JP5394016B2 - Resist pattern forming method - Google Patents

Description

  The present invention relates to a method for forming a fine resist pattern using a charged particle beam. Specifically, the present invention relates to charge-up using a charged particle beam by forming a conductive material made of an acidic group-substituted conductive polymer on a resist surface. The present invention relates to a method for forming a fine resist pattern by preventing the influence from the environment.

  A pattern forming technique using charged particle beams such as an electron beam and an ion beam is expected as a next generation technique of optical lithography.

  In pattern formation using charged particle beams, improving the sensitivity of the resist is the most useful method for improving the productivity of semiconductors. Acid is generated at the exposed or irradiated portions, followed by post-exposure baking. A chemical amplification type resist that improves the sensitivity by performing a heat treatment called (PEB) treatment to promote a crosslinking reaction or a decomposition reaction has become mainstream.

  However, a chemically amplified resist that expresses a resist function by generating a catalytic amount of acid has a demerit that it is difficult to handle because it is easily affected by the use environment. For example, in a semiconductor factory, an aqueous solution of 2.38% (mass%, the same applies hereinafter) tetramethylammonium hydroxide (TMAH) is used in the development process, and the clean room is made basic by the amine component that volatilizes from this solution. In the environment. Therefore, a phenomenon in which the catalyst amount of acid generated in the exposed portion of the substrate stored while waiting for the next step after exposure is neutralized by the amine component, and cannot be developed into a desired pattern (post-exposure delay: PED). ) Has occurred.

  On the other hand, in the pattern formation method using charged particle beams such as electron beams and ion beams, the substrate is charged particularly when the substrate is insulative, and the trajectory of the charged particle beam incident by the electric field generated by the charged charge. It is known that a technique of coating the surface of a substrate with a conductive polymer is effective in preventing the phenomenon of bending of the substrate (for example, see Patent Document 1).

  Under such circumstances, a conductive composition having a water-soluble conductive polymer as a conductive component (for example, Patent Document 2) has already been proposed. In this conductive composition, since the conductive component is water-soluble, environmental safety is greatly improved by using water as a solvent. However, depending on the substrate, there is a problem that coatability is not sufficient.

  Furthermore, a composition comprising a water-soluble conductive polymer as a conductive component and a water-soluble polymer having a nitrogen-containing functional group and a hydrophobic end has been proposed (see, for example, Patent Document 3). This composition has the property that it can be applied directly onto a resist by using a water-soluble polymer having a nitrogen-containing functional group and a hydrophobic end instead of a surfactant, and does not corrode a chemically amplified resist. However, when applied to chemically amplified resists with higher sensitivity in recent years, the film thickness becomes thinner compared to the pattern of the resist alone when exposure, PEB treatment and development are carried out with the conductor formed on the resist. Or the subject that the shape of a pattern changes remains.

  In order to solve these problems, it has been proposed to perform PEB treatment and development by peeling the conductor after exposure while the conductor is formed on the conductive resist (for example, Patent Document 4). In this method, the pattern shape change due to PEB treatment can be suppressed, but when the holding time (PCD) after forming the conductor on the chemically amplified resist is long, ion components such as basic compounds in the conductive film are chemically There has been a problem that the pattern shape is changed by moving to an amplification type resist.

Japanese Patent Laid-Open No. 4-032848 JP-A-8-041320 JP 2002-226721 A JP 2003-307856 A

  An object of the present invention is to develop a method for forming a fine and accurate resist pattern without being affected by PED, PCD or the like in forming a resist pattern using a charged particle beam.

   The present invention relates to a conductive material comprising a water-soluble conductive polymer (A) having a sulfonic acid group or a carboxyl group on a resist applied to a substrate and a basic compound (B) having a dissociation constant pKa at 25 ° C. of 10 or less. A conductive composition coating process for coating the composition to form a conductor, a heating process for heating the conductor at 70 to 140 ° C., and then forming a resist pattern with charged particle beams on the substrate on which the conductor is formed This is a resist pattern forming method including a charged particle beam irradiation step.

  According to the present invention, charge-up due to charged particle beams is further prevented, and a fine and accurate desired resist pattern can be formed. Furthermore, a change in the resist shape due to the basic compound remaining in the conductor can be suppressed.

