JPH11271976A - Pattern forming method of chemical amplification type resist - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a 'chemical amplification type resist pattern forming method' capable of forming rectangular resist patterns by suppressing the 'formation of a surface hardly solubilized layer occurring in acid transpiration on the resist surface' which occur when a chemical amplification type resist is used. SOLUTION: In the pattern forming method using the chemical amplification type resist pattern, a pre-exposure baking treatment is executed in such a manner that the residual solvent amt. in the resist film attains '<=1 vol.%' and a post-exposure baking treatment is executed at '<=10%' of the transpiration rate of the acid. As a result, the transpiration of the acid may be suppressed and the resist patterns are prevented from being formed to a T shape. The resist patterns having the excellent rectilinearity may be formed as the resist patterns 102 formed on a wafer 101 and the definition, depth of focus and dimensional accuracy are improved. An effect of enabling the high integration of the semiconductor devices is produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method of forming a resist pattern in a semiconductor integrated circuit manufacturing process, and more particularly to a method of forming a resist pattern using a chemically amplified resist.

[0002]

2. Description of the Related Art Conventionally, a method of forming a resist pattern has
A photoresist film formed on a semiconductor substrate is exposed through a reticle or mask on which a desired semiconductor integrated circuit pattern is drawn, baked after exposure, and then developed using a developer to form a photoresist pattern. Met. The mainstay of the conventional photoresist pattern forming technology is that g-line (436 nm) and i-line (365 nm)
m) and an exposure technique in which a novolak-based resist is combined with an exposure apparatus.

However, with the high integration of LSI devices, lithography using excimer laser light (248 nm, 193 nm), which is far ultraviolet light advantageous for further miniaturization, is required. When a resist was used, the light absorption was large, a good resist shape could not be obtained, and the sensitivity was greatly reduced. Therefore, a “chemically amplified resist that utilizes the acid-catalyzed reaction of an acid generated from a photoacid generator” has been proposed, and is mainly used as a resist for short-wavelength photolithography and a resist for electron beam lithography. Is coming.

A chemically amplified resist is composed of a polyhydroxystyrene resin in which at least a part of a hydroxyl group is substituted by a hydrophobic alkyl group (protecting group) and a photoacid generator (for example, see Japanese Patent Application Laid-Open No. HEI 9-163572). 4-44045, JP-A-5-80516
In the film using such a chemically amplified resist (chemically amplified resist film), when exposed to light, an acid is generated from a photoacid generator, and a deprotection group reaction occurs by an acid catalyst reaction. When the protecting group is removed from the polyhydroxystyrene resin, the resin becomes hydrophilic and becomes soluble in the developing solution.

[0005] As described above, the chemically amplified resist film is
Since acid catalytic reaction is used, the acid generated by exposure is lost by evaporation in the resist film surface area or neutralized by base in the air and deactivated, reducing the acid concentration in the resist film Or solubilization reaction (deprotection group reaction)
Does not proceed sufficiently, and a surface insoluble layer is formed, which causes a problem that the resolution, the depth of focus, and the dimensional accuracy are impaired.

The above problem will be further described with reference to FIG. FIG. 6 is a schematic cross-sectional view of a resist pattern using a conventional chemically amplified resist. In a resist film using a conventional chemically amplified resist, as described above, if the acid in the resist film disappears or is deactivated and the acid concentration decreases, the solubilization reaction (deprotection group reaction) sufficiently proceeds. Instead, a hardly-solubilized surface layer is formed, and as shown in FIG. 6, the resist pattern 602 on the wafer 601 obtained after the development has a “T-shaped shape”, and the resolution, depth of focus,
The dimensional accuracy will be impaired.

As a means for solving this problem, several methods have been proposed in the past, for example, a method is known in which the atmosphere during baking is replaced with an inert gas to prevent acid deactivation. (See JP-A-4-369211).

[0008]

However, in the conventional "method for preventing acid deactivation", even if acid deactivation itself during baking treatment can be suppressed, it is necessary to prevent acid evaporation. Can not. When the acid concentration in the resist surface region decreases due to the evaporation of the acid due to the post-exposure bake treatment, the “formation of the hardly-solubilized surface layer” cannot be prevented even by the above-described conventional method, and the resist pattern shape after developing However, they have a drawback that they tend to be “T-type” (see the resist pattern 102 in FIG. 6 described above).

