Patent Application
20080026314
The present invention is described below in more detail by examples. However, these examples should not be construed as limiting the present invention.
Mw of the polysiloxanes obtained in the Examples and Comparative Examples described below and the polymers obtained in the Preparation Example described below was measured by gel permeation chromatography (GPC) using GPC columns (manufactured by Tosoh Corp., G2000HXL×2, G300HXL×1, G400HXL×1) under the following conditions. Flow rate: 1.0 ml/minute, eluate: tetrahydrofuran, column temperature: 40° C., standard reference material: monodispersed polystyrene
A three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 220 g of triethoxysilane and 198 g of 5-(1-methylcyclopentyl)oxycarbonylbicyclo[2.2.1 ]hept-2-ene. The mixture was stirred at room temperature and 1 ml of a 0.2 mol chloroplatinic acid (H2PtCl6) solution in i-propyl alcohol was added to initiate the reaction. After heating the reaction mixture at 100° C. for 30 hours, additional 1 ml of a 0.2 mol i-propyl alcohol solution of chloroplatinic acid was added with heating at 100° C. for five hours. The reaction mixture was allowed to cool to room temperature, diluted with n-hexane, and filtered through a suction funnel spread with celite. The solvent was removed from the filtrate by evaporation under reduced pressure to obtain a crude product. The crude product was purified by distillation under reduced pressure to obtain 262 g of a compound as a fraction with a boiling point of 137° C. at 0.06 mmHg.
As a result of 1H-NMR spectrum (chemical shift δ) measurement, this compound was identified to be a compound shown by the above formula (I-1-1) (hereinafter referred to as “compound (a-1)”).
δ (unit ppm):
3.8 (CH2 group in ethoxy group), 2.7-1.3 (CH group in norbornane ring, CH2 group in norbornane ring, CH3 group, CH2 group in cyclohexane ring), 1.2 (ethoxy group)
A compound of the above formula (I-1-2) was obtained in the same manner as in Synthesis Example 1, except for using
5-(1-ethylcyclopentyl)oxycarbonylbicyclo[2.2.1 ]hept-2-ene instead of
5-(1-methylcyclopentyl)oxycarbonylbicyclo[2.2.1 ]hept-2-ene.
A compound of the above formula (I-1-4) was obtained in the same manner as in Synthesis Example 1, except for using
5-(1-ethylcyclohexyl)oxycarbonylbicyclo[2.2.1 ]hept-2-ene instead of
5-(1-methylcyclopentyl)oxycarbonylbicyclo[2.2.1 ]hept-2-ene.
A three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 36.3 g of the compound (a-1), 41.32 g of a silane compound of the following formula (b-1) (hereinafter referred to as “compound (b-1)”), 22.39 g of a silane compound of the following formula (b-2) (hereinafter referred to as “compound (b-2)”), 100 g of 4-methyl-2-pentanone, and 23.0 g of a 1.75 wt % aqueous solution of oxalic acid. The mixture was reacted at 60° C. for six hours while stirring. The reaction vessel was cooled with ice to terminate the reaction.
34.0 g of distilled water and 47.7 g of triethylamine were added to the reaction solution and stirred at 80° C. in a nitrogen stream for six hours, followed by cooling with ice. An aqueous solution of 35.9 g of oxalic acid dissolved in 476.5 g of distilled water was added to the mixture, followed by further stirring. The reaction solution was poured into a separating funnel to remove the water layer. The organic layer was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The solvent was evaporated from the organic layer under reduced pressure to obtain 62.1 g of polysiloxane (1). Mw of the obtained polysiloxane (1) was 1,740.
A three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 22.27 g of the compound (a-1), 42.36 g of a silane compound of the following formula (b-3), 19.77 g of a silane compound of the following formula (b-4), 100 g of 4-methyl-2-pentanone, and 14.1 g of a 1.75 wt% aqueous solution of oxalic acid. The mixture was reacted at 60° C. for six hours while stirring. The reaction vessel was cooled with ice to terminate the reaction.
21.4 g of distilled water and 29.3 g of triethylamine were added to the reaction solution and stirred at 80° C. in a nitrogen stream for six hours, followed by cooling with ice. An aqueous solution of 22.0 g of oxalic acid dissolved in 292.4 g of distilled water was added to the mixture, followed by further stirring. The reaction solution was poured into a separating funnel to remove the water layer. The organic layer was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The solvent was evaporated from the organic layer under reduced pressure to obtain 74.2 g of polysiloxane (1). Mw of the obtained polysiloxane (1) was 2,060.