(Conductive polymer (A))
The conductive polymer (A) in the present invention is a conductive polymer having a sulfonic acid group, a carboxylic acid group or both groups, and many known polymers can be used (for example, JP-A-61-197633). No. 1, JP-A-1-301714, JP-A-5-226238, JP-A-07-41756, etc.). Specifically, a π-conjugated polymer containing a phenylene vinylene, carbazole, vinylene, thienylene, pyrrolylene, phenylene, iminophenylene, isothianaphthene, furylene, carbazolylene monomer as a repeating unit, A water-soluble conductive polymer having a sulfonic acid group and / or a carboxylic acid group, or an alkyl group substituted with a sulfonic acid group and / or a carboxylic acid group or an alkyl group containing an ether bond on a nitrogen atom . Of these, soluble conductive polymers containing thienylene, pyrrolylene, iminophenylene and isothianaphthene monomers are particularly excellent. The conductive polymer (A) is preferably water-soluble because it can be applied to and removed from the substrate with an aqueous solvent.

  As a preferable conductive polymer (A), the conductive polymer which has at least 1 sort (s) of the repeating unit represented by following formula (1)-(3) is mentioned.

In formula (1), R ^{1 to} R ² are each independently H, —SO ₃ ^— , —SO ₃ H, —R ¹¹ SO ₃ ^— , —R ¹¹ SO ₃ H, —OCH ₃ , —CH _{3. ^{, -C 2 H 5, -F,}} -Cl, -Br, -I, -N (R 12) 2, -NHCOR 12, -OH, -O -, -SR 12, -OR 12, -OCOR 12, _{^{-NO 2, -COOH, -R 11 COOH}} , -COOR 12, -COR 12, a -CHO or ^{-CN, R 11} is an alkylene group having 1 to 24 carbon atoms, or an arylene group having 1 to 24 carbon atoms an aralkylene group having 1 to 24 carbon ^{atoms, R 12} is an alkyl group having 1 to 24 carbon atoms, an aralkyl group an aryl group or a 1 to 24 carbon atoms having 1 to 24 carbon ^atoms, the R 1, ^{R 2} out at least one _{of, ^-SO} 3 _-, ^-SO 3 H -R ¹¹ SO ₃ ^-, a ^-R 11 _SO 3 H, -COOH or ^-R 11 COOH.

In formula (2), R ^{3 to} R ⁶ are each independently H, —SO ₃ ^— , —SO ₃ H, —R ¹¹ SO ₃ ^— , —R ¹¹ SO ₃ H, —OCH ₃ , —CH _{3. ^{, -C 2 H 5, -F,}} -Cl, -Br, -I, -N (R 12) 2, -NHCOR 12, -OH, -O -, -SR 12, -OR 12, -OCOR 12, _{^{-NO 2, -COOH, -R 11 COOH}} , -COOR 12, -COR 12, a -CHO or ^{-CN, R 11} is an alkylene group having 1 to 24 carbon atoms, or an arylene group having 1 to 24 carbon atoms an aralkylene group having 1 to 24 carbon ^{atoms, R 12} is an alkyl group having 1 to 24 carbon atoms, an aralkyl group an aryl group or a 1 to 24 carbon atoms having 1 to 24 carbon ^atoms, the R 3 to R ⁶ out at least one _{of, ^-SO} 3 _-, ^-SO 3 H -R ¹¹ SO ₃ ^-, a ^-R 11 _SO 3 H, -COOH or ^-R 11 COOH.

In Formula (3), R ^{7 to} R ¹⁰ are each independently H, a linear or branched alkoxy group having 1 to 24 carbon atoms, or a sulfonic acid group, and at least one of R ^{7 to} R ¹⁰ is A sulfonic acid group.

As for the ratio of the repeating unit represented by Formula (1)-(3), 20-100 mol% is preferable among all the repeating units (100 mol%) which comprise a conductive polymer (A).
The conductive polymer (A) preferably has 10 or more repeating units represented by the formulas (1) to (3) in one molecule.

5000-1 million are preferable and, as for the mass average molecular weight of a conductive polymer (A), 5000-20000 are more preferable. When the mass average molecular weight of the conductive polymer (A) is 5000 or more, the conductivity, film formability and film strength are excellent. When the mass average molecular weight of the conductive polymer (A) is 1000000 or less, the solubility in a solvent is excellent.
The mass average molecular weight of the conductive polymer (A) is a mass average molecular weight (in terms of polyethylene glycol) measured by GPC.

(Basic compound (B))
The basic compound (B) is used to form a salt with the acidic group of the conductive polymer (A) to increase the solubility. Those having a dissociation constant pKa at 25 ° C. of 10 or less are used because they are easily volatilized. The pKa is preferably 4 or more. The dissociation constant is a numerical value described in “Chemical Handbook Basic Edition II” (The Chemical Society of Japan, published by Maruzen, 41.925, Showa).

