CN100478780C - Resist pattern thickening material, resist pattern and its forming process, semiconductor device and its producing process - Google Patents
Resist pattern thickening material, resist pattern and its forming process, semiconductor device and its producing process Download PDFInfo
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- CN100478780C CN100478780C CNB021527709A CN02152770A CN100478780C CN 100478780 C CN100478780 C CN 100478780C CN B021527709 A CNB021527709 A CN B021527709A CN 02152770 A CN02152770 A CN 02152770A CN 100478780 C CN100478780 C CN 100478780C
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Abstract
A resist pattern thickening material has resin, a crosslinking agent and a compound having a cyclic structure, or resin having a cyclic structure at a part. A resist pattern has a surface layer on a resist pattern to be thickened with etching rate (nm/s) ratio of the resist pattern to be thickened the surface layer of 1.1 or more, under the same condition, or a surface layer to a resist pattern to be thickened. A process for forming a resist pattern includes applying the thickening material after forming a resist pattern to be thickened on its surface. A semiconductor device has a pattern formed by the resist pattern. A process for manufacturing the semiconductor device has applying, after forming a resist pattern to be thickened, the thickening material to the surface of the resist pattern to be thickened, and patterning the underlying layer by etching, the pattern as a mask.
Description
The cross reference of related application
The application is the Japanese patent application No.2001-361505 in November 27 calendar year 2001 with the applying date, the applying date is the Japanese patent application No.2002-139317 on May 14th, 2002, with the applying date be on November 12nd, 2002 Japanese patent application No.2002-328931 for the basis and require its right of priority, be incorporated herein its content as a reference.
Technical field
The present invention relates to the resist pattern thickening material, it is used on the resist pattern that the ArF resist forms to thicken resist, can form fine pattern, can also improve the corrosion stability of resist pattern above the light source exposure limit of exposure sources; The invention still further relates to the resist pattern of formation such as available ArF excimer laser, it has fine structure, and outstanding corrosion stability; The present invention relates to form effective technology of this resist pattern; The effective technology that also relates to semiconductor devices and make this semiconductor devices with the fine pattern that forms by this resist pattern.
Background technology
Recently, the SIC (semiconductor integrated circuit) height is integrated.LSI and VLSI have been realized.Therefore, wiring diagram has reached the magnitude that is lower than 0.2 μ m now, and minimum figure has reached 0.1 μ m or lower.In order to form forming fine wiring figure, the development photoetching technique just becomes very important, photoetching refers to following these steps: the processing substrate with the etchant resist cover film forms, after selecting exposure, form resist pattern by developing, and utilize this resist pattern to carry out dry etching as mask.Afterwards, by remove resist pattern obtain the figure of wanting also very important.
In order to form forming fine wiring figure, must shorten the optical source wavelength of exposure sources, and research has the high-resolution erosion resistant based on light source characteristic.Yet, in order to shorten the wavelength of light source on the exposure sources, upgrading exposure sources and be absolutely necessary, this causes the rising of appropriate litigation fees.The erosion resistant that research is suitable for short wave length exposure is not easy to yet.
The technology of making semiconductor devices comprises: at first form fine pattern with resist pattern, use this resist pattern and mask then attentively.Therefore, resist pattern will have outstanding corrosion stability.Yet such problem is but arranged: the resist pattern that is used in the exposure is undesirable aspect corrosion stability for up-to-date technology--exposure of ArF (argon fluoride) excimer laser--.Can use KrF (KrF) resist, but not have enough resistance to corrosions again in the so below sometimes situation of KrF resist: abominable etching condition, thick processing layer, form fine pattern and thin resist thickness.Need a kind of technology to form the outstanding resist pattern of etch resistant properties, and utilize this resist pattern to form fine pattern.
In the open No.10-73927 of Japanese patent application the technology that is called RELACS has been described, wherein (wavelength: deep UV light beam 248nm) is as the exposure light source of resist by using KrF (KrF) excimer laser.This technology comprises: by KrF (KrF) excimer laser (wavelength: 248nm) form resist pattern, provide by adopting the water soluble resin complex with the film that covers resist pattern, by using residual acid solution in the material of resist pattern resist pattern on this film and the surface of contact is interacted thickening (hereinafter also often being called expansions) resist pattern as exposure light source exposure resist (eurymeric or minus), thereby the distance between the shortening resist pattern is with the formation fine pattern is provided.
Yet in this case, KrF (KrF) resist is the anime complex, such as polyhydroxy styrene, naphthoquinones basudin etc.Because the aromatic rings in the anime complex absorbs the ArF excimer laser, ArF (argon fluoride) excimer laser can't penetrate the KrF resist.Therefore, wavelength ArF (argon fluoride) excimer laser that is shorter than the KrF excimer laser can not be used as exposure light source.
From forming the viewpoint of forming fine wiring figure, preferred, also can use ArF (argon fluoride) excimer laser.
Therefore, when composition, utilize ArF (argon fluoride) excimer laser as the exposure device light source so that the technology that forms the fine pattern with outstanding corrosion stability with low cost does not also provide.
Summary of the invention
An object of the present invention is to provide a kind of resist pattern thickening material that can form fine pattern,, can surpass the light source exposure limit of exposure sources, improve the corrosion stability of resist pattern by using this resist pattern thickening material with low cost.
Further aim of the present invention provides a kind of resist pattern of the ArF of utilization excimer laser composition, and it has fine structure, and has outstanding corrosion stability.
Another object of the present invention provides a kind of ArF excimer laser that can utilize as exposure light source, form resist pattern with outstanding mass production capabilities, and surpass the expose technology of limit formation fine pattern of light source with resist pattern low-cost, simple and easy and that improved corrosion stability.
A further object of the invention just provides a kind of high-performance semiconductor device with fine pattern that forms by resist pattern.
For achieving the above object, the invention provides a kind of resist pattern thickening material, it is characterized in that this resist pattern thickening material is applied on the corrosion-resisting pattern so that thicken this corrosion-resisting pattern, this resist pattern thickening material comprises: resin; Crosslinking chemical; Compound with ring texture; And pure water.
According to above-mentioned resist pattern thickening material of the present invention, wherein this resist pattern thickening material is a kind of in water miscible and alkali-soluble.
According to above-mentioned resist pattern thickening material of the present invention, the compound that wherein has ring texture, it is water-soluble to be 0.1g or as many as 100g more in 25 ℃ of water, perhaps its alkali solubility is 0.1g or bigger in 25 ℃ the 2.38% mass percent tetramethylammonium hydroxide aqueous solution.
According to above-mentioned resist pattern thickening material of the present invention, the compound that wherein has ring texture has two or more polar groups.
According to above-mentioned resist pattern thickening material of the present invention, wherein polar group is selected these from following: hydroxyl, amino, sulfonyl, carboxyl and carbonyl.
According to above-mentioned resist pattern thickening material of the present invention, the compound that wherein has ring texture is selected from aromatics, alicyclic compound and heterogeneous ring compound.
According to above-mentioned resist pattern thickening material of the present invention, wherein aromatics is selected these from following: polyphenyl phenolic compounds, aromatic carboxylic compound, Benzophenone compound, flavonoids, and their derivant and glucoside,
Alicyclic compound is selected these from following: poly-cycloalkanes, cycloalkanes, steroids, and their derivant and glucoside, and
Heterogeneous ring compound is selected these from following: pyrrolidine, pyridine, imidazoles, oxazole, morphorine, pyrrolidone, furans, pyrans and carbohydrate.
According to above-mentioned resist pattern thickening material of the present invention, wherein the part of this resin has ring texture.
According to above-mentioned resist pattern thickening material of the present invention, wherein ring texture is selected from aromatics, alicyclic compound and heterogeneous ring compound.
According to above-mentioned resist pattern thickening material of the present invention, the resin content that wherein partly has ring texture is 5mol% or bigger.
According to above-mentioned resist pattern thickening material of the present invention, wherein resin is water miscible or alkali-soluble.
According to above-mentioned resist pattern thickening material of the present invention, wherein resin is a kind of for selecting from polyvinyl alcohol (PVA), polyvinyl acetal, polyvinyl acetate at least.
According to above-mentioned resist pattern thickening material of the present invention, wherein resin contains the polyvinyl acetal of 5% mass percent to 40% mass percent.
According to above-mentioned resist pattern thickening material of the present invention, wherein resin has two or more polar groups.
According to above-mentioned resist pattern thickening material of the present invention, wherein polar group is selected these from following: hydroxyl, amino, sulfonyl, carboxyl and carbonyl.
According to above-mentioned resist pattern thickening material of the present invention, wherein crosslinking chemical is to be selected from a kind of in melamine derivative, urea derivative, the uril derivant at least.
According to above-mentioned resist pattern thickening material of the present invention, further comprise surfactant.
According to above-mentioned resist pattern thickening material of the present invention, wherein surfactant is to be selected from following a kind of in these at least: non-ionic surface activator, cation surfactant, anionic surfactant and ampholyte surfactant.
According to above-mentioned resist pattern thickening material of the present invention, wherein the non-ionic surface activator is selected from following a kind of in these at least: polyoxyethylene alkane-oxygen ethene alkane enriched compound, polyethylene glycol alkyl ether compound, polyoxyethylene alkyl ether compound, polyoxyethylene derivative compound, sorbitan aliphatic ester compound, glycerine fatty acid ester compounds, primary alconol ethoxy compound, phenol ethoxy compound, alkoxylate surfactant, fatty acid ester surfactant, acid amides surfactant, ethanol surfactant, ethylenediamine surfactant; Cation surfactant is selected from following a kind of in these at least: base cations surfactant, acid amide type quaternary cation surfactant and ester type quaternary cation surfactant; The ampholyte surfactant is selected from following a kind of in these at least: amine oxide surfactant and betaine surfactant.
According to above-mentioned resist pattern thickening material of the present invention, further comprise organic solvent.
According to above-mentioned resist pattern thickening material of the present invention, wherein organic solvent is to be selected from a kind of in spirit solvent, chain ester solvent, cyclic ester solvent, ketone solvent, chain ether solvents, the cyclic ether solvents at least.
The present invention also provides a kind of resist pattern thickening material, it is characterized in that this resist pattern thickening material comprises: the resin that has ring texture on a part; Crosslinking chemical; And pure water.
The present invention also provides a kind of resist pattern, it is characterized in that this resist pattern has superficial layer on the resist pattern that will thicken, and the ratio of corrosion rate is 1.1 or bigger under the same conditions; The ratio of corrosion rate is the resist pattern that will the thicken ratio with the corrosion rate of superficial layer, corrosion rate unit is nm/s, wherein after forming the resist pattern that will thicken, according to resist pattern thickening material recited above, cover the surface of the resist pattern that will thicken in the surface-coated of the resist pattern that will thicken.
According to above-mentioned resist pattern of the present invention, wherein superficial layer contains the compound with ring texture.
According to above-mentioned resist pattern of the present invention, the content that wherein has the compound of ring texture successively decreases to inside from superficial layer.
The present invention also provides a kind of technology that forms resist pattern, the technology that it is characterized in that this formation resist pattern comprises: after forming the resist pattern that will thicken, apply the resist pattern thickening material to cover the step on the resist pattern surface that will thicken, wherein the resist pattern thickening material is according in the above mentioned resist pattern thickening material any one.
According to the technology of above-mentioned formation resist pattern of the present invention, wherein the coating resist pattern thickening material that is developed in of resist pattern thickening material carries out afterwards.
According to the technology of above-mentioned formation resist pattern of the present invention, wherein develop and carry out with deionized water.
According to above-mentioned technology of the present invention, wherein resist pattern has the superficial layer that is provided on the resist pattern that will thicken, and the ratio of corrosion rate is 1.1 or bigger under the same conditions; The ratio of corrosion rate is the resist pattern that will the thicken ratio with the corrosion rate of superficial layer, and corrosion rate unit is nm/s.
According to the technology of above-mentioned formation resist pattern of the present invention, wherein superficial layer contain at least compound with ring texture and to small part have ring texture resin the two one of.