In the formation of a fine pattern, the deterioration of the resist pattern shape, the resolution, the depth of focus, and the dimensional accuracy caused by the above-mentioned “formation of the surface insoluble layer” are as follows.
It is fatal, and in order to solve this problem, a pattern forming method that prevents the evaporation of acid is required.

The present invention has been made in view of the above-mentioned drawbacks and problems, and it is an object of the present invention to provide the above-mentioned "acid transpiration on the resist surface" which occurs when a chemically amplified resist is used. Of hardly-solubilized surface layer due to odor "
It is an object of the present invention to provide a method of forming a resist pattern capable of suppressing the formation of a T-shaped resist pattern after development. As a result, a rectangular resist pattern can be obtained, the resolution, the depth of focus, and the dimensional accuracy can be improved, and a method of forming a resist pattern that enables high integration of a semiconductor device can be provided. is there.

[0011]

As will be described in detail later, the present invention relates to a method for measuring the amount of residual solvent in a resist film before exposure and the amount of acid evaporation during baking after exposure to resist patterns to be formed. The baking treatment before exposure is performed so that the amount of the residual solvent in the resist film becomes 1 vol% or less. By reducing the amount of the remaining solvent to 1 vol% or less by the pre-bake treatment, it is characterized in that the post-exposure bake treatment can be performed with the amount of acid evaporated to 10% or less.

That is, the invention according to claim 1 of the present invention provides:
"In a pattern forming method using a chemically amplified resist containing at least a polyhydroxystyrene resin whose polarity is changed by an acid catalyst and a photoacid generator which generates an acid by exposure light, the amount of residual solvent in the resist film is 1 vol. %, Wherein a pre-exposure bake treatment is carried out so as to be at most 0.1%.
According to a second aspect of the present invention, there is provided a method for forming a pattern using a chemically amplified resist according to the first aspect, wherein the exposure is performed when the amount of acid evaporated is 10% or less. Perform post-bake processing. "

In the invention according to the first aspect, the "means for performing the pre-exposure bake treatment so that the amount of the residual solvent in the resist film becomes 1 vol% or less" is as follows. (Claim 3) ・ The baking time before exposure is lengthened (Claim 4).

Further, the present invention (the invention according to claims 1 to 4)
The "chemically-amplified resist" of the present invention is characterized by "containing a photoacid generator that generates aromatic sulfonic acid" (claim 5), and the solvent of the chemically-amplified resist is "ethyl lactate" Or "propylene glycol monomethyl ether acetate" (claims 6 and 7).

According to the method for forming a pattern of a chemically amplified resist according to the present invention, the amount of the solvent remaining in the resist film after the pre-exposure bake (pre-bake) treatment is set to “1 vol% or less”, whereby the post-exposure bake ( The amount of acid transpiration during PEB) treatment is "10% or less of the total amount of acid generated in the resist film"
Can be As a result, the decrease in the acid concentration in the resist surface region can be suppressed, and the T-shaped resist pattern can be prevented. As a result, a rectangular resist pattern can be obtained, and the resolution, depth of focus, The dimensional accuracy is improved, and the effect of enabling high integration of the semiconductor device is produced.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below. Prior to this, experiments conducted by the present inventors [the amount of residual solvent in a resist film before exposure, An experiment for confirming the fact that the amount of acid evaporation "affects the shape of a formed resist pattern"] will be described.

The present inventors first investigated the cause of the cross-sectional shape of the resist pattern to be formed into a “T-shape” (see the resist pattern 102 in FIG. 6 described above). A "two-component chemically amplified resist" comprising a hydroxystyrene resin having a t-butoxycarbonyl group (t-BOC group) and a photoacid generator that generates benzenesulfonic acid is used.・ Propylene glycol monomethyl ether acetate
The following experiments 1 to 5 were performed using (PGMEA) and ethyl lactate (EL).

In the following Experiments 1 to 5, the above-mentioned "two-component chemically amplified resist" was used as the resist, and the resist used was "propylene glycol monomethyl ether acetate (PGMEA)" as the solvent. Is abbreviated as “PGMEA resist”, and the resist using “ethyl lactate (EL)” is referred to as “EL resist”.
Abbreviated. The pre-exposure bake processing is referred to as “pre-bake processing”, and the post-exposure bake processing is referred to as “PEB processing”.

[Experiment 1] A PGMEA resist was spin-coated on a silicon substrate and prebaked at 90 ° C. for 90 seconds. The wafer was exposed to a test pattern using a KrF excimer laser stepper in an atmosphere free of basic impurities (in an atmosphere in which basic impurities were removed with a chemical filter), and subjected to PEB treatment at 100 ° C. for 90 seconds.
Thereafter, a developing process was performed. When the cross-sectional shape of the obtained pattern was confirmed by SEM, it was confirmed that the pattern had a “T-shaped shape” as shown in FIG. 6 described above.

