CN1145199C - Semiconductor device and method for manufacturing the same - Google Patents
Semiconductor device and method for manufacturing the same Download PDFInfo
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- CN1145199C CN1145199C CNB971234957A CN97123495A CN1145199C CN 1145199 C CN1145199 C CN 1145199C CN B971234957 A CNB971234957 A CN B971234957A CN 97123495 A CN97123495 A CN 97123495A CN 1145199 C CN1145199 C CN 1145199C
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000002253 acid Substances 0.000 claims abstract description 51
- 238000004132 cross linking Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims description 39
- -1 methoxyl group Chemical group 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 24
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 22
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 15
- 229920002120 photoresistant polymer Polymers 0.000 claims description 14
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 229930192627 Naphthoquinone Natural products 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 8
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 150000002791 naphthoquinones Chemical class 0.000 claims description 7
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 230000001235 sensitizing effect Effects 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
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- 238000005530 etching Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 2
- 239000002195 soluble material Substances 0.000 claims 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 150000003918 triazines Chemical class 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 29
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 15
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- 230000008569 process Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
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- 238000001259 photo etching Methods 0.000 description 5
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- UOALPZOXWBEIDZ-UHFFFAOYSA-N CON(C1=NC(=NC(=N1)N)N)CO.C(O)NC1=NC(=NC(=N1)N)N Chemical compound CON(C1=NC(=NC(=N1)N)N)CO.C(O)NC1=NC(=NC(=N1)N)N UOALPZOXWBEIDZ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- BSUNTQCMCCQSQH-UHFFFAOYSA-N triazine Chemical compound C1=CN=NN=C1.C1=CN=NN=C1 BSUNTQCMCCQSQH-UHFFFAOYSA-N 0.000 description 3
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical class C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 2
- KGWYICAEPBCRBL-UHFFFAOYSA-N 1h-indene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)C=CC2=C1 KGWYICAEPBCRBL-UHFFFAOYSA-N 0.000 description 2
- OJAWWBFNVXFHQF-UHFFFAOYSA-N CON(C(=O)N)CO.C(O)NC(=O)N Chemical compound CON(C(=O)N)CO.C(O)NC(=O)N OJAWWBFNVXFHQF-UHFFFAOYSA-N 0.000 description 2
- ZFSFDELZPURLKD-UHFFFAOYSA-N azanium;hydroxide;hydrate Chemical compound N.O.O ZFSFDELZPURLKD-UHFFFAOYSA-N 0.000 description 2
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- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
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- WQRHIUAMPXRIMI-UHFFFAOYSA-N 4-(trichloromethyl)triazine Chemical compound ClC(Cl)(Cl)C1=NN=NC=C1.ClC(Cl)(Cl)C1=NN=NC=C1 WQRHIUAMPXRIMI-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- APQXGPGESMCFQZ-UHFFFAOYSA-N C(C)(C)(C)OC(=O)O.C(CCC)OC(=O)O Chemical compound C(C)(C)(C)OC(=O)O.C(CCC)OC(=O)O APQXGPGESMCFQZ-UHFFFAOYSA-N 0.000 description 1
- XDWNVMSNWWDLOI-UHFFFAOYSA-N ClC=1C(=NN=NC1)C.N1=NN=CC=C1 Chemical class ClC=1C(=NN=NC1)C.N1=NN=CC=C1 XDWNVMSNWWDLOI-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- UYGWZYGMZJOWNU-UHFFFAOYSA-N OC1=CC=C(C=C)C=C1.C=C.OC1=CC=CC=C1 Chemical class OC1=CC=C(C=C)C=C1.C=C.OC1=CC=CC=C1 UYGWZYGMZJOWNU-UHFFFAOYSA-N 0.000 description 1
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- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- YRUMDWGUXBZEPE-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1.C1CCCCC1 YRUMDWGUXBZEPE-UHFFFAOYSA-N 0.000 description 1
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- JQOAQUXIUNVRQW-UHFFFAOYSA-N hexane Chemical compound CCCCCC.CCCCCC JQOAQUXIUNVRQW-UHFFFAOYSA-N 0.000 description 1
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- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
A first resist pattern capable of generating acid is formed on a semiconductor device layer, and a second resist layer capable of generating crosslinking reaction under the condition of acid existence is formed on the first resist pattern; after that a crosslinking film is formed at the junction part of the second resist layer and the first resist by the function of the acid from the first resist, and then the non-crosslinking part of the second resist is removed to form a resist pattern with fine intervals. The resist pattern with fine intervals is utilized as a mask to etch the semiconductor device layer so as to form micro-intervals or micropores.