According to the technology of above-mentioned formation resist pattern of the present invention, wherein have the compound of ring texture and successively decrease to inside from superficial layer to one the content of resin in the two that small part has a ring texture.
The present invention also provides a kind of semiconductor devices, it is characterized in that this semiconductor devices has by according to the formed figure of above mentioned any one resist pattern.
The present invention also provides a kind of technology of making semiconductor devices, the technology that it is characterized in that this manufacturing semiconductor devices comprises following these steps: form resist pattern, on bottom, form after the resist pattern that will thicken, cover the resist pattern surface that will thicken by coating according to above mentioned any one resist pattern thickening material and thicken this resist pattern that will thicken to form resist pattern; And bottom carried out composition, utilize that the formed resist pattern that has thickened corrodes as mask in form the resist pattern step.
According to the technology of above-mentioned manufacturing semiconductor devices of the present invention, wherein resist pattern is formed by the ArF resist.
According to the technology of above-mentioned manufacturing semiconductor devices of the present invention, wherein the ArF resist is for being selected from following a kind of in these at least: third rare resist, cyclenes-maleic anhydride resist, and cyclenes resist.
According to above-mentioned semiconductor device manufacturing process of the present invention, further comprise: before forming the resist pattern step, in the step of the surface-coated non-ionic surface activator of the resist pattern that will thicken; Wherein the non-ionic surface activator is one type that is selected from polyoxyethylene alkane-oxygen ethene alkane enriched compound, polyethylene glycol alkyl ether compound, polyoxyethylene alkyl ether compound, polyoxyethylene deriv compound, sorbitan aliphatic ester compound, glycerine fatty acid ester compounds, primary alconol ethoxy compound, the phenol ethoxy compound at least.
The compound that resist pattern thickening material of the present invention contains resin, crosslinking chemical and has ring texture, perhaps it contains resin and the crosslinking chemical that part has ring texture.
When the resist pattern thickening material is coated on the resist pattern, in coated resist pattern thickening material, near the part at resist pattern interface infiltrate resist pattern and with the material of resist pattern crosslinked (mixing).The resist pattern thickening material shows the good affinity of resist pattern.Therefore, formed superficial layer (mixolimnion) effectively on resist pattern (the resist pattern thickening material has thickened resist pattern effectively) surface, at the superficial layer place, resist pattern thickening material combination (mixing) is in resist pattern.
Because superficial layer is formed by the resist pattern thickening material, and comprises compound with ring texture or the resin that has ring texture to small part, the superficial layer in the resist pattern has outstanding corrosion stability.As a result, formed resist pattern (after this being called " resist pattern ") is thickened by the resist pattern thickening material, and the formed figure of resist pattern has meticulousr structure, has surpassed the exposure limit.
Resist pattern of the present invention contains a superficial layer on the resist pattern that will thicken, and under the same conditions, the ratio of the corrosion rate of superficial layer and this resist pattern (nm/s) (resist pattern/superficial layer that will thicken) is 1.1 or bigger.Resist pattern can utilize the ArF excimer laser to form as exposure light source.Because this resist pattern has high corrosion stability superficial layer, it is applicable to etching process, and is applicable to the formation fine pattern.
The technology that the present invention forms resist pattern comprises that coating resist pattern thickening material of the present invention is to cover the step on the surface of the resist pattern that will thicken after forming the resist pattern that will thicken.When the resist pattern thickening material is applied on the resist pattern that will thicken, in coated resist pattern thickening material, near the part at resist pattern interface infiltrate the resist pattern that will thicken and with the material of resist pattern crosslinked (mixing).Therefore, the resist pattern thickening material is attached to (formation mixolimnion) in the resist pattern that will thicken.Superficial layer is formed by the resist pattern thickening material, and comprises compound with ring texture or the resin that has ring texture to small part, so superficial layer has outstanding corrosion stability.The resist pattern of Xing Chenging is thickened by the resist pattern thickening material like this.Therefore, the formed figure of resist pattern has meticulousr structure, has surpassed the exposure limit.
Semiconductor devices of the present invention comprises by the formed figure of resist pattern of the present invention.
Because this semiconductor laser has by the formed fine pattern of this resist pattern, so it has high-quality and high-performance.
The technology that the present invention makes semiconductor devices comprises the step that forms resist pattern, this step forms on bottom after the resist pattern that will thicken, and covers the resist pattern surface that will thicken with resist pattern thickening material of the present invention and thickens the resist pattern that will thicken to form this resist pattern; This technology also comprises and formedly in the step that utilize to form resist pattern thickens resist pattern carries out composition to bottom by corrosion as mask step.
In the technology of making semiconductor devices, after the resist pattern that will thicken formed on bottom, the resist pattern thickening material was applied on the resist pattern that will thicken.The resist pattern that the resist pattern thickening material infiltration at the close resist pattern interface that will thicken will thicken is also crosslinked with the resist pattern material.Therefore, on the resist pattern that will thicken, form the superficial layer that combines with the resist pattern that will thicken.Because superficial layer (mixolimnion) is formed by the resist pattern thickening material and comprises compound with ring texture and the resin that has the structure of changing the outfit to small part, so the superficial layer in the final resist pattern has outstanding corrosion stability, can be suitable for etching process etc.Because final resist pattern thickened by the resist pattern thickening material, by the gap ratio of the formed figure of this resist pattern by the formed spacing of resist pattern littler (meticulousr) before thickening, to the degree of resist pattern thickening material thickening.The formed more fine pattern of this resist pattern has surpassed the exposure limit of light source.
By eroding resist pattern mask, internal layer has been carried out fine patterning with outstanding corrosion stability.
As a result, can form effectively and have the extremely semiconductor devices of fine pattern.
Description of drawings
Figure 1A to 1C illustrates by using the synoptic diagram that thickens mechanism according to the resist pattern of resist pattern thickening material of the present invention.
Fig. 2 A to 2E is the synoptic diagram of a certain embodiment that the technology of resist pattern formed according to the present invention is shown.
Fig. 3 A and 3B are the upper surface figure of a FLASH EPROM, and it is an embodiment of semiconductor device according to the invention.
Fig. 4 A to 4C is the constructed profile (1) that the manufacturing process of FLASH EPROM is shown, and this technology is an embodiment of the technology of semiconductor devices constructed in accordance.
Fig. 5 D to 5F is the constructed profile (2) that the manufacturing process of FLASH EPROM is shown, and this technology is an embodiment of the technology of semiconductor devices constructed in accordance.
Fig. 6 G to 6I is the constructed profile (3) that the manufacturing process of FLASH EPROM is shown, and this technology is an embodiment of semiconductor device according to the invention manufacturing process.
Fig. 7 A to 7C is the constructed profile that FLASH EPROM manufacturing process is shown, and this technology is another embodiment of the technology of semiconductor devices constructed in accordance.
Fig. 8 A to 8C is the constructed profile that FLASH EPROM manufacturing process is shown, and this technology is another embodiment of the technology of semiconductor devices constructed in accordance.
Fig. 9 A to 9D illustrates the constructed profile that resist pattern is used to make a certain Application Example of magnetic head, and this resist pattern uses resist pattern thickening material of the present invention to thicken.
Figure 10 illustrates the constructed profile of technology (1) that resist pattern is used to make a certain Application Example of magnetic head, and this resist pattern uses resist pattern thickening material of the present invention to thicken.
Figure 11 illustrates the constructed profile of technology (2) that resist pattern is used to make a certain Application Example of magnetic head, and this resist pattern uses resist pattern thickening material of the present invention to thicken.
Figure 12 illustrates the constructed profile of technology (3) that resist pattern is used to make a certain Application Example of magnetic head, and this resist pattern uses resist pattern thickening material of the present invention to thicken.
Figure 13 illustrates the constructed profile of technology (4) that resist pattern is used to make a certain Application Example of magnetic head, and this resist pattern uses resist pattern thickening material of the present invention to thicken.
Figure 14 illustrates the constructed profile of technology (5) that resist pattern is used to make a certain Application Example of magnetic head, and this resist pattern uses resist pattern thickening material of the present invention to thicken.
Figure 15 illustrates the constructed profile of technology (6) that resist pattern is used to make a certain Application Example of magnetic head, and this resist pattern uses resist pattern thickening material of the present invention to thicken.
Figure 16 is the planimetric map that is illustrated in an embodiment of the magnetic head of making in the technology of Figure 10-15.
Embodiment
(resist pattern thickening material)
Resist pattern thickening material of the present invention is water-soluble or the alkali solubility complex, is applicable in the aqueous solution.These complexs can be present in the sol solution, in the newborn solution, or the like.
The preferred embodiment of resist pattern thickening material of the present invention comprises first and second embodiments.
The compound that the resist pattern thickening material of first embodiment contains resin, crosslinking chemical and has ring texture further contains surfactant, organic solvent and other composition as required.Resin can partly have ring texture.
The resin that the resist pattern thickening material of second embodiment contains crosslinking chemical and partly has ring texture.This resist pattern thickening material further contains resin, has the compound of ring texture, non-ionic surface activator, organic solvent and other component.
-resin-
Resin is not particularly limited, can suitably selects for use according to purposes.Yet preferred embodiment comprises water soluble resin and alkali soluble resins.Preferred embodiment comprises the resin that can cause cross-linking reaction, or the resin that can mix with crosslinking chemical.These resins can use separately, but also two or more mix use.
When resin was water soluble resin, its water-soluble degree preferably was 0.1g or bigger in water under 25 ℃, and preferred is 0.3g or bigger in water, and preferred especially is 0.5g or bigger in water.
The embodiment of water soluble resin comprises: polyvinyl alcohol (PVA), polyvinyl acetal, polyvinyl acetate, polyacrylic acid, tygon arsenic are pressed against alkane ketone, polyethyleneimine, polyethylene oxide, phenylethylene-maleic diacid copolymer, polyvinylamine, polyarylamine, azoles quinoline base-contain water soluble resin, water-soluble melamine resin, water soluble urea resin, alkyd resin, sulfonamide resin oh, etc.
When resin when being alkali-soluble, its alkali solubility is being 0.1g or bigger in tetramethylammonium hydroxide (TMAH) aqueous solution in 2.38% (mass percent) preferably under 25 ℃, preferred is 0.3g or bigger in TMAH, and particularly preferred is 0.5g or bigger in TMAH.
The embodiment of alkali soluble resins comprises: novolac resin, vinyl-phenyl resin, polyacrylic acid, poly-methyl-prop diluted acid (polymethaacryl acid), poly-p-coumaric acid fat (poly p-hydroxyphenylacrylate), poly-p-hydroxyphenyl methacrylate (polyp-hydroxyphenylmethacrylate), their multipolymer, etc.
Wherein preferably use polyvinyl alcohol (PVA), polyvinyl acetal and polyvinyl acetate.In the present invention, resin preferably contains polyvinyl acetal, and more preferably contains 5% (mass percent) to 40% (mass percent) polyvinyl acetal, because by crosslinked easy change solubleness.
In the present invention, relate in the situation of first embodiment at the resist pattern thickening material, resin can partly contain ring texture.The resist pattern thickening material that relates to second embodiment mainly comprises the resin that part has ring texture, and can further comprise this resin.The embodiment of ring texture is not particularly limited, and can carry out preferably according to purposes.Embodiment can choose from aromatics, alicyclic compound and heterogeneous ring compound.
The embodiment of aromatics comprises: multivalence oxybenzene compound, polyphenyl phenolic compounds, fragrant polyphenyl phenolic compounds, aromatic carboxylic compound, hydrogen peroxide naphthalene compound (perhydroxynaphthalene compound), Benzophenone compound, flavonoids, pounce on luxuriant and rich with fragrance alkali (porphine), water-soluble phenoxy resin, contain fragrant water colo(u)r (aromatic-containing water-soluble pigment), their derivant and glucoside, etc.They can use separately, but also two or more mix use.
The embodiment of multivalence oxybenzene compound comprises: resorcin, [4] aromatic hydrocarbon resorcin (resorcin[4] arene), pyrogaelol, gallic acid, and their derivant and glucoside, etc.