In Experiment 1, since the experiment was performed in an atmosphere free of basic impurities, the cause of the T-shaped shape was not "deactivation of acid" due to basic impurities but "evaporation of acid". Conceivable.

[Experiment 2] Then, in order to obtain knowledge on the transpiration of acid, the case of using each of the PGMEA resist and the EL resist was examined under the “exposure conditions (exposure amount: 10 mJ / cm ² , 20 mJ / cm). ² , 50mJ / cm ² , 100mJ / cm ² ) ”for the pre-bake treatment conditions (treatment temperature: 110 ° C,
90 ° C, 70 ° C) and “with or without PEB treatment (treatment temperature: 100 ° C)”
m ³ ) ”” was measured. The measurement of the amount of acid in the resist film was performed by a colorimetric method using tetrabromophenol blue as an acid indicator.

The results obtained are shown in FIGS. In addition,
FIGS. 2 and 3 are graphs showing the results of Experiment 2, showing the relationship between the amount of exposure and the amount of acid in the resist film. FIG. 2 shows the case of the PGMEA resist. FIG. 3 shows the case of an EL resist.

FIGS. 2 and 3 showing the measurement results of Experiment 2 show that (a) the “acid amount” in the resist film is reduced by the PEB treatment (this is because the “acid transpiration” by the PEB treatment is reduced). (B) that the lower the pre-bake treatment temperature, the greater the amount of acid reduction in the resist film after PEB treatment (that is, the greater the evaporation of acid), and (c) In the case of using the PGMEA resist and the case of using the EL resist, the amount of reduction in the acid in the resist film after the PEB treatment is larger when PGMEA is used as a solvent than when EL is used as a solvent. (That is, the transpiration of the acid is large).

[Experiment 3] Next, PGMEA resist, E
In the case where each of the L resists was used, the relationship between the processing temperature of the pre-bake treatment and the amount of the solvent remaining in the resist film was examined. In addition, the measurement of the residual solvent amount is as follows.
The measurement was performed by gas chromatography-mass spectrometry (GC-MS method). FIG. 4 shows the obtained results. Note that FIG.
FIG. 4 is a graph of the results of FIG. 3, showing the relationship between the prebake temperature and the amount of residual solvent in the resist film.

FIG. 4 showing the measurement results of Experiment 3 shows that
(d) The higher the pre-baking temperature, the smaller the amount of residual solvent in the resist film after the pre-baking process. In other words, the lower the pre-baking temperature, the greater the amount of the residual solvent in the resist film after the pre-baking process. (E) It was found that the amount of residual solvent in the resist film after the pre-bake treatment was smaller when the EL solvent was used than when the PGMEA solvent was used.

[Experiment 4] Next, the relationship between the “residual solvent amount” in the resist film after the pre-bake treatment and the “acid transpiration amount” during the PEB treatment was examined. The result is shown in FIG. From FIG. 5, the “evaporation amount of acid” during the PEB treatment differs depending on the type of the solvent (PGMEA, EL), but is substantially proportional to the amount of the remaining solvent in the resist film after the pre-bake treatment. It was found that the smaller the “residual solvent amount”, the smaller the “acid transpiration amount”.

From the above Experiments 1 to 4, it was clarified that "the amount of the residual solvent in the resist film after the pre-bake treatment affects the acid transpiration during the PEB treatment". In particular, when the “plot of“ evaporation amount of acid ”versus“ remaining solvent amount ”in FIG. 5 showing the results of Experiment 4 is extended to the side with the smaller remaining solvent amount, the remaining solvent amount is“ 1 vol% or less ”. In Table 1, it was found that the amount of acid transpiration was “10% or less”.

[Experiment 5] Based on the knowledge obtained as described above, the relationship between the T-shape and the amount of residual solvent in the resist film after the pre-bake treatment was examined with an EL resist. As a result, the smaller the amount of the residual solvent, the closer the T-shaped shape becomes to a rectangular shape. In particular, when the amount of the residual solvent is “1 Vol% or less”, the completely rectangular shape as shown in FIG. It was found that a resist pattern was obtained.
In addition, it is recognized from FIG. 5 described above that the “acid transpiration amount” at the time of the PEB treatment is “10% or less” of the total acid amount generated by exposure, as described above.