Description
The present invention relates to utilize the resist figure of fine isolation to make the method for semiconductor device, and relate to the semiconductor device of making according to this method.The invention particularly relates to the method for the resist figure of making fine isolation, in semiconductor fabrication, form the resist figure that isolation size or opening size dwindle.
Along with the raising of semiconductor device integrated level, require link width and isolation width in the manufacturing process more and more tiny.Generally make the resist figure, and make the various types of bottom films of mask etching with the resist figure and generate Micropicture with photoetching technique.
With regard to this meaning, as the starting point of microfabrication, photoetching technique is extremely important.Photoetching technique comprises resist-coating, mask centering, exposure and development.Because the restriction of exposure wavelength, this technical limitations the miniaturization degree.
As mentioned above, when using conventional photoetching technique, very difficult formation surmounts the fine resist figure of wavelength restriction.
The invention provides the fine interval of a kind of usefulness resist figure and dwindle the method that technology is made semiconductor device, the semiconductor device of making according to the method also is provided.The present invention especially provides a kind of method that forms the resist figure that fine interval dwindles, and can form the figure that surmounts the wavelength restriction with this method.
According to an aspect of the present invention, in making the method for semiconductor device, formation can be on semiconductor device layer the acidic first resist figure.Forming second resist layer that cross-linking reaction takes place under the situation that has acid on first resist.Form cross linking membrane in second resist zone that contacts with first resist.Because the effect from the acid of first resist forms cross linking membrane.Second resist does not have crosslinked part to be removed, and forms the resist figure.Then, utilize the resist figure to make the mask etching semiconductor device layer.
According to another aspect of the present invention, in the method for making semiconductor device, the first resist figure and second resist layer are heated the formation cross linking membrane.
According to another aspect of the present invention, in making the method for semiconductor device, the first resist figure can be formed by acidic resist during by exposure.
According to another aspect of the present invention, in the method for making semiconductor device, have only the presumptive area of the first resist figure optionally to expose.
According to another aspect of the present invention, in the method for making semiconductor device, the first resist figure is made up of the resist that wherein contains acid.
According to another aspect of the present invention, in the method for making semiconductor device, the first resist figure is formed by having carried out the surface-treated resist with acid solution.
According to another aspect of the present invention, in the method for making semiconductor device, the first resist figure is made up of the mixture of phenolic resins (novolac-based resin) and naphthoquinones two nitrine (naphtho-quinone diazide) sensitising agent.
According to another aspect of the present invention, in the method for making semiconductor device, the first resist figure also comprises the chloromethylated triazine (chloro-methyl-triazine) as acid-producing agent.
According to another aspect of the present invention, in making the method for semiconductor device, the first resist figure is formed by polycarboxylated styrene (poly-hydroxy-styrene) derivative and salt (oniumsalt) mixture as Photoacid generator.
According to another aspect of the present invention, in the method for making semiconductor device, second resist layer is made up of the crosslinking agent that comprises resist, and this crosslinking agent can under the situation that has acid to exist cross-linking reaction take place.
According to another aspect of the present invention, in the method for making semiconductor device, second resist layer a kind of material in the group below being selected from is formed: polyvinyl acetal (polyvinylacetal), the mixture of polyvinyl acetal and methoxyl group methylolurea (methoxy-methylol-urea), the mixture of polyvinyl acetal and methoxyl group methylol melamine (methoxy-methylol-melamine), or the mixture of methoxyl group methylol melamine (methoxy-methylol-melamine) and polypropylene-base amine (polyallyl-amine).
According to another aspect of the present invention, in the method for making semiconductor device, the solvent that is used for second resist is selected from the mixture of pure water or pure water and alcohols.This solvent can dissolve raw polymer and cross-linking compounds, can not dissolve first resist, and has very high solubility parameter.The liquid developer that is used for second resist is selected from pure water or alkaline aqueous solution.
According to another aspect of the present invention, in making the method for semiconductor device, be used for the solvent of second resist and liquid developer and be selected from and dissolve raw polymer and crosslinkable, can not dissolve first resist, have organic solvent than low solubility parameter.
According to another aspect of the present invention, in the method for making semiconductor device, first resist is selected from the negative resist of being made up of the mixture of crosslinkable, acid-producing agent and raw polymer.