The embodiment of polyphenyl phenolic compounds and derivant thereof comprises: catechol, anthocyanidin (pelargonidin type (pelargonidine type) (4 '-hydroxyl), cyanogen type (cyanidin type) (3 ', 4 '-dihydroxy), delphinin type (delphinidin type) (3 ', 4 ', 5 '-trihydroxy), deoxidation flavones-3,4-glycol, proantocyanidin, their derivant and glucoside, etc.
The embodiment of aromatic carboxylic compound and derivant thereof comprises: salicylic acid, phthalic acid, dicarboxyl benzoic acid, tannic acid, and their derivant and glucoside, etc.
The hydrogen peroxide naphthalene compound (perhydroxy naphthalene compound) and the embodiment of derivant thereof comprise: naphthalene glycol, naphthalene triol, and their derivant and glucoside, etc.
The embodiment of Benzophenone compound and derivant thereof comprises: allizarin yellow, and its derivant and glucoside, etc.
The embodiment of flavonoids and derivant thereof comprises: flavones, isoflavones, flavanols, flavanone, flavonols, flavan-3-alcohol, aurone, chalcone, dihydrochalcone, quercetin, and their derivant and glucoside, etc.
The embodiment of alicyclic compound comprises: poly-cycloalkanes, cycloalkanes, concentrated ring (condensedring), and their derivant and glucoside, etc.They can use separately, but also two or more mix use.
The embodiment of poly-cycloalkanes comprises: norcamphane, diamantane, norpinane, sterane, etc.
The embodiment of cycloalkanes comprises: cyclopentane, cyclohexylamine, etc.
The embodiment that concentrates ring comprises steroids etc.
The suitable embodiment of heterogeneous ring compound comprises: nitrogenous ring compound, as pyrrolidine, pyridine, imidazoles, oxazole, morphorine, pyrrolidone etc.; Ether ring shape compound is as furans, pyrans, polysaccharide (comprising pentose, hexose) etc.
Have in the resin of ring texture at resin and part, have at least an outstanding angle to consider from the water-soluble or alkali solubility of this resin, the resin that preferred resin or part have ring texture should have two or more polar groups.
The not special restriction of the embodiment of polar group can be selected according to purpose.Suitable embodiment comprises: hydroxyl, cyano group, alkoxy (alkoxyl group), carboxyl, carbonyl, amino, amide group, alkoxy carbonyl group, hydroxyalkyl, sulfonyl, hydrogen base (hydride group), lactone group, cyanic acid base, isocyanate group, ketone base, etc.In those polar groups, more suitably embodiment comprises: hydroxyl, carboxyl, carbonyl, amino, sulfonyl, etc.
When resin contains part when having the compound of ring texture, the remainder of ring texture can be selected according to purpose, as long as it is water miscible or alkali-soluble.Embodiment comprises: water soluble resin, as polyvinyl alcohol (PVA), Pioloform, polyvinyl acetal etc.; Alkali soluble resins is as novolac resin, vinyl-phenyl resin etc.
When resin partly had ring texture, the mol content of ring texture had no particular limits, and can select according to purpose.If resin needs high corrosion stability, then mol content 5mol% or bigger preferably more preferably, is 10mol% or bigger.
Mol content can pass through, and for example, NMR etc. measure.
The mol content of resin can suitably be determined according to purpose in the resist pattern thickening material.Although can change with type, the content of crosslinking chemical, the compound with ring texture and surfactant can be selected according to purpose.
-crosslinking chemical-
The not special restriction of crosslinking chemical can be selected any according to purpose.Preferred water dissolubility or alkali solubility crosslinking chemical.Also can be preferably can be by heat or acid and crosslinked those.Suitable embodiment comprises amino-type crosslinking chemical etc.
The suitable embodiment of amino-type crosslinking chemical comprises: melamine derivative, urea derivative, uril derivant, etc.These can be used alone or in combination.
The embodiment of urea derivative comprises: urea, alkoxy methylene urea, N-alkoxy methylene urea, ethylene urea, ethylene urea carboxylic acid, their derivant etc.
The embodiment of melamine derivative comprises alkoxymethyl melamine and derivant thereof etc.
The embodiment of uril derivant comprises: benzoguanamine, glycouril, their derivant etc.
Although the content of crosslinking chemical changes with type, content etc. in the resist pattern thickening material, it can suitably be selected according to purpose, and the resin and the surfactant that contain the compound with ring texture can not be adjusted indiscriminately.
-have the compound of ring texture-
Embodiment with compound of ring texture can be compound or resin.More preferably, those resins or compound are water miscible or alkali-soluble.Because resist pattern thickening material of the present invention contains the compound with ring texture, it may significantly improve the corrosion stability that thickens resist pattern.
If it is water miscible having the compound of ring texture, preferred water-soluble be 0.1g or as many as 100g more in 25 ℃ of water, or more preferably be 0.3g or as many as 100g more in 25 ℃ of water, particularly preferably be 0.5g or as many as 100g more in 25 ℃ of water.
When the compound with ring texture when being alkali-soluble, preferred alkali solubility is 0.1g or bigger in 25 ℃ 2.38% tetramethyl-ammonium hydroxide solution, more preferably being 0.3g or bigger in 25 ℃ 2.38% tetramethyl-ammonium hydroxide solution, particularly preferably is 0.5g or bigger in 25 ℃ 2.38% tetramethyl-ammonium hydroxide solution.
Embodiment with compound of ring texture comprises: aromatics, alicyclic compound, heterogeneous ring compound, etc.The specific embodiments of those compounds illustrates in the above.
Have in the compound of ring texture at those, consider from the water-soluble of this compound or angle that alkali solubility is outstanding, this compound with ring texture preferably has two or more polar groups, 3 or more a plurality of polar group are more preferably arranged, 4 or more a plurality of polar group are particularly preferably arranged.
Polar group has no particular limits; can suitably select arbitrary polar group according to purpose; comprise: hydroxyl, cyano group, alkoxy (alkoxyl group), carboxyl, carbonyl, amino, amide group, alkoxy carbonyl group, hydroxyalkyl, sulfonyl, hydrogen base (hydride group), lactone group, cyanic acid base, isocyanate group, ketone base, etc.Wherein, suitable embodiment comprises: hydroxyl, carboxyl, carbonyl, amino, sulfonyl.
When the compound with ring texture was resin, the mol content that has the compound of ring texture in the resin had no particular limits, and can suitably select according to purpose.If this resin needs high corrosion stability, this content is preferably 5mol% or bigger so, more preferably is 10mol% or bigger.Mol content can be measured with NMR etc.
The content that has the compound of ring texture in the resist pattern thickening material can suitably be determined according to the type of resin, crosslinking chemical, surfactant etc. and content.
-surfactant-
When resist pattern thickening material and the affinity that is coated in the resist pattern (for example, the ArF resist pattern) on the resist pattern thickening material are not enough, can suitably adopt surfactant.When in the resist pattern thickening material, containing surfactant, under the conforming state in outstanding plane resist pattern can effectively be thickened with effectively, be formed uniformly fine pattern, and can suppress the foam of resist pattern thickening material effectively.
Surfactant there is not special restriction, arbitrary surfactant be can suitably select according to purpose, non-ionic surface activator, cation surfactant, anionic surfactant, ampholyte surfactant, silicones type surfactant etc. comprised.These can be used alone or in combination.Wherein, owing to do not comprise metallic ion in the structure of non-ionic surface activator, so preferred non-ionic surface activator.
The non-ionic surface activator has no particular limits, and can select according to purpose.The specific embodiments of non-ionic surface activator is selected from following material: alkoxylate (alkoxylate) surfactant, fatty acid ester surfactant, acid amides surfactant, ethanol surfactant, ethylenediamine surfactant.The specific embodiments of those surfactants comprises: polyoxyethylene alkane-oxygen ethene alkane enriched compound, the polyethylene glycol alkyl ether compound, the polyoxyethylene alkyl ether compound, the polyoxyethylene derivative compound, the sorbitan aliphatic ester compound, the glycerine fatty acid ester compounds, the primary alconol ethoxy compound, the phenol ethoxy compound, the nonyl phenol ethoxylate type, octyl phenol ethoxylate type, lauryl alcohol ethoxylate type, oleyl alcohol ethoxylate type, fatty acid type, acid amide type, naturally pure type (natural alcohol type), the ethylene diamine type, inferior alcohol ethoxylate type (secondary alcoholethoxylate type), etc.
Cation surfactant has no particular limits, and can select according to purpose.Embodiment comprises: base cations surfactant, acid amide type quaternary cation surfactant, ester type quaternary cation surfactant, etc.
The ampholyte surfactant has no particular limits, and can select according to purpose.Embodiment comprises amine oxide surfactant and betaine surfactant etc.
Though the content of the surfactant in the resist pattern thickening material is along with the difference of above-mentioned resin, crosslinking chemical, the kind with compound etc. of ring texture, content etc. and change, but can suitably determine the content of the surfactant in the resist pattern thickening material, and can not indiscriminately adjust.
-organic solvent-
By in the resist pattern thickening material, adding organic solvent, can improve the dissolving resin that resin, the crosslinking chemical in the above-mentioned resist pattern thickening material, the compound with ring texture and part have ring texture.
Organic solvent is not had special restriction, can suitably select arbitrary organic solvent, comprise alcohol organic solvent, chain ester organic solvent, cyclic ester organic solvent, ketone organic solvent, chain ether organic solvent, cyclic ethers organic solvent etc. according to purpose.
The embodiment of alcohol organic solvent comprises methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols etc.
The embodiment of chain ester organic solvent comprises Solactol fat, propylene glycol methyl ether acetate (PGMEA) etc.
The embodiment of cyclic ester organic solvent comprises lactone type, such as gamma-butyrolacton etc.
The embodiment of ketone organic solvent comprises the ketone type, such as acetone, cyclohexanone, heptanone etc.
The embodiment of chain ether organic solvent comprises ethylene glycol dimethyl ether etc.
The embodiment of cyclic ethers organic solvent comprises tetrahydrofuran, dioxane etc.
These organic solvents can be used alone or in combination.In these organic solvents, because will thicken subtly, preferably using its mid-boiling point is about 80-200 ℃ organic solvent.
Though the content of the organic solvent in the resist pattern thickening material is along with the different of above-mentioned resin, crosslinking chemical, the kind with the compound of ring texture and surfactant etc., content etc. and change, but can suitably determine the content of the organic solvent in the resist pattern thickening material, and can not indiscriminately adjust.
-other composition-
To other composition only otherwise weakening effect of the present invention does not just have special restriction, can suitably select arbitrary other compositions, comprise various known additives according to purpose.Suitable embodiment comprises: hot acid (thermal acid) generator, the quenching agent by performances such as amine types, acid amide type, ammonium salt.
Though the content of other composition in the resist pattern thickening material is along with the different of the kind of above-mentioned resin, crosslinking chemical, the compound with ring texture, surfactant and organic solvent etc., content etc. and change, but can suitably determine the content of other composition in the resist pattern thickening material, and can not indiscriminately adjust.
-use etc.-
Resist pattern thickening material of the present invention can be used for being coated on the resist pattern.
In coating, surfactant can separately apply before applying the resist pattern thickening material, needn't be included in the resist pattern thickening material.
When the resist pattern thickening material being coated on the resist pattern that will thicken,, resist pattern thickens resist pattern so being thickened to have formed.
By thickening the figure that resist pattern forms, with respect to the formed figure of aforesaid resist pattern, the spacing of the diameter of via hole image and line and space figure is all littler.Apply the resist pattern thickening material and allow a figure to form meticulousr figure, surpass and be used for resist pattern is carried out the exposure limit of the exposure sources of composition.For example, when using the ArF excimer laser, the resist pattern that is obtained is thickened by resist pattern thickening material of the present invention, has formed to thicken resist pattern.When doing like this, thicken figure that resist pattern forms and have the fine pattern that can compare favourably with the formed figure of electron beam by changing.
The thickening of resist pattern can be controlled in the scope of an expectation, depend on glutinousness, the material therefor of resist pattern thickening material thickness, stoving temperature, cure the time etc.
