanolamine of 0.2 quality % constitute, preparation solid content weight is the negative resist material of 7.0 quality %.
In addition, use spinner on silicon wafer substrate, be coated with organic class antireflection film " AR-19 " (trade name, Shipley society system), made it dry in 60 seconds, organic class antireflection film of formation thickness 82nm under 215 ℃, firing on the electric hot plate.On this antireflection film, be coated with above-mentioned negative resist material with spinner, at 140 ℃, it is dry that prebake made it in 60 seconds, forms the resist film of thickness 150nm on above-mentioned antireflection film.
Use " by prism irradiation two-beam interference light; the two-beam interference exposure device (experimental provision of ニ コ Application society of Co., Ltd. system) of the light of simulation pattern exposure ", making maceration extract is pure water, and light source uses the ArF excimer laser of wavelength 193nm, and aforesaid substrate is carried out impregnated exposure.In addition, the prism of the device of use contacts with resist film below by pure water.
After the above-mentioned exposure, under 130 ℃, 60 seconds condition, carry out PEB and handle, further developed 60 seconds with alkaline-based developer at 23 ℃.As alkaline-based developer, use the 2.38wt% tetramethylammonium hydroxide aqueous solution.
Observe the lines of the 90nm obtain like this and be spaced apart 1: 1 resist pattern with scanning electron microscope (SEM), the profile of this pattern is good, does not see that pattern such as swelling is bad.
In addition, the line edge roughness (LER) with SEM observes this resist pattern equally is 4.2nm.
(reference example 1)
Use the anticorrosive additive material the same with embodiment 1, but, in exposure-processed, do not carry out impregnated exposure, and the conventional dry type exposure of the passing through mask pattern (exposure device: NSR-s302inline: ニ コ Application society system), obtain the lines of same 160nm and be spaced apart 1: 1 resist pattern of enforcement.Observe the line edge roughness of this moment, be 5.2nm.
(comparative example 1)
Making the crosslinking chemical among the embodiment 1 is the trimethoxy methylated melamines, in addition, uses complete identical operations, attempts to form the lines of 160nm and is spaced apart 1: 1 resist pattern, expands but violent pattern takes place.
As mentioned above, according to the present invention,
(i) be applied to liquid for immersion exposure process by containing resinous principle and liquid being soaked the negative resist material that the crosslinking chemical of medium indissoluble forms, can obtain high-resolution negative resist pattern.
(ii), in liquid for immersion exposure process, can obtain the good negative resist pattern of shape by using the crosslinking chemical that liquid is soaked the medium indissoluble.
Susceptibility during (iii) with respect to the dry process of routine, the susceptibility change during immersion exposure can be controlled at ± 5% in.
(iv) compare, can reduce line edge roughness with technology formation resist pattern by routine.
That is to say, according to the present invention, owing to can form to have the resist film of high patience with the maceration extract headed by the water, therefore in immersion exposure process, the resist pattern does not become bad developments such as the fluctuating, wire drawing video picture of check surface, the pattern of resist patterns such as T-top shape, can obtain susceptibility height, resist pattern contour shape excellence, resist pattern that precision is high.Therefore, if use negative resist material of the present invention, can use liquid for immersion exposure process effectively to form the resist pattern.
List of references (References):
1.Journal of Vacuum Science﹠amp; Technology B (J.Vac.Sci.Technol.B) ((distribution state) U.S.), 1999, the 17th volume, No. 6,3306-3309 page or leaf.
2.Journal of Vacuum Science﹠amp; Technology B (J.Vac.Sci.Technol.B) ((distribution state) U.S.), calendar year 2001, the 19th volume, No. 6,2353-2356 page or leaf.
3.Proceedings of SPIE Vol.4691 ((distribution state) U.S.) 2002, the 4691st volume, 459-465 page or leaf.
Claims (21)
1. a liquid for immersion exposure process negative resist material is characterized in that, contains the crosslinking chemical composition of resinous principle and this resinous principle, and it is slightly solubility that above-mentioned crosslinking chemical composition soaks medium to liquid.
2. the described liquid for immersion exposure process of claim 1 negative resist material, it is characterized in that, the following formation of liquid for immersion exposure process: reach at the light of offset printing exposure on the above-mentioned at least resist film in path of resist film, Jie is under the state of the maceration extract of the low specific thickness of refractive index ratio air height and the above-mentioned resist film of refractive index ratio, above-mentioned resist film is exposed, improve the resolution of resist pattern.
3. the described liquid for immersion exposure process of claim 1 negative resist material is characterized in that, above-mentioned crosslinking chemical composition is a slightly water-soluble.
4. the described liquid for immersion exposure process of claim 3 negative resist material, it is characterized in that, above-mentioned slightly water-soluble crosslinking chemical composition each molecule at least has being cross-linked to form property functional group more than 3, and the being cross-linked to form property functional group that has nitrogen-atoms in this being cross-linked to form property functional group is below 1.
