Composition and a method for manufacturing a component

Abstract

Compositions are for formation of etch-resistant resins. Such resins are useful for manufacturing components or devices.

Claims

1. A composition comprising: a first compound; a second compound; and a silane coupling agent; wherein: the first compound has a structure represented by Formula (D): ##STR00004## the second compound has at least two polymerizable groups; the silane coupling agent is as represented by Formula (G): ##STR00005## and a resin generated by curing the composition has a dry etching rate less than or equal to 140 nm/min.

2. The composition of claim 1, wherein the composition has a viscosity less than or equal to 104800 mPa.Math.s.

3. The composition of claim 1, wherein the composition is photo-curable.

4. The composition of claim 1, wherein: the resin has a dry etching rate less than or equal to 131 nm/min; and the dry etching rate is measured in a plasma generated under a condition in which a flow rate of O.sub.2 is 10 sccm.

5. The composition of claim 1, wherein the second compound that has at least two cyclic moieties.

6. The composition of claim 1, wherein the first compound has an Ohnishi parameter less than or equal to 2.60.

7. The composition of claim 1, wherein the first compound in itself has a viscosity less than or equal to 150 mPa.Math.s.

8. The composition of claim 1, wherein the first compound has at least two cyclic moieties.

9. The composition of claim 1, wherein the first compound contains at most three oxygen atoms.

10. The composition of claim 1, wherein the composition has an Ohnishi parameter less than or equal to 2.59.

11. The composition of claim 1, wherein the second compound includes a fluorene structure.

12. The composition of claim 1, further comprising: at least one selected from the group consisting of a surfactant containing at least one fluorine atom and a polymeric surfactant.

13. The composition of claim 1, further comprising: a phosphoric acid.

14. The composition of claim 13, wherein the phosphoric acid is as represented by Formula (H): ##STR00006##

15. A method for manufacturing a component utilizing nanoimprint technology, the method comprising: preparing the composition of claim 1; forming a coating film of the composition; contacting a mold having a concave portion and a convex portion with the coating film; and forming a resin by curing at least the composition so as to form a component having a plurality of concavities therein.

16. The method of claim 15, wherein each of the plurality of concavities has a width less than or equal to 1000 nm.

17. The method of claim 15, wherein each of the plurality of concavities has a width less than or equal to 100 nm.

18. The method of claim 15, further comprising: etching the resin.

19. A method of manufacturing a device, the method comprising: preparing the composition of claim 1; forming a coating film of the composition; forming a resin by curing the coating film; and processing the resin to obtain a device.

20. The method according to claim 19, further comprising: contacting a mold having a concave portion and a convex portion with the coating film, wherein the resin has a plurality of concavities therein.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) In the drawings, which illustrate what is currently considered to be the best mode for carrying out the invention:

(2) FIG. 1 shows a typical manufacturing process for a component or a device utilizing a composition relating to an aspect of the disclosure.

DETAILED DESCRIPTION

(3) Compositions are prepared by mixing Initiator A or B acting as a radical initiator with at least one of groups consisting of Compound A, Compound B, Compound C, Compound D, Compound E and Compound F. Among Compounds A-F, each of compounds other than Compound B contains at least one aromatic group which can contribute to improvement of etch-resistant property. Compound G or Compound H can be used as a constituent of the compositions as appropriate while at least one surfactant can be used as a constituent of the compositions as appropriate. Surfactant A, Surfactant B, Surfactant C and Surfactant D are Polyflow No. 75 (Kyoeisya Chemical Co., Ltd.), Polyflow No. 99C (Kyoeisya Chemical Co., Ltd.), MEGAFACE F-554 (DIC Corporation) and MEGAFACE F-552 (DIC Corporation), respectively. Each of Surfactant A and Surfactant B has a polymeric moiety while each of Surfactant C and Surfactant D has at least one fluorine atom.

