CN1263896A - Resin for chemical reinforced slushing compound - Google Patents
Resin for chemical reinforced slushing compound Download PDFInfo
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- CN1263896A CN1263896A CN 99122019 CN99122019A CN1263896A CN 1263896 A CN1263896 A CN 1263896A CN 99122019 CN99122019 CN 99122019 CN 99122019 A CN99122019 A CN 99122019A CN 1263896 A CN1263896 A CN 1263896A
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Abstract
The present invention relates to a resin for chemically amplified resist and resist compositions comprising the resin. It is an object of the present invention to provide new polymeric resins which can be applied to a chemically amplified resist that can form superior micro patterns on a wafer by sensitive response to deep ultraviolet light in a photolithography process, to increase the safety of the post exposure delay (PED), and to provide the relevant applicable resist compositions. The chemically amplified resist compositions that comprise alkali developable polymeric resin selected can form micro patterns having a superior degree of resolution on a wafer by responding to deep ultra-violet light in a photolithography process.
Description
The present invention relates to a kind of resist composition that can be used as the fluoropolymer resin of chemical reinforced slushing compound and contain this resin.In more detail, the present invention relates to a kind of new type resin that is used for the resist composition, and they can be enough to make them can form accurate pattern in photoetching process on film to far ultraviolet susceptibility, also relate to the resist composition that can be coated with accordingly.
In the making of semiconductor element, photoetching process is a kind of method for preparing circuit, and it is by a kind of resist of coating on matrix, transcribes in advance through the irradiation designed pattern, then according to the pattern etching matrix of being transcribed again.
Photoetching process comprises:
A) application step is distributed to the resist composition on the film matrix equably;
B) slight drying step is except that desolvating protective membrane to be adhered on the film from film by evaporation;
C) step of exposure is used for protective membrane is exposed under light source such as the UV-light, thereby the circuit pattern in the photomask is painted in the protective layer;
D) development step is by adopting photographic developer, selectively removing in film because exposure changes those parts of physicals (as solvability);
E) sclerosis baking procedure is after developing, and remaining photoresists film is solidificated on the matrix;
F) etching step makes the pattern that is imprinted on the matrix have predetermined electrical property; With
G) strip step is being removed unwanted film after etching step.
We know that the integrated horizontal of unicircuit will improve four times in general per 3 years, and for dynamic random memory (DRAM), 64 M DRAM are in the mass production stage, and the exploitation of 1C DRAM also begins.Traditional 16M DRAM employing has live width and is lower than 0.5 μ m technology, and 64M DRAM adopts live width to be lower than the technology of 0.3 μ M, and G DRAM then needs to develop the resist composition that some photoetching resolutions (resolution) are lower than 1/4th microns.
Traditional resist composition is not enough to satisfy above-mentioned needs, and this is because their these systems have very big absorption to the shortwave that is lower than 300nm, when they are exposed in the shortwave that is lower than 300nm, and the pattern contour havoc.Therefore, must work out the pattern that can reach a kind of immobilising sudden change profile.
In order to form above-mentioned pattern on matrix, the step calibration device that adopt stepping in a kind of minute and repetition stepped form is as exposure tool.This exposure tool can be classified by the light source that is adopted, for example G line of mercuryvapour lamp (wavelength is 436nm) or I line (wavelength is 365nm) and be used for the KrF (wavelength is 248nm) or the ArF (wavelength is 193nm) of excimer laser.In order to obtain accurate pattern on film, resolving power should be very little, and it is very favourable adopting the shortwave light beam according to mathematical expression 1.
[mathematical expression 1]
R＝κλ/NA
Wherein R is a theoretical resolution
κ is a constant,
λ by employing light wavelength (nm) and
NA is an aberration of lens.
In order to realize being lower than 1/4th microns high resolving power, should improve the resolving power of photoetching process.Thereby the light that adopts shorter wavelength is effective as light source and the aberration that increases the optical lens in the exposure tool.
Therefore, adopting KrF and ArF excimer laser to obtain high-resolution resist composition has been at commercially available product, and these resists mainly are chemical reinforced slushing compounds.
Chemistry enhanced resist can produce a kind of acid through the effect of extreme ultraviolet (UV) line, and the acid that is produced can make sour unsettled blocking group go protection and produce a kind of acid again.Owing to chemical enhanced notion has been introduced in the effect of this acid.
Chemistry enhanced resist can be divided into negative-type or positive type.
The negative-type resist is existing in document (Jour.Vacuum Science Technology.Vol.B6,1988) mentions that it comprises that a kind of adhesive resin of alkali soluble, a kind of linking agent, a kind of acid-producing agent and a kind of solvent are as main ingredient.In these resists, adopt rotary coating to form protective membrane, then slight dry this protective membrane is also transcribed by the exposure of light net, has only the part through exposure can produce acid usually.After exposure, when then heat-treating, will from acid-producing agent, produce a kind of acid, and this thus acid activation linking agent, the adhesive resin indissoluble that just becomes.After developing, just can form negative pattern.
In above-mentioned chemistry strengthens,, can realize high sensitivity owing to being by the acid that acid-producing agent produced as a part of catalyzer of a large amount of linking agents of activation.And, because degree of absorption is lower than traditional photoresists, can obtain high resolving power.In addition because phenolic resin can be used in the adhesive resin as traditional photoresists, it also have can tolerate after the advantage of dry etch step.The negative film chemical reinforced slushing compound is made up of three kinds of components: a kind of novolac resin, a kind of melamine crosslinkers resin and a kind of acid-producing agent.