Can be easy to the many eye-catching advantage more intactly being familiar with and understanding preferably the present invention and have with reference to following detailed and accompanying drawing.
The mask graph that is used for the hole of Fig. 1 (a) expression fine interval formed according to the present invention resist figure;
The mask graph that is used for spacing of Fig. 1 (b) expression fine interval formed according to the present invention resist figure;
Fig. 2 (a)-2 (f) illustrates that first embodiment of the invention forms the technological process of the method for fine interval resist figure;
Fig. 3 (a)-3 (e) illustrates the technological process of the method that forms fine interval resist figure second embodiment of the invention;
Fig. 4 (a)-4 (g) illustrates that the 3rd execution mode according to the present invention forms the technological process of the method for fine interval resist figure;
First to the 3rd execution mode of the present invention is described with reference to the drawings, and reference number identical in whole accompanying drawings is represented same or corresponding part.
First execution mode
Fig. 1 (a) and Fig. 1 (b) expression are used to form the mask graph of the illustrated fine interval resist figure of the present invention.More particularly, Fig. 1 (a) is the mask graph 100 that is used for micropore, and Fig. 1 (b) is the mask graph 200 that is used for little spacing.Fig. 2 (a)-2 (f) is used for illustrating that first embodiment of the invention forms the process chart of the method for fine interval resist figure; With reference to figure 1 (a) and Fig. 1 (b), and Fig. 2 (a) is to Fig. 2 (f), described the method that the method that forms fine interval resist figure and first embodiment of the invention are made semiconductor device among the figure.
Beginning is shown in Fig. 2 (a), and coating is by therefrom acidic first photoresist 1 of radiation energy (for example, thick about 0.7 micron) on semiconductor chip 3.Preliminary drying first photoresist 1 (about 1 minute of 70-100 ℃ of following heat treatment) utilizes mask exposure by having the figure shown in Fig. 1 (a) or Fig. 1 (b) of the g line of mercury vapor lamp emission or i line (for example corresponding to about 200mJ/cm2 time for exposure) then.If desired, the heat treatment (for example 100-130 ℃ PEB temperature) of (PEB) is dried by the fire in the back of exposing to the photoresist of the light that exposed to the sun, so has improved the resolution of photoresist.Use Tetramethylammonium hydroxide TMAH (tetra-methyl-ammonium hydroxide) dilute aqueous solution of about 2 percent weight ratios to develop then.The figure of the resist 1 that Fig. 2 (b) expression forms.
If necessary, the back baking (for example back baking under about 110 ℃ temperature) of also can developing.The follow-up hybrid reaction of this heat treatment influence should be carried out under suitable temperature.Except using the acidic resist 1 of energy, above process is similar to the process that forms the resist figure according to known resist technology.
After having formed the figure shown in Fig. 2 (b), on semiconductor chip 3, form second resist 2 as Fig. 2 (c) shown in, it be included in crosslinkable under the situation that acid exists, can be dissolved in the interior crosslinkable of solvent that can not dissolve first resist 1.
Notice that the solvent that is used to dissolve second resist does not allow the figure of first resist to be dissolved in it, this point is very important.In order to form second resist, make water (pure water), or the mixture of water (pure water) and alcohols (for example isopropyl alcohol (isopropyl alcohol (IPA))).
For second resist, can use water miscible polyvinyl acetal.Also can use the mixture of polyvinyl acetal and methoxyl group methylolurea (methoxy-methylol-urea), the mixture of polyvinyl acetal and methoxyl group methylol melamine (methoxy-methylol-melamine), and the mixture of methoxyl group methylol melamine (methoxy-methylol-melamine) and polypropylene-base amine (polyallyl-amine).These mixtures are all by anticorrosive additive material and crosslinkable, or crosslinking agent is formed.
If necessary, also can in above composition, add acrylate copolymer, polyvinylpyrrolidone (polyvinyl-pyrrolidone), polyvinyl alcohol (polyvinylalcohol) etc. as raw polymer.
If necessary, can carry out preliminary drying (for example about 85 ℃) to second resist 2 of coating.The follow-up hybrid reaction of this heat treatment influence should be carried out under suitable temperature.
Next step is shown in Fig. 2 (d), exposes under the g of mercury vapor lamp line or i line (for example corresponding to about 200-1000mJ/cm2 time for exposure) in the whole surface of semiconductor chip 3, therefore makes first resist 1 produce acid.According to present embodiment, applied second resist 2 after, substrate 3 exposure makes to produce acid in first resist 1.
