US20030175624A1 - Resist pattern swelling material, and method for patterning using same - Google Patents

Resist pattern swelling material, and method for patterning using same Download PDF

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Publication number
US20030175624A1
US20030175624A1 US10/408,735 US40873503A US2003175624A1 US 20030175624 A1 US20030175624 A1 US 20030175624A1 US 40873503 A US40873503 A US 40873503A US 2003175624 A1 US2003175624 A1 US 2003175624A1
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Prior art keywords
resist
resist pattern
swelling
pattern
cross linking
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Koji Nozaki
Miwa Kozawa
Takahisa Namiki
Junichi Kon
Ei Yano
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Fujitsu Ltd
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Fujitsu Ltd
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Publication of US20030175624A1 publication Critical patent/US20030175624A1/en
Priority to US12/213,820 priority Critical patent/US8334091B2/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B41/00—Electrically erasable-and-programmable ROM [EEPROM] devices comprising floating gates
    • H10B41/40—Electrically erasable-and-programmable ROM [EEPROM] devices comprising floating gates characterised by the peripheral circuit region
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31127—Etching organic layers
    • H01L21/31133—Etching organic layers by chemical means
    • H01L21/31138—Etching organic layers by chemical means by dry-etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/04—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body
    • H01L27/10—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body including a plurality of individual components in a repetitive configuration
    • H01L27/105—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body including a plurality of individual components in a repetitive configuration including field-effect components
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B41/00—Electrically erasable-and-programmable ROM [EEPROM] devices comprising floating gates
    • H10B41/40—Electrically erasable-and-programmable ROM [EEPROM] devices comprising floating gates characterised by the peripheral circuit region
    • H10B41/42—Simultaneous manufacture of periphery and memory cells
    • H10B41/43—Simultaneous manufacture of periphery and memory cells comprising only one type of peripheral transistor
    • H10B41/48—Simultaneous manufacture of periphery and memory cells comprising only one type of peripheral transistor with a tunnel dielectric layer also being used as part of the peripheral transistor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer

Definitions

  • the present invention relates to a resist pattern swelling material, a method of forming a microscopic pattern, a method of manufacturing a miniaturized device and a method of manufacturing a semiconductor device and more specifically to a technique for swelling a pattern provided on the resist exceeding the exposure limit by providing a film on the surface of resist pattern formed through the exposure and then swelling the resist pattern through reaction between the resist pattern and the relevant film.
  • the deep ultraviolet ray has been put into the practical use as the light to be used for exposing a photo-resist and a microscopic pattern of a certain degree can be drawn through employment of KrF (krypton fluoride) excimer laser beam (wavelength: 248 nm). Since the technique called ‘RELACS’ which enables easier drawing of a further microscopic resist pattern by utilizing this KrF (krypton fluoride) is already proposed, this method will be introduced below.
  • KrF krypton fluoride
  • Japanese Unexamined Patent Publication (Kokai) No. 10-73927 published on Mar. 17, 1998, discloses a method.
  • a resist pattern is first obtained by exposing the photoresist which may be exposed with the KrF (krypton fluoride) excimer laser beam.
  • KrF krypton fluoride
  • a film is formed to cover the relevant resist pattern and this film reacts with a resist material at the interface thereof.
  • the resist material is swelled and a microscopic hole, for example, in the case of a hole pattern, can be formed exceeding the limitation of exposure.
  • any type of positive or negative resist materials can be used, a novolak resin and a photosensitive agent based on naphthoquinone diazido may be listed and a chemical amplification type resist including acid generation mechanism can also be applied.
  • polyacrylic acid polyvinyl acetal, polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene imine, polyethyleneoxydo, sthylene-maleic acid copolymer, polyvinyl amine resin, polyallylamine, water-soluble resin containing oxazoline group, water-soluble melamine resin, water-soluble urea resin, alkyd resin, sulfone amide resin or the like are effective in regard to the resin compositions used to form a film, any limitation is not provided when mixing with a water-soluble cross linking agent is possible if cross linking reaction is generated or not generated under the existence of an acidic element, and these material listed above can also be used as a discrete material or mixed material.
  • the related art explained above also discloses that the cross linking agents based on urea such as urea, alcoxy-methylene urea, N-alcoxymethylene urea, ethylene urea, ethylene urea calbonic acid, the cross linking agents based on amine such as benzoguanamine and glucore can be used as the cross linking agent to form a film, but there is no particular limitation to the cross linking agent based on amine and any type of a water-soluble cross linking agent which forms a cross linking with acid can be used.
  • urea such as urea, alcoxy-methylene urea, N-alcoxymethylene urea, ethylene urea, ethylene urea calbonic acid
  • the cross linking agents based on amine such as benzoguanamine and glucore
  • an object of the present invention is establishment of the technique which can introduce a pattern swelling method into the exposure with the ArF (argon fluoride) excimer laser beam by forming a film to the resist film after formation of the pattern like the RELACS technique of the related art.
  • the present invention provides, e.g., following means.
  • a swelling material formed by coating to cover the surface of a resist pattern is constructed by containing a resin composition consisting of at least a kind of resin selected from polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate, a water-soluble composition including at least a cross linking agent selected from a group of the cross linking agents consisting of melamine derivative, urea derivative and ulyl derivative and at least an interfacial active agent selected from a group of the polyoxyethylene-polyoxypropylene condensation product based, polyoxyalkylenealkylether based, polyoxyethylenealkylether based, polyoxyethylene derivative based, solbitane fatty acid ester based, glycerine fatty acid ester based, primary alcohol ethoxylate based and phenolethoxylate based interfacial active agents.
  • a resin composition consisting of at least a kind of resin selected from polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate
  • a swelling material formed by coating to cover the surface of the resist pattern is comprised from a resin composition consisting of at least a kind of resins selected from polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate, a water-soluble composition including at least a kind of the cross linking agents selected from a group of the cross linking agents consisting of melamine derivative, urea derivative and uryl derivative and at least a kind of phenol based resin.
  • a swelling material formed by coating to cover the surface of the resist pattern is comprised from a phenol resin, at least a kind of cross linking agent selected from a group of the cross linking agents consisting of melamine derivative, urea derivative and uryl derivative and a solvent which does not easily dissolve a pattern resist as the under layer.
  • a resist pattern swelling method in which any one of the swelling materials described in the items (1) to (3) is coated to cover the surface of the relevant resist pattern after this resist pattern is formed. Or a method of forming a microscopic pattern employing the above resist pattern swelling method. Or a method of manufacturing a miniaturized device employing the above resist swelling method. Or a method of manufacturing a semiconductor device employing the above resist pattern swelling method.
  • a method of swelling a resist pattern comprising the steps of coating the surface of the relevant resist pattern, after formation of the resist pattern, with a aqueous solution containing an interfacial active agent selected from a group of the polyoxyethylene-polyoxypropylene condensation product based, polyoxyalkylenealykylether based, polyoxyethylenealkylether based, polyoxyethylene derivative based, solbitane fatty acid ester based, glycerine fatty acid ester based, primary alcohol ethoxylate based and phenol ethoxylate based interfacial active agents, and then coating the surface of the resist pattern with a resin composition consisting of at least a kind of the resins selected from polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate and with a water-soluble composition including at least a kind of cross linking agent selected from a group of the cross linking agents consisting of melamine derivative, urea derivative and uryl derivative.