But, form in the method for patterning at this chemical reinforced slushing compound by novolac resin, the problem that exists is at document (Jour.Vacuum Science Technologh.Vol.B7,1989) point out in, if exactly traditional G line or I linear light are replaced with excimer laser, because the sorption of adhesive resin and cross-linking agent resin, formed pattern becomes back taper.
Also existing people proposes another kind of idea (Proc.SPIE.Vol.1262, p32,1990) for positive type chemical reinforced slushing compound.This chemical reinforced slushing compound is a kind of by the polymerizable compound of acid activation, and as a kind of multicomponent composition, it comprises a kind of acid-producing agent and a kind of compound that can react with acid when rayed.This compound is easy to be decomposed by acid, and it mainly is the same low polymerizable compound with polyethylene-phenol derivatives of a kind of its short wavelength's absorption region.This transparent chemical reinforced slushing compound has high susceptibility (because the resist reaction is to carry out with chain reaction acid catalyst by a kind of) and good resolving power.
The salt of chemical reinforced slushing compound comprises poly-(hydroxy styrenes) and a kind of protected tert-butoxycarbonyl; people such as Ito are at document (American Chemial Society; " Polymers in Electronics ", ACS Sym.Series has made report in No.242).In addition, people such as Ueno have reported a kind of chemical reinforced slushing compound and a kind of acid-producing agent that contains poly-(to vinylbenzene oxygen base tetrahydroxy pyranyl) in document (36th JapaneseApplied Physics Society, Book Preview, lp-k-7,1989).In addition, contain dihydroxyphenyl propane and pyrogallol methylsulfonic acid fat and do not contain three component resists of novolac resin and tert-butoxycarbonyl, by people such as Schlegel at document (37
ThJapanese Applied Physics Society, Book Preview, 18p-ZF-4,1990) in made report.The technology that relates to this preparation method also is disclosed in the flat 2-27660 of Japanese Patent No., the flat 5-232706 of Japan bulletin patent No., the flat 5-249683 of Japan bulletin patent No., U.S.4,491,628, and U.S.5,310,629.
Though these chemical reinforced slushing compounds have good resolving power, also some problems may appear.Exist post-exposure to postpone (PED) if dry (post-exposure-bake) up to post-exposure behind the micro-pattern-forming that exposes, then produce line point phenomenon (footingphenomena) owing to reacting with matrix.
Therefore, will consider that when using above-mentioned protecting layer compositions post-exposure postpones the security of (PED), need a kind of resist composition that is applicable to polymerizable compound, said composition will have high sensitivity and have high resolving power to being lower than the 300nm wavelength.
An object of the present invention is to provide and can be applicable to the novel resin that a kind of chemistry strengthens positive resist composition, it can form superfine pattern by the sensitivity reaction to extreme ultraviolet light on film in photoetching process, and can improve the security that post-exposure postpones (PED), corresponding resist composition applicatory also is provided.
Other purpose of the present invention, advantage and a new feature part are listed in following specification sheets, and a part is very clearly by following detection to those skilled in the art, perhaps can obtain understanding by implementing the present invention.Objects and advantages of the present invention are achieved by concrete material and the composition that proposes in appending claims.
Now preferred implementation of the present invention is done detailed explanation.
Be applicable to that the novel polymeric resin that chemistry strengthens the positive resist can pass through the represented polymkeric substance of a kind of Chemical formula 1, the polymkeric substance that a kind of Chemical formula 2 is represented, the polymkeric substance that a kind of chemical formula 3 is represented and a kind of chemical formula 4 represented polymkeric substance and obtain:
[Chemical formula 1]
R
1Be chlorine, bromine, hydroxyl, cyano group, tert.-butoxy, CH
2NH
2, CONH
2, CH=NH, CH (OH) NH
2Or C (OH)=NH,
R
2For hydrogen or methyl and
The numerical value of x is 0.1-0.9;
[Chemical formula 2]
Wherein
R ＇
1With R ＇
2Be respectively hydrogen or methyl,
R ＇
3Be methyl, ethyl, normal-butyl, 4-hydroxybutyl or cyclohexyl,
R ＇
4Be chlorine, bromine, hydroxyl, cyano group, tert.-butoxy, CH
2NH
2, CONH
2, CH=NH, CH (OH) NH
2Or C (OH)=NH,
R ＇
5Be hydrogen or methyl,
The numerical value of x ＇ be 0.1-0.8 and
The numerical value of y ＇ is 0.1-0.8;
[chemical formula 3]
Wherein
R "
1Be chlorine, bromine, hydroxyl, cyano group, tert.-butoxy, CH
2NH
2, CONH
2, CH=NH, CH (OH) NH
2Or C (OH)=NH,
R "
2Be hydrogen or methyl,
X " numerical value be 0.1-0.9 and
N is 1 or 2;
[chemical formula 4]
Wherein
R
1With R
2Be respectively hydrogen or methyl
R
3Be methyl, ethyl, normal-butyl, 4-hydroxybutyl or cyclohexyl,
R
4Be chlorine, bromine, hydroxyl, cyanogen, tert.-butoxy, CH
2NH
2, CONH
2, CH=NH, CH (OH) NH
2Or C (OH)=NH,
R
5Be hydrogen or methyl,
The numerical value of x be 0.1-0.8 and
The numerical value of y is 0.1-0.8;
N is 1 or 2.
