Self-assembled structures, method of manufacture thereof and articles comprising the same

A technology of composition and grafted polymer, which is applied in the photoplate making process of patterned surface, photosensitive materials used in optomechanical equipment, instruments, etc., and can solve the problems of light intensity modulation loss and so on

Inactive Publication Date: 2014-09-17
ROHM & HAAS ELECTRONIC MATERIALS LLC +1
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AI-Extracted Technical Summary

Problems solved by technology

However, top-down lithography, as far as optical lithography is concerned, is limited by the smallest pattern it can form because light diffracts t...
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Method used

[0087] The grafted block copolymers can be used as templates to decorate or fabricate other surfaces that can be used in fields such as electronics, semiconductors, and the like. The graft block copolymers described above have a number of important advantages over other block copolymers that can self-assemble and be used to form photoresists. Large area vertical alignment of graft block copolymers is achieved in films having a thickness of less than 50 nanometers (nm), preferably less than 30 nm, by using graft block copolymers that are highly controlled during synthetic chemistry, The supramolecular assembly process required for other comparable forms of linear block copolymer lithography is not required. The structural and morphological characteristics of the grafted block copolymers can be tuned in the transverse and longitudinal directions, thus enabling the preparation of highly sensitive photoresists. In addition, the structural and morpho...
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Abstract

The invention discloses a composition comprising grafted block copolymer, a photo-acid generator, and a crosslinking agent. The grafted block copolymer comprises first block polymer and second block polymer; wherein the first block polymer comprises main chain polymer and first grafted polymer, the first grafted polymer comprises a part with reduced surface energy, the second block polymer is connected to the first block polymer through a covalent bond, the second bock polymer comprises main chain polymer and second grafted polymer, and the second grafted polymer comprises an functional group effective on the crosslinked grafted block polymer.

Application Domain

Photosensitive material processingPhotosensitive materials for photomechanical apparatus

Technology Topic

Surface energyCovalent bond +3

Image

  • Self-assembled structures, method of manufacture thereof and articles comprising the same
  • Self-assembled structures, method of manufacture thereof and articles comprising the same
  • Self-assembled structures, method of manufacture thereof and articles comprising the same

Examples

  • Experimental program(9)