  • an interfacial active agent selected
  • the effect of swelling of pattern cannot be obtained for the ArF (argon fluoride) excimer laser beam because it can be assumed that when a photoresist composition corresponding to the ArF excimer laser beam is used, affinity between the film formed by coating to accelerate the swelling after formation of the photoresist pattern and the photoresist pattern as the foundation layer, unlike the situation that the photoresist corresponding to the KrF excimer laser beam is used is remarkably deteriorated. Therefore, the concept of the present invention can be attained by the invention to adjust the composition of the film in order to improve the affinity between the photoresist pattern corresponding to the ArF excimer laser beam as the lower layer and the film formed as the upper layer.
  • a pattern is swelled depending on the cross linking reaction due to the diffusion of acid, but according to the pattern swelling technique of the present invention, it can be easily supposed that such cross linking reaction resulting from diffusion of acid disclosed in the related art is not utilized because the pattern swelling effect, which can be assured through application of this technique into the wafer immediately after the exposure thereof, has also been detected in the wafer even when it has been left at the outside of the clean room for about a month after the exposure thereof.
  • it can also be supposed that such swelling effect can be attained depending on the phase-solubility of resin between the resist pattern and swelling film.
  • the interfacial active agent within the film can improve affinity with the resist pattern surface and thereby the sufficient pattern swelling effect of the material can be attained.
  • the affinity of the resist pattern surface is improved with an aqueous solution including the interfacial active agent and subsequently the resist pattern surface is coated with a water-soluble composition including the particular resin and the particular cross linking agent.
  • the affinity of the resist pattern surface can be improved by formation of the pattern swelling material through the coating thereof and sufficient swelling effect can be assured.
  • a material containing a resin including polyvinyl alcohol and polyvinyl acetal in the weight ratio of 8:2, a cross linking agent and an interfacial active agent is formed by coating as a resist pattern swelling film to cover the entire surface of a positive resist pattern where hole patterns are opened.
  • the film thickness is at least about 1000 ⁇ or more preferably about 2000 to 5000 ⁇ .
  • the thickness of 3790 ⁇ after the development is reduced to 3780 ⁇ by 0.3% when it is left for two minutes after the reaction with the rest pattern swelling film.
  • the thickness of 3840 ⁇ is reduced to 3820 ⁇ by 0.5%.
  • PEB FT FT FT amount (%) 20 wt % GBL 3600 3510 3480 ⁇ 120 ⁇ 3.3 20 wt % NMP 3670 3660 3700 30 0.8 20 wt % glyme 3490 3510 3490 0 0 20 wt % EL 3730 3720 3700 ⁇ 30 ⁇ 0.8 20 wt % PGME 3820 3830 3850 30 ⁇ 0.8 20 wt % acetone 3740 3710 3700 ⁇ 40 ⁇ 1.1 20 wt % dioxane 3620 3640 3630 10 0.2 5 wt % KS-2010 3690 3710 3700 10 0.3
  • the thickness of 3620 ⁇ detected when the baking process is completed after the exposure of the resist material forming the pattern is increased up to 3650 ⁇ showing an increase rate of 30 ⁇ after the resist pattern is processed using the solution consisting of a mixture of polyvinyl alcohol and polyvinyl acetal as the swelling material. Namely, the thickness is increased by 0.8% with the swelling process.
  • the thickness of 3610 ⁇ detected when the baking process is completed after the exposure of the resist material forming the pattern is increased up to 3690 ⁇ showing amount of change of thickness of 80 ⁇ and increase rate of 2.2% after the swelling process.
  • FIG. 1 is a graph showing changing rates (%) of thickness of the resist pattern when amount of addition of the GBL is changed.
  • an interfacial active agent to construct a pattern swelling material through the mixing into a resin composition consisting of at least a resin selected from polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate and into a water-soluble composition including at least a cross linking agent selected from a group of the cross linking agents consisting of melamine (hexamethylol melamine) derivative, urea (N,N′-methoxymethy methoxyethylene urea) derivative, uryl (tetramethoxymethy grycol uryl) derivative will be discussed below.
  • a non-ionic interfacial active agent (Clean-through, KS-2010 produced by Kao Co., Ltd.) is adapted to a resin selected from polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate.
  • the agent is not an inorganic alkali salt, because if an interfacial active agent including alkali metal such as Na (sodium) or the like is used, it will probably deteriorate in some cases the surface of element region of a semiconductor device. Therefore, it is recommended to avoid use of the interfacial active agent based on inorganic alkali salt in order to improve the manufacturing yield. According to the finding of the inventors of the present invention, in more practical, amount of alkali metal contained shall be set 0.1 ppm or less.
  • Table 4 shows changes of thickness of the pattern when amount of addition (wt %) of the interfacial active agent to the entire part of the pattern swelling film is changed.
  • addition amount altering amount increasing ratio (wt %) ( ⁇ ) (%) 1 59 1.7 3 140 3.8 4 240 6.7 5 500 13.9 * 7 700 19.9 * 10 420 11.4 *
  • FIG. 2 is a graph showing the relationship between amount of addition of the interfacial active agent and change of film thickness and this graph suggests that increase rate (%) of film thickness (vertical axis) increases or decreases depending on increase or decrease of the amount of addition (wt %) of the interfacial active agent. According to this graph, under the conditions explained above, it can be understood that the increase rate of film thickness becomes optimal when amount of addition of the interfacial active agent is 7 wt % and it can be said in general that increase in amount of addition of the interfacial active agent is only the best selection.
  • the inventors of the present invention have conducted for the example where the other interfacial active agent is added to the water-soluble composition including an uryl derivative as a cross linking agent into a resin material consisting of a mixture of polyvinyl alcohol and polyvinyl acetal.
  • the interfacial active agent the clean-through (RI-100, manufactured by Kao Co., Ltd.) (amphipatic interfacial active agent) has been used.
  • Table 5 shows the result of experiments for checking the changes in amount of increase of film thickness ( ⁇ ) and increase rate of film thickness (%) for the amount of addition (wt %) of the interfacial active agent.
  • the interfacial active agent when amount of addition of the interfacial active agent is 4 wt % or more, the surface of resist pattern is roughed (nebula is generated), and such event can be prevented by utilizing addition of an organic solvent as a means.
  • This example is based on the concept that affinity with pattern swelling material is improved to enhance the pattern swelling effect through a little dissolving of the resist pattern surface.
  • the official names of the compound melamine, urea and uryl used as the cross linking agents are sequentially hexamethylol melamine, N,N′-methoxymethylmethoxyethylene urea and tetramethoxymethyl glycol uryl.
  • Resin solvent Maruzen PVP (polyvinyl phenol resin)+ethylene glycol+propylene glycol methylether are mixed in the ratio of 1:6.5:3.5.
  • Negative resist A Resin solvent (i) of 9 pts.wt. (parts by weight) and cross linking agent C (ii) of 1 pts.wt. are mixed.
  • Negative resist B Resin solvent (i) of 9 pts.wt. and cross linking agent D (iii) of 1 pts.wt. are mixed.
  • Pattern swelling material A A composition obtained by adding the uryl derivative as the cross linking agent to a resin composition mixing polyvinyl alcohol and polyvinyl acetal is mixed with the negative resist A in the ratio of 9:1.