The weight-average molecular weight that above-mentioned polymkeric substance has (Mw) scope is 3000-30000, is 1.01-3.00 because of polymeric reaction condition changes molecular weight distribution (Mw/Mn) scope that obtains.
The monomer that is used for replacement of the present invention has enough restraining effect to the photographic developer of unexposed area; but in the exposure area; blocking group is then removed with catalysis process, and then, unprotected acidic moiety changes the solvability of resist polymer in the alkaline-based developer significantly.
With polymer application of the present invention during in photosensitive composition, said composition comprises
A) at least a or multiple Chemical formula 1, Chemical formula 2, chemical formula 3 and the chemical formula 4 represented resins of being selected from;
B) photosensitive acid propellant;
C) solvent; With
D) additive (amine, tensio-active agent, inhibitor or promotor).
The 0.1-50% that above-mentioned a) fluoropolymer resin accounts for photoresists composition weight is preferred.
Above-mentioned b) to account for the 0.1-50% of this resist weight also be preferred to acid-producing agent, and it is one or more compounds, is selected from sulfosalt, salt compounded of iodine, N-imino-sulfonate, two sulfones, diaryl sulphonyl diazomethane and aryl carbonyl arylsulfonyl diazomethane.
Above-mentioned sulfosalt comprises following example:
Above-mentioned salt compounded of iodine comprises following example:
Above-mentioned N-imino-sulfonate comprises following example:
Above-mentioned two sulfones comprise following example:
(wherein, each R be H ,-CH
3, or-C (CH
3)
3).
Above-mentioned diaryl sulphonyl diazomethane comprises following example:
(wherein, each R be H ,-CH
3, or-C (CH
3)
3).
Above-mentioned aryl carbonyl arylsulfonyl diazomethane comprises following example:
(wherein, each R be H ,-CH
3, or-C (CH
3)
3).
Above-mentioned c) to account for the 0.1-99% of resist composition weight be preferred to solvent, it is one or more compounds, is selected from ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, the ether acetic ester, the normal-butyl acetic ester, methyl iso-butyl ketone (MIBK), the lactic acid ethyl ester, 3-oxyethyl group-propionic acid ethyl ester, 3-methoxyl group-methylpropionate, TC, 2-heptanone, Pyranton, the 'beta '-methoxy methyl isobutyrate, propylene glycol monomethyl ether, the propylene glycol monomethyl propionic ester, the lactic acid methyl ester, the lactic acid butyl ester, Pyruvic Acid Ethyl ester (ethyl pirubate), and gamma-butyrolactone.
Photosensitive erosion resistant agent composite of the present invention also can comprise a kind of dissolution inhibitor, to improve the dissolubility resistent of unexposed area.Use dissolution inhibitor, the solvability of the solvability by enlarging unexposed area and exposure area differing between the two helps to improve contrast gradient.The consumption that is added to this dissolution inhibitor additive in the composition is the 0.1-50% of fluoropolymer resin weight.
Now to adopting resist composition of the present invention to describe with the method that obtains precise pattern.
Handle with alkaline aqueous solution after forming thin film on the egative film if contain the photosensitive erosion resistant agent composite of polymkeric substance of the present invention, then because the solvability of this polymkeric substance is low, this composition can not dissolve.But if this photosensitive erosion resistant agent composite is to adopt UV photo-irradiation treatment far away, then the acid-producing agent in the photosensitive erosion resistant agent composite can produce a kind of acid, and sour unsettled blocking group that can be in decomposing copolymer under the heating condition has acid to produce then again.Consequently, because the acid that is produced can cause the chain reaction of multiple decomposition,, it strengthens phenomenon so presenting chemistry.Thereby the solvability of polymkeric substance greatly improves in the exposure area, and in the developing process that adopts alkaline aqueous solution, exposure area and unexposed area solvability between the two shows very big difference.This performance has its significant advantage, and this is that it can reach the resolving power higher to the resist composition because with the positive resist of prior art G-line, I-line and the susceptibility of UV far away are compared.
Preferred implementation of the present invention describes by following example and Comparative Examples.
The present invention is elaborated with preferred implementation, but those skilled in the art can understand, and under the situation of design of the present invention that does not depart from claims to be proposed and scope, can be used for various modifications and replace.
Embodiment 1
Synthesizing of 4-cyano methyl vinylbenzene (CyMS):
In the 4 neck round-bottomed flasks of the 500ml that has mechanical stirrer, add 49.01g sodium cyanide, 70.07g water and 50.96g ethanol, mix, with mixture heating up, make it dissolving up hill and dale under 60 ℃ of temperature.
Add the 4-chloro vinyl toluene of 87.50g lentamente in this mixture, stir the mixture then, reaction mixture reflux 3 hours is cooled to then and is lower than 40 ℃, then removes by filter formed sodium-chlor in the reaction.
To in the refrigerative reaction product, add the 100g diethyl ether, separate the diethyl ether layer then.
The organic layer that this is separated extracts it for three times with 300g moisture.
Organic layer adopted anhydrous magnesium sulfate drying 1 day, then, adopted rotatory evaporator to remove organic solvent from the exsiccant organic layer.
Thick product is defined as 4-cyano methyl vinylbenzene, and yield is 80%.
Above-mentioned syntheticly carry out according to reaction formula 1.