-resist pattern (resist pattern that will thicken) material-
Material to resist pattern (resist pattern that will thicken) does not have special restriction, can from known anticorrosive additive material, suitably select according to purpose, anticorrosive additive material can be eurymeric or minus, comprise that chemistry amplifies anticorrosive additive material, its representative has: g-line resist, i-line resist, KrF resist, ArF resist, F2 resist, electron sensitive resist etc., they can be by compositions such as g-line, i-line, KrF excimer laser, ArF excimer laser, F2 excimer laser, electron beams.Those can be chemical amplifying types, also can be non-chemical amplifying types.Wherein, preferred KrF resist, ArF resist etc.More preferably ArF resist.
The embodiment of resist pattern material comprises: novolaks (novolac) resist, PHS resist, third rare resist, cyclenes-maleic anhydride (COMA type) resist, cyclenes resist, hybrid (alicyclic acrylates-COMA multipolymer) resist, etc.Those resists can have been fluoridized.
The formation technology of resist pattern, size, thickness etc. have no particular limits, and can suitably select according to purpose.Especially, thickness is set to about 0.2 μ m to 200 μ m usually, although it can suitably be determined according to the bottom that will process, etching condition etc.
Resist pattern thickening material of the present invention thickening resist pattern adopted in explanation with reference to the accompanying drawings hereinafter.
Shown in Figure 1A, on substrate (base material) 5, form resist pattern (resist pattern that will thicken) 3, then resist pattern thickening material 1 is coated to the surface of resist pattern (resist pattern that will thicken) 3, and prebake (heating and oven dry) is to form film.What resist pattern thickening material 1 took place on the surface of contact between resist pattern (resist pattern that will thicken) 3 and the resist pattern thickening material 1 subsequently sneaks into (infiltration) resist pattern (resist pattern that will thicken) 3.It is crosslinked sneaking into (infiltration) part, and mixolimnion just comprises the resist pattern 3 and the resist pattern thickening material 1 that will thicken like this.Shown in Figure 1B, resist pattern comprises the mixolimnion superficial layer 10a on the resist pattern 10b (resist pattern 3 that will thicken) that will thicken.
Therefore, shown in Fig. 1 C, carry out developing process, thus make in the resist pattern thickening material 1 of coating not dissolved and dispose with the crosslinked part of the resist pattern that will thicken 3, to form Figure 10 against corrosion that (development) thickens.
Development step can be water development or develop with the alkali developer.
Figure 10 against corrosion is included in the resist pattern 10b that will thicken and goes up by sneaking into the superficial layer 10a that (infiltration) and crosslinked resist pattern thickening material 1 form.Because thickening Figure 10 against corrosion is thickened to the extension of superficial layer 10a thickness part, compare with resist pattern (resist pattern that will thicken) 3, less than by resist pattern 3 formed figures, and meticulous by the spacing that thickens the formed figure of Figure 10 against corrosion by thickening the formed figure of Figure 10 against corrosion.This feasible more fine pattern that can form above the light source exposure limit of exposure sources.By thickening the formed figure of Figure 10 against corrosion than meticulousr by resist pattern 3 formed figures.
The superficial layer 10a that thickens among Figure 10 against corrosion is formed by resist pattern thickening material 1, and resist pattern thickening material 1 comprises compound with ring texture or the resin that partly has ring texture, and like this, the resist pattern thickening material has outstanding corrosion stability.Therefore, even the resist pattern 3 that will thicken is formed by the material of corrosion resistivity difference, the Figure 10 against corrosion that thickens that the surface has the outstanding superficial layer 10a of corrosion stability has very outstanding corrosion stability thus.
-use-
Resist pattern thickening material of the present invention is applicable to thickening resist pattern, refining figure, surpassing the exposure limit.The resist pattern thickening material can further be applicable to and thicken the resist pattern that will thicken, and is specially adapted to resist pattern of the present invention and forms technology and semiconductor devices of the present invention and manufacturing process thereof.
Resist pattern thickening material of the present invention contains compound with ring texture or the resin that partly has ring texture.Therefore, this resist pattern thickening material is applicable to plasma etc., also is applicable to apply and thicken the figure that the needs that formed by resin improve surperficial corrosion stability.Particularly when the material of the resist pattern that will thicken did not comprise the compound with ring texture or partly has the resin of ring texture, this resist pattern thickening material was more suitable.
(resist pattern)
Resist pattern of the present invention comprises the superficial layer on the resist pattern that will thicken.
Compare with the resist pattern that will thicken, preferably have the superficial layer of outstanding corrosion stability, and preferred rate of corrosion (nm/s) is little.Particularly, the ratio (internal layer resist pattern/superficial layer) preferred 1.1 or higher of resist pattern that thicken and the rate of corrosion of superficial layer (nm/s), more preferably 1.2 or higher, preferred especially 1.3 or higher.
Rate of corrosion (nm/s) can pass through, and for example, uses known corrosion device to carry out etching process within the predetermined time, and the amount that the reduction of the film by measuring samples and unit of account time inner membrance reduce is measured.
Superficial layer preferably contains compound with ring texture or the resin that has ring texture to small part, and can use resist pattern thickening material of the present invention suitably to form.
Whether superficial layer contains compound with ring texture or the resin that has ring texture to small part, can pass through, and for example, analyzes the IR or the UV absorption spectra of this superficial layer and determines.
Resist pattern can contain in compound with ring texture or the resin that has ring texture to small part one of at least.From shifting the angle of the resist pattern that will thicken, present embodiment also is preferred.
Resist pattern of the present invention can have the structure of boundary clearly or unsharp boundary between resist pattern that will thicken and superficial layer.In preceding a kind of structure, from the superficial layer to inside, have the compound of ring texture and have the common discontinuous minimizing of content of the resin of ring texture to small part, and in a kind of structure in back, from the superficial layer to inside, the content that has the compound of ring texture and have the resin of ring texture to small part reduces usually gradually.
Technology according to following formation resist pattern of the present invention can suitably form the present invention ground resist pattern.
Resist pattern of the present invention is applicable to such as mask graph, rectile figure, magnetic head, LCD (LCD), PDP (plasma display), SAW wave filter functional parts such as (surface acoustic wave filters); Be used for the optics that the light wiring connects; Micro-component such as little gearing etc.; Semiconductor devices etc., and be applicable to the semiconductor devices of introducing later of the present invention.
(forming the technology of resist pattern)
The formation technology of resist pattern of the present invention is included in and applies the step of resist pattern thickening material with the surface that covers the resist pattern that will thicken after the resist pattern that formation will thicken.
The material of the resist pattern that thickens comprises the above-mentioned resist pattern thickening material of the present invention that is used for.A preferred embodiment is the ArF resist.
The resist pattern that thickens can form according to known technology.
The resist pattern that thickens can be formed by bottom (base material).Bottom (base material) is not had special restriction, can suitably select any bottom (base material) according to purpose.When the resist pattern picture that will thicken was formed on the semiconductor devices usually, the embodiment of substrate comprised silicon, various oxidation films etc.
Usage to the resist pattern thickening material does not have special restriction, can suitably comprise spin coating etc. by suitably selecting any technology in the known technique for applying according to purpose.The condition of spin coating, for example, rotating speed is made as about 100rpm to 10000rpm, preferred 800rpm to 5000rpm, the coating time was made as about 1 second to 10 minutes, preferred 1 second to 90 seconds.
In the coating used material thickness be about usually 10nm to 1000nm (
Extremely
), more preferably be 50nm to 500nm (
Extremely
).
In coating, surfactant can separately apply before applying the resist pattern thickening material, needn't be included in the resist pattern thickening material.
Owing to can impel effectively and the resist pattern thickening material takes place on the surface of contact between the resist pattern that will thicken and resist pattern thickening material sneak in the resist pattern that (infiltrations) will thicken, preferred prebake (heat and dry) resist pattern thickening material in coating or afterwards.
As long as resist pattern is softening, the condition of prebake (heating and oven dry), technology etc. just there are not special restriction, can suitably select any according to purpose.For example, temperature is made as about 40 ℃ to 120 ℃, and preferred 70 to 100 ℃, the time was made as about 10 seconds to 5 minutes, preferred 40 to 100 seconds.
Because the cross-linking reaction of mixing (infiltrations) part on the surface of contact between the resist pattern that will thicken and the resist pattern thickening material can be carried out effectively, preferred crosslinked the curing (cross-linking reaction) of the resist pattern thickening material that applies afterwards in prebake (heat and dry).
The condition of crosslinked curing (cross-linking reaction), technology etc. are not had special restriction, can suitably select any according to purpose.Usually, the temperature conditions of employing is higher than the temperature of prebake (heating and oven dry).The condition of crosslinked curing (cross-linking reaction), for example, temperature is made as about 70 ℃ to 150 ℃, and preferred 90 ℃ to 130 ℃, the time was made as about 10 seconds to 5 minutes, preferred 40 seconds to 100 seconds.
The preferred development step of the resist pattern thickening material that applies afterwards crosslinked curing (cross-linking reaction), in this case, in the resist pattern thickening material that applies not with the crosslinked part of the resist pattern that will thicken and weak crosslinked (mixing) partly (highly-water-soluble part) can be dissolved and dispose, (acquisition) the present invention is thickening the resist pattern that forms under the state with development.
Development step as hereinbefore.
Formation technology below with reference to description of drawings resist pattern of the present invention.
Shown in Fig. 2 A, anticorrosive additive material 3a is coated on the substrate (base material) 5, and then, shown in Fig. 2 B, composition is to form resist pattern (resist pattern that will thicken) 3.Resist pattern thickening material 1 is coated on the surface of the resist pattern 3 that will thicken, and prebake (heating and oven dry) is filmed with formation.What resist pattern thickening material 1 took place on the surface of contact between resist pattern (resist pattern that will thicken) 3 and the resist pattern thickening material 1 sneaks into (infiltration) resist pattern (resist pattern that will thicken) 3.
Shown in Fig. 2 D, when under crosslinked curing (cross-linking reaction) is being higher than the temperature of prebake (heating and oven dry), carrying out, on the surface of contact between the resist pattern 3 that will thicken and the resist pattern thickening material 1 to mix (infiltrations) layer generation crosslinked.Subsequently, shown in Fig. 2 E, carry out development step, thereby make in the resist pattern thickening material 1 of coating not dissolved and dispose, to form Figure 10 against corrosion that (development) has the superficial layer 10a on the resist pattern 10b that will thicken (resist pattern 3 that will thicken) with resist pattern (resist pattern that will thicken) 3 parts of mixing and weak crosslink part (highly-water-soluble part).
Development step can adopt the aqueous solution of water development or alkali to develop.Preferred water is developed, because development step can low cost be carried out effectively.
Thicken on the surface that Figure 10 against corrosion is included in the resist pattern 10b (resist pattern 3 that will thicken) that will thicken and resist pattern thickening material 1 to be mixed the superficial layer 10a that forms with the resist pattern 3 that will thicken.Partly thicken owing to thickening the thickness of Figure 10 against corrosion by superficial layer 10a, (resist pattern 10b) compares with the resist pattern 3 that will thicken, by thickening figure spacing that Figure 10 against corrosion forms less than the figure spacing that forms by the resist pattern 3 that will thicken (internal layer resist pattern 10b), and meticulousr by thickening the figure that Figure 10 against corrosion forms.
Thicken Figure 10 against corrosion and between internal layer resist pattern 10b and superficial layer 10a, can have clear and definite or indefinite border.
The resist pattern that forms according to the formation technology of resist pattern of the present invention is a resist pattern of the present invention.Resist pattern is included on the surface of the resist pattern that will thicken and resist pattern thickening material of the present invention is mixed the superficial layer that forms with the resist pattern that will thicken.Therefore, even the resist pattern that thickens is formed by the material of corrosion stability difference, the resist pattern that has outstanding corrosion stability superficial layer on the surface of the resist pattern that will thicken can form efficiently according to the formation technology of resist pattern of the present invention because the resist pattern thickening material contain at least compound with ring texture and part have ring texture resin the two one of.The resist pattern that the formation technology that thickens resist pattern according to the present invention forms is thickened by the thickening of superficial layer, compares with the resist pattern that will thicken, and the figure spacing that is formed by the resist pattern of making is less than by thickening the spacing degree that the preceding resist pattern that will thicken forms.According to the formation technology of resist pattern of the present invention, can form fine pattern efficiently.