The present invention has been made based on the above findings, and is based on a chemical amplification system containing a polyhydroxystyrene resin whose polarity is changed by an acid catalyst and a photoacid generator which generates an acid by exposure light. In the pattern forming method using the resist, the amount of the residual solvent in the resist film is 1 vol
%, And is characterized in that the PEB treatment can be performed when the amount of acid transpiration is 10% or less.

In the present invention, the method of “performing the pre-bake treatment so that the amount of the solvent remaining in the resist film is 1 vol% or less” includes: i) a method of increasing the pre-bake treatment temperature and performing a short pre-bake treatment; ii) Either of a method of lowering the pre-bake temperature and a method of performing the pre-bake processing for a longer time can be employed.

However, in the above method i), if the prebaking temperature is too high, the “polyhydroxystyrene resin whose polarity is changed (substituted by a protecting group) by an acid catalyst” used in the present invention is thermally decomposed. It is not preferable. Therefore, the upper limit of the prebake treatment temperature is a temperature at which this thermal decomposition does not occur, and varies depending on the type of the polyhydroxystyrene resin used, but is preferably lower than 140 ° C. In the method ii), the treatment time varies depending on the type of the solvent to be used and the like, but is preferably 90 to 180 seconds.

However, in the present invention, the processing temperature and the processing time are not limited to the above, and the processing temperature should be a temperature at which the thermal decomposition does not occur.
Any temperature can be used as long as the thermal decomposition does not occur, and the processing time is also arbitrary. In short, in the present invention, any processing temperature and processing time can be used except for the above-mentioned thermal decomposition temperature, as long as "the amount of the residual solvent can be reduced to 1 vol%".
The treatment time can be appropriately selected depending on the type of the polyhydroxystyrene resin, the type of the solvent, the content ratio of the resist, and the like.

The “polyhydroxystyrene resin whose polarity is changed by an acid catalyst” used in the present invention includes carbonyloxystyrene resin substituted with an alkoxy group, trimethylsilylated polyoxystyrene,
Examples thereof include phenol resins protected with an acetal group such as tetrahydropyranyl-substituted styrene and 1- (ethoxy) -ethoxystyrene.

The "photoacid generator which generates an acid by exposure light" used in the present invention includes onium salts such as benzenediazonium salt, diphenyliodonium salt and triphenylsulfonium salt, and trichloromethyltriazine and the like. Examples thereof include halogenated organic compounds and diazomethane-based photoacid generators such as bis- (benzenesulfonyl).

The "resist solvent" used in the present invention includes, in addition to the above-mentioned propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate (EL), methyl 3-methoxypropionate,
2-Heptanone, ethyl cellosolve acetate, diethylene glycol dimethyl ether and the like can be used.

In the present invention, "a chemically amplified resist"
In addition to the above-mentioned "polyhydroxystyrene resin whose polarity is changed by an acid catalyst" and "a photoacid generator which generates an acid by exposure light", it is insoluble in an alkaline solution before exposure, but is generated by exposure. A “third component” that is decomposed by an acid and promotes dissolution may be added. Examples of such a third component include colic acid and t-butyl ester.

[0037]

Next, the present invention will be described in detail with reference to examples of the present invention.

(Example 1) In this Example 1, a t-butoxycarbonyl group was used as a protecting group for a chemically amplified resist.
A two-component chemically amplified resist composed of a hydroxystyrene resin having a (t-BOC group) and a photoacid generator that generates benzenesulfonic acid was used. “Ethyl lactate (EL)” was used as a solvent for this resist.

The resist material was spin-coated on a silicon substrate, and prebaked at 130 ° C. for 90 seconds to reduce the amount of solvent remaining in the resist film to 1 vol%. Place this wafer under an atmosphere free of basic impurities (Note)
Then, the test pattern was exposed with a KrF excimer laser stepper, subjected to PEB treatment at 100 ° C. for 90 seconds, and then developed. (Since the residual solvent amount was reduced to “1 vol%” by the pre-bake treatment, the acid divergence amount in this case may be “10% or less of the total acid amount generated by exposure” from FIG. 5 described above. (Understand.) (Note): In an atmosphere in which basic impurities have been removed with a chemical filter

The resist pattern thus obtained will be described with reference to FIG. 1 (a schematic sectional view of a resist pattern obtained in the embodiment of the present invention). As shown in FIG. The resist pattern 102 formed on the wafer 101 by No. 1 was an excellent resist pattern having a completely rectangular shape.