5. the described liquid for immersion exposure process of claim 4 negative resist material is characterized in that, above-mentioned slightly water-soluble crosslinking chemical composition is the glycoluril derivant.
6. the described liquid for immersion exposure process of claim 5 negative resist material is characterized in that, above-mentioned glycoluril derivant has the structure of following general formula (1) expression.
(in the formula, R
1Be the alkyl of carbon number 1～10, n is 1～5 alkyl chain)
7. the described liquid for immersion exposure process of claim 6 negative resist material is characterized in that, the glycoluril derivant with structure of above-mentioned general formula (1) expression is the butoxymethyl glycoluril.
8. the described liquid for immersion exposure process of claim 1 negative resist material is characterized in that, above-mentioned resinous principle is to have the polymkeric substance that is selected from least a kind of monomeric unit in α-(hydroxyalkyl) acrylic acid and α-(hydroxyalkyl) acrylate.
9. the described liquid for immersion exposure process of claim 1 negative resist material, it is characterized in that, above-mentioned resinous principle is to have at least a kind of monomeric unit that is selected from α-(hydroxyalkyl) acrylic acid and α-(hydroxyalkyl) alkyl acrylate, and the multipolymer that is selected from least a kind of monomeric unit in other ethene unsaturated carboxylic acid and the ethene esters of unsaturated carboxylic acids.
10. the described liquid for immersion exposure process of claim 1 negative resist material is characterized in that, above-mentioned resinous principle is the polymkeric substance with dicarboxylic acid monoesters unit.
11. the described liquid for immersion exposure process of claim 10 negative resist material, it is characterized in that above-mentioned polymkeric substance with dicarboxylic acid monoesters unit is dicarboxylic acid monoesters unit and the multipolymer that is selected from least a kind of monomeric unit in α-(hydroxyalkyl) acrylic acid, α-(hydroxyalkyl) acrylate and other ethene unsaturated carboxylic acid or the ethene esters of unsaturated carboxylic acids.
12. the described liquid for immersion exposure process of claim 1 negative resist material is characterized in that above-mentioned maceration extract is the water that is made of pure water or deionized water.
13. the described liquid for immersion exposure process of claim 1 negative resist material is characterized in that, above-mentioned maceration extract is by containing the liquid that fluorous solvent constitutes.
14. a resist pattern formation method forms the resist pattern with liquid for immersion exposure process, comprising:
On substrate, use to contain resinous principle at least and liquid is soaked the anticorrosive additive material that the crosslinking chemical composition of medium indissoluble forms to form photoresist film,
At lamination on the aforesaid substrate of above-mentioned resist film directly the configuration maceration extract,
By the pattern light of aforesaid liquid to above-mentioned resist film irradiation regulation, as required, carry out heat treated,
Remove above-mentioned maceration extract from above-mentioned postradiation resist film,
The resist film of having removed aforesaid liquid is developed, obtain the resist pattern.
15. the described resist pattern of claim 14 formation method, it is characterized in that, the following formation of above-mentioned liquid for immersion exposure process: reach at the light of offset printing exposure on the above-mentioned at least resist film in path of resist film, Jie is under the state of the maceration extract of the low specific thickness of refractive index ratio air height and the above-mentioned resist film of refractive index ratio, above-mentioned resist film is exposed, improve the resolution of resist pattern.
16. the described resist pattern of claim 14 formation method, it is characterized in that, above-mentioned each molecule of slightly water-soluble crosslinking chemical composition has the being cross-linked to form property functional group more than 3 at least, and the being cross-linked to form property functional group that has nitrogen-atoms in this being cross-linked to form property functional group is below 1.
17. the described resist pattern of claim 16 formation method is characterized in that, above-mentioned slightly water-soluble crosslinking chemical composition is the glycoluril derivant.
18. the described resist pattern of claim 17 formation method is characterized in that, above-mentioned glycoluril derivant has the structure of following general formula (1) expression.
(in the formula, R
1Be the alkyl of carbon number 1～10, n is 1～5 alkyl chain)
19. the described resist pattern of claim 18 formation method is characterized in that above-mentioned glycoluril derivant is the butoxymethyl glycoluril.
20. the described resist pattern of claim 14 formation method is characterized in that above-mentioned maceration extract is the water that is made of pure water or deionized water.
21. the described resist pattern of claim 14 formation method is characterized in that, above-mentioned maceration extract is by containing the liquid that fluorous solvent constitutes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003057766 | 2003-03-04 | ||
| JP057766/2003 | 2003-03-04 | ||
| JP092769/2003 | 2003-03-28 |
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| CN1756994A true CN1756994A (en) | 2006-04-05 |
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| CN 200480005913 Pending CN1756994A (en) | 2003-03-04 | 2004-03-04 | Resist material for liquid immersion exposure process and method of forming resist pattern with the resist material |
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| CN (1) | CN1756994A (en) |
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