It should be noted, except whole semiconductor substrate 3 exposures, also can expose with the exposed mask selectivity.The part that exposed mask allow to need is selectivity exposure separately by this way, make second resist be divided into uncrosslinked zone and with the crosslinked zone of the first resist figure, 1 intersection.
Next step heat-treats (60-130 ℃) to semiconductor chip 3 shown in Fig. 2 (e), thereby sour various piece from first resist 1 is spread to second resist 2.This cause second resist 2 with the interface of first resist 1 on cross-linking reaction (for example baking temperature/time=60-130 ℃/90 seconds) takes place.By means of this, in second resist 2, form the cross-linked layer 4 that is covered with the first resist part 1 by cross-linking reaction.
Next shown in figure (f), develop, remove second resist 2 in uncrosslinked zone with liquid developer (for example water or TMAH solution).By above-mentioned processing, can obtain the diameter in hole or the resist figure that interval width all dwindles.More particularly, the width at interval is 0.4 μ m in the first resist figure, when the applied thickness of second resist is 400nm (4000 dust), and the thick 0.1 μ m of the cross-linked layer of formation (mixed layer).After having separated the uncrosslinked zone of second resist, the interval width of final resist figure is 0.3 μ m.
In the manufacture method shown in Fig. 2 (a)-Fig. 2 (f), described by exposure and produced acid from first resist 1.The present inventor finds, when polyvinyl acetal is used as second resist 2, need not expose in order to produce acid, under suitable temperature (for example baking temperature), figure be heat-treated (for example 150 ℃), be crosslinked with the interface of the first resist figure.In this case, preferably water (pure water) is made solvent.
Fig. 2 (a)-Fig. 2 (f) has illustrated the figure of the fine interval resist part that forms on semiconductor chip 3.What needn't illustrate is, according to the manufacture craft of semiconductor device, this figure can be done on such as the insulating barrier of silicon oxide film or do on the conductive layer such as polysilicon film.In brief, this figure can be done on the substrate of needed any other type.In order to obtain semiconductor device, as the various types of bottom films of mask etching, therefore in underlying membrane, form little spacing or micropore with the fine interval resist figure that forms.
Make the exposure of first resist 1 like this according to the present invention, by being covered with second resist 2 thereon, so can accurately control what of the acid that produces in first resist 1 by the control exposure.So just can accurately control the thickness of conversion zone 4.By regulating heating and crosslinking time (mixing stoving time), the thickness of cross-linked layer can be controlled at its desired value.
In addition, if come semiconductor chip is optionally exposed with suitable exposed mask, to be divided into exposed areas and unexposed area, just may with the exposure area of the second resist figure of the boundary member of the first resist figure in form crosslinked zone.Similarly, if come optionally semiconductor chip to be exposed,, just may form uncrosslinked zone then in non-exposed areas with suitable exposed mask.This allows to form on the same semiconductor chip micropore and little spacing of different size.
When realization was of the present invention, the solvent that is used for second resist 2 was a kind of solvent that can not dissolve first resist 1.This is beneficial to the diffusion of the acid that produces in afterwards the step.
In first execution mode of the present invention, the most handy phenolic resins (novolac-based resin) as acid-producing agent, forms positive corrosion-resisting agent from its mixture with naphthoquinones two nitrine (naphthoquinone diazide) sensitising agent as raw material.It is also noted that, naphthoquinones two nitrine (naphthoquinone diazide) sensitising agent usually the exposure situation under produce indene carboxylic acid (indene carboxylic acids), be used for producing the semiconductor devices.The object lesson of this sensitising agent comprises 1, and 2-naphthoquinones two nitrine-5-sulfonic acid (1,2-naphthoquinonediazido-5-sulfonicacid) and the carboxylate that constitutes of hydroxyl (hydroxy) compound.Also can use when exposure and can produce 1 of sulfonic acid, the carboxylate that 2-naphthoquinones two nitrine-4-sulfonic acid (1,2-naphthoquinonediazido-4-sulfonic acid) and hydroxyl (hydroxy) compound constitute.
The positive corrosion-resisting agent that the mixture that the most handy phenolic resins/naphthoquinones two nitrine (novolac/naphthoquinone diazide) that added triazine (triazine) acid-producing agent are sensitising agent is formed is as first resist.Triazine (triazine) is that the example of acid-producing agent comprises trichloromethyl triazine (trichloromethyl-triazine).