A three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 48.08 g of the compound (a-1), 51.92 g of the compound (b-1), 100 g of 4-methyl-2-pentanone, and 30.53 g of a 1.75 wt % aqueous solution of oxalic acid. The mixture was reacted at 60° C. for six hours while stirring. The reaction vessel was cooled with ice to terminate the reaction.
The reaction solution was poured into a separating funnel to remove the water layer. The organic layer was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The solvent was evaporated from the organic layer under reduced pressure to obtain 51.1 g of polysiloxane (1). Mw of the obtained polysiloxane (1) was 1,530.
A three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 31.35 g of the compound (a-1), 17.58 g of the compound (b-1), 50.79 g of the compound (b-2), 100 g of 4-methyl-2-pentanone, and 29.86 g of a 1.75 wt % aqueous solution of oxalic acid. The mixture was reacted at 60° C. for six hours while stirring. The reaction vessel was cooled with ice to terminate the reaction. 44.1 g of distilled water and 61.9 g of triethylamine were added to the reaction solution and stirred at 40° C. in a nitrogen stream for six hours, followed by cooling with ice. An aqueous solution of 46.5 g of oxalic acid dissolved in 617.6 g of distilled water was added to the mixture, followed by further stirring. The reaction solution was poured into a separating funnel to remove the water layer. The organic layer was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The solvent was evaporated from the organic layer under reduced pressure to obtain 63.1 g of polysiloxane (1). Mw of the obtained polysiloxane (1) was 2,540.
A three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 34.68 g of a silane compound shown by the following formula (r-1), 42.36 g of the compound (b-1), 22.96 g of the compound (b-2), 100 g of 4-methyl-2-pentanone, and 23.6 g of a 1.75 wt % aqueous solution of oxalic acid. The mixture was reacted at 60° C. for six hours while stirring. The reaction vessel was cooled with ice to terminate the reaction.
34.9 g of distilled water and 48.9 g of triethylamine were added to the reaction solution and stirred at 80° C. in a nitrogen stream for six hours, followed by cooling with ice. An aqueous solution of 36.8 g of oxalic acid dissolved in 488.5 g of distilled water was added to the mixture, followed by further stirring. The reaction solution was poured into a separating funnel to remove the water layer. The organic layer was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The solvent was evaporated under reduced pressure from the organic layer to obtain 60.9 g of polysiloxane. Mw of the polysiloxane was 1,910.
A separable flask equipped with a thermometer was charged with 100 parts by weight of acenaphthylene, 78 parts by weight of toluene, 52 parts by weight of dioxane, and 3 parts by weight of azobisisobutyronitrile in a nitrogen atmosphere. The mixture was stirred for five hours at 70° C. Next, 5.2 parts by weight of p-toluenesulfonic acid monohydrate and 40 parts by weight of paraformaldehyde were added. After heating to 120° C., the mixture was stirred for six hours. The reaction solution was poured into a large amount of isopropyl alcohol. The resulting precipitate was collected by filtration and dried at 40° C. under reduced pressure to obtain a polymer having a Mw of 22,000.
10 parts by weight of the obtained polymer, 0.5 part by weight of bis(4-t-butylphenyl)iodonium 10-camphorsulfonate, 0.5 part by weight of 4,4′-[1-{4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl } ethylidene]bisphenol, and 89 parts by weight of cyclohexanone were mixed to prepare a homogeneous solution. The solution was filtered using a membrane filter with a pore diameter of 0.1 μm to prepare an under layer film-forming composition.
Composition solutions were prepared by homogenously mixing 100 parts (by weight, hereinafter the same) of polysiloxanes shown in Table 1, 900 parts of 2-heptanone, the acid generators (B) shown in Table 1, and 8 mol % of 2-phenylbenzimidazole for the total amount of the acid generator (B).
The composition solutions were applied onto a silicon wafer substrate with an under layer film previously formed thereon using a spin coater and pre-baked for 90 seconds on a hot plate at 100° C. to form a resist film with a thickness of 1,500 Å.
The under layer film used here was a film with a thickness of 3,000 Å prepared by applying the above-mentioned under layer film forming composition onto a silicon wafer by spin coating and baking on a hot plate for 60 seconds at 180° C. and further baking for 120 seconds at 300° C.
The resist films were exposed to an ArF excimer laser (wavelength: 193 nm, NA: 0.78, σ: 0.85) through a photomask using an ArF excimer laser exposure apparatus (“S306C” manufactured by Nikon Corp.), while changing the exposure dose. The films were then heated on a hot plate maintained at 80° C. or 95° C. for 90 seconds (PEB). The resist films were developed using a 2.38 wt % tetramethylammonium hydroxide aqueous solution at 23° C. for 60 seconds, washed with water, and dried to form positive-tone resist patterns.