The resist pattern that the formation technology that thickens resist pattern according to the present invention forms goes for such as mask graph, graticule (reticle) figure, magnetic head, LCD (LCD), PDP (plasma display), SAW wave filter functional parts such as (surface acoustic wave filters); Be used for optics by light wiring connection; Micro-component such as little gearing; Semiconductor devices etc., and be applicable to semiconductor devices and the manufacturing process thereof that the present invention introduces below.
(technology of semiconductor devices and manufacturing semiconductor devices)
Semiconductor devices of the present invention is not had special restriction except that the resist pattern with the invention described above, can from well known elements, suitably select according to purpose.
The object lesson of semiconductor devices of the present invention comprises flash memory, DRAM, FRAM etc.
Be suitable for forming semiconductor devices of the present invention according to following production process of semiconductor device of the present invention.
Production process of semiconductor device of the present invention comprises the step of the resist pattern that formation will thicken and the step of composition, also comprises other operation of suitably selecting according to concrete needs.
The step that forms resist pattern comprises, the surface by applying the resist pattern that the resist pattern thickening material will thicken with covering after substrate (bottom) is gone up the resist pattern that formation will thicken is to thicken the step that the resist pattern that will thicken forms the formation resist pattern of resist pattern.The embodiment of substrate (bottom) comprises the superficial layer of the various parts in the semiconductor devices, and is suitable for adopting for example substrate and the superficial layer thereof of silicon wafer.The resist pattern that thickens is same as described above.Coating processes is also same as described above.After the coating, preferably carry out above-mentioned prebake, crosslinked cure etc.
The step of composition comprises that employing forms in resist pattern forms step thickens resist pattern (as mask graph), by corrosion, substrate (bottom) is carried out composition.
Etching process there is not special restriction, can be according to purpose by suitably selecting any technology in the known technology, suitable technology comprises dry etching etc.Etching condition is not had special restriction, can suitably select according to purpose.
The suitable example of other technology comprises step, step of developing of coating surface activator etc.
The step of coating surface activator is included in the surface-coated surfactant that forms before the resist pattern at the resist pattern that will thicken.
Surfactant can be selected according to purpose.Embodiment comprises above-mentioned those, more suitably be: polyoxyethylene-polyoxypropylene enriched compound, the polyoxyalkylene alkyl compound, the polyoxyethylene alkyl ether compound, the polythene derivative compound, the sorbitan aliphatic ester compound, the glycerine fatty acid ester compounds, the primary alconol ethoxy compound, the phenol ethoxy compound, the nonyl phenol ethoxylate type, octyl phenol ethoxylate type, lauryl alcohol ethoxylate type, naturally pure type (natural alcohol type), the ethylene diamine type, inferior alcohol ethoxylate type (secondary alcoholethoxylate type), alkyl cationic (alkylcationictype), acid amide type quaternary cationic (amide type quaternary cationic type), fat type quaternary cationic (ester type quaternary cationic type), amine oxide type, betaine type, etc.
Development step is included in after the step that forms resist pattern and the resist pattern thickening material step of developing to applying before the pattern step.Development step is same as described above.
The manufacturing process of semiconductor device according to the invention for example, comprises that various types of semiconductor devices of flash memory, DRAM, FRAM etc. all can be made efficiently.
[embodiment]
Following more specific description embodiments of the invention, but the present invention is not limited by these embodiment.
(embodiment 1)
The preparation of-resist pattern thickening material-
Preparation have the composition shown in the table 1 according to resist pattern thickening material 1A-1J of the present invention.In table l, a quality of the unit representation of the numeral in the parenthesis.In " resin " row, " KW3 " represents polyvinyl acetal resin (being made by SEKISUICHEMICAL company limited), and " PVA " expression polyvinyl alcohol resin (made by KURARAY company limited, Poval 117).In " crosslinking chemical " row, " Uril " represents tetramethoxymethylglycoluril, " urea " expression N, N ,-dimethoxy-methyl dimethoxy ethylene urea, and " melamine " expression HMMM.In " surfactant " row, a kind of non-ionic surface activator of " TN-80 " representative (by the primary alcohol ethoxylate type surfactant of ASAHIDENKA company limited manufacturing), a kind of non-ionic surface activator of " PC-6 " representative (ASAHI DENKA company limited, a kind of special phenol ethoxylate type surfactant), a kind of non-ionic surface activator of " PC-8 " representative (ASAHI DENKA company limited, a kind of special phenol ethoxylate type surfactant), " PC-12 " represents a kind of non-ionic surface activator (ASAHI DENKA company limited, a kind of special phenol ethoxylate type surfactant).As the primary solvent composition except above-mentioned resin, crosslinking chemical and contain the compound of ring texture, also used the potpourri of pure water (deionized water) and isopropyl alcohol (mass ratio of pure water (deionized water) and isopropyl alcohol=98.6: 0.4).
Table 1
| Resin | Crosslinking chemical | Compound with ring texture | Surfactant | |
| 1A | KW-3(16) | Uril(1.16) | Catechol (5) | Do not have |
| 1B | KW-3(16) | Urea (1.16) | Catechol (5) | Do not have |
| 1C | KW-3(16) PVA(3) | Three chlorocyanamides (0.8) | Catechol (5) | Do not have |
| 1D | KW-3(16) | Uril(1.16) | Catechol (5) | TN-80(0.25) |
| 1E | KW-3(16) | Urea (1.16) | Catechol (5) | PC-8(0.25) |
| 1F | KW-3(16) PVA(3) | Three chlorocyanamides (0.8) | Catechol (5) | PC-12(0.25) |
| 1G | KW-3(16) | Uril(1.16) | Delphinidin (5) | Do not have |
| 1H | KW-3(16) | Uril(1.16) | Resorcinol (5) | TN-80(0.25) |
| 1I | KW-3(16) | Urea (1.16) | 1,3-naphthalene glycol (5) | PC-8(0.25) |
| 1J | KW-3(16) | Uril(1.16) | 4-hydroxyadamantane-2-carboxylic acid (0.8) | PC-6(0.25) |
-resist pattern and formation thereof-
Each of these ready resist pattern thickening material 1A-1J by at first 1000rpm/5s then being spun under the condition at 3500rpm/40s by the ArF resist (make by SUMITOMO CHEMICAL company limited, PAR700, the alicyclic ring resist) in the via hole image of Xing Chenging, and stands prebake under the 85 ℃/70s condition and crosslinked the curing under the 110 ℃/70s condition.The resist pattern thickening material 1A-1J of gained is through the flushing of 60 seconds pure water (deionized water) then, removing uncrosslinked part, and the resist pattern that develops and thickened by resist pattern thickening material 1A-1J, thereby formed each resist pattern.
The size of the formed via hole image of resist pattern (by the size that thickens the resist pattern formed via hole image of resist pattern afterwards) is shown in Table 2 with initial graphics size (size of the formed via hole image of resist pattern that will thicken).In table 2, " 1A "-" 1J " be corresponding resist pattern thickening material 1A-1J respectively.
Table 2
| Initial graphics size (nm) | Dimension of picture (nm) after thickening | |
| 1A | 200.5 | 175.2 |
| 1B | 203.3 | 181.2 |
| 1C | 199.8 | 180.0 |
| 1D | 205.7 | 154.4 |
| 1E | 202.6 | 171.7 |
| 1F | 203.9 | 160.3 |
| 1G | 198.8 | 171.1 |
| 1H | 201.1 | 148.7 |
| 1I | 200.8 | 165.6 |
| 1J | 202.6 | 178.6 |
Each of these ready resist pattern thickening material 1A-1J by at first 1000rpm/5s then being spun under the condition at 3500rpm/40s by the ArF resist (make by SUMITOMO CHEMICAL company, PAR700) in line of Xing Chenging and the space figure, and stand prebake under the 85 ℃/70s condition and crosslinked the curing under the 110 ℃/70s condition.The resist pattern thickening material 1A-1J of gained is through the flushing of 60 seconds pure water (deionized water) then, removing uncrosslinked part, and the resist pattern that develops and thickened by resist pattern thickening material 1A-1J, thereby formed each resist pattern.
Be shown in Table 3 with the size of initial graphics (size of the space figure that forms by the resist pattern that will thicken) by the size that thickens the formed space of resist pattern figure (size of the space figure that forms by the resist pattern that thickens after the resist pattern).In table 3, " 1A "-" 1J " be corresponding resist pattern thickening material 1A-1J respectively.
Table 3
| Initial graphics void size (nm) | Figure void size (nm) after thickening | |
| 1A | 165.2 | 135.2 |
| 1B | 162.3 | 143.8 |
| 1C | 159.8 | 137.7 |
| 1D | 155.7 | 116.9 |
| 1E | 158.5 | 128.8 |
| 1F | 160.2 | 123.0 |
| 1G | 163.4 | 125.4 |
| 1H | 160.0 | 121.1 |
| 1I | 158.0 | 120.5 |
| 1J | 163.8 | 138.1 |
Obviously, by the result of table 2 and table 3 as seen, resist pattern thickening material of the present invention is applicable to that via hole image and line and space figure are all to thicken them.When resist pattern thickening material of the present invention is used to form via hole image, can make the narrow diameter of via hole image and meticulous, when being used to form linear figure, the width (spacing between the resist of formation line graph) of linear figure is diminished with meticulous, when being used to form isolation pattern, can increase the area of isolation pattern.
Resist pattern thickening material 1D of the present invention, 1H, 1I and 1J apply respectively and are linked on the resist surface that is formed on the silicon substrate, to form the thick superficial layer of 0.5 μ m thereon.These superficial layers (are made by SHIPLEY with KrF resist as a comparison, UV-6) and polymethylmethacrylate (PMMA) by using etching machine (parallel-plate-type RIE device, make by FUJITSU company limited) at P μ=200W, pressure=0.02Torr, CF
4Corrosion is 3 minutes under the condition of gas=100sccm, and the reduction of the film of measuring samples, and to calculate rate of corrosion, the rate of corrosion according to the KrF resist carries out relative assessment to it then.
Table 4
Obviously, by the result of table 4 as seen, the corrosion stability of resist pattern thickening material of the present invention and KrF resist near and outstanding than PMMA.
When resist pattern thickening material 1A-1J is coated to when allowing the exposure back to place on the resist pattern that will thicken on one month the wafer substrates, can obtain the thicken effect similar with the figure of horse back coating after exposure clean room outside.
Can suppose that by this result resist pattern thickening material of the present invention is not to adopt cross-linking reaction to thicken the resist pattern that will thicken by diffusing through of acid as the prior art that is called RELACS, but the compatibility of the resist that depends on and will thicken.
(embodiment 2)
The preparation of-resist pattern thickening material-
Preparation have the composition shown in the table 5 according to resist pattern thickening material 2A-2M of the present invention.In table 5, a quality of the unit representation of the numeral in the parenthesis.In " resin " row, " resin 1 ", " resin 2 " and " resin 3 " are following synthetic.In " crosslinking chemical " row, " Uril " represents tetramethoxymethylglycoluril, " urea " expression N, N '-dimethoxy-methyl dimethoxy ethylene urea, and " melamine " expression HMMM.In " surfactant " row, a kind of non-ionic surface activator of " TN-80 " representative (by the primary alcohol ethoxylate type surfactant of ASAHI DENKA company limited manufacturing).As the primary solvent composition except above-mentioned resin, crosslinking chemical and surfactant, also used the potpourri of pure water (deionized water) and isopropyl alcohol (mass ratio of pure water (deionized water) and isopropyl alcohol=16: 0.75)." resin 1 " is following synthetic tygon-β-resorcinol acetal resin.That is, 10g PVA 500 (being made by KANTOKAGAKU) is dissolved in the 100g deionized water, adds 0.8g concentrating hydrochloric acid salt therein, then this deionized water is stirred three hours down at 40 ℃.Further in this deionized water, add β-resorcinol acetaldehyde (making) of 2.36g, then this deionized water was stirred six hours down at 40 ℃ by TOKYO KASEI KOGYO company limited.After the temperature of reaction solution dropped to room temperature, the TMAH (tetramethylammonium hydroxide) that adds 15% mass percent in this deionized water neutralized.Reaction solution is splashed in the 2L ethanol so that resin is separated from reaction solution.Filter this resin with glass filter, in the low pressure of vacuum(-)baking case, dried six hours down then at 45 ℃.Repeat just to have synthesized tygon-β-resorcinol acetal resin after this process three times.Output is 6.8g.By the ratio of NMR acetalation (acetalization) 20.6% mol number percent.