The most handy in addition other class positive corrosion-resisting agent is as first resist.This positive corrosion-resisting agent is by forming as polycarboxylated styrene ester (polyhydroxystyrene) derivative of raw material with as the mixture of the salt (onium salt) of Photoacid generator.The example of polycarboxylated styrene ester derivant comprises the carboxylate of polycarboxylated styrene ester and full butoxy carboxylic acid (tert-butoxycarboxylic acid).
The solvent of second resist that first embodiment of the invention is used is the mixed solvent of pure water or pure water and alcohols preferably.This solvent should be able to dissolve the mixture of raw polymer and crosslinkable, can not dissolve first resist, and has very high solubility parameter (SP).Under latter event, mixed solvent is no more than 10% alcohols when preferably comprising with water as solvent, isopropyl alcohol (isopropyl alcohol (IPA)) for example, ethanol (ethyl alcohol (EtOH)) etc.Because the solubility parameter (SP) of first resist is medium, therefore preferably use the high solvent of this solubility parameter (SP).Used alcohols preferably comprises isopropyl alcohol (isopropyl alcohol).
Again, as the solvent of second resist, the most handy mixture that can dissolve raw polymer and crosslinkable can not dissolve first resist, has the organic solvent than low solubility parameter (SP).As mentioned above, because the solubility parameter of first resist 1 is medium, use the organic solvent of low solubility parameter (SP) useful to this purpose.The best example of this organic solvent is chlorobenzene (chlorobenzene), benzene (benzene), n-hexane (n-hexane), cyclohexane (cyclohexane) etc.
As for second resist, preferably use the water-soluble polyvinyl acetal of energy.Polyvinyl acetal is a kind of because the anticorrosive additive material of the interaction energy generation cross-linking reaction of acid.Because nationality helps acid energy self-crosslinking, therefore needn't add any crosslinkable in polyvinyl acetal.Certainly, can in polyvinyl acetal, add methoxyl group methylolurea or methoxyl group methylol melamine as crosslinkable.Here polyvinyl acetal forms second resist, by the heat treatment of proper temperature, with the interface generation cross-linking reaction of the first resist figure.Therefore needn't expose in order to produce acid.In this case, as mentioned above, the solvent that is used for polyvinyl acetal can be water (pure water).
Second resist can be made up of the mixture of polyvinyl acetal and methoxyl group methylolurea or methoxyl group methylol melamine.In addition, second resist also can be made up of the mixture of methoxyl group methylol melamine and polypropylene-base amine.This mixture comprises anticorrosive additive material and crosslinking agent.
In a word, the crosslinking agent that can comprise in second resist comprises urea or melamine derivative, for example methoxyl group methylolurea or methoxyl group methylol melamine.
Can find out obviously that from the above description second resist that cross-linking reaction can take place comprises anticorrosive additive material as cross-linkable mixtures or material itself when having acid to exist.Second resist that cross-linking reaction can take place when having acid to exist also comprises as the compound of anticorrosive additive material and as the mixture of the crosslinkable of crosslinkable agent.
If necessary, can add the polyacrylic acid based polymer, polyvinylpyrrolidone, polyvinyl alcohol etc. are as raw polymer.
More than having described first resist is the formation of the resist figure of positivity.In the first embodiment, not only to be confined to be positive corrosion-resisting agent to first resist.Within the scope of the invention, also can use negative resist.Negative resist used in practice of the present invention can be made up of the mixture that for example following composition constitutes: comprise the melamine derivative such as methoxyl group methylolurea or methoxyl group methylol melamine, the crosslinkable that organic halogen is acid-producing agent, and such as the raw polymer of polycarboxylated styrene, phenolic resins etc.
Second execution mode
Following Fig. 3 (a)-3 (e) illustrates the method that forms fine interval resist figure second embodiment of the invention.With reference to figure 1 (a), 1 (b), and Fig. 3 (a)-3 (e) set forth the method for the fine interval of the formation resist figure of describing according to second execution mode, and make the method for semiconductor device with this resist figure.
Shown in Fig. 3 (a), first photoresist 11 that comprises a small amount of acid material covers on the semiconductor chip 3.Preliminary drying first photoresist 1 (is 70-100 ℃ of following heat treatment in temperature), g line or the i line with mercury vapor lamp exposes to it by the mask with figure shown in Fig. 1 (a) or 1 (b) then.The first resist figure 11 that forms after the step of Fig. 3 (b) expression through Fig. 3 (a).