The line-and-space patterns were evaluated according to the following procedure. The evaluation results are shown in Table 2.
An optimum exposure dose at which a line-and-space pattern (1L1S) with a line width of 100 nm in a 1:1 line width was formed was taken as sensitivity (1L1S).
The line width (CD) of the line pattern when a 1 line-5 space (1L5S) with a line width of 180 nm was formed at this optimum exposure dose was measured. The larger the value of CD, the better the I-D bias. The acid generators (B) in Table 1 are as follows.
Composition solutions were prepared by homogeneously mixing 100 parts (by weight, hereinafter the same) of polysiloxanes shown in Table 2, 900 parts of 2-heptanone, acid generators (B) shown in Table 2, and 2-phenylbenzimidazole in an amount of 8 mol % of the total amount of the acid generator (B).
Positive-tone resist patterns were formed in the same manner as in Evaluation Examples 1-5 and Comparative Evaluation Example 2.
A substrate for development defect inspection was prepared as follows. The composition solutions were applied to the surface of a silicon wafer substrate with an antireflection film (“ARC29A” manufactured by Nissan Chemical Industries, Ltd.) with a thickness of 77 nm previously formed thereon, in an amount to form a film with a dry thickness of 150 nm. The coating was pre-baked (PB) for 90 seconds at 140° C. to obtain resist films. The resist films were exposed to an ArF excimer laser (wavelength: 193 nm, NA:0.78, σ: 0.85) through a photomask using an ArF excimer laser exposure apparatus (“S306C” manufactured by Nikon Corp.) to form a contact holes with a pore diameter of 110 nm at a pitch of 300 nm. The films were then heated on a hot plate maintained at 140° C. for 90 seconds (PEB). Then, the resist film was developed at 23° C. for 60 seconds in a 2.38 wt % tetramethylammonium hydroxide aqueous solution, washed with water, and dried to form a substrate for development defect inspection. Application of the composition solutions, PB, PEB, and development were carried out using an inline system (“ACT8” manufactured by Tokyo Electron Ltd.).
Line-and-space patterns, contact hole patterns, and the number of development defects were evaluated according to the procedures described below. The evaluation results are shown in Table 2.
The cross-sectional configuration of the line patterns of line-and-space (1L1S) patterns with a line width of 100 nm was inspected using a scanning electron microscope.
An optimum exposure dose at which a hole-and-space pattern (1H1S) with a contact hole diameter of 100 nm in a 1:1 line width was formed was taken as the sensitivity (1H1S).
A hole-and-space pattern (1H1S) with a contact hole diameter of 100 nm was formed by irradiating light at an optimum exposure dose while moving the focus to determine a focus range in which the contact hole diameter was 90 nm to 110 nm. The result was regarded as depth of focus (DOF (1H1S)).
Using a substrate for inspecting development defects and a defect inspector (“KLA2351” manufactured by KLA-Tencor Corp.), the number of development defects was calculated by detecting development defects extracted from the difference obtained by superposing the pixel units and a reference image in an array mode of the defect inspector at a pixel size of 0.16 μm and a ceiling value of 13.
The acid generators (B) in Table 2 are as follows.
A three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 36.3 g of the silane compound (a-1), 41.3 g of a silane compound of the following formula (a-2) (hereinafter referred to as “silane compound (a-2)”), 22.4 g of the silane compound (b-1), 100 g of 4-methyl-2-pentanone, and 23.0 g of a 1.75 wt % aqueous solution of oxalic acid. The mixture was reacted at 60° C. for six hours while stirring. The reaction vessel was cooled with ice to terminate the reaction.
34.0 g of distilled water and 47.7 g of triethylamine were added to the reaction solution and stirred at 80° C. in a nitrogen stream for six hours, followed by cooling with ice. An aqueous solution of35.9 g of oxalic acid dissolved in 476.5 g of distilled water was added to the mixture, followed by further stirring. The reaction solution was poured into a separating funnel to remove the water layer. The organic layer was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The solvent was evaporated from the organic layer under reduced pressure to obtain 62.1 g of polysiloxane (1-1). Mw of the obtained polysiloxane (1-1) was 2,140.
A three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 13.2 g of the silane compound (a-1), 24.5 g of a silane compound of the following formula (a-3) (hereinafter referred to as “silane compound (a-3)”), 62.3 g of the silane compound (b-4), 100 g of 4-methyl-2-pentanone, and 16.7 g of a 1.75 wt % aqueous solution of oxalic acid. The mixture was reacted at 60° C. for six hours while stirring. The reaction vessel was cooled with ice to terminate the reaction.