  • Pattern swelling material B A composition obtained by adding the uryl derivative as the cross linking agent to a resin composition mixing polyvinyl alcohol and polyvinyl acetal is mixed with the negative resist B in the ratio of 9:1.
  • the inventors have also discussed addition of a plurality of cross linking agents to the pattern swelling materials A and B explained above.
  • the cross linking agents the melamine derivative, urea derivative and uryl derivative have been used respectively.
  • the baking is conducted for 120 seconds at 115° C. and the development is conducted through reaction with the aqueous solution of 0.238% TMAH (Tetramethyl Ammonium Hydroxide).
  • TMAH Tetramethyl Ammonium Hydroxide
  • amount of reduction of hole pattern is ⁇ 29.1 nm for the melamine derivative, ⁇ 29.7 nm for the urea derivative and ⁇ 32.4 nm for the uryl derivative. From these results, it can be assumed that swelling of resist pattern is surely promoted and hole pattern is also reduced even when any type of cross linking agent listed above is employed. It can also be understood that there is no large difference in the swelling effects, reduction of hole pattern of about 20 to 30 nm in the cross-sectional diameter can be realized but when the uryl derivative is used, amount of reduction of the hole pattern can be further improved a little. In regard to such this result, the inventors of the present invention presumes as follows.
  • the melamine, urea and uryl respectively have six, two and four coupling hands to contribute to the cross linking within one molecule thereof and therefore the melamine is most useful for the cross linking from point of view of the number of coupling hands for contribution to the cross linking.
  • the melamine having six coupling hands within one molecule is used as the cross linking agent, since the cross linking extremely progresses within the pattern swelling film itself and the cross linking property is extinguished within the pattern swelling film, the swelling effect of the resist pattern used as the lower layer of the pattern swelling film will be reduced.
  • the cross linking property of the urea derivative is weak and therefore it can be assumed that the resist pattern is not sufficiently swelled and the hole pattern reduction effect is rather low.
  • the melamine assuring very high cross linking property and the urea assuring very low cross linking property show rather low resist pattern swelling effect and the uryl assuring an intermediate cross linking property shows the highest resist pattern swelling effect.
  • the content of the polyvinyl phenol based negative resist is set as much as 30 wt %, it can be understood that the pattern is surely deformed but the reason thereof can be presumed that when amount of the polyvinyl phenol based negative resist increases, amount of isopropyl alcohol included therein also increases.
  • the swelling profile of pattern has been observed by changing the baking temperature in order to know the effect of baking temperature when the polyvinyl phenol based negative resist is added to the resin F formed by mixing polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate in the weight ratio of 75:10:15.
  • the hole pattern diameter of 344.2 nm is changed to 335.9 nm for the baking temperature of 85° C., 318.9 nm for the temperature of 115° C., 286.6 nm for the temperature of 125° C. and 285.9 nm for the temperature of 135° C.
  • content of the polyvinyl phenol based negative resist is set to 10 wt % and urea is included as the cross linking agent.
  • the baking is conducted for 120 seconds and the spin coating is conducted for 5 seconds at 850 rpm and 40 seconds at 3500 rpm in order to form the coated pattern swelling material film.
  • the 0.238% TMAH tetramethyl ammonium hydroxide
  • the hole pattern is reduced when the baking temperature is raised through the comparison of results when the baking temperature is set to 85° C., 115° C., 125° C. and 135° C. and when the pattern swelling process is not conducted.
  • the inventors of the present invention have also conducted experiments to know the pattern swelling Effect when addition of the cross linking agent (urea) to the polyvinyl phenol based negative resin composition is increased.
  • Experimental conditions are that the polyvinyl phenol based negative resin composition and urea are mixed in the weight ratio of 8:2, a solution mixing the ethylene glycol and propylene glycol methylether in the ratio of 65:35 is used as the solvent, the baking temperature is set to 85° C. for 70 seconds and thereafter to 115° C. for 70 seconds, the 1.5% TMAH is used as the developer and the developing period is set to 30 seconds.
  • the hole pattern diameter is 333.5 nm, but this diameter is increased to 347.6 nm, on the contrary, when amount of the urea as the cross linking agent is increased. From this result, the inventors have obtained the conclusion that the pattern swelling effect is never increased even when the amount of urea as the cross linking agent is increased.
  • the inventors have also searched the influence on the reaction property when the polyvinyl acetal is added to the polyvinyl phenol based negative resin composition.
  • the polyvinyl phenol based negative resist resin, urea and polyvinyl acetal (KW-3; Sekisui Chemical) are mixed in the ratio of 8:1:1, a solution mixing the ethylene glycol and propylene glycol methylether in the ratio of 65:35 is used as the solvent, the baking temperature is set to 85° C. for 70 seconds and thereafter to the following temperatures for 70 seconds, the 1.5% TMAH is used as the developer and the developing period is set to 30 seconds. In this case, when the baking temperature is set respectively to 115° C., 120° C.
  • the hole pattern diameter on the resist is 333.5 nm.
  • the hole pattern diameter when the temperature of the baking process (latter half processes) is set to 115° C. is 327.3 nm at the stage where the baking process (former half processes is completed and 339.1 nm when the processes are completed up to the latter half processes.
  • the hole pattern diameter when the temperature of the baking process (latter half processes) is set to 120° C. is 326.6 nm when the baking process (former half processes) is completed and 335.2 nm when the latter half processes are completed.
  • the hole pattern diameter when the temperature of the baking process (latter half processes) is set to 125° C. is 328.1 nm when the baking process (former half processes) is completed and 333.6 nm when the processes are completed up to the latter half processes. From these results, it can be understood that addition of polyvinyl acetal itself does not control the pattern swelling effect even when the polyvinyl acetal is added when the phenol based resin is included in the pattern swelling material.
  • the pattern swelling film is formed of a material film mixing the polyvinyl acetal (KW-3, Sekisui Chemical) and cross lining agent (composition: urea or uryl in the weight ratio of 16:x, following change of effect can be confirmed.
  • the solvent is formed by mixing the pure water (deionized water) and isopropyl alcohol in the ratio of 82.6:0.4 and the interfacial active agent is not used.
  • the spin coating is conducted for 5 seconds at 850 rpm and thereafter for 40 seconds at 3500 rpm.
  • the baking process the baking is conducted for 70 seconds at 85° C. and thereafter for 70 seconds at 115° C.
  • the hole pattern diameter of the resist is 333.5 nm.
  • the hole pattern diameter when the former baking process is completed is 334.4 nm and the hole pattern diameter when the latter baking process is completed is 322.7 nm.
  • the hole pattern diameter when the former baking process is completed is 333.6 nm and the hole pattern diameter when the latter baking process is completed is 316. 4 nm.
  • the hole pattern diameter when the former baking process is completed is 334. 4 nm and the hole pattern diameter when the latter baking process is completed is 325.0 nm.
  • the hole pattern diameter when the former baking process is completed is 332.8 nm and the hole pattern diameter when the latter baking process is completed is 319.5 nm.
  • the hole pattern diameter when the former baking process is completed is 339.0 nm and the hole pattern diameter when the latter baking process is completed is 310.2 nm.
  • the hole pattern diameter when the former baking process is completed is 336.0 nm and the hole pattern diameter when the latter baking process is completed is 319.5 nm.