" resin 2 " is following synthetic " tygon-2,3-dihydroxyphenyl acetal resin ".That is, 3, the synthesis technique of 4-dihydroxyphenyl acetal resin is identical with the operation of " resin 1 ", and except with 2,3-dihydroxyphenyl acetaldehyde replaces outside β-resorcinol acetaldehyde.Output is 6.6g.By the ratio of NMR acetalation (acetalization) 20.1% mol number percent.
" resin 3 " is following synthetic tygon-β-resorcinol acetal resin.That is, 10g polyvinyl alcohol (PVA) 500 (being made by KANTO KAGAKU) is dissolved in the 100g deionized water, adds 0.4g concentrating hydrochloric acid salt therein, then this deionized water is stirred three hours down at 40 ℃.In this deionized water, add β-resorcinol acetaldehyde (making) of 0.5g, then this deionized water was stirred six hours down at 40 ℃ by TOKYO KASEIKOGYO company limited.The temperature of reaction solution drops to environment temperature, and the TMAH (tetramethylammonium hydroxide) that adds 15% mass percent in this deionized water neutralizes.Reaction solution is splashed in the 2L ethanol so that resin is separated from reaction solution.Filter this resin with glass filter, in the low pressure of vacuum(-)baking case, dried six hours down then at 45 ℃.Repeat just to have synthesized tygon-β-resorcinol acetal resin after this process three times.Output is 4.1g.By the ratio of NMR acetalation (acetalization) 3.7% mol number percent.
Table 5
| The lubricant title | Resin | Crosslinking chemical | Surfactant |
| 2A | Resin 1 (1) | Uril(0.5) | Do not have |
| 2B | Resin 1 (1) | Urea (0.5) | Do not have |
| 2C | Resin 1 (1) | Three chlorocyanamides (0.25) | Do not have |
| 2D | Resin 1 (1) | Uril(0.5) | TN-80(0.0025) |
| 2E | Resin 1 (1) | Urea (0.5) | TN-80(0.0025) |
| 2F | Resin 1 (1) | Three chlorocyanamides (0.25) | TN-80(0.0025) |
| 2G | Resin 2 (1) | Uril(0.5) | Do not have |
| 2H | Resin 2 (1) | Urea (0.5) | Do not have |
| 2I | Resin 2 (1) | Three chlorocyanamides (0.25) | Do not have |
| 2J | Resin 2 (1) | Uril(0.5) | TN-80(0.0025) |
| 2K | Resin 2 (1) | Urea (0.5) | TN-80(0.0025) |
| 2L | Resin 2 (1) | Three chlorocyanamides (0.25) | TN-80(0.0025) |
| 2M | Resin 2 (1) | Uril(0.5) | Do not have |
-resist pattern and formation thereof-
Each of these ready resist pattern thickening material 2A to 2L by at first 1000rpm/5s then being spun under the condition at 3500rpm/40s by the ArF resist (make by SUMITOMO CHEMICAL company limited, PAR700, the alicyclic ring resist) in the via hole image of Xing Chenging, and stands prebake under the 85 ℃/70s condition and crosslinked the curing under the 110 ℃/70s condition.The resist pattern thickening material 2A to 2L of gained is through the flushing of 60 seconds pure water (deionized water) then, removing uncrosslinked part, and the resist pattern that develops and thickened by resist pattern thickening material 2A to 2L, thereby formed each resist pattern.
The size of the formed figure of formed resist pattern (thickening resist pattern) is shown in Table 6 with initial graphics size (size of the formed via hole image of resist pattern before thickening).In table 6, " 2A " to " 2L " be corresponding resist pattern thickening material 2A to 2L respectively.
Table 6
| The lubricant title | Initial graphics size (nm) | Dimension of picture (nm) after lubricated |
| 2A | 201.5 | 194.2 |
| 2B | 203.1 | 197.4 |
| 2C | 199.8 | 190.9 |
| 2D | 205.1 | 191.8 |
| 2E | 195.6 | 187.4 |
| 2F | 196.9 | 170.3 |
| 2G | 198.0 | 190.0 |
| 2H | 201.0 | 194.8 |
| 2I | 200.6 | 189.6 |
| 2J | 199.8 | 184.6 |
| 2K | 204.1 | 191.0 |
| 2L | 200.8 | 173.9 |
These ready resist pattern thickening material 2A-2L each by at first 1000rpm/5s then being spun under the condition at 3500rpm/40s by the ArF resist (make by SUMITOMO CHEMICAL company, PAR700 alicyclic ring resist) in line of Xing Chenging and the space figure, and stands prebake under the 85 ℃/70s condition and crosslinked the curing under the 110 ℃/70s condition.The resist pattern thickening material 2A-2L of gained is through the flushing of 60 seconds pure water (deionized water) then, removing uncrosslinked part, and the resist pattern that develops and thickened by resist pattern thickening material 2A-2L, thereby formed each resist pattern.
Be shown in Table 7 with the size of initial graphics (thickening the line before this resist pattern and the size of space figure) by the size of the formed figure of resist pattern.In table 7, " 2A "-" 2L " be corresponding resist pattern thickening material 2A-2L respectively.
Table 7
| The lubricant title | Initial graphics void size (nm) | Figure void size (nm) after lubricated |
| 2A | 160.2 | 147.2 |
| 2B | 158.8 | 148.5 |
| 2C | 159.6 | 147.2 |
| 2D | 157.7 | 128.6 |
| 2E | 160.5 | 139.8 |
| 2F | 161.2 | 129.4 |
| 2G | 160.4 | 140.1 |
| 2H | 163.0 | 145.2 |
| 2I | 156.8 | 136.5 |
| 2J | 162.1 | 129.4 |
| 2K | 161.8 | 131.8 |
| 2L | 155.6 | 123.9 |
Obviously, by the result of table 6 and table 7 as seen, resist pattern thickening material of the present invention is applicable to that via hole image and line and space figure are all to thicken them.When resist pattern thickening material of the present invention is used to form via hole image, can make the narrow diameter of via hole image and meticulous, when being used to form linear figure, the spacing (spacing between the resist of formation line graph) of linear figure is diminished with meticulous, when being used to form isolation pattern, can increase the area of isolation pattern.
Resist pattern thickening material 2A of the present invention, 2G and 2M apply respectively and are linked on the resist surface that is formed on the silicon substrate, to form the thick superficial layer of 0.5 μ m thereon.These superficial layers (are made by SHIPLEY with KrF resist as a comparison, UV-6) and polymethylmethacrylate (PMMA) by using etching machine (parallel-plate-type RIE device, make by FUJITSU company limited) at P μ=200W, pressure=0.02Torr, CF
4Corrosion is 3 minutes under the condition of gas=100sccm, and the reduction of the film of measuring samples, and to calculate rate of corrosion, the rate of corrosion according to the KrF resist carries out relative assessment to it then.
Table 8
Obviously, by the result of table 8 as seen, the corrosion stability of resist pattern thickening material of the present invention and KrF resist near and outstanding than PMMA.
The content of aryl acetal is less than 5%mol number percent among the resist pattern thickening material 2M.The corrosion stability of resist pattern thickening material 2M is than a little bit poorer a little more than or equal to the resist pattern thickening material 2A of 5%mol number percent and G of the content of aryl acetal.
When resist pattern thickening material 2A-2M is coated to when allowing the exposure back to place on the resist pattern that will thicken on one month the wafer substrates clean room outside, can obtain with horse back after exposing apply the figure of resist pattern thickening material identical thicken effect.
Can suppose that by this result resist pattern thickening material of the present invention is not to adopt cross-linking reaction to thicken resist pattern by diffusing through of acid as the conventional art that is called RELACS, but depend on the compatibility with resist.
(embodiment 3)
-flash memory and manufacturing thereof-
Fig. 3 A and 3B are the upper surface figure (planimetric map) that is called the FLASH EPROM of FLOTOX type or ETOX type.Fig. 4 A to 4C, Fig. 5 D to 5F and Fig. 6 G to 6I show the schematic cross sectional view of an embodiment of the manufacturing process that is used for FLASH EPROM, wherein Fig. 4 A is that horizontal (the X-direction among Fig. 3 A and the 3B) schematic cross section (A-directional profile) of grid that forms the parts of the MOS transistor with floating gate electrode in memory cell block (first element region) is schemed to the left side figure of 6I, in figure be that part vertical (Y-direction in Fig. 3 A and the 3B) schematic cross section (B-directional profile) at grid vertical with the X-direction identical with left figure in storage unit part schemed, right side figure be in peripheral circuit part (second element region), be used to form MOS transistor the schematic cross section (A-directional profile among Fig. 3 A and the 3B) of part scheme.
Shown in Fig. 4 A, on p-type Si substrate 22 by SiO
2The field oxide film 23 that forms optionally is formed on the element marker space.Therefore, in the MOS transistor of storage unit part (first element region) by thermal oxidation by SiO
2Formation thickness be 10nm to 30nm (
) first grid dielectric film 24a, in another operation in the MOS transistor of peripheral circuit part (second element region) by thermal oxidation also by SiO
2Formation thickness be 10nm to 50nm (
) second grid dielectric film 24b.When the first grid dielectric film 24a that forms had identical thickness with second grid dielectric film 24b, oxidation film can form in identical operation simultaneously.
Have the MOS transistor of n-umbilicate type raceway groove in order to form in storage unit part (left side among Fig. 4 A and middle figure), in order to reach the purpose of control threshold voltage, peripheral circuit part (the right figure among Fig. 4 A) is covered by resist film 26.For the zone that is used to form channel region under floating gate electrode just in time, phosphorus (P) or arsenic (As) inject with 1 * 10 by ion as n-type impurity
11-1 * 10
14Cm
-2Dosage introduce, to form first threshold key-course 25a.The dosage of impurity and conduction type can and be piled up type and suitably select according to selected pit-type.
Have the MOS transistor of n-umbilicate type raceway groove in order to form in peripheral circuit part (the right figure among Fig. 4 B), in order to reach the purpose of control threshold voltage, storage unit part (left side among Fig. 4 B and middle figure) is covered by resist film 27.For the zone that is used to form channel region under gate electrode, phosphorus (P) or arsenic (As) inject with 1 * 10 by ion as n-type impurity
11-1 * 10
14Cm
-2Dosage be introduced into, to form the second threshold value control layer 25b.
Thick 50nm-200nm (
) first polysilicon film (first conducting film) 28 be formed on whole surface, as the gate electrode of the MOS transistor of the floating gate electrode of the MOS transistor of storage unit part (left side among Fig. 4 C and middle figure) and peripheral circuit part (the right figure among Fig. 4 C).
Shown in Fig. 5 D, as mask first polysilicon film 28 is carried out composition with the resist film 29 that forms, with the floating gate electrode 28a in the MOS transistor that is formed on storage unit part (left side among Fig. 5 D and middle figure).At this moment, shown in Fig. 5 D, carry out composition,, do not carry out composition, covered by resist film 29 to stay this floor of zone that is used to form S/D district floor in the Y-direction to obtain the final size width in the X-direction.