If necessary, the heat treatment (temperature is 100-130 ℃) of the back baking of exposing to improve the resolution of photoresist, is developed with the dilute aqueous solution that contains about 2% TMAH then.
Then, can develop if necessary back baking.This heat treatment is influential to follow-up hybrid reaction, should carry out under suitable temperature.Except using the resist that contains acid in practice of the present invention, these steps are identical with known resist figure forming process.
After having formed the figure shown in Fig. 3 (b), on semiconductor chip (disk) 3, form second resist 12 shown in Fig. 3 (c), include crosslinkable crosslinkable under the sour situation about existing in second resist, and can be dissolved in the solvent that can not dissolve first resist 11.
The solvent that is used to dissolve second resist can not dissolve the first resist figure, and this point is very important.The solvent that for example is used for second resist is the mixture of water (pure water) or water (pure water) and alcohols, for example isopropyl alcohol (isopropyl alcohol).
Identical with first execution mode, with water-soluble polyvinyl acetal as second resist 12 in the present embodiment.In addition, the mixture of polyvinyl acetal and methoxyl group methylolurea or methoxyl group methylol melamine, and the mixture of methoxyl group methylol melamine and polypropylene-base amine can be as second resist.These mixtures are by anticorrosive additive material and crosslinkable, or crosslinking agent is formed.Crosslinking agent in second resist comprises melamine derivative usually, for example the methoxyl group methylol melamine.
If necessary, can add the polyacrylic acid based polymer as first execution mode, polyvinylpyrrolidone, polyvinyl alcohol is as raw material.
If necessary, after forming second resist 12, this resist can be by preliminary drying.The follow-up hybrid reaction of this heat treatment influence should be carried out under suitable temperature.
Then shown in Fig. 3 (d), semiconductor chip 3 is heat-treated (temperature is 60-130 ℃), make a small amount of acidic materials diffusion that is included in first resist 11.This makes near second resist 12 the interface of the first resist part 11 that cross-linking reaction take place.Thus, in being covered with second resist 12 of first resist 11, form cross-linked layer 14.
Then, shown in Fig. 3 (e), use liquid developer, for example water or TMAH solution develop, and remove the uncrosslinked part of second resist 12.Like this, may obtain the resist figure that bore dia or interval width dwindle.
Find out clearly that from top description second embodiment of the invention, be used to form second resist 12 owing to can not dissolve the solvent of first resist 11, therefore the acid that produces by follow-up heat treatment is easy to be diffused in second resist and goes.
First resist 11 in second execution mode needn't expose to produce acid, still contains acid in resist film 11.Resist film 11 is heat-treated generation acid, and the acid diffusion produces crosslinked.The preferably low-molecular-weight carboxylic acid of the acid that contains in first resist (carboxylicacids).
Should be noted that first anticorrosive additive material and second anticorrosive additive material used in first execution mode also can be used for second execution mode.
By forming such fine interval resist figure as mask on various types of semiconductor chips, this method of making little spacing or micropore on semiconductor chip in the first embodiment is feasible.
The 3rd execution mode
Fig. 4 (a)-4 (g) is the flow chart that the 3rd execution mode according to the present invention forms the method for fine resist figure.With reference to figure 1 (a), 1 (b), and Fig. 4 (a)-4 (g), description forms the method for fine interval resist figure according to the 3rd execution mode and makes the method for semiconductor device with this resist figure.
As forming the first photoetching resist 21 on Fig. 4 (a) institute semiconductor chip that is shown in 3.After to its preliminary drying (about 1 minute of 70-100 ℃ of following heat treatment), apparatus exposes photoresist 21 just like the mask of figure shown in Fig. 1 (a) or 1 (b) under the g of mercury vapor lamp line or i line.If necessary, to the expose heat treatment of back baking (100-130 ℃) of this photoresist 21, to improve its resolution, the dilute aqueous solution with the Tetramethylammonium hydroxide (TMAH) that contains about 2wt% develops then.The final graphics 21 of Fig. 4 (b) expression first resist.
Then, can develop if necessary back baking.This heat treatment is influential to follow-up hybrid reaction, should carry out under suitable temperature.These steps are identical with the manufacturing process that forms technology according to known resist.