[reaction formula 1]
Synthesizing of 4-(1-cyano ethyl) vinylbenzene (CyES):
In the 4 neck round-bottomed flasks of the 500ml that has mechanical stirrer, mix THF (tetrahydrofuran (THF)) and the 9.75g potassium hydride KH (be dispersed in the mineral oil, concentration is 35%) of 180ml, make it dissolving.
In this mixture, inject the resulting solution of THF that is dissolved in 50ml by the 4-cyano methyl vinylbenzene 12.17g of above-mentioned preparation lentamente, be lasted for 1 hour.Stir the mixture, reacted 1 hour.In mixture, add the 5.3ml methyl iodide then, stir the mixture, make it at room temperature to react 24 hours.
After reaction finishes, in reaction product, add the 100g diethyl ether, separate the diethyl ether layer then.The organic layer that this is separated extracts it for three times with 300g moisture.Water layer extracts with the 50g diethyl ether, and extract is mixed in the organic layer.
Organic layer adopted anhydrous magnesium sulfate drying 1 day, then, adopted rotatory evaporator to remove organic solvent from the exsiccant organic layer.
Product is defined as 4-(1-cyano ethyl) vinylbenzene, and yield is 80%.
Above-mentioned syntheticly carry out according to reaction formula 2.
[reaction formula 2]
Synthesizing of 4-2-(2-cyano group-4-tert-butoxycarbonyl) butylstyrene (CBCBS):
In the 4 neck round-bottomed flasks of the 500ml that has mechanical stirrer, mix above-mentioned 4-(1-cyano ethyl) vinylbenzene, the 1.4g triton b that is dissolved in 40 weight % water and the 40g diox of 62.89g, make it dissolving.
In this mixture, add 102.54g tertiary butyl acrylate lentamente, be lasted for 30 minutes, mixture stirs then, makes it to be 60 ℃ in temperature and reacts 24 hours down.
Reaction is used the aqueous hydrochloric acid neutralization reaction product after finishing, then to add the 100g diethyl ether in the neutral reaction product.Separate the diethyl ether layer, the organic layer of separating then extracts it for three times with 300g moisture.Water layer extracts with the 50g diethyl ether, and extract is mixed in the organic layer.
Organic layer adopted anhydrous magnesium sulfate drying 1 day, then, removed organic solvent from the exsiccant organic layer.
Then, adopt underpressure distillation to remove unreacted monomer from organic layer, product adopts methyl alcohol to carry out recrystallization.
Product is defined as CBCBS, and yield is 80%, is light yellow.
Above-mentioned syntheticly carry out according to reaction formula 3.
[reaction formula 3]
Poly-(HS-co-CBCBS's) is synthetic:
In having 4 neck round-bottomed flasks of reflux exchanger and temperature regulator, CBCBS that 4-acetoxystyrene, the 36.55g of adding 48.65g is above-mentioned and the AIBN of 0.98g stirred 30 minutes under room temperature in nitrogen atmosphere.Heated mixt makes it to reflux 24 hours.
After reaction finished, reaction mixture adopted 3 liter hexanes to make it precipitation to room temperature, then filter, and with the hexane wash several of 2 liters, vacuum-drying then.
Then in flask, the exsiccant polymkeric substance is dissolved in the methyl alcohol of 300ml.Adding 50ml concentration is 29% ammonium hydroxide aqueous solution in this polymers soln, stirs down at 50 ℃ and thoroughly dissolves until polymkeric substance.
Adopt this polymers soln of 1.51 water precipitations, obtain product.
Filter resulting precipitation, and wash for several times with 2 liter moisture, vacuum-drying is 2 days under 50 ℃ temperature.
Product is poly-(HS-co-CBCBS) fluoropolymer resin of 60.48g.
Above-mentioned syntheticly carry out according to reaction formula 4.
[reaction formula 4]
The chemical reinforced slushing compound composition:
The chemical reinforced slushing compound composition be by with fluoropolymer resin that can alkaline development promptly by the represented embodiment 1 of following Chemical formula 1 a poly-(HS-co-CBCBS) with by the represented acid-producing agent of chemical formula 5, chemical formula 6, chemical formula 7 or chemical formula 8, be dissolved among the propylene glycol methyl ether acetate (PGMEA) and preparation, as listed in the table 1.
[Chemical formula 1 a]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
Composition changes with the rotating speed of 2200rpm and is coated with, and 100 ℃ of slight down dry 90 seconds film forming on the silica gel sheet, the thickness of film is as shown in table 1.
In above-mentioned film, be provided with photomask, adopt 248nm light to shine, then film was toasted under 110 ℃ 90 seconds again, strengthen with activating chemical and go protection to use.
The tetramethyl ammonium hydroxide aqueous solution that adopts 2.38wt% with de-ionate washing, drying, just can obtain the pattern of precision with film development 60 seconds on film.
The relative sensitivity of precise pattern and resolving power, as shown in table 1.
Comparative Examples 1 and 2
Adopt the method steps identical with example 2-6; prepare poly-(hydroxy styrenes) of containing of other of useful tert-butoxycarbonyl protection resist composition as polymeric matrix; and make their precise pattern, like this so that they and resist of the present invention compare.
[chemical formula 9]
Wherein
A is the protection degree, and its scope is 0.1-0.9.
The relative sensitivity of precise pattern and resolving power, as shown in table 1.