(Comparative Example 1) For comparison, propylene glycol monomethyl ether acetate (P) was used instead of "ethyl lactate (EL)" as a solvent for the resist.
GMEA) ", and the same processing as in Example 1 was performed.

In Comparative Example 1, PGMEA was used as the solvent.
This is an example in which a pre-bake treatment was performed at 130 ° C. for 90 seconds, similarly to the first embodiment. In this case, the “amount of residual solvent in the resist film after the pre-bake treatment” is different from the case where the EL solvent of Example 1 is used, and is “about 1.7 vol%” as is apparent from FIG. This is an example outside the range of “the amount of the residual solvent in the resist film is 1 vol% or less”, which is limited in the present invention. The resist pattern obtained in Comparative Example 1 did not become a complete rectangular pattern as shown in FIG. This is considered to be because “about 1.7 vol%” of the solvent remained in the resist film.

(Example 2) "Propylene glycol monomethyl ether acetate (PGMEA)" was used instead of "ethyl lactate (EL)" as a solvent for the resist, and prebaking was performed at "130 ° C for 180 seconds". The same processing as in Example 1 was performed, except that the amount of the residual solvent in the resist film was reduced to 1 vol%. The obtained resist pattern was an excellent resist pattern having a completely rectangular shape as shown in FIG. 1, as in the case of Example 1.

Comparative Example 2 For comparison, a PGMEA solvent was used in the same manner as in Example 2 except that the pre-bake treatment was performed at 140 ° C. for 90 seconds. In Comparative Example 2, no pattern was formed. This is “140
This is considered to be due to thermal decomposition of the t-BOC group at "° C".

[0045]

As described in detail above, the method of forming a pattern of a chemically amplified resist according to the present invention is based on "performing a pre-exposure bake treatment so that the amount of residual solvent in the resist film is 1 vol% or less". , T unique to chemically amplified resist
Formation of a mold-shaped resist pattern can be prevented, and a rectangular resist pattern can be obtained. By obtaining such a rectangular resist pattern, resolution,
The depth of focus and dimensional accuracy are improved, and the effect of enabling high integration of semiconductor devices is produced.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a resist pattern obtained in an example of the present invention.

FIG. 2 is a diagram showing a relationship between “exposure amount” and “acid amount in a resist film” when “propylene glycol monomethyl ether acetate (PGMEA)” is used as a solvent.

FIG. 3 is a diagram showing a relationship between “exposure amount” and “acid amount in a resist film” when “ethyl lactate (EL)” is used as a solvent.

FIG. 4 is a diagram showing a relationship between a pre-bake temperature and a residual solvent amount in a resist film.

FIG. 5 is a diagram showing the relationship between the amount of residual solvent in a resist film and the amount of acid evaporation.

FIG. 6 is a schematic sectional view of a resist pattern when a conventional chemically amplified resist is used.

[Explanation of symbols]

 101,601 Wafer 102,602 Chemical amplification resist pattern

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 21/027 H01L 21/30 566 568

Claims (7)

[Claims] 1. A pattern forming method using a chemically amplified resist containing a polyhydroxystyrene resin whose polarity is changed by an acid catalyst and a photoacid generator which generates an acid by exposure light, the solvent remaining in the resist film 1vol%
A method for forming a pattern of a chemically amplified resist, comprising performing a pre-exposure bake treatment as described below. 2. A pattern forming method using a chemically amplified resist according to claim 1, wherein a bake treatment is performed after exposure when the amount of acid evaporated is 10% or less. . 3. The pattern forming method using a chemically amplified resist according to claim 1, wherein the amount of the solvent remaining in the resist film is 1 vol% by increasing the pre-exposure bake treatment temperature.
A method for forming a pattern of a chemically amplified resist characterized by the following. 4. A pattern forming method using a chemically amplified resist according to claim 1, wherein the amount of solvent remaining in the resist film is reduced to 1 vol% by extending the baking time before exposure.
A method for forming a pattern of a chemically amplified resist characterized by the following. 5. The method for forming a pattern of a chemically amplified resist according to claim 1, wherein said chemically amplified resist contains a photoacid generator for generating an aromatic sulfonic acid. . 6. The pattern forming method for a chemically amplified resist according to claim 1, wherein the solvent of the chemically amplified resist is ethyl lactate. 7. The method for forming a pattern of a chemically amplified resist according to claim 1, wherein the solvent of the chemically amplified resist is propylene glycol monomethyl ether acetate.