  Specific examples of the basic compound include amines having a pka of 10 or less: 2-aminoethanol (pKa = 9.5), diethanolamine (pKa = 9.0), triethanolamine (pKa = 7.7), Trimethylamine (pKa = 9.8), α-picoline (pKa = 6.2), β-picoline (pKa = 5.5), γ-picoline (pKa = 6.0), piperidine, pyridine (pKa = 5.2) , Benzylamine (pKa = 9.4), methoxyethylamine, aminopyridine, ethylenediamine and the like. These amines may be mixed in two or more.

(solvent)
The conductive composition used in the present invention includes a conductive polymer (A), a basic compound (B), and a solvent for dissolving them.

Examples of the solvent include water; a mixed solvent of water and an organic solvent soluble in water.
Specifically, water or alcohols such as methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol, ketones such as acetone and ethyl isobutyl ketone, ethylene glycols such as ethylene glycol and ethylene glycol methyl ether, propylene glycol, Examples include propylene glycols such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether and propylene glycol propyl ether, amides such as dimethylformamide and dimethylacetamide, and pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone. It is done. Of these, water or a mixed solvent is preferable, and water or a mixed solvent of water and alcohols is particularly preferably used, and further preferably contains 50% by mass or more of water.

  0.5-10 mass parts is preferable with respect to 100 mass parts of solvent, and, as for the usage-amount of the conductive polymer (A) of this invention, More preferably, it is 0.5-5 mass parts. Use of 0.5 parts by mass or more provides conductivity necessary for preventing charge-up, and use of 10 parts by mass or more increases the film thickness of the conductor after coating, resulting in deterioration of the pattern shape. .

  0.01-5 mass parts is preferable with respect to 100 mass parts of solvent, and, as for the usage-amount of the basic component (B) of this invention, 0.01-2 mass parts is still more preferable. Here, when the amount of the component (B) used is 0.01 parts by mass or less, the pH of the conductive composition is lowered, which may adversely affect the application to the resist surface and deteriorate the pattern shape. On the other hand, when the amount is 10 parts by mass or more, the pH of the conductive composition becomes high, and when applied to the resist surface, it may move to the resist surface and adversely affect the pattern shape.

The pH of the conductive composition at 25 ° C. is preferably in the range of 2-6.
When the pH is lower than 2, in the positive chemically amplified resist, the film thickness of the resist film dissolved by acid becomes remarkable, and in the negative chemically amplified resist, the T-top phenomenon occurs in which the resist film becomes insoluble by acid. When it is larger than 6, the resist pattern is greatly deteriorated due to the influence of the base component in the composition.

  Known additives can be mixed in the conductive composition. Any additive can be used as long as it improves the coating property to the resist, film-forming properties, and film-forming properties. Nonionic surfactants, anionic surfactants, cationic surfactants, water-soluble polymers Amino acids are used.

The resist pattern forming method of the present invention is formed from seven steps: a resist coating step on a substrate, a resist drying step, a conductive composition coating step, a heating step, a charged particle beam irradiation step, a PEB step, and a development step.
The role of the conductor in the present invention is to prevent resist performance change caused by a basic substance from the environment and to prevent charge-up by a charged particle beam.

(Resist application process to the substrate)
As a resist coating method, a known method such as a spin coating method, a spray coating method, a dip coating method, a roll coating method, a gravure coating method, a reverse coating method, a roll brush method, an air knife coating method, or a curtain coating method is appropriately used. It is done.
(Resist drying process)
The drying temperature of the resist varies depending on the solvent used for the resist, but is usually from room temperature to 300 ° C. or less.

The drying time of the resist is set depending on the resist coating film thickness, the substrate thickness, the type of dryer, and the like, but is usually about several seconds to 1 hour.
(Conductive composition coating process)
The conductive composition application step is a step of forming a conductor by applying a conductive composition containing a water-soluble conductive polymer and a basic compound to a resist on a substrate. The coating method can be performed by a known method similar to the resist coating method, such as spin coating method, spray coating method, dip coating method, roll coating method, gravure coating method, reverse coating method, roll brush method, air knife coating method. And curtain coat method.
(Heating process)
The heating step is a step of removing the basic compound (B) in the conductor formed in the above step by volatilizing it from the conductor. The heating temperature is preferably in the range of 70 to 140 ° C, more preferably in the range of 100 to 140 ° C.
When the heating temperature is less than 70 ° C., the basic compound (B) in the conductor cannot be sufficiently removed from the conductor and the pattern shape of the resist may change. When heated at a temperature higher than 140 ° C., the conductive composition There is a risk that components in the product may be decomposed.