After having formed the figure shown in Fig. 4 (b), with semiconductor chip (disk) 3 usefulness acid solutions dipping, shown in Fig. 4 (c).This dipping can be finished by common stirring developing method.Also can spray acid solution.Both can use organic acid also can use inorganic acid as acid solution.The acetic acid of handy low concentration.In this step, acid is absorbed by the surface of the first resist figure 21, forms the thin layer that contains acid.Then shown in Fig. 4 (d), should the surface with pure water rinsing.
Coating second resist 22 on the first resist figure 21 then, shown in Fig. 4 (e), including in second resist under the situation that acid exists can be crosslinked, can be dissolved in the crosslinkable in the solvent that can not dissolve first resist 21.
The solvent that is used to dissolve second resist can not dissolve the first resist figure, and this point is very important.For example solvent comprises the mixed solution of the alcohols of water (pure water) or water (pure water) and for example isopropyl alcohol.
Identical with aforementioned embodiments, use polyvinyl acetal as second resist.Polyvinyl acetal is the anticorrosive additive material by the interaction energy generation cross-linking reaction of acid.In addition, the mixture of polyvinyl acetal and methoxyl group methylolurea or methoxyl group methylol melamine, and the mixture of methoxyl group methylol melamine and polypropylene-base amine can be formed second resist.These mixtures are made up of anticorrosive additive material and cross-linked material.
Crosslinking agent in second resist can be melamine derivative, for example methoxyl group methylol melamine usually.
If necessary, can add the polyacrylic acid based polymer, polyvinylpyrrolidone and polyvinyl alcohol are as raw polymer.
If necessary, after having applied second resist 22, this resist can be by preliminary drying.Follow-up hybrid reaction or the cross-linking reaction of this heat treatment influence should be carried out under suitable temperature.
Then as Fig. 4 (f) shown in, semiconductor chip 3 is toasted (temperature is 60-130 ℃), make under situation about having, near the interface of 21 of second resist 22 and resists, cross-linking reaction takes place from the acid existence of resist 21.The result forms cross-linked layer 4 in second resist 22 of each part that is covered with resist 21.
Then, shown in Fig. 4 (g), develop, remove the uncrosslinked part of second resist 22 with the liquid developer of water for example or TMAH solution.The resist figure that finally obtains has bore dia or the interval width that dwindles.
According to the 3rd execution mode of the present invention, all be unnecessary by exposure acidic any step in first resist.In the present embodiment, before forming second resist film, first resist is carried out surface treatment with acid solution.Heat-treat then, make the acid diffusion, thereby in second resist, produce crosslinked.
In the 3rd execution mode, first photoresist 21 can be the positive corrosion-resisting agent that for example the used mixture by phenolic resins/naphthoquinones two nitrine system or para hydroxybenzene ethene (para-hydroxy-styrene) derivative and Photoacid generator (for example salt (onium Salts)) is formed in first execution mode.
Used first resist and other material of second resist also can be used for the 3rd execution mode in first execution mode.
By forming such fine interval resist figure as mask on various types of semiconductor chips, this method of making little spacing or micropore on semiconductor chip in the first embodiment is feasible.
Above detailed description according to the method that the invention provides the fine interval of the formation resist figure that is used for making Micropicture, make can make to surmount the Micropicture that wavelength limits, for example little spacing or micropore figure.The result can form the figure of diameter less than the hole of the resist of common process, or interval width is less than the figure of the spacing of the resist of common process.
As mask, can on semiconductor chip, form the spacing or the hole at little interval with the fine interval resist figure of such formation.When using said method in addition, can obtain hole and spacing fine isolated semiconductor device mutually.
According to the telling about clearly as can be seen of above technology, the present invention may have a large amount of other improvement and variations.Therefore can put into practice the present invention by the mode beyond specifically describing at this, this also within the scope of the appended claims, this should be understood.
Claims (13)
1. method of making semiconductor device may further comprise the steps:
The acidic first resist figure when on semiconductor device layer, being formed on exposure;
Second resist layer of cross-linking reaction takes place under the situation that is formed on the acid existence on described first resist, and described second resist is made of water-soluble material;
By residuing in the effect of patterned surface acid partly after forming from the first resist figure, partly form cross linking membrane at described second resist that contacts with described first resist;
Remove the uncrosslinked part of described second resist, form the resist figure;
Utilize described resist figure to make the described semiconductor device of mask etching.