  • the pattern swelling film is formed of a material film by mixing the polyvinyl acetal (KW-3, Sekisui Chemical), cross linking agent (composition: urea or uryl), pure water (deionized water) and isopropyl alcohol in the weight ratio of 16:1:82.6:0.4 and the interfacial active agent is included in the 2 pts.wt., following changes of effect can be confirmed by changing the interfacial active agent and cross linking agent.
  • the spin coating is conducted for 5 seconds at 850 rpm and thereafter for 40 seconds at 3500 rpm to form a film and the baking process is conducted for 70 seconds at 85° C. and subsequently for 70 seconds at 115° C.
  • the hole pattern diameter of the resist of 337.5 nm before the pattern swelling process is reduced to 313.3 nm after the pattern swelling process.
  • the hole pattern diameter of resist of 340.4 nm before the pattern swelling process is reduced to 318.8 nm after the pattern swelling process.
  • the hole pattern diameter of resist of 336.7 nm before the pattern swelling process is reduced to 310.9 nm after the pattern swelling process. According to these results, it can be understood that amount of reduction of the hole pattern is increased as much as about 10 nm with addition of the interfacial active agent. Moreover, when L-64 is used as the non-ionic interfacial active agent, the surface seems to be more easily roughed than the case where B-733 is used.
  • the pattern swelling film is formed by a material film obtained by mixing the polyvinyl acetal (KW-3, Sekisui Chemical), cross linking agent, pure water (deionized water) and isopropyl alcohol in the weight ratio of 16:1:82.6:0.4 and moreover the non-ionic interfacial active agent TN-80 (Asahi Denka) is also mixed, change of the swelling effect has been confirmed.
  • the coater is rotated at 540 rpm for 5 seconds and thereafter rotated at 3500 rpm for 40 seconds during the spin coating to form a film of the pattern swelling material and the baking is conducted for 70 seconds at 85° C. and thereafter for 70 seconds at 115° C.
  • the urea or uryl is employed as the cross linking agent and the interfacial active agent (TN-80) is changed to 0.5 pts.wt. and 0.25 pts.wt.
  • the profile of the pattern swelling effect is as follows. In the example where the non-ionic interfacial active agent TN-80 (Asahi Denka) is set to 0.5 pts.wt. and the urea is used as the cross linking agent, the hole pattern diameter of resist of 343.0 nm after completion of the former baking is reduced to 275.8 nm after completion of the latter baking. When TN-80 is set to 0.5 pts.wt.
  • the hole pattern diameter of resin of 342.6 nm after completion of the former baking is reduced to 263.4 nm after completion of the latter baking.
  • TN-80 is set to 0.25 pts.wt. and the urea is used as the cross linking agent
  • the hole pattern diameter of resist of 335.0 nm after completion of the former baking is reduced to 335.9 nm after completion of the latter baking.
  • TN-80 is set to 0.25 pts.wt. and the uryl is used as the cross linking agent
  • the hole pattern diameter of resist of 337.5 nm after completion of the former baking is reduced to 296.1 nm after completion of the latter baking.
  • the pattern swelling film is formed of a material film formed by mixing the polyvinyl acetal (KW-3, Sekisui Chemical), cross linking agent (composition: urea or uryl), pure water (deionized water) and isopropyl alcohol in the weight ratio of 16:1:82.6:0.4 and moreover the non-ionic interfacial active agent TN-80 (Asahi Denka) of 0.25 pts.wt. and GBL ( ⁇ -butyloractone) of 2 pts.wt. are further mixed to such material film, following changes of swelling effect have been confirmed.
  • TN-80 Asahi Denka
  • GBL ⁇ -butyloractone
  • the coater is rotated at 850 rpm for 5 seconds and thereafter rotated at 3500 rpm for 40 seconds during the spin coating to form the pattern swelling film and the baking is conducted for 70 seconds at 85° C. and thereafter for 70 seconds at 115° C.
  • the urea or uryl is used as the cross linking agent in above experiments and the resist pattern swelling profile of each case is as follows.
  • the hole pattern diameter in the resist of 335.9 nm after completion of the former baking process is increased up to 375.6 nm after completion of the latter baking process.
  • the uryl is selected as the cross linking agent, the hole pattern diameter in the resist of 338.9 nm after completion of the former baking process is reduced up to 252.3 nm after completion of the latter baking process. Namely, change of shape at the area near the hole pattern opening can be detected with addition of GBL but distinctive hole pattern reduction (resist pattern swelling) effect cannot be detected.
  • the pattern swelling film is formed of a material film formed by mixing the polyvinyl acetal (KW-3, Sekisui Chemical), cross linking agent (urea), pure water (deionized water) and isopropyl alcohol in the weight ratio of 16:1:82.6:0.4 and the polyvinyl phenol based negative resist of 10 wt % is further mixed this material film, the pattern swelling profiles have been observed by changing the interfacial active agent.
  • the spin coating is conducted for 5 seconds at 850 rpm and thereafter for 40 seconds at 3500 rpm, the baking is conducted for 120 seconds at 115° C. and the 0.238% TMAH (tetramethyl ammonium hydroxide) is used as the developer.
  • TMAH tetramethyl ammonium hydroxide
  • the pattern swelling material is formed of a material film formed by mixing the polyvinyl acetal (KW-3, Sekisui Chemical), cross linking agent (urea), pure water (deionized water) and isopropyl alcohol in the weight ratio of 16:1:82.6:0.4 and the polyvinyl phenol based negative resist of 10 wt % is still mixed thereto, results of the pattern swelling are as follows.
  • the results of the contrast experiment where the same interfacial active agent is used the resin F formed by mixing the polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate in the weight ratio of 75:10:15 is used as the pattern swelling material and the urea is added thereto as the cross linking agent are also shown.
  • the pattern swelling material is formed of a material film formed by mixing the polyvinyl acetal (KW-3, Sekisui Chemical), cross linking agent (urea), pure water (deionized water) and isopropyl alcohol in the weight ratio of 16:1:82.6:0.4 and moreover the polyvinyl phenol based negative resist of 10 wt % is mixed to such swelling material film, the hole pattern diameter in the resist is 325.8 nm when L-64 is 2 pts.wt. and 281.2 nm when RI-100 is 3 pts.wt. In the case where the interfacial active agent is not mixed, such hole pattern diameter is 342.9 nm.
  • the hole pattern diameter is 297.6 nm when L-64 is 2 pts.wt. and 187.5 nm when the RI-100 is 3 pts.wt.
  • the hole pattern diameter is 344.2 nm.
  • the polyvinyl alcohol is an important element to control the resist pattern swelling effect.
  • the resist pattern swelling effect is small and when the polyvinyl acetal and polyvinyl alcohol are used in combination, a certain multiplier effect can be obtained.
  • the pattern swelling effect can be enhanced and more preferably when such polyvinyl acetal is set to 10 to 30 wt %, the pattern swelling effect can be increased in the maximum degree.
  • FIG. 1 is a graph showing changing rates (%) of the thickness of the resist pattern when amount of addition of the GBL is changed;
  • FIG. 2 is a graph showing the relationship between amount of addition of the interfacial active agent and change of film thickness
  • FIG. 3 is a graph showing the relationship between amount of addition of RI-100 and change of film thickness
  • FIG. 4 is schematic cross-sectional views showing the profiles of a resist pattern before and after the swelling process (an example where the polyvinyl phenol based negative resist composition is added to the resin as the base material such as polyvinyl alcohol);
  • FIG. 5 is cross-sectional views (Part 1) for explaining a method of manufacturing an EPROM as the first embodiment of the present invention
  • FIG. 6 is cross-sectional views (Part 2) for explaining a method of manufacturing an EPROM as the first embodiment of the present invention
  • FIG. 7 is cross-sectional views (Part 3) for explaining a method of manufacturing an EPROM as the first embodiment of the present invention.