Shown in the left side among Fig. 5 E and middle figure, after resist film 29 removes, comprise SiO by thermal oxidation formation
2The thickness of film be about 20nm-50nm (
) capacitor insulating film 30a, to cover floating gate electrode 28a.At this moment, on first polysilicon film 28 of peripheral circuit part (the right figure among Fig. 5 E), also form and comprise SiO
2 Capacitor insulating film 30b, SiO is here only arranged
2The capacitor insulating film 30a and the 30b that form can be by comprising SiO
2Film and Si
3N
4Film rolls the composite membrane of formation with layer 2-3.
Shown in Fig. 5 E, form thickness as control grid electrode and be 50nm to 200nm (
) second polysilicon film (second conducting film) 31, to cover floating gate electrode 28a and capacitor insulating film 30a.
Then, shown in Fig. 5 F, storage unit part (left side among Fig. 5 F and middle figure) is covered with resist film 32, connects by corrosion and directly removes second polysilicon film 31 and capacitor insulating film 30b to expose first polysilicon film 28.
Only second polysilicon film 31, capacitor insulating film 30a and the first polysilicon film 28a of the storage unit of X-direction composition part (left side among Fig. 6 G and middle figure) with resist film 32 as mask at Y-direction composition, thereby shown in Fig. 6 G, obtain the final size of first grid part 33a, thus, form the wide lamination of forming by control grid electrode 31a/ capacitor insulating film 30c/ floating gate electrode 28c of about 1 μ m in the Y-direction.First polysilicon film 28 of peripheral circuit part (the right figure among Fig. 6 G) also carries out composition with resist film 32 as mask, thereby obtains the final size of second grid part 33b, thus, forms the wide gate electrode 28b of about 1 μ m.
By adopting the lamination of being made up of control grid electrode 31a/ capacitor insulating film 30c/ floating gate electrode 28c in the storage unit part (left side among Fig. 6 H and middle figure) as mask, phosphorus (P) or arsenic (As) inject with 1 * 10 by ion
14-1 * 10
16Cm
-2Dosage be introduced in Si substrate 22 in component forming region, to form n-type S/D district floor 35a and 35b.Subsequently, the gate electrode 28b by adopting peripheral circuit part (the right figure among Fig. 6 H) is as mask, and phosphorus (P) or arsenic (As) inject with 1 * 10 by ion
14-1 * 10
16Cm
-2Dosage be incorporated into Si substrate 22 in the component forming region, to form S/ D district floor 36a and 36b.
By psg film, form thickness and be about 500nm (
) inner layer insulating film 37, with the first grid part 33a that covers storage unit part (left side among Fig. 6 I and middle figure) and the second grid part 33b of peripheral circuit part (the right figure among Fig. 6 I).
After this, form contact hole 38a and 38b and contact hole 39a and 39b in the inner layer insulating film 37 that on S/ D district floor 35a and 35b and S/ D district floor 36a and 36b, forms, form S/ D electrode 40a and 40b and 41a and 41b then.
According to above-mentioned, the FLASH EPROM of manufacturing is the semiconductor devices shown in Fig. 6 I.
In this FLASH EPROM, the second gate insulating film 24b of (the right figure of Fig. 4 A in the 5F) is always covered (the right figure among Fig. 4 C to 5F) by first polysilicon film 28 or gate electrode 28b after forming because peripheral circuit part, so the thickness when the second gate insulating film 24b keeps just forming.Therefore, carry out the THICKNESS CONTROL of the second gate insulating film 24b easily, and also be used for the adjusting of the conductive impurity concentration of threshold voltage control easily.
In the above-described embodiments, at first carry out composition to form first grid part 33a at horizontal (the X-direction among Fig. 3 A and the 3B) width in accordance with regulations of grid, then grid vertically (the Y-direction among Fig. 3 A and the 3B) composition to form the width of final regulation, but also can be conversely, earlier grid vertically (the Y-direction among Fig. 3 A and the 3B) composition to form the width of regulation, then grid laterally (the X-direction among Fig. 3 A and the 3B) composition to form the width of final regulation.
Same as the previously described embodiments at Fig. 7 A to the embodiment of the manufacturing FLASH EPROM shown in the 7C, except change the operation after operation shown in Fig. 5 F in the above-mentioned embodiment shown in the 7C at Fig. 7 A.That is, the difference in the foregoing description be on first polysilicon film 28 of second polysilicon film 31 of storage unit part (left side among Fig. 7 A and middle figure) and peripheral circuit part (the right figure among Fig. 7 A), to form thickness be about 200nm (
) by tungsten (W) film or the film formed high melting point metal film of titanium (Ti) (the 4th conducting film) 42, so that the polyacid film to be provided.Operation after Fig. 7 A or undertaken by identical mode to 6I with Fig. 6 G to the operation shown in the 7C at Fig. 7 B.Omit the explanation to the 6I same processes with Fig. 6 G, Fig. 7 A in the 7C with Fig. 6 G in the identical identical label of part demonstration.
According to above-mentioned, the FLASH EPROM of manufacturing is the semiconductor devices shown in Fig. 7 C.
In this FLASH EPROM,, can further reduce resistance on control grid electrode 31a and gate electrode 28b because high melting point metal film (the 4th conducting film) 42a and 42b are provided.
As high melting point metal film (the 4th conducting film),, also can use refractory metal silicide film such as titanium silicide (TiSi) etc. except above-mentioned high melting point metal film (the 4th conducting film) 42a and 42b.
Same as the previously described embodiments at Fig. 8 A to the embodiment of the manufacturing FLASH EPROM shown in the 8C, except constituting the second grid part 33c of peripheral circuit part (second element region) (right figure among Fig. 8 A), to obtain first grid part 33a with storage unit part (first element region) (left side among Fig. 8 A and middle figure) similarly by the first polysilicon film 28b (first conducting film)/SiO
2The structure that film 30d (capacitor insulating film)/second polysilicon film 31b (second conducting film) forms, and the short circuit first polysilicon film 28b and the second polysilicon film 31b are to form the gate electrode shown in Fig. 8 B or 8C.
Shown in Fig. 8 B, for example, with the different position of second grid part 33c shown in Fig. 8 A, on dielectric film 54, form the extend through first polysilicon film 28b (first conducting film)/SiO
2The opening portion 52a of film 30d (capacitor insulating film)/second polysilicon film 31b (second conducting film), and the 3rd conducting film, for example, be embedded among the opening portion 52a as refractory metal films such as W film, Ti films, thereby make the first polysilicon film 28b and the second polysilicon film 31b short circuit.Shown in Fig. 8 C, form the extend through first polysilicon film 28b (first conducting film)/SiO
2The opening portion 52b of film 30d (capacitor insulating film), lower floor with the first polysilicon film 28b of the bottom that is exposed to opening portion 52b, and the 3rd conducting film, for example, be embedded among the opening portion 52a as refractory metal films such as W film, Ti films, thereby make the first polysilicon film 28b and the second polysilicon film 31b short circuit.
In this FLASH EPROM, because the second grid part 33c of peripheral circuit part has the identical structure of first grid part 33a with the storage unit part, therefore, the peripheral circuit part can form simultaneously with the storage unit part, to simplify manufacturing process effectively.
Except that above-mentioned independent formation, the 3rd conducting film 53a and 53b and high melting point metal film (the 4th conducting film) 42 can be used as public high melting point metal film and forms simultaneously.
(embodiment 4)
The manufacturing of-magnetic head-
Embodiment 4 relates to the manufacturing of magnetic head, as adopting resist pattern thickening material according to the present invention to apply the embodiment of resist pattern of the present invention.In embodiment 4, adopt the technology identical to thicken Figure 102 against corrosion and 126 with embodiment 1 and 2 by using according to resist pattern thickening material of the present invention.
Fig. 9 A to 9D shows the process flow diagram of making magnetic head.
Shown in Fig. 9 A, forming thickness on inner insulation layer 100 is the resist film of 6 μ m, also develops to be formed for forming Figure 102 against corrosion that will thicken with opening portion of spiral thin film solenoid with post-exposure.
Shown in Fig. 9 B, on the Figure 102 against corrosion that will thicken and its, form the part of the Figure 102 against corrosion that will thicken or on the exposed surface of the opening portion on the inner insulation layer 100 104, form the plating bottom of forming by the rhythmo structure of the thick Cu adhesion layer of the thick Ti adhesion layer of 0.01 μ m and 0.05 μ m 106 by evaporation.
Shown in Fig. 9 C, do not form in the part of the Figure 102 against corrosion that will thicken thereon, or on the surface of electroplating bottom 106 on the exposed that is formed on opening portion 104 on the inner insulation layer 100, form the thin film conductor of forming by the thick Cu coherent film of 3 μ m 108.
Shown in Fig. 9 D, dissolved and remove and when inner insulation layer 100 is removed as the Figure 102 against corrosion that will thicken, the spiral figure by thin film conductor 108 forms thin-film electro magnetic coil 110.
According to above-mentioned, made magnetic head.
In the magnetic head of gained, owing to can form spiral figure subtly by using thickening material according to the present invention to thicken the Figure 102 against corrosion that will thicken, thin-film electro magnetic coil 110 is very fine, and also very outstanding in batch process.
Figure 10 to 15 shows the process flow diagram of the manufacturing of another magnetic head.
As shown in figure 10, form clearance layer 114 on the ceramic non magnetic substrate 112 by sputtering at.Mainly be formed on the non magnetic substrate 112 by insulation course and the unshowned conductive substrate that forms by the Ni-Fe permalloy that monox forms by sputter, and further form the magnetic layer that forms by the Ni-Fe permalloy thereon.Pass through to use heat cured resin-shaped resin insulation course 116 in the zone of the regulation on clearance layer 114 except the magnetic nose part of unshowned formation magnetic layer.Then on resin insulating barrier 116 the coated with resins material to form resin molding 118.
As shown in figure 11, resin molding 118 is subsequently through overexposure and development, to form spiral figure.As shown in figure 12, the resin molding 118 of spiral figure is about 1 hour of hundreds of ℃ following heat setting, to form first spiral figure 120 of convex.Further form in its surface and comprise the conductive substrate 122 of Cu to cover it.
As shown in figure 13, apply anticorrosive additive material by being spin-coated on the conductive substrate 122, forming resist film 124, and on first spiral figure 120 composition resist film 124, to form Figure 126 against corrosion.
As shown in figure 14, on the surface of the exposure of conductive substrate 122 or in the part that does not form Figure 126 against corrosion thereon, form Cu conductor layer 128 by electroplating.After this, as shown in figure 15, Figure 126 against corrosion is removed from conductive substrate 122, form spiral thin film solenoid 130 by Cu conductor layer 128 by dissolving and removal.
As mentioned above, shown in the planimetric map as shown in figure 16, magnetic head made from the teeth outwards with the magnetosphere 132 on resin insulating barrier 116 and thin-film electro magnetic coil 130.
In the magnetic head of gained and since by use Figure 126 against corrosion that thickening material according to the present invention thickens the spiral figure of meticulous formation, thin-film electro magnetic coil 130 is very fine, and also very outstanding in batch process.
According to the present invention, can provide and be used for forming the resist pattern thickening material of fine pattern by applying this resist pattern thickening material with low cost, surpassed the light source exposure limit of exposure sources, improved the corrosion stability of resist pattern.
Further, according to the present invention, can provide the resist pattern that can use ArF excimer laser composition, it has fine structure and outstanding corrosion stability.
According to the present invention, can provide a kind of technology, mass production capabilities that can be outstanding forms can be with the resist pattern of ArF excimer laser as light source, and with low-cost, simple and easy and improved corrosion stability above the expose meticulous manufacturing fine pattern of resist pattern of the limit of light source.
According to the present invention, can provide high-performance semiconductor device with the formed fine pattern of resist pattern.
Further,, can utilize the ArF excimer laser as exposure light source according to the present invention, also can provide make high-performance semiconductor device with fine pattern efficiently with the technology of producing in batches.
Claims (36)
1. resist pattern thickening material is characterized in that this resist pattern thickening material is applied on the corrosion-resisting pattern so that thicken this corrosion-resisting pattern, and this resist pattern thickening material comprises:
Resin;
Crosslinking chemical;
Compound with ring texture; And
Pure water.