2. according to the method for the manufacturing semiconductor device of claim 1, the figure of wherein said first resist and described second resist layer are heated to form described cross linking membrane.
3. according to the method for the manufacturing semiconductor device of claim 1, wherein the figure to described first resist carries out the selectivity exposure.
4. according to the method for the manufacturing semiconductor device of claim 1, the figure of wherein said first resist is formed by the resist that wherein contains acid.
5. according to the method for the manufacturing semiconductor device of claim 1, wherein the described figure of first resist forms by having carried out the surface-treated resist with acid solution.
6. according to the method for the manufacturing semiconductor device of claim 1, the figure of wherein said first resist is that the mixture of sensitising agent is formed by comprising phenolic resins and naphthoquinones two nitrine.
7. according to the method for the manufacturing semiconductor device of claim 6, the figure of wherein said first resist also comprises the chloromethylated triazine as acid-producing agent.
8. according to the method for the manufacturing semiconductor device of claim 1, the described figure of wherein said first resist is further formed by comprising as the polycarboxylated styrene derivative of Photoacid generator and the mixture of salt.
9. according to the method for the manufacturing semiconductor device of claim 1, wherein said second resist layer is formed by being included in the resist that the crosslinking agent of cross-linking reaction takes place under the situation about being existed by acid.
10. according to the method for the manufacturing semiconductor device of claim 1, wherein said second resist layer is by being selected from the group that material beneath is formed: polyvinyl acetal, the mixture of polyvinyl acetal and methoxyl group methylolurea, the mixture of polyvinyl acetal and methoxyl group methylol melamine, or the mixture of methoxyl group methylol melamine and polypropylene-base amine.
11. method according to the manufacturing semiconductor device of claim 1, the solvent that wherein is used for described second resist is selected from the mixture of pure water or pure water and alcohols, this solvent can dissolve raw polymer and crosslinkable, can not dissolve described first resist, have high solubility parameter, the liquid developer that is used for described second resist is selected from pure water or alkaline aqueous solution.
12., wherein be used for the solvent of described second resist and liquid developer and be selected from and dissolve raw polymer and crosslinkable, can not dissolve described first resist, have organic solvent than low solubility parameter according to the method for the manufacturing semiconductor device of claim 1.
13. according to the method for the manufacturing semiconductor device of claim 1, wherein said first resist is selected from the negative resist of being made up of crosslinkable, acid-producing agent and raw polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB971234957A CN1145199C (en) | 1997-12-31 | 1997-12-31 | Semiconductor device and method for manufacturing the same |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB971234957A CN1145199C (en) | 1997-12-31 | 1997-12-31 | Semiconductor device and method for manufacturing the same |
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| CN1221971A CN1221971A (en) | 1999-07-07 |
| CN1145199C true CN1145199C (en) | 2004-04-07 |
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| CNB971234957A Expired - Lifetime CN1145199C (en) | 1997-12-31 | 1997-12-31 | Semiconductor device and method for manufacturing the same |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3850772B2 (en) * | 2002-08-21 | 2006-11-29 | 富士通株式会社 | Resist pattern thickening material, resist pattern manufacturing method, and semiconductor device manufacturing method |
| US7160665B2 (en) * | 2002-12-30 | 2007-01-09 | International Business Machines Corporation | Method for employing vertical acid transport for lithographic imaging applications |
| JP2005003840A (en) * | 2003-06-11 | 2005-01-06 | Clariant Internatl Ltd | Material and method for forming fine pattern |
| WO2005008340A1 (en) * | 2003-07-17 | 2005-01-27 | Az Electronic Materials (Japan) K.K. | Material for forming fine pattern and method for forming fine pattern using the same |
| CN100356513C (en) * | 2003-11-19 | 2007-12-19 | 旺宏电子股份有限公司 | Semi conductor element having reduced spacing and its forming method |
| US7226873B2 (en) * | 2004-11-22 | 2007-06-05 | Taiwan Semiconductor Manufacturing Co., Ltd. | Method of improving via filling uniformity in isolated and dense via-pattern regions |
| CN102023476B (en) * | 2009-09-15 | 2013-06-12 | 中芯国际集成电路制造(上海)有限公司 | Semiconductor photoetching process method for forming micro-sized structure |
| CN113314400A (en) | 2020-02-27 | 2021-08-27 | 长鑫存储技术有限公司 | Semiconductor device and method for manufacturing the same |
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