24.7 g of distilled water and 34.6 g of triethylamine were added to the reaction solution and stirred at 80° C. in a nitrogen stream for six hours, followed by cooling with ice. An aqueous solution of 26.0 g of oxalic acid dissolved in 345.7 g of distilled water was added to the mixture, followed by further stirring. The reaction solution was poured into a separating funnel to remove the water layer. The organic layer was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The solvent was evaporated from the organic layer under reduced pressure to obtain 73.5 g of polysiloxane (1-1). Mw of the obtained polysiloxane (1-1) was 2,060.
A three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 24.6 g of the silane compound (a-3), 30.1 g of the silane compound (b-1), 45.4 g of the silane compound (b-4), 100 g of 4-methyl-2-pentanone, and 16.7 g of a 1.75 wt % aqueous solution of oxalic acid. The mixture was reacted at 60° C. for six hours while stirring. The reaction vessel was cooled with ice to terminate the reaction. 24.7 g of distilled water and 34.7 g of triethylamine were added to the reaction solution and stirred at 80° C. in a nitrogen stream for six hours, followed by cooling with ice. An aqueous solution of 26.1 g of oxalic acid dissolved in 346.2 g of distilled water was added to the mixture, followed by further stirring. The reaction solution was poured into a separating funnel to remove the water layer. The organic layer was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The solvent was evaporated from the organic layer under reduced pressure to obtain 73.3 g of a polysiloxane. Mw of the polysiloxane was 2,160.
Composition solutions were prepared by homogenously mixing 100 parts (by weight, hereinafter the same) of siloxane resins shown in Table 3, 900 parts of 2-heptanone, the acid generators (B) shown in Table 1, and 8 mol % of 2-phenylbenzimidazole for the total amount of the acid generator (B).
The composition solutions were applied onto a silicon wafer substrate with an under layer film previously formed thereon using a spin coater and pre-baked for 90 seconds on a hot plate at 100° C. to form a resist film with a thickness of 1,500 Å. The under layer film was prepared in the same manner as in Evaluation Examples 1-5 and Comparative Evaluation Example 1.
The resist films were exposed to an ArF excimer laser (wavelength: 193 nm, NA: 0.78, σ: 0.85) through a photomask using an ArF excimer laser exposure apparatus (“S306C” manufactured by Nikon Corp.), while changing the exposure dose. The films were then heated on a hot plate maintained at 100° C. for 90 seconds (PEB). The resist films were developed using a 2.38 wt % tetramethylammonium hydroxide aqueous solution at 23° C. for 60 seconds, washed with water, and dried to form a positive-tone resist pattern.
The line-and-space patterns were evaluated according to the following procedure.
An optimum dose at which a line-and-space pattern (1L1S) with a line width of 90 nm in a 1:1 line width was formed was taken as sensitivity (1L1S).
A line-and-space pattern (1L1S) with a line width of 90 nm was formed by irradiating light at an optimum exposure dose while moving the focus to determine a focus range in which the line width of the line pattern was from 81 nm to 99 nm. The result was regarded as depth of focus (DOF (1L1S)).
The acid generators (B) in Table 3 are as follows.
The silane compound (I) of the present invention is particularly suitable for use as a raw material for synthesizing the polysiloxane (1) of the present invention.
Because it is possible to decrease a PEB temperature and control diffusion of the acid generated by exposure, the radiation-sensitive resin composition of the present invention comprising the polysiloxane (1) as a resin component excels in I-D bias and the process margin of depth of focus (DOF) in both the line-and-space pattern and hole-and-space pattern, and exhibits high sensitivity, excellent pattern profile, resolution, dry etching resistance, and developability.
In addition, the radiation-sensitive resin composition of the present invention comprising the polysiloxane (1-1) containing two types of acid dissociable groups with different acid dissociation properties as a resin component excels in the process margin of depth of focus (DOF) in both the line-and-space pattern and hole-and-space pattern, and exhibits high sensitivity, excellent resolution, dry etching resistance, and developability.
Furthermore, the radiation-sensitive resin composition of the present invention comprising the polysiloxane (1) and polysiloxane (1-1) exhibits excellently balanced afore-mentioned properties.
Therefore, the radiation-sensitive resin composition of the present invention is extremely suitable as a chemically-amplified resist for microfabrication using various radiations such as deep ultraviolet radiation, electron beams, and X-rays.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2003-355112 | Oct 2003 | JP | national |
| 2003-356898 | Oct 2003 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP04/15150 | 10/14/2004 | WO | 00 | 7/31/2007 |