Example Embodiment

[0104] Example 1
[0105] The first polymer-(NB-P(TFpHS) 12 )Synthesis. This example is intended to illustrate the manufacture of the first polymer. The terms used here are as follows: NB-norbornene with chain transfer agent; TF-tetrafluoro; pHS-p-hydroxystyrene; P(TFpHS) 12 )-Poly(tetrafluoro-p-hydroxystyrene) with 12 repeating units.
[0106] The first polymer is produced as follows. The norbornene-chain transfer agent (NB-CTA) (301 milligrams (mg), 0.782 millimoles (mmol)), tetrafluoro-p-hydroxystyrene (TFpHS) (4.49g, 23.4mmol), azobis Isobutyronitrile (AIBN) (12.7 mg, 78.2 micromoles (μmol)), and 10.5 mL of 2-butanone were added to a 25 mL Schlenk flask equipped with a magnetic stir bar. 2 The atmosphere is dried by flames. The mixture was stirred at room temperature (RT) for 10 minutes (min) and degassed through five freeze-pump-thaw cycles. After the last cycle, the reaction mixture was stirred at RT for 10 minutes and immersed in a pre-heated oil bath at 65°C to start the copolymerization reaction. After 11 hours (h), by using liquid nitrogen (N 2 ) Cool the reaction flask to quench the polymerization reaction. The copolymer was purified by precipitation into 300 milliliters (mL) of hexane twice. The light red oil was collected by centrifugation, washed with 300 mL of hexane, and kept under vacuum overnight to remove residual solvent. The product is 1.4 grams (g) of product, 60% yield, based on about 45% monomer conversion. M n, GPC =2,750 Daltons (Da) (laser detector), PDI=1.07. 1 HNMR (500MHz, DMSO-d6) δ 10.95-11.90 (m, phenol OH), 7.42-7.84 (m, ArH from RAFT functionality), 6.08 (s, NB CH=CH), 5.10-5.30 (br , The end of the main chain CH), 3.90-4.10 (m, NB CH 2 OC(O)), 1.02-3.45(m, all CH from the main chain of the TFPHS unit and the NB ring 2 And CH). 13 C NMR (125MHz, DMSO-d6) δ206.9, 172.2, 145.6, 144.3, 144.1, 138.7, 137.2, 136.5, 135.0, 133.8, 129.3, 127.0, 123.2, 108.4, 73.1, 68.4, 63.0, 45.0, 43.5, 42.4 , 41.5, 40.5, 38.3, 37.9, 35.8, 34.6, 34.4, 33.2, 31.4, 31.1, 29.6, 29.4, 28.9. IR(cm -1 ): 2610-3720,1714,1658,1523,1495,1459,1351,1245,1142,1048,947,866. T g =150°C.
[0107] [48] ​​Example 2
[0108] This example is intended to illustrate the manufacture of another first polymer.
[0109] The first polymer-(NB-P(TFpHS) 10 )Synthesis. The terms used here are as follows: NB-norbornene with chain transfer agent; TF-tetrafluoro; pHS-p-hydroxystyrene; P(TFpHS) 10 )-Poly(tetrafluoro-p-hydroxystyrene) with 10 repeating units.
[0110] The first polymer is produced as follows. Add NB-CTA (510mg, 1.32mmol), TFPHS (5.06g, 26.4mmol), AIBN (12.9mg, 79.2μmol), and 12mL of 2-butanone into a 25mL Schlenk flask equipped with a magnetic stir bar. The flask is already in N 2 The atmosphere is dried by flames. The mixture was stirred at room temperature for 10 minutes and degassed through five freeze-pump-thaw cycles. After the last cycle, the reaction mixture was stirred at RT for 10 minutes and immersed in a pre-heated oil bath at 65°C to start the copolymerization reaction. After 11h, by using liquid N 2 The reaction flask was cooled to quench the polymerization reaction. The copolymer was purified by precipitation into 300 mL of hexane twice. The light red oil was collected by centrifugation, washed with 300 mL of hexane, and kept under vacuum overnight to remove residual solvent. Produced 1.7 g of product, 61% yield, based on about 45% monomer conversion. M n, GPC =2,450Da (laser detector), PDI=1.08. 1 HNMR, 13 C NMR and IR spectra are similar to those of the first polymer 1 HNMR, 13 C NMR and IR spectroscopy. Glass transition temperature (T g )=150°C.