[table 1]
(relative sensitivity wherein is optimum capacity (EOP)).
| Classification | The resist composition | Pattern performance | ||||
| Polymkeric substance (parts by weight) | Acid-producing agent (parts by weight) | Solvent (parts by weight) | Film thickness (μ m) | Relative sensitivity (mj/cm 2) | Resolving power (μ m) | |
| Example 2 | Chemical formula 1 a (100) | Chemical formula 5 (5) | ??PGMEA ??(550) | ??0.70 | ?28 | ??0.24 |
| Example 3 | Chemical formula 1 a (100) | Chemical formula 6 (5) | ??PGMEA ??(550) | ??0.72 | ?32 | ??0.22 |
| Example 4 | Chemical formula 1 a (100) | Chemical formula 7 (5) | ??PGMEA ??(550) | ??0.72 | ?24 | ??0.20 |
| Example 5 | Chemical formula 1 a (100) | Chemical formula 5 (3) chemical formulas 8 (2) | ??PGMEA ??(550) | ??0.70 | ?33 | ??0.20 |
| Example 6 | Chemical formula 1 a (100) | Chemical formula 6 (3) chemical formulas 8 (2) | ??PGMEA ??(550) | ??0.70 | ?38 | ??0.26 |
| Comparative Examples 1 | Chemical formula 9 (100) | Chemical formula 5 (5) | ??PGMEA ??(550) | ??0.74 | ?58 | ??0.48 |
| Comparative Examples 2 | Chemical formula 9 (100) | Chemical formula 6 (5) | ??PGMEA ??(550) | ??0.72 | ?52 | ??0.45 |
Embodiment's 7 poly-(HS-co-EEHS-co-CBCBS) is synthetic:
In the 4 neck round-bottomed flasks of the 500ml that has temperature regulator, add poly-(HS-co-CBCBS) and the THF of 200ml of 60g example 1, make it dissolving.
In this mixture, add 18g ethyl vinyl ether and 0.5g tosic acid mono-hydrate, stirred 24 hours down at 25 ℃.
After reaction finishes,, and in 41 water, obtain polymkeric substance through precipitation by the methyl alcohol diluted reaction mixture of interpolation 100ml.
Filter resulting product, and use 41 water washings, drying under reduced pressure under 50 ℃ temperature.
Product is poly-(HS-co-EEHS-co-CBCBS) fluoropolymer resin of 62g.
Above-mentioned syntheticly carry out according to reaction formula 5.
[reaction formula 5]
Example 8-12
The chemical reinforced slushing compound composition is by will be by the represented embodiment 7 of Chemical formula 2 a poly-(HS-co-EEHS-co-CBCBS) with by the represented acid-producing agent of chemical formula 5, chemical formula 6, chemical formula 7 or chemical formula 8, be dissolved among the propylene glycol methyl ether acetate (PGMEA) and preparation, they are all listed in the table 2.
[Chemical formula 2 a]
27 pages of original texts
Composition changes with the rotating speed of 2200rpm and is coated with, 100 ℃ down through slight dry 90 seconds film forming on the silica gel sheet, the thickness of film is as shown in table 2.
In above-mentioned film, be provided with photomask, adopt 248nm light to shine, then go to protect with the acid functional group of a kind of chemical enhanced form with resist, this is to carry out in 90 seconds by the post exposure bake under 110 ℃.
The tetramethyl ammonium hydroxide aqueous solution that adopts 2.38wt% with de-ionate washing, drying, just can obtain the pattern of precision with film development 60 seconds on film.
The relative sensitivity of precise pattern and resolving power, as shown in table 2.
[table 2]
(relative susceptibility wherein is optimum capacity (EOP)).
| Classification | The resist composition | Pattern performance | ||||
| Polymkeric substance (parts by weight) | Acid-producing agent (parts by weight) | Solvent (parts by weight) | Film thickness (μ m) | Relative sensitivity (mj/cm 2) | Resolving power (μ m) | |
| Example 8 | Chemical formula 2 a (100) | Chemical formula 5 (5) | ??PGMEA ??(550) | ?0.72 | ??24 | ??0.24 |
| Example 9 | Chemical formula 2 a (100) | Chemical formula 6 (5) | ??PGMEA ??(550) | ?0.72 | ??28 | ??0.22 |
| Example 10 | Chemical formula 2 a (100) | Chemical formula 7 (5) | ??PGMEA ??(550) | ?0.72 | ??24 | ??0.22 |
| Example 11 | Chemical formula 2 a (100) | Chemical formula 5 (3) chemical formulas 8 (2) | ??PGMEA ??(550) | ?0.72 | ??32 | ??0.20 |
| Example 12 | Chemical formula 2 a (100) | Chemical formula 6 (3) chemical formulas 8 (2) | ??PGMEA ??(550) | ?0.72 | ??34 | ??0.20 |
Embodiment 13
Synthesizing of 4-(3-cyano group-two-1,5-tert-butoxycarbonyl amyl group) vinylbenzene (COCPS):
In the 4 neck round-bottomed flasks of the 500ml that has mechanical stirrer, mix 4-cyano methyl vinylbenzene 62.89g among the above embodiment 1, be dissolved in 1.4g triton b and 40g diox in the 40 weight % water, make it dissolving.
In this mixture, add 102.54g tertiary butyl acrylate lentamente, be lasted for 30 minutes, then mixture is stirred, make it to be 60 ℃ and reacted 24 hours down in temperature.