  • FIG. 8 is plan views for explaining a method of manufacturing an EPROM as the first embodiment of the present invention.
  • FIG. 9 is cross-sectional views for explaining a method of manufacturing an EPROM as the second embodiment of the present invention.
  • FIG. 10 is cross-sectional views for explaining a method of manufacturing an EPROM as the third embodiment of the present invention.
  • Si substrate semiconductor substrate
  • 31 , 31 b Second polysilicon film (second conductive material film);
  • 35 a, 35 b, 36 a, 36 b, 45 a, 45 b, 46 a, 46 b Source/drain region layer
  • Control gate electrode (refractory metal film; fourth conductive material film);
  • 53 a, 53 b Refractory metal film (third conductive material film).
  • FIGS. 4 ( a ) to 4 ( e ) are cross-sectional views showing profiles of the resist pattern before and after the swelling process.
  • the cross-sectional views of the essential portion including the resist pattern are sequentially shown in FIGS. 4 ( a ) to 4 ( e ).
  • a silicon oxide film for example, is formed to the entire surface as an interlayer insulation film with the CVD (Chemical Vapor Deposition) method.
  • CVD Chemical Vapor Deposition
  • a positive resist is formed on the flat surface by the uniform coating process with the well known spin coating method.
  • the positive resist material it is preferable as explained above to select the alicyclic group based resist from the viewpoint of the resolution and resistance for dry-etching.
  • the resist film 1 is patterned with the well known photolithography method to form a resist pattern 1 a.
  • this film is irradiated with the ArF (argon fluoride) excimer laser beam for the purpose of exposure.
  • the film is then baked and developed to form a hole pattern.
  • amount of exposure is set, for example, to 50 mJ/cm 2 to realize the film thickness of 5060 ⁇ after the development.
  • the interfacial active agent may be added in the development process in order to improve the development property.
  • a swelling material 2 is formed by coating on the interlayer insulation film 3 , covering the entire surface of the resist pattern 1 a.
  • a material in which the interfacial active agent of several % is added to the resin base material obtained by mixing the polyvinyl acetal and polyvinyl alcohol is used as the swelling material 2 .
  • the swelling material is constructed by mixing the resin composition including the polyvinyl acetal and polyvinyl alcohol in the weight ratio of 7:3, a water soluble composition including at least a cross linking agent selected from a group of the cross linking agents consisting of the melamine derivative, urea derivative and uryl derivative and at least a kind of the interfacial active agent such as polyoxyethylene-polyoxypropylene condensation product.
  • a cross linking agent selected from a group of the cross linking agents consisting of the melamine derivative, urea derivative and uryl derivative
  • the interfacial active agent such as polyoxyethylene-polyoxypropylene condensation product.
  • the film thickness is increased by 4% (the part indicated with the numeral “4” in the figure), and therefore it can be assumed that the swelling of pattern is surely generated.
  • the baking processes before and after the exposure are respectively conducted at 130° C. and 140° C. and the amount of exposure is set to 50 mJ/cm 2
  • increase of the thickness of 3.5% has been recognized in comparison with the thickness detected immediately after the development.
  • the second invention of the present invention namely an embodiment of the swelling material to be formed by coating to cover the surface of resist pattern is constructed with a phenol resin and a solvent which includes at least a kind of cross linking agent selected from a group of the cross linking agents consisting of melamine derivative, urea derivative and uryl derivative and does not easily dissolve the resist material as the lower layer on which a pattern is already formed.
  • This second embodiment is intended, by forming a film on the resist pattern surface with a material obtained through addition of the particular cross linking agent and a resin material known as the resist material to the particular resin composition, to assure excellent affinity with the resist pattern surface with a little dissolution of the pattern surface by reaction of the existing resist material in the film with the relevant resist pattern surface in order to realize that the material explained above can fully show the pattern swelling effect.
  • a silicon oxide film for example, is formed as an interlayer insulation film on the entire surface with the CVD (Chemical Vapor Deposition) method.
  • CVD Chemical Vapor Deposition
  • a positive resist is formed on the entire surface thereof by the coating process.
  • a resist for example, corresponding to the alicyclic group based ArF excimer laser beam exposure may be used.
  • an acryl based resist having the adamantly group in the side chain may be used.
  • this film is irradiated with the ArF (argon fluoride) excimer laser beam to open a hole pattern on the positive resist.
  • ArF argon fluoride
  • a material containing a phenol resin including the PVP (PolyVinyl Phenol) based negative resist, for example, in the weight ratio of 9:1, a cross lining agent and an interfacial active agent is coated to form a resist pattern swelling film in the manner to cover the entire surface of the positive resist pattern on which the hole pattern is opened.
  • the well known spin coating is executed for film formation and it is preferable that the film is formed in the thickness of about 1000 ⁇ and more preferably about 2000 ⁇ to 5000 ⁇ .
  • the resist After coating of material with the spin coating method, the resist is baked for 120 seconds at 115° C. and is then developed for 30 seconds with the 0.238% TMAH (TetraMethyl Ammonium Hydroxide). Thereby, the hole pattern has been reduced (namely, swelling of resist pattern) by about 30 nm.
  • TMAH TetraMethyl Ammonium Hydroxide
  • the third invention of the present invention namely an embodiment of the resist pattern swelling method or the like will be explained, in which after formation of a resist pattern, the surface of the relevant resist pattern is coated first with an aqueous solution including a non-ionic interfacial active agent, for example, a polyoxyethylene-polyoxypropylene condensation product based interfacial active agent or other agents, thereafter coated with a resin composition selected from polyvinyl alcohol or the like and with a water-soluble composition including a cross linking agent consisting of melamine derivative, urea derivative and uryl derivative.
  • a non-ionic interfacial active agent for example, a polyoxyethylene-polyoxypropylene condensation product based interfacial active agent or other agents
  • affinity of the resist pattern surface is previously improved with the aqueous solution including the interfacial active agent and thereafter affinity of the resist pattern surface is improved before coating and formation of the pattern swelling material by coating the resist pattern surface with the water-soluble composition including the particular resin and the particular cross linking agent to realize sufficient swelling effect.
  • the fourth embodiment depends on the invention of the present invention, namely a resist pattern swelling material constructed by adding the swelling material of the first invention to be coated and formed to cover the surface of resist pattern to a resin composition consisting of at least a kind of resin selected from polyvinyl alcohol, polyvinyl acetal and polyvinyl acetate and to a water-soluble composition including at least a cross linking agent selected from a group of the cross linking agents consisting of melamine derivative, urea derivative and uryl derivative and moreover containing a kind of non-ionic interfacial active agent, for example, a polyoxyethylene-polyoxypropylene condensation product based interfacial active agent.
  • this embodiment is different from the first invention in the point that the swelling gent is changed.
  • a resist corresponding to the alicyclic group based ArF excimer laser beam exposure is selected.