After the heating step, the substrate is irradiated with a charged particle beam such as an electron beam from the conductor side (charged particle beam irradiation step). After the irradiation, heat treatment is appropriately performed (post-exposure baking, PEB process), the substrate is immersed in an alkaline developer, and the exposed portion is dissolved and removed in the developer (development process). Any known alkaline developer may be used. Then, after development, the substrate is appropriately rinsed with pure water or the like. In this way, a resist pattern is formed on the substrate.
Usually, a substrate on which a resist pattern is formed is appropriately heat-treated (post-baked) to strengthen the resist, and a portion without the resist is selectively etched. After etching, the resist is usually removed using a release agent.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Conductive polymer (A))
Conductive polymer (A-1): Pyridinium of poly (2-sulfo-5-methoxy-1,4-iminophenylene) produced by the method described in “Production of conductive polymer (A-1)” in Production Example 1. Salt ).
Conductive polymer (A-2): Poly (2-sulfo-5-methoxy-1,4-iminophenylene) triethyl produced by the method described in “Production of conductive polymer (A-2)” in Production Example 1 Ammonium salt).

The conductive polymer (A-3): TA Chemical Co., Esupeisa 100 (sulfonic acid group-containing soluble polythiophene derivative), the structural units has the formula ^{(1) (R 1 = H} , R 2 = CH 2 SO 3 -) be , The proportion of all repeating units (100 mol%) is 100 mol%.

Basic compound (B-2): Triethylamine, a Kanto chemical special grade reagent, was used. (Pka = 10.9)

(Additive (C))
Additive (C-1): As a water-soluble polymer, dodecyl-terminated poly (N-vinylpyrrolidone) produced in Production Example 2 described later was used.

[Production Example 1]
Production of conductive polymer (A-1):
100 mmol of 2-aminoanisole-4-sulfonic acid was dissolved in 4 mol / L pyridine aqueous solution at 25 ° C., and 100 mmol of ammonium peroxodisulfate was added dropwise to the solution while stirring the solution. After completion of dropping, the mixture was further stirred at 25 ° C. for 12 hours. The reaction product is filtered off, washed and dried to obtain 10g of powder port Li (2-sulfo-5-methoxy-1,4-pyridinium salt of iminophenylene). The content of pyridine was 4 parts by mass in 100 parts by mass of the polymer powder.

Production of conductive polymer (A-2):
100 mmol of 2-aminoanisole-4-sulfonic acid was dissolved in 4 mol / L triethylamine aqueous solution at 25 ° C., and 100 mmol of ammonium peroxodisulfate was added dropwise to the solution while stirring the solution. After completion of dropping, the mixture was further stirred at 25 ° C. for 12 hours. Filtered reaction product was washed and dried to obtain 12g of powder port Li (2-sulfo-5-methoxy-1,4-triethylammonium salt of iminophenylene). The content of triethylamine was 5 parts by mass in 100 parts by mass of the polymer powder.

[Production Example 2]
Preparation of additive (C-1) 55 g of N-vinylpyrrolidone, 3 g of azobisisobutyronitrile as a polymerization initiator, and 1 g of n-dodecyl mercaptan as a chain transfer agent were stirred and dissolved in isopropyl alcohol as a solvent. The solution was slowly dropped into isopropyl alcohol heated to 80 ° C. while maintaining the temperature at 80 ° C. to perform drop polymerization. After completion of the dropwise addition, the mixture was further aged at 80 ° C. for 2 hours, allowed to cool, concentrated under reduced pressure, and redissolved in a small amount of acetone. The white precipitate obtained by dropping the acetone solution of this polymer into excess n-hexane was filtered, washed, and dried to obtain 45 g of a white polymer of dodecyl-terminated poly (N-vinylpyrrolidone). Obtained.

<Formation and evaluation method of resist pattern>
1. Preparation of Conductive Composition The conductive composition was prepared by dissolving at room temperature in the blending ratio of each component shown in Table 1 below. The pH of the adjusted conductive composition at 25 ° C. was measured.

(Conductivity evaluation)
The conductive composition is spin-coated on a glass substrate (500 rpm × 5 sec + 2000 rpm × 60 sec) to form a conductor film, followed by heat treatment at 70 ° C. for 2 minutes on a hot plate. The conductivity was measured by a two-terminal method (distance between electrodes: 20 mm) using -HT260 (manufactured by Mitsubishi Chemical Corporation). It confirmed that the coating film had sufficient electroconductivity in all the Examples and the comparative examples.