2. according to the resist pattern thickening material of claim 1, wherein this resist pattern thickening material is a kind of in water miscible and alkali-soluble.
3. according to the resist pattern thickening material of claim 1 or 2, the compound that wherein has ring texture, it is water-soluble to be 0.1g or as many as 100g more in 25 ℃ of water, and perhaps its alkali solubility is 0.1g or bigger in 25 ℃ the 2.38% mass percent tetramethylammonium hydroxide aqueous solution.
4. according to the resist pattern thickening material of claim 1, the compound that wherein has ring texture has two or more polar groups.
5. according to the resist pattern thickening material of claim 4, wherein polar group is selected these from following: hydroxyl, amino, sulfonyl, carboxyl and carbonyl.
6. according to the resist pattern thickening material of claim 1, the compound that wherein has ring texture is selected from aromatics, alicyclic compound and heterogeneous ring compound.
7. according to the resist pattern thickening material of claim 6, wherein aromatics is selected these from following: polyphenyl phenolic compounds, aromatic carboxylic compound, Benzophenone compound, flavonoids, and their derivant and glucoside,
Alicyclic compound is selected these from following: poly-cycloalkanes, cycloalkanes, steroids, and their derivant and glucoside, and
Heterogeneous ring compound is selected these from following: pyrrolidine, pyridine, imidazoles, oxazole, morphorine, pyrrolidone, furans, pyrans and carbohydrate.
8. according to the resist pattern thickening material of claim 1, wherein the part of this resin has ring texture.
9. resist pattern thickening material according to Claim 8, wherein ring texture is selected from aromatics, alicyclic compound and heterogeneous ring compound.
10. resist pattern thickening material according to Claim 8, wherein to have the resin content of ring texture be 5mol% or bigger to part.
11. according to the resist pattern thickening material of claim 1, wherein resin is water miscible or alkali-soluble.
12. according to the resist pattern thickening material of claim 1, wherein resin is a kind of for selecting from polyvinyl alcohol (PVA), polyvinyl acetal, polyvinyl acetate at least.
13. according to the resist pattern thickening material of claim 1, wherein resin contains the polyvinyl acetal of 5% mass percent to 40% mass percent.
14. according to the resist pattern thickening material of claim 1, wherein resin has two or more polar groups.
15. according to the resist pattern thickening material of claim 14, wherein polar group is selected these from following: hydroxyl, amino, sulfonyl, carboxyl and carbonyl.
16. according to the resist pattern thickening material of claim 1, wherein crosslinking chemical is to be selected from a kind of in melamine derivative, urea derivative, the uril derivant at least.
17. the resist pattern thickening material according to claim 1 further comprises surfactant.
18. according to the resist pattern thickening material of claim 1, wherein surfactant is to be selected from following a kind of in these at least: non-ionic surface activator, cation surfactant, anionic surfactant and ampholyte surfactant.
19. according to the resist pattern thickening material of claim 18,
Wherein the non-ionic surface activator is selected from following a kind of in these at least: polyoxyethylene alkane-oxygen ethene alkane enriched compound, the polyethylene glycol alkyl ether compound, the polyoxyethylene alkyl ether compound, the polyoxyethylene derivative compound, the sorbitan aliphatic ester compound, the glycerine fatty acid ester compounds, the primary alconol ethoxy compound, the phenol ethoxy compound, the alkoxylate surfactant, the fatty acid ester surfactant, the acid amides surfactant, the ethanol surfactant, the ethylenediamine surfactant; Cation surfactant is selected from following a kind of in these at least: base cations surfactant, acid amide type quaternary cation surfactant and ester type quaternary cation surfactant; The ampholyte surfactant is selected from following a kind of in these at least: amine oxide surfactant and betaine surfactant.
20. the resist pattern thickening material according to claim 1 further comprises organic solvent.
21. according to the resist pattern thickening material of claim 20, wherein organic solvent is to be selected from a kind of in spirit solvent, chain ester solvent, cyclic ester solvent, ketone solvent, chain ether solvents, the cyclic ether solvents at least.
22. a resist pattern thickening material is characterized in that this resist pattern thickening material comprises:
The resin that on a part, has ring texture;
Crosslinking chemical; And
Pure water.
23. a resist pattern is characterized in that this resist pattern has superficial layer on the resist pattern that will thicken, the ratio of corrosion rate is 1.1 or bigger under the same conditions; The ratio of corrosion rate is the resist pattern that will the thicken ratio with the corrosion rate of superficial layer, corrosion rate unit is nm/s, wherein after forming the resist pattern that will thicken, according to any one resist pattern thickening material in the claim 1 to 22, cover the surface of the resist pattern that will thicken in the surface-coated of the resist pattern that will thicken.
24. according to the resist pattern of claim 23, wherein superficial layer contains the compound with ring texture.
25. according to the resist pattern of claim 23 or 24, the content that wherein has the compound of ring texture successively decreases to inside from superficial layer.
26. a technology that forms resist pattern is characterized in that the technology of this formation resist pattern comprises:
After forming the resist pattern that will thicken, apply the resist pattern thickening material to cover the step on the resist pattern surface that will thicken, wherein the resist pattern thickening material according in the claim 1 to 22 any one.
27. according to the technology of the formation resist pattern of claim 26, wherein being developed in of resist pattern thickening material carried out after applying the resist pattern thickening material.
28., wherein develop and carry out with deionized water according to the technology of the formation resist pattern of claim 27.
29. according to any one technology in the claim 26 to 28, wherein resist pattern has the superficial layer that is provided on the resist pattern that will thicken, the ratio of corrosion rate is 1.1 or bigger under the same conditions; The ratio of corrosion rate is the resist pattern that will the thicken ratio with the corrosion rate of superficial layer, and corrosion rate unit is nm/s.
30. according to the technology of the formation resist pattern of claim 29, wherein superficial layer contain at least compound with ring texture and to small part have ring texture resin the two one of.
31., wherein have the compound of ring texture and successively decrease to inside from superficial layer to one the content of resin in the two that small part has a ring texture according to the technology of the formation resist pattern of claim 29 or 30.
32. semiconductor devices is characterized in that this semiconductor devices has by according to the formed figure of any one resist pattern in the claim 23 to 25.
33. a technology of making semiconductor devices is characterized in that the technology of this manufacturing semiconductor devices comprises following these steps:
Form resist pattern, on bottom, form after the resist pattern that will thicken, cover the resist pattern surface that will thicken by coating according to any one resist pattern thickening material in the claim 1 to 22 and thicken this resist pattern that will thicken to form resist pattern; And
Bottom is carried out composition, utilize that the formed resist pattern that has thickened corrodes as mask in form the resist pattern step.
34. according to the technology of the manufacturing semiconductor devices of claim 33, wherein resist pattern is formed by the ArF resist.
35. according to the technology of the manufacturing semiconductor devices of claim 34, wherein the ArF resist is for being selected from following a kind of in these at least: third rare resist, cyclenes-maleic anhydride resist, and cyclenes resist.
36., further comprise according to any one process for fabrication of semiconductor device in the claim 33 to 35:
Before forming the resist pattern step, in the step of the surface-coated non-ionic surface activator of the resist pattern that will thicken;
Wherein the non-ionic surface activator is one type that is selected from polyoxyethylene alkane-oxygen ethene alkane enriched compound, polyethylene glycol alkyl ether compound, polyoxyethylene alkyl ether compound, polyoxyethylene deriv compound, sorbitan aliphatic ester compound, glycerine fatty acid ester compounds, primary alconol ethoxy compound, the phenol ethoxy compound at least.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001361505 | 2001-11-27 | ||
| JP2001361505 | 2001-11-27 | ||
| JP2002139317 | 2002-05-14 | ||
| JP2002139317 | 2002-05-14 | ||
| JP2002328931A JP4316222B2 (en) | 2001-11-27 | 2002-11-12 | Resist pattern thickening material, resist pattern and manufacturing method thereof, and semiconductor device and manufacturing method thereof |
| JP2002328931 | 2002-11-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200710005436XA Division CN101034256B (en) | 2001-11-27 | 2002-11-27 | Resist pattern thickening material, resist pattern and forming process thereof, and semiconductor device and manufacturing process thereof |
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| CN1421744A CN1421744A (en) | 2003-06-04 |
| CN100478780C true CN100478780C (en) | 2009-04-15 |
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| CNB021527709A Expired - Fee Related CN100478780C (en) | 2001-11-27 | 2002-11-27 | Resist pattern thickening material, resist pattern and its forming process, semiconductor device and its producing process |
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| Country | Link |
|---|---|
| JP (1) | JP4316222B2 (en) |
| CN (1) | CN100478780C (en) |
| TW (1) | TWI310118B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1586112B1 (en) * | 2003-01-22 | 2006-12-27 | E.I. du Pont de Nemours and Company | Binder diffusion patterning of a thick film paste layer |
| JP4485241B2 (en) | 2004-04-09 | 2010-06-16 | Ａｚエレクトロニックマテリアルズ株式会社 | Water-soluble resin composition and pattern forming method using the same |
| JP4490228B2 (en) * | 2004-06-15 | 2010-06-23 | 富士通株式会社 | Resist pattern thickening material, resist pattern forming method, semiconductor device and manufacturing method thereof |
| JP4657899B2 (en) | 2005-11-30 | 2011-03-23 | 富士通株式会社 | Resist pattern thickening material, resist pattern forming method, semiconductor device and manufacturing method thereof |
| KR101185950B1 (en) | 2005-12-30 | 2012-09-26 | 에스케이하이닉스 주식회사 | Method for forming fine contact hole of semiconductor device |
| JP4801477B2 (en) * | 2006-03-24 | 2011-10-26 | 富士通株式会社 | Resist composition, method for forming resist pattern, semiconductor device and method for manufacturing the same |
| JP4809705B2 (en) * | 2006-03-28 | 2011-11-09 | 富士通セミコンダクター株式会社 | Manufacturing method of semiconductor device |
| JP4724073B2 (en) * | 2006-08-17 | 2011-07-13 | 富士通株式会社 | Resist pattern forming method, semiconductor device and manufacturing method thereof |
| JP5270839B2 (en) * | 2007-01-23 | 2013-08-21 | 東京応化工業株式会社 | COATING FORMING AGENT FOR PATTERN REFINEMENT AND METHOD FOR FORMING FINE PATTERN USING THE |
| TWI401546B (en) * | 2007-01-23 | 2013-07-11 | Tokyo Ohka Kogyo Co Ltd | A patterning agent for patterning and a method for forming a fine pattern using the same |
| KR100814407B1 (en) | 2007-02-08 | 2008-03-18 | 삼성전자주식회사 | Composition for forming a fine pattern and method of forming a pattern using the same |
| JP5845556B2 (en) * | 2008-07-24 | 2016-01-20 | Jsr株式会社 | Resist pattern refinement composition and resist pattern forming method |
| JP5251985B2 (en) * | 2008-09-19 | 2013-07-31 | Ｊｓｒ株式会社 | Resist pattern coating agent and resist pattern forming method |
| US10269623B2 (en) * | 2015-06-22 | 2019-04-23 | Intel Corporation | Image tone-reversal with a dielectric using bottom-up cross-linking for back end of line (BEOL) interconnects |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6268108B1 (en) * | 1997-07-16 | 2001-07-31 | Tokyo Ohka Kogyo Co., Ltd. | Composition for forming antireflective coating film and method for forming resist pattern using same |
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2002
- 2002-11-12 JP JP2002328931A patent/JP4316222B2/en not_active Expired - Fee Related
- 2002-11-26 TW TW91134356A patent/TWI310118B/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6268108B1 (en) * | 1997-07-16 | 2001-07-31 | Tokyo Ohka Kogyo Co., Ltd. | Composition for forming antireflective coating film and method for forming resist pattern using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1421744A (en) | 2003-06-04 |
| TWI310118B (en) | 2009-05-21 |
| JP4316222B2 (en) | 2009-08-19 |
| TW200300867A (en) | 2003-06-16 |
| JP2004046060A (en) | 2004-02-12 |
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