Reaction is used the aqueous hydrochloric acid neutralization reaction product after finishing, then to add the 100g diethyl ether in the neutral reaction product.Separate the diethyl ether layer, the organic layer of separating then extracts it for three times with 300g moisture.
Organic layer adopts anhydrous magnesium sulfate drying, and under reduced pressure it is concentrated.Then, adopt the vacuum distilling method to remove unreacted matters from organic layer, product adopts methyl alcohol to carry out recrystallization.
Product is defined as CBCPS, and yield is 60%, is light yellow.
Above-mentioned syntheticly carry out according to reaction formula 6.
[reaction formula 6]
Poly-(HS-co-CBCPS's) is synthetic:
In having 4 neck round-bottomed flasks of reflux exchanger and temperature regulator, add 4-acetoxystyrene, the CBCPS of 51.35g and the AIBN of 1.25g of 48.65g, in nitrogen atmosphere, under room temperature, stirred 30 minutes.Heated mixt makes it to reflux 24 hours.
After reaction finished, reaction mixture adopted 3 liter hexanes to make it precipitation to room temperature, then filter, and with the hexane wash several of 2 liters, vacuum-drying then.
Then in flask, the exsiccant polymkeric substance is dissolved in the methyl alcohol of 300ml.Adding 50ml concentration is 29% ammonium hydroxide aqueous solution in this polymers soln, stirs down at 50 ℃ and thoroughly dissolves until polymkeric substance.
Adopt 1.5 these polymers solns of liter water precipitation, obtain product, filter, and wash for several times with 2 liter moisture.Vacuum-drying is 2 days under 50 ℃ temperature.
Product is poly-(HS-co-CBCPS) fluoropolymer resin of 70.23g.
Above-mentioned syntheticly carry out according to reaction formula 7.
[reaction formula 7]
Embodiment 14 to 18
The chemical reinforced slushing compound composition is by will be by the represented embodiment 13 of chemical formula 3a poly-(HS-co-CBCPS) with by the represented acid-producing agent of chemical formula 5, chemical formula 6, chemical formula 7 or chemical formula 8, be dissolved among the propylene glycol methyl ether acetate (PGMEA) and preparation, they all list in the table 3:
[chemical formula 3a]
Composition changes with the rotating speed of 2200rpm and is coated with, 100 ℃ down through slight dry 90 seconds film forming on the silica gel sheet, the thickness of film is as shown in table 3.
In above-mentioned film, be provided with photomask, adopt 248nm light to shine, then film was toasted under 110 ℃ 90 seconds again, strengthen with activating chemical and go provide protection.
The tetramethyl ammonium hydroxide aqueous solution that adopts 2.38wt% with de-ionate washing, drying, just can obtain the pattern of precision to film development 60 seconds on film.
The relative sensitivity of precise pattern and resolving power, as shown in table 3.
[table 3]
(relative sensitivity wherein is optimum capacity (EOP)).
| Classification | The resist composition | Pattern performance | ||||
| Polymkeric substance (parts by weight) | Acid-producing agent (parts by weight) | Solvent (parts by weight) | Film thickness (μ m) | Relative sensitivity (mj/cm 2) | Resolving power (μ m) | |
| Example 14 | Chemical formula 3a (100) | Chemical formula 5 (5) | ??PGMEA ??(550) | ??0.72 | ???25 | ?0.24 |
| Example 15 | Chemical formula 3a (100) | Chemical formula 6 (5) | ??PGMEA ??(550) | ??0.72 | ???30 | ?0.22 |
| Example 16 | Chemical formula 3a (100) | Chemical formula 7 (5) | ??PGMEA ??(550) | ??0.72 | ???22 | ?0.22 |
| Example 17 | Chemical formula 3a (100) | Chemical formula 5 (3) chemical formulas 8 (2) | ??PGMEA ??(550) | ??0.73 | ???31 | ?0.20 |
| Example 18 | Chemical formula 3a (100) | Chemical formula 6 (3) chemical formulas 8 (2) | ??PGMEA ??(550) | ??0.72 | ???35 | ?0.20 |
Embodiment 19
Poly-(HS-co-BEHS-co-CBCPS's) is synthetic:
In the 4 neck round-bottomed flasks of the 500ml that has temperature regulator, add poly-(HS-co-CBCBS) and the THF of 200ml of 60g example 13, make it dissolving.
In this mixture, add 24g butyl vinyl ether and 0.5g tosic acid mono-hydrate, stirred 24 hours down at 25 ℃.
After reaction finishes,, and in 4 liter water, obtain polymkeric substance through precipitation by the methyl alcohol diluted reaction mixture of interpolation 100ml.
Filter resulting product, and with 4 liter water washings, vacuum-drying under 50 ℃ temperature.
Product is poly-(HS-co-BEHS-co-CBCBS) fluoropolymer resin of 62g.
Above-mentioned syntheticly carry out according to reaction formula 8.
[reaction formula 8]
Embodiment 20-24
The chemical reinforced slushing compound composition is by will be by the represented embodiment 19 of chemical formula 4a poly-(HS-co-EEHS-co-CBCPS) with by the represented acid-producing agent of chemical formula 5, chemical formula 6, chemical formula 7 or chemical formula 8, be dissolved among the propylene glycol methyl ether acetate (PGMEA) and preparation, they are all listed in the table 4.
[chemical formula 4a]
Composition changes with the rotating speed of 2200rpm and is coated with, 100 ℃ down through slight dry 90 seconds film forming on the silica gel sheet, the thickness of film is as shown in table 4.