  • the alicyclic group resist those which are well known as the ArF resist, for example, acryl based resist having the adamantly group in the side chain, COMA-based resist, hybrid (alicyclic group acryl-based and COMA-based copolymer) resist and cyclo-olefine based resist may be used.
  • an alicyclic group acryl based resist is used.
  • This resist has the properties to assure excellent transparency for the ArF excimer laser beam as explained above and also assure higher resolution and dry-etching resistance.
  • Such positive resist film is exposed in the amount of exposure of 30 mJ/cm 2 using the ArF excimer laser beam and is then developed to open a hole pattern to the positive resist.
  • a material containing a resin including polyvinyl alcohol and polyvinyl acertal in the weight ratio of 7:3, a cross linking agent and an interfacial active agent is formed by coating process as the resist pattern swelling film to in the manner to cover the entire surface of the positive resist pattern where the hole pattern is opened.
  • the spin coating method is enough for film formation and the thickness of film is at least about 1000 ⁇ and more preferably about 2000 ⁇ to 5000 ⁇ .
  • the resist pattern swelling material contains at least a kind of organic solvent among the alcohol based, chain ester based, cyclic ester based, ketone based, chain ether based and cyclic ether based organic solvents in addition to the water-soluble composition or alkali-soluble composition consisting of a resin and a cross linking agent
  • PMEA lactic acid ethyl and propyleneglycolmethylether acetate
  • lactone based organic solvent as an example of the cyclic ester based organic solvent.
  • the ⁇ -butyloractone (GBL) based organic solvent can be used preferably.
  • the ketone based organic solvent the acetone, cyclohexanone or heptanone or the like may be used.
  • the chain ether based organic solvent the tetra-hydrofurane may be used.
  • an organic solvent having the boiling point of about 80 to 200° C The organic solvent having such boiling point assures fine drawing of the resist patterns.
  • the present invention is applicable also to the EB resist, which is designed for Electron Beam Exposure.
  • the resist pattern swelling material of the present invention can be applicable to not only chemical amplified resist but also non-chemical amplified resist. Same effect can be acquired by an application non-chemical amplified resist as well as chemical amplified resist.
  • Electron Beam patternable conventional type PMMA (polymethyl methacrylate) resist which is not workable as a chemical amplifed resist is employed.
  • a trench pattern of 130 nm width is patterned by using electron beam exposing apparatus of 50 KeV energy.
  • the solution which is comprised from polyvinyl acetal (KW-3; Sekisui Chemical Co.)(16), crosslinking agent (uryl)(1), pure water (deionized water) (82.6), and isopropyl alcohol(0.4) (weight ration for each is noted in each corresponding parenthesis) is mingled with the non-ionic interfacial active agent TN-80 (Asahi Denka Co.) (0.25 weight part).
  • This solution is employed as resist pattern swelling material for treating the above Electron Beam patternable conventional type PMMA (polymethyl methacrylate) resist, and thereby pattern swelling width is resulted as 55.2 nm. And also, replacing the weight part of the above non-ionic interfacial active agent TN-80 by 0.0625 weight part, swelling width of the resist pattern is resulted as 28.2 nm in case that such solution having 0.0625 weight part TN-80 is employed as resist pattern swelling material.
  • FIG. 1 Another embodiment employing another EB-patternable conventional type resist, which is not a chemical amplified resist, is exemplified in below.
  • the resist material is comprised from methyl methacrylate-methacrylic acid copolymer (copolymer ratio 9:1).
  • trench pattern of 130 nm width is patterned by using electron beam exposing apparatus of 50 KeV energy.
  • resist pattern swelling material having TN-80 as 0.25 weight ratio which is embodied in the fifth embodiment, the swelling width is resulted as 58.5 nm.
  • total amount of TN-80 is 0.0625 weight ratio of the resist pattern swelling material, swelling width is resulted as 32.2 nm.
  • Another embodiment employing another EB-patternable conventional type resist, which is not a chemical amplified resist, is exemplified in below.
  • trench pattern of 130 nm width is patterned by using electron beam exposing apparatus of 50 KeV energy.
  • swelling width is resulted as 60.1 nm.
  • the resist is treated by using the resist pattern swelling material having TN-80 of 0.0625 weight ratio, the resist pattern is swelled 33.7 nm width.
  • the resist pattern swelling material of the present invention is applicable to both chemical amplified resist and non-chemical amplified resist.
  • PMMA polymethyl methacrylate
  • ZEP-520A of 0.15 ⁇ m thickness
  • second resist layer on the first resist layer.
  • trench pattern is patterned by using electron beam exposing apparatus of 50 KeV energy.
  • the trench pattern is developed by using MIBK (methyl isobuthyl kethone). As a result of the above, the trench pattern is formed as having 130 nm width.
  • the resist pattern swelling material can work for swelling pattern in first resist layer of PMMA (polymethyl methacrylate).
  • PMMA polymethyl methacrylate
  • the resist embodied in the sixth or seventh embodiment is employed as the first layer, same result as aforementioned can be obtained. That is, the first (lower) resist layer is swelled but the second (upper) resist layer is not altered.
  • PMMA polymethyl methacrylate
  • PMGI polydimethylglutarimide
  • Micro Lithography Chemical Co. of U.S.A. Micro Lithography Chemical Co. of U.S.A.
  • ZEP-520A 0.15 ⁇ m thickness
  • the third resist layer (upper layer) is developed by using MIBK (methyl isobuthyl keton), and the second resist layer (intermediate layer) is developed by using TMAH solution, and the first resist layer is developed by using MIBK solution.
  • MIBK methyl isobuthyl keton
  • the second resist layer (intermediate layer) is developed by using TMAH solution
  • the first resist layer is developed by using MIBK solution.
  • the resist pattern swelling material of the present invention is applicable also to bi-level or tri-level resist system, and it can acquire the same favorable result as single layer resist system.
  • the essential processes of the present invention have been explained above based on a plurality of embodiments thereof, but an outline of flash memory manufacturing processes will then be explained below as an example of the semiconductor device manufacturing processes combining these patterning processes.
  • the internal diameter of hole pattern of resist can be reduced by introducing the resist pattern swelling technique into the hole pattern forming process, moreover an interval between the linear patterns can also be reduced by introducing into the linear pattern forming process and an isolated pattern having the enlarged area can also be provided by introducing into the isolated pattern forming process.
  • FIGS. 5 ( a ) to 5 ( c ), FIGS. 6 ( d ) to 6 ( f ) and FIGS. 7 ( g ) to 7 ( i ) are cross-sectional diagrams for explaining the manufacturing method of a FLOTOX or ETOX type FLASH EPROM as the first application example.
  • the left side diagrams are the cross-sectional views in the gate width direction(X direction) of the memory cell (first element region), namely the part where a MOS transistor having the floating gate electrode is formed, while the center diagrams are the cross-sectional views of the memory cell of the same part as the left side diagrams in the gate length direction (Y direction) in the right angle to the X direction and the right side diagrams are the cross-sectional views of a MOS transistor of the peripheral circuit portion (second element region).
  • FIGS. 8 ( a ) and 8 ( b ) show the plan views of FIG. 6( d ) and FIG. 7( g ).
  • the cross-sectional view along the line A-A of FIG. 8( a ) corresponds to the cross-sectional view in the X direction
  • the cross-sectional view along the line B-B corresponds to the cross-sectional view in the Y direction.