Example Embodiment

[0111] Example 3
[0112] The second polymer-(NB-P(pHS 13 --PhMI 13 ))Synthesis. This example is intended to illustrate the manufacture of the second polymer. The terms used here are as follows: NB-norbornene with chain transfer agent; pHS-p-hydroxystyrene; PhMI-N-phenylmaleimide; P(pHS13-co-PhMI13)-poly(p- Hydroxystyrene-co-N-phenylmaleimide), in which p-hydroxystyrene is polymerized to contain 13 repeating units and N-phenylmaleimide is polymerized to poly(p-hydroxystyrene ) And also has 13 repeating units.
[0113] The second polymer is produced as follows. Add NB-CTA (635mg, 1.65mmol), pHS (3.95g, 33.0mmol), PhMI (5.76g, 33.0mmol), AIRN (26.7mg, 165μmol), and 35mL of anhydrous 1,4-dioxane Into a 100mL Schlenk flask equipped with a magnetic stir bar. 2 The atmosphere is dried by flames. The mixture was stirred for 10 minutes at RT and degassed through four freeze-pump-thaw cycles. After the last cycle, the reaction mixture was stirred at RT for 15 minutes and immersed in a pre-heated oil bath at 65°C to start the copolymerization reaction. After 6.5 hours, by using liquid N 2 The reaction flask was cooled to quench the polymerization reaction. The copolymer was purified by precipitation into 600 mL of diethyl ether twice. The light red precipitate was collected by centrifugation, washed with 200 mL diethyl ether and 200 mL hexane, and kept under vacuum overnight to remove residual solvent. Produced 3.4 g of product, 60% yield, based on about 55% conversion of the two monomers. M n, GPC =3,520Da (differential refractive index detector), M n, GPC =6,870Da (laser detector), PDI=1.20. 1 H NMR (500MHz, DMSO-d6) δ9.20-9.80 (br, phenol OH), 6.20-7.92 (m, ArH), 6.08 (br, NB CH=CH), 5.10-5.43 (br, main chain end CH ), 3.90-4.13 (m, NB CH 2 OC(O)), 0.76-3.22(m, all CH from the main chain of the pHS unit and the NB ring 2 And CH, all CH from the MI unit). 13 C NMR (125MHz, DMSO-d6) δ204.9, 176.8, 171.8, 156.7, 154.9, 136.8, 136.2, 132.0, 129.7, 129.0, 128.8, 126.8, 115.5, 114.7, 68.0, 61.9, 51.6, 44.6, 43.2, 42.2 , 41.1, 37.6, 34.8, 34.6, 34.4, 33.2, 31.4, 31.1, 29.6, 29.4, 28.9. IR(cm -1 ): 3118-3700, 2790-3090, 1774, 1701, 1610, 1506, 1450, 1380, 1262, 1185, 845, 750. Glass transition temperature (T g )=130°C.

Example Embodiment

[0114] Example 4
[0115] The second polymer-(NB-P(pHS 8 -Total-PhMI 8 ))Synthesis. This example is also intended to illustrate the manufacture of the second polymer. The terms used here are as follows: NB-norbornene with chain transfer agent; pHS-p-hydroxystyrene; PhMI-N-phenylmaleimide; P(pHS 8 -Total-PhMI 8 )-Poly(p-hydroxystyrene-co-N-phenylmaleimide), in which p-hydroxystyrene is polymerized to contain 8 repeating units and N-phenylmaleimide is polymerized to poly (P-hydroxystyrene) and also has 8 repeating units.
[0116] The second polymer is produced as follows. Add NB-CTA (802mg, 2.08mmol), pHS (2.50g, 20.8mmol), PhMI (3.60g, 20.8mmol), AIBN (16.9mg, 104μmol), and 20mL of anhydrous 1,4-dioxane Into a 50mL Schlenk flask equipped with a magnetic stir bar. 2 The atmosphere is dried by flames. The mixture was stirred for 10 minutes at RT and degassed through four freeze-pump-thaw cycles. After the last cycle, the reaction mixture was stirred at RT for 15 minutes and immersed in a pre-heated oil bath at 65C to start the copolymerization reaction. After 4.5 hours, by using liquid N 2 The reaction flask was cooled to quench the polymerization reaction. The copolymer was purified by precipitation into 600 mL of diethyl ether twice. The light red precipitate was collected by centrifugation, washed with 400 mL diethyl ether and 400 mL hexane, and kept under vacuum overnight to remove residual solvent. Produced 2.8 g of product, 73% yield, based on a conversion of the two monomers of about 60%. M n, GPC =2,730Da (differential refractive index detector), M N, GPC =3,800Da (laser detector), PDI=1.12. 1 HNMR, 13 C NMR and IR spectra are similar to those measured in Example 3 1 HNMR, 13 C NMR and IR spectroscopy. Glass transition temperature (T g )=130℃.

PUM

PropertyMeasurementUnit
Glass transition temperature130.0°C
Thickness18.0 ~ 25.0nm
Roughness<= 0.2nm

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