In above-mentioned film, be provided with photomask, adopt 248nm light to shine, then film was toasted under 110 ℃ 90 seconds again, strengthen with activating chemical and go provide protection.
The tetramethyl ammonium hydroxide aqueous solution that adopts 2.38wt% with de-ionate washing, drying, just can obtain the pattern of precision with film development 60 seconds on film.
The relative sensitivity of precise pattern and resolving power, as shown in table 4.
[table 4]
(relative sensitivity wherein is optimum capacity (EOP)).
| Classification | The resist composition | Pattern performance | ||||
| Polymkeric substance (parts by weight) | Acid-producing agent (parts by weight) | Solvent (parts by weight) | Film thickness (μ m) | Relative sensitivity (mj/cm 2) | Resolving power (μ m) | |
| Example 20 | Chemical formula 4a (100) | Chemical formula 5 (5) | ??PGMEA ??(550) | ?0.73 | ??23 | ?0.23 |
| Example 21 | Chemical formula 4a (100) | Chemical formula 6 (5) | ??PGMEA ??(550) | ?0.72 | ??28 | ?0.20 |
| Example 22 | Chemical formula 4a (100) | Chemical formula 7 (5) | ??PGMEA ??(550) | ?0.70 | ??20 | ?0.22 |
| Example 23 | Chemical formula 4a (100) | Chemical formula 5 (3) chemical formulas 8 (2) | ??PGMEA ??(550) | ?0.73 | ??29 | ?0.20 |
| Example 24 | Chemical formula 4a (100) | Chemical formula 6 (3) chemical formulas 8 (2) | ??PGMEA ??(550) | ?0.72 | ??33 | ?0.20 |
This chemical reinforced slushing compound composition, it comprises that the polymer resin of alkali-developable is selected from by the represented compound of Chemical formula 1, the represented compound of Chemical formula 2, the group that compound that chemical formula 3 is represented and chemical formula 4 represented compounds are formed, by far ultraviolet effect, it can form on film has more high-resolution precise pattern in photoetching process.
Claims (14)
1. one kind by the represented polymkeric substance of Chemical formula 1:
[Chemical formula 1]
Wherein
R
1Be chlorine, bromine, hydroxyl, cyano group, tert.-butoxy, CH
2NH
2, CONH
2, CH=NH, CH (OH) NH
2, or C (OH)=NH,
R
2For hydrogen or methyl and
The numerical value of x is 0.1-0.9.
2. the described polymkeric substance of claim 1, wherein the weight-average molecular weight of polymkeric substance (Mw) scope is 3000-30000, the molecular weight distribution of polymkeric substance (Mw/Mn) scope is 1.01-3.00.
3. one kind by the represented polymkeric substance of Chemical formula 2:
[Chemical formula 2]
Wherein
R ＇
1With R ＇
2Be respectively hydrogen or methyl,
R ＇
3Be methyl, ethyl, normal-butyl, 4-hydroxybutyl or cyclohexyl,
R ＇
4Be chlorine, bromine, hydroxyl, cyano group, tert.-butoxy, CH
2NH
2, CONH
2, CH=NH, CH (OH) NH
2, or C (OH)=NH,
R ＇
5Be hydrogen or methyl,
The numerical value of x ＇ be 0.1-0.8 and
The numerical value of y ＇ is 0.1-0.8.
4. the described polymkeric substance of claim 3, wherein the weight-average molecular weight of polymkeric substance (Mw) scope is 3000-30000, the molecular weight distribution of polymkeric substance (Mw/Mn) scope is 1.01-3.00.
5. one kind by chemical formula 3 represented polymkeric substance:
[chemical formula 3]
Wherein
R "
1Be chlorine, bromine, hydroxyl, cyano group, tert.-butoxy, CH
2NH
2, CONH
2, CH=NH, CH (OH) NH
2, or C (OH)=NH,
R "
2Be hydrogen or methyl,
X " numerical value be 0.1-0.9 and
N is 1 or 2.
6. the described polymkeric substance of claim 5, wherein the weight-average molecular weight of polymkeric substance (Mw) scope is 3000-30000, the molecular weight distribution of polymkeric substance (Mw/Mn) scope is 1.01-3.00.
7. one kind by the represented polymkeric substance of chemical formula 4:
[chemical formula 4]
Wherein
R
1With R
2Be respectively hydrogen or methyl,
R
3Be methyl, ethyl, normal-butyl, 4-hydroxyl fourth or cyclohexyl,
R
4Be chlorine, bromine, hydroxyl, cyano group, tert.-butoxy, CH
2NH
2, CONH
2, CH=NH, CH (OH) NH
2, or C (OH)=NH,
R
5Be hydrogen or methyl,
The numerical value of x is 0.1-0.8,
The numerical value of y is 0.1-0.8,
N is 1 or 2.
8. the described polymkeric substance of claim 7, wherein the weight-average molecular weight of polymkeric substance (Mw) scope is 3000-30000, the molecular weight distribution of fluoropolymer resin (Mw/Mn) scope is 1.01-3.00.