  • a first gate insulation film 24 a of a MOS transistor of a memory cell portion (first element region) consisting of the SiO 2 film in the thickness of 100 to 300 ⁇ and a second gate insulation film 24 b of a MOS transistor of the peripheral circuits (second element region) consisting of SiO 2 film in the thickness of 100 to 500 ⁇ are formed with the thermal oxidation method in the different processes.
  • the oxide film may be formed simultaneously in the same process on the occasion of forming the first and second gate insulation films 24 a, 24 b in the same thickness.
  • the peripheral circuit portion is masked with a resist film 26 to control a threshold voltage and a first threshold value control layer 25 a is formed by ion implantation of phosphorus (P) or arsenic (As) with the dose of 1 ⁇ 10 11 to 1 ⁇ 10 14 cm ⁇ 2 as the n-type impurity into a region which will become a channel region just under a floating gate.
  • P phosphorus
  • As arsenic
  • the memory cell portion is masked with the resist film 27 to control the threshold voltage and a second threshold value control layer 25 b is formed (FIG. 5( b )) by implantation of phosphorus (P) or arsenic (As) in the dose of 1 ⁇ 10 11 to 1 ⁇ 10 14 cm ⁇ 2 as the n-type impurity into a region which will become a channel region just under the gate electrode.
  • P phosphorus
  • As arsenic
  • a first polysilicon film (first conductive material layer) 28 is formed on the entire surface in the thickness of 500 to 2000 ⁇ which will become a floating gate electrode of the MOS transistor of the memory cell portion and a gate electrode of the MOS transistor of the peripheral circuit portion (FIG. 5( c )).
  • the first polysilicon film 28 is patterned with the resist film 29 used as a mask to form a floating gate electrode 28 of the MOS transistor of the memory cell portion (FIG. 6( d )).
  • the patterning is conducted to set the width in the X direction to the final size, while the patterning is not conducted in the Y direction to keep as it is the covered region which will become the S/D region layer.
  • the floating gate electrode 28 a is covered by the thermal oxidation to form a capacitor insulation film 30 a consisting of SiO 2 film in the thickness of about 200 to 500 ⁇ .
  • a SiO 2 film 30 b is also formed on the first polysilicon film 28 of the peripheral circuit portion.
  • a film of the two to three layers including the SiO 2 -film/SiO 3 N 4 -film may be formed as a capacitor insulation film.
  • the floating gate 28 a and capacitor insulation film 30 a are covered to form a second polysilicon film (second conductive material film) 31 in the thickness of 500 to 2000 ⁇ which will become a control gate electrode (FIG. 6( e )).
  • the memory cell portion is masked with the resist film 32 and the second polysilicon film 31 and the SiO 2 film 30 b of the peripheral circuit portion are sequentially removed to expose the first polysilicon film 28 (FIG. 6( f )).
  • the patterning is conducted in the Y direction, using the resist film 32 as the mask, to the second polysilicon film 31 , SiO2 film 30 b and the first polysilicon film 28 a which is patterned only in the X direction of the memory cell portion to provide the final size of the first gate 33 a in order to form control electrode 31 a /capacitor insulation film 30 c /floating gate electrode 28 c in the width of about 1 ⁇ m in the Y direction.
  • the patterning is conducted, using the resist film 32 as the mask, to the first polysilicon film 28 of the peripheral circuit portion to provide the final size of the second gate 33 b in view of forming the gate electrode 28 b in the width of about 1 ⁇ m (FIG. 7( g ) and FIG. 8( b )).
  • the n-type S/D region layers 35 a , 35 b are formed by ion implantation of phosphorus (P) or arsenic (As) in the dose of 1 ⁇ 10 14 to 1 ⁇ 10 16 cm ⁇ 2 to the Si substrate 22 of the element forming region using the control gate electrode 31 /capacitor insulation film 30 a /floating gate electrode 28 a of the memory cell portion as the mask.
  • P phosphorus
  • As arsenic
  • the S/D region layers 36 a , 36 b are formed by ion implantation of phosphorus (P) or arsenic (As) in the dose of 1 ⁇ 10 14 to 1 ⁇ 10 16 cm ⁇ 2 to the Si substrate 22 of the element forming region using the gate electrode 28 b of the peripheral circuit portion as the mask (FIG. 7( h )).
  • the first gate 33 a of the memory cell portion and the second gate 33 b of the peripheral circuit portion are covered to form an interlayer insulation film 37 consisting of a PSG film in the thickness of about 5000 ⁇ .
  • contact holes 38 a , 38 b , 39 a , 39 b are formed to the interlayer insulation film 37 on the S/D region layers 35 a , 35 b , 36 a , 36 b and then the S/D electrodes 40 a , 40 b , 41 a , 41 b are also formed to complete a FLASH EPROM (FIG. 7( i )).
  • the capacitor insulation film 30 a is formed by covering the pattern of the first polysilicon film 28 a of the memory cell portion as shown in FIG. 6( e ). Thereafter, the second polysilicon film 31 is formed continuously to the memory cell portion and peripheral circuit portion and this second polysilicon film 31 is patterned in direct to form the first gate 33 a consisting of the first gate insulation film 24 a /floating gate lectrode 28 c /capacitor insulation film 30 c /control gate electrode 31 a as shown in FIG. 7( g ).
  • capacitor insulation film 30 c is always protected, after formation thereof, with the first and second polysilicon films 28 a , 31 (FIGS. 6 ( e ) and 6 ( f )), a high quality capacitor insulation film 30 c covering the floating gate electrode 28 c can be formed by preventing contamination by particles or the like.
  • the second insulation film 24 b of the peripheral circuit portion is always covered, after formation thereof, with the first polysilicon film 28 (FIG. 5( c ) to FIG. 6( f )), the thickness of the second gate insulation film 24 b is maintained since it is initially formed. Therefore, thickness of the second gate insulation film 24 can be easily controlled and concentration of the conductive impurity for control of the threshold voltage can also be adjusted easily.
  • the patterning is conducted in the predetermined width in the gate width direction and thereafter the patterning is also conducted in the gate length direction to obtain the final gate width.
  • FIGS. 9 ( a ) to 9 ( c ) are cross-sectional views for explaining a manufacturing method of FLASH EPROM of the FLOTO type or ETOX type as the second application example of the present invention.
  • the left side diagrams show the cross sectional views of the memory cell portions in the gate length direction (X direction) of the part where a MOS transistor having a floating gate electrode is formed.
  • the center diagrams show the cross sectional views of the memory cell portions of the same portion as the left side diagrams in the gate width direction (Y direction) in the right angle to the X direction and the right side diagrams show the cross sectional views of the MOS transistor of the peripheral circuit.
  • the second application example is different from the first application example in the point that after the process of FIG. 6( f ) in the first application example, a refractory metal film (fourth conductive material film) 42 consisting of a W film or a Ti film is formed, for example, in the thickness of about 2000 ⁇ as a polycide film, as shown in FIG. 9( a ), on the first polysilicon film 28 of the peripheral circuit and on the second polysilicon film 31 of the memory cell portion.
  • a FLASH EPROM is completed through the similar processes as FIGS. 7 ( g ) to 7 ( i ).
  • the patterning in the Y direction is conducted to obtain the final size of the first gate 44 a using the resist film 43 as the mask to the refractory metal film 42 , second polysilicon film 31 , SiO 2 film 30 b and the first polysilicon film 28 a which is patterned only in the X direction.