2. Formation of Conductor After 2 ml of the conductive composition was dropped onto a 4 inch silicon wafer coated and dried with a chemically amplified electron beam resist, spin coating was applied (500 rpm × 5 sec + 2000 rpm × 60 sec) to form a transparent conductor. . After the formation, heat treatment was performed under the conditions shown in Table-2.

3. Resist pattern formation A chemically amplified electron beam resist (Electron beam positive resist OEBR-CAP009 manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied and spin-coated with the conductive composition shown in Table 1 on the resist-coated surface of a silicon wafer ( 500 rpm × 5 sec + 2000 rpm × 60 sec), and after forming the conductor film, a heat treatment was performed on the hot plate for 5 minutes under the conditions shown in Table-2. After heating, it was left for the period shown in Table 2 (PCD), exposed with a charged particle beam, and the resist pattern after carrying out predetermined PEB and development was evaluated. The resist pattern evaluation was performed for the resist remaining film rate and the pattern shape.

B) Resist remaining film ratio The film thickness of an unexposed portion of the resist (portion where no charged particle beam was irradiated) was measured and compared with a blank. The blank was defined as the film thickness when the conductive composition coating, drying, and peeling processes were not performed. Evaluation was based on the following.
○: Residual film ratio is 90% or more compared to blank.
Δ: Residual film ratio is 80% or more compared to blank.
X: Residual film ratio is 80% or less as compared with the blank.
B) Pattern shape The pattern shape of the resist was observed with a scanning electron microscope and evaluated as follows.
○: A pattern is formed on the resist as set.
Δ: Shape slightly changed ×: No pattern is formed on the resist.

[Examples 1-6, Comparative Examples 1-5]
Said conductive evaluation and board | substrate state evaluation were performed using the conductive compositions 1-5, respectively. The evaluation results are shown in Table 2.

The conductive compositions 1 and 3 were analyzed for volatile components using a heat generation gas mass spectrometry (EGA-MS) method. The results are shown in FIGS.
Measurement condition:
Measurement temperature: 50 ° C. to 200 ° C. (heating rate 5 ° C./min)
The results are shown in FIGS.
FIG. 1 shows the result of observing the volatilization of representative ions (m / z) = 79 of pyridine (pka = 5.2, boiling point 115 ° C.) with respect to the conductive composition 1 by EGA-MS. From this result, it can be seen that pyridine starts to evaporate from the conductor and is removed from around 70 ° C.
FIG. 2 shows the result of observing the volatilization of representative ions (m / z) = 86 of triethylamine (pka = 10.9, boiling point 90 ° C.) with respect to the conductive composition 3 by EGA-MS. From this result, in the range up to 150 ° C., most of the triethylamine does not volatilize and remains in the conductor. Residual triethylamine is considered to adversely affect the resist pattern.
FIG. 3 shows the result of observing the volatilization of typical ions (m / z) = 64 of sulfur oxide in the conductive composition 3 by EGA-MS. From this result, the generation of sulfur oxide (acid gas) derived from the decomposition of the conductive polymer was observed from around 150 ° C. For this reason, it is considered that heating exceeding 150 ° C. causes an adverse effect on the resist pattern.

It is the result of observing volatilization of pyridine (pka = 5.2, boiling point 115 ° C.) with respect to the conductive composition 1 by EGA-MS. It is the result of having observed the volatilization of the triethylamine (pka = 10.9, boiling point 90 degreeC) about the electrically conductive composition 3 by EGA-MS. It is the result of having observed volatilization of the sulfur oxide about the electrically conductive composition 3 by EGA-MS.

Claims (5)

  A conductive composition containing a conductive polymer (A) having a sulfonic acid group or a carboxyl group and a basic compound (B) having a dissociation constant pKa at 25 ° C. of 10 or less is applied on a resist applied to a substrate. Conductive composition coating step for forming a conductor, heating step for heating the conductor at 70 to 140 ° C., and charged particle beam irradiation step for forming a resist pattern with a charged particle beam on the substrate on which the conductor is formed A resist pattern forming method comprising:   The resist pattern forming method according to claim 1, wherein the heating step is a step of removing the basic compound (B) from the conductor.   The resist pattern forming method according to claim 1, further comprising a leaving step (PCD) after the heating step. The conductive polymer (A) having the sulfonic acid group or carboxyl group is a conductive polymer having at least one repeating unit represented by the following formula (3). The resist pattern formation method as described in any one of.



In formula (3), R7 to R10 are each independently H, a linear or branched alkoxy group having 1 to 24 carbon atoms, or a sulfonic acid group, and at least one of R7 to R10 is a sulfonic acid group. It is. The resist pattern formation method according to any one of claims 1 to 4, wherein the basic compound (B) is a pyridine derivative.