9. chemical reinforced slushing compound composition, it comprises:
A) at least a or multiple polymers is selected from the group of being made up of represented polymkeric substance of the represented polymkeric substance of the represented polymkeric substance of Chemical formula 1, Chemical formula 2, chemical formula 3 and chemical formula 4 represented polymkeric substance:
[Chemical formula 1]
Wherein
R
1Be chlorine, bromine, hydroxyl, cyano group, tert.-butoxy, CH
2NH
2, CONH
2, CH=NH, CH (OH) NH
2, or C (OH)=NH,
R
2For hydrogen or methyl and
The numerical value of x is 0.1-0.9;
[Chemical formula 2]
Wherein
R ＇
1And R '
2Be respectively hydrogen or methyl,
R ＇
3Be methyl, ethyl, normal-butyl, 4-hydroxybutyl or cyclohexyl,
R ＇
4Be chlorine, bromine, hydroxyl, cyano group, tert.-butoxy, CH
2NH
2, CONH
2, CH=NH, CH (OH) NH
2, or C (OH)=NH,
R ＇
5Be hydrogen or methyl,
The numerical value of x ＇ is 0.1-0.8,
The numerical value of y ＇ is 0.1-0.8;
[chemical formula 3]
Wherein
R "
1Be chlorine, bromine, hydroxyl, cyano group, tert.-butoxy, CH
2NH
2, CONH
2, CH=NH, CH (OH) NH
2, or C (OH)=NH,
R "
2Be hydrogen or methyl,
X " numerical value be 0.1-0.9,
N is 1 or 2; With
[chemical formula 4]
Wherein
R
1With R
2Be respectively hydrogen or methyl,
R
3Be methyl, ethyl, normal-butyl, 4-hydroxyl fourth or cyclohexyl,
R
4Be chloro, bromo, hydroxyl, cyano group, tert.-butoxy, CH
2NH
2, CONH
2, CH=NH, CH (OH) NH
2, or C (OH)=NH,
R
5Be hydrogen or methyl,
The numerical value of x is 0.1-0.8,
The numerical value of y is 0.1-0.8,
N is 1 or 2;
B) photosensitive acid propellant;
C) solvent; With
D) additive.
10. the described resist composition of claim 9, a) polymkeric substance wherein accounts for the 0.1-50% of resist weight.
11. the described resist composition of claim 9, b wherein) acid-producing agent accounts for the 0.1-50% of resist weight.
12. the described resist composition of claim 9, b wherein) the photosensitive acid propellant is one or more compounds, is selected from the group of being made up of sulfosalt, salt compounded of iodine, N-imino-sulfonate, two sulfones, diaryl sulphonyl diazomethane and aryl carbonyl arylsulfonyl diazomethane:
Sulfosalt wherein comprises:
With
Salt compounded of iodine comprises:
N-imino-sulfonate comprises:
Two sulfones comprise:
(wherein, each R be H ,-CH
3, or-C (CH
3)
3);
Diaryl sulphonyl diazomethane comprises:
(wherein, each R be H ,-CH
3, or-C (CH
3)
3); With
Aryl carbonyl arylsulfonyl diazomethane comprises:
(wherein, each R be H ,-CH
3, or-C (CH
3)
3).
13. the described resist composition of claim 9, c wherein) solvent accounts for the 0.1-99% of resist weight.
14. the described resist composition of claim 9, c wherein) solvent is one or more compounds, is selected from ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, ether acetic ester, normal-butyl acetic ester, methyl iso-butyl ketone (MIBK), lactic acid ethyl ester, 3-oxyethyl group-propionic acid ethyl ester, 3-methoxyl group-methylpropionate, TC, 2-heptanone, Pyranton, 'beta '-methoxy methyl isobutyrate, propylene glycol monomethyl ether, propylene glycol monomethyl propionic ester, lactic acid methyl ester, lactic acid butyl ester, Pyruvic Acid Ethyl ester and γ-Ding lactones.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990005544A KR100316974B1 (en) | 1999-02-19 | 1999-02-19 | Resin for chemically amplified resist |
| KR5543/1999 | 1999-02-19 | ||
| KR5542/1999 | 1999-02-19 | ||
| KR5541/1999 | 1999-02-19 | ||
| KR1019990005543A KR100316973B1 (en) | 1999-02-19 | 1999-02-19 | Resin for chemically amplified resist |
| KR1019990005542A KR100316972B1 (en) | 1999-02-19 | 1999-02-19 | Resin for chemically amplified resist |
| KR1019990005541A KR100316971B1 (en) | 1999-02-19 | 1999-02-19 | Resin for chemically amplified resist |
| KR5544/1999 | 1999-02-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1263896A true CN1263896A (en) | 2000-08-23 |
| CN1209388C CN1209388C (en) | 2005-07-06 |
Family
ID=27483341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99122019 Expired - Fee Related CN1209388C (en) | 1999-02-19 | 1999-09-22 | Resin for chemical reinforced slushing compound |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1209388C (en) |
| TW (1) | TW445396B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113809509A (en) * | 2020-06-11 | 2021-12-17 | 华为技术有限公司 | Antenna forming method, cover plate assembly and terminal equipment |
-
1999
- 1999-09-22 TW TW88116246A patent/TW445396B/en not_active IP Right Cessation
- 1999-09-22 CN CN 99122019 patent/CN1209388C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113809509A (en) * | 2020-06-11 | 2021-12-17 | 华为技术有限公司 | Antenna forming method, cover plate assembly and terminal equipment |
| CN113809509B (en) * | 2020-06-11 | 2023-07-18 | 华为技术有限公司 | Antenna forming method, cover plate assembly and terminal equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1209388C (en) | 2005-07-06 |
| TW445396B (en) | 2001-07-11 |
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