  • the control gate electrodes 42 a and 31 a , capacitor insulation film 30 c and floating gate electrode 28 c are formed in the width of about 1 ⁇ m in the Y direction of the memory cell portion and moreover the pattern is conducted to provide the final size of the second gate 44 b using the resist film 42 as the mask to the refractory metal film 42 and the first polysilicon film 28 .
  • the gate electrodes 42 b and 28 b are formed in the width of about 1 ⁇ m in the peripheral circuit (FIG. 9( b )).
  • the n-type S/D region layers 45 a , 45 b are formed by ion injection of phosphorus (P) or arsenic (As) in the dose of 1 ⁇ 10 14 to 1 ⁇ 10 16 cm ⁇ 2 on the Si substrate 22 of the element forming region with the control gate electrodes 42 a , 31 a /capacitor insulation film 30 a /floating gate electrode 28 a of the memory cell portion used as the mask and the S/D region layers 46 a , 46 b are also formed by ion injection of phosphorus (P) or arsenic (As) in the dose of 1 ⁇ 10 14 to 1 ⁇ 10 16 cm ⁇ 2 As the n-type impurity on the Si substrate 22 of the element forming region with the gate electrodes 42 b and 28 b of the peripheral circuit portion used as the mask.
  • the interlayer insulation film 47 consisting of the PSG film is formed in the thickness of about 5000 ⁇ by covering the first gate 44 a of the memory cell portion and the second gate 44 b of the peripheral circuit. Thereafter, the contact holes 48 a , 48 b , 49 a , 49 b are formed on the interlayer insulation film 47 on the S/D region layers 45 a , 45 b , 46 a , 46 b and the S/D electrodes 50 a , 50 b , 51 a , 51 b are then formed to complete the FLASH EPROM (FIG. 9( c )).
  • the reference numerals like those of the first application example designate the like elements.
  • an electrical resistance value can further be reduced by forming the refractory metal films (fourth conductve material films) 42 a , 42 b on the polysilicon film as the control gate electrodes 42 a , 31 a and gate electrodes 42 b , 28 b.
  • the refractory metal films 42 a , 42 b are used as the fourth conductive material film on the polysilicon film but a refractory metal film silicide such as titanium silicide(TiSi) may also be used.
  • FIGS. 10 ( a ) to 10 ( c ) are cross-sectional views for explaining a method of manufacturing a FLOTOX type or ETOX type FLASH EPROM as the third application example of the present invention.
  • the left side diagram is the cross-sectional view of the memory cell portion in the gate length direction (X direction) of the part where a MOS transistor having the floating gate electrode is formed.
  • the center diagram is the cross-sectional view of the memory cell portion of the same part as the left side diagram in the gate width direction (Y direction) in the right angle to the X direction.
  • the right side diagrams are cross-sectional views of the MOS transistor in the peripheral circuit portion.
  • the third application example is different from the first application example in the point that the second gate 33 c of the peripheral circuit portion (second element region) is also formed, like the first gate 33 a of the memory cell portion (first element region), in the construction of the first polysilicon film (first conductive material film) 28 b /SiO 2 film (capacitor insulation film) 30 d /second polysilicon film (second conductive material film) 31 b and the first and second polysilicon films 28 b and 31 b are placed in the short-circuit condition with the method shown in FIG. 10( b ) or FIG. 10( c ) to form the gate electrode.
  • the opening 52 a provided through the second polysilicon film 31 b , SiO 2 film 30 d as the upper layers and the first polysilicon film 28 b as the lower layer is formed to the area, for example, on the insulation film 54 which is different from the area where the second gate 33 c is formed as shown in FIG. 10( a ) and the first and second polysilicon films 28 b and 31 b are placed in the short-circuit condition by embedding, into the opening 52 a , the third conductive material film, for example, the refractory metal film 53 a such as W film or Ti film.
  • the third conductive material film for example, the refractory metal film 53 a such as W film or Ti film.
  • the opening 52 b is formed through the second polysilicon film 31 b and SiO 2 film 30 d as the upper layers to expose the first polysilicon film 28 b as the lower layer at the bottom part of the opening 52 b .
  • the first and second polysilicon films 28 b and 31 b are placed in the short-circuit condition by embedding, into the opening 52 b , the third conductive material film, for example, the refractory metal film 53 b such as W film or Ti film.
  • the peripheral circuit portion can be formed simultaneously with formation of the memory cell portion and thereby the manufacturing process can be simplified.
  • the conductive material film 53 a or 53 b of the third application example and the fourth conductive material film 42 of the second application example are formed individually, but these can also be formed simultaneously as the common refractory metal film.
  • a non-ionic interfacial active agent may be selected, for example, from a group of the polyoxyethylene-polyoxypropylene condensation product based, polyoxyalkylenealkylether based, polyoxyethylenealkylether based, polyoxyethylene derivative based, solbitane fatty acid ester based, glycerine fatty acid ester based, primary alcohol ethoxylate based and phenol ethoxylate based interfacial active agents but the compounds other than that listed above, if these are non-ionic interfacial active agents, may be used in the same manner and thereby similar basic effects can also be obtained.
  • the resist corresponding to the exposure with the excimer laser beam of the acryl based ArF having adamantly in the side chain is used but it may also be replaced with the resist corresponding to the exposure with the excimer laser beam of the acryl based ArF having the norbornane in the side chain and the resist corresponding to the exposure with the excimer laser beam of the COMA (cyclo-olefine maleic acid anhydride) based ArF may also be used.
  • the COMA cyclo-olefine maleic acid anhydride
  • the resist corresponding to the exposure with the excimer laser beam of the cyclo-olefine based (alicyclic group such as adamantly or norbornane based) ArF may also be used.
  • the resist in which a part of the main chain or side chain is formed as fluoride among these resins listed above may also be used.
  • the resist may more preferably be used for further microscopic process as the resist film corresponding to the F2 excimer laser beam.
  • a method of manufacturing a semiconductor device has been explained above, but the effect of the present invention can also be obtained by respectively applying the present invention to the devices including the microscopic patterns, for example, the functional components such as mask pattern, reticle pattern, magnetic head, LCD (Liquid Crystal Display), PDP (Plasma Display Panel), SAW (Surface Acoustic Wave) filter, optical components used for connection of optical wiring and microscopic components such as micro-actuator.
  • the manufacturing process of a flash memory has been explained above, but the similar effects can also be obtained by applying the present invention to the manufacturing process of logic devices and the manufacturing process of DRAM and FRAM or the like.
  • the present invention provides the effects that since a swelling pattern can easily be formed exceeding the limit of exposure using the deep ultraviolet ray such as the excimer laser beam (wavelength: 193 nm) of ArF (Argon Fluoride) which enables drawing of the more microscopic patterns, an extremely microscopic pattern can be drawn using the exposure beam in place of use of exposure by electron beam which provides a low throughput and thereby mass-productivity can be maintained for manufacture of devices.
  • the deep ultraviolet ray such as the excimer laser beam (wavelength: 193 nm) of ArF (Argon Fluoride) which enables drawing of the more microscopic patterns
  • ArF ArF (Argon Fluoride)

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US8334091B2 (en) 2012-12-18
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EP2397901A1 (en) 2011-12-21
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CN1802606A (zh) 2006-07-12
KR100914800B1 (ko) 2009-09-02

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