(4) ##STR00001## ##STR00002##

(5) TABLE-US-00001 TABLE 1 Table Constituents (ratio by weight) of compositions and characteristic values Compositions 1 2 3 4 5 6 Compound A 95 Compound B 95 Compound C 95 Compound D 95 Compound E 95 Compound F 95 Compound G Compound H Initiator A 5 5 5 5 5 5 Initiator B Surfactant A Surfactant B Surfactant C Surfactant D Ohnishi Parameter 2.03 4.36 2.59 2.58 2.48 2.41 Viscosity (mPa .Math. s) 0.7 120 150 18 >100,000 >100,000 Spin coating g g g g Adhesion to substrate g g g g Filling time (100 nm) 1 min 1 min 15 min 15 min Filling time (1000 nm) 1 min 1 min 15 min 15 min Pattern profile u f f c f f Dry etching rate (nm/min) O.sub.2 gas 187 134 91 88 C.sub.3F.sub.8 gas 192 114 109 106 Ratio of dry etching rate O.sub.2 gas 1.000 0.717 0.487 0.471 C.sub.3F.sub.8 gas 1.000 0.594 0.568 0.552 e: excellent; g: good; f: fine; c: cohesive failure; u: uncured

(6) Table 1 shows compositions prepared by mixing a radical initiator with one of the group consisting of Compound A, Compound B, Compound C, Compound D, Compound E and Compound F.

(7) Spin coating in the table means coating property of the composition. g indicates that a coating film of the solution disposed on the substrate has no deficit after removal of the solvent from the solution while ng indicates that a coating film of the solution disposed on the substrate has deficit after solvent is removed from the solution by heating the applied solution at 80 degrees Celsius for 2 minutes.

(8) Adhesion to substrate is evaluated by cross-cut tests. The cross-cut tests are carried out as follows. Each of solutions of the resin compositions is applied to a substrate by spin coating. Solvent is removed from the solution by heating the applied solution at 80 degrees Celsius for 2 minutes. A film is formed by exposing the applied solution to a light of 1 J/cm2 under a nitrogen atmosphere. A cut is made in the film in a grid and the film with cut in the grid is exfoliated with tape. g indicates that the film with cut in the grid shows no exfoliation from the substrate while e indicates that the film with cut in the grid shows no exfoliation from the substrate even in cross-section observation by scanning electron microscopy method.

(9) Filling time (100 nm) and Filling time (1000 nm) mean press time required for each of the compositions to be filled in a concave portion having width of 100 nm and a concave portion having width of 1000 nm, respectively. Relatively short filling time is one of important factors for applicability of the composition to nanoimprint technology.

(10) Pattern profile means pattern shape of a resin formed by curing each of the compositions. f indicates that pattern shape is formed in a form predetermined by pattern formed in the mold while c indicates that pattern shape is not formed in the form by cohesive failure. n means that the composition is not cured.

(11) Dry etching rate means the dry etching rate of the resin obtained by curing the composition measured after exposure to oxygen and fluorine plasma.

(12) Dry etching rates are evaluated as follows. Each of films is formed by curing resin composition disposed on a substrate with a light of 1 J/cm2 under a nitrogen atmosphere. The surface of the substrate is exposed by removing a part of the film. A gap between the exposed surface of the substrate and the surface of the film is measured by a film thickness meter at predetermined time intervals from the start of exposure of the film to plasma. Dry etching rates are evaluated by changes of the gap with the passage of time measured by the film thickness meter.

(13) Oxygen plasma is generated by application of a radio wave under a condition in which a flow rate of O.sub.2 is 10 sccm. The intensity of the radio wave to create plasma is 350 W while the frequency of the radio wave is 13.56 MHz. That the dry etching rate is low usually means that the resin is etch-resistant.

(14) Fluorine plasma is generated by utilizing ICP-RIE device under condition in which a flow rate of C3F8 is 20 sccm. The fluorine plasma is generated under condition in which the ICP power, the bias power and the internal temperature are 600 W, 50 W and 23 degrees Celsius, respectively.

(15) Ratio of dry etching rate means a ratio of the dry etching rate of a resin formed by curing a composition to that of the resin formed by curing the composition (Composition 2) containing 95 percent by weight of Compound B and 5 percent by weight of the radical initiator.

(16) The dry etching rate of the resin obtained by curing the composition (Composition 2) containing 95 percent by weight of Compound B and 5 percent by weight of the radical initiator is relatively high compared to resins obtained from the other compositions shown in Table 1. In connection with this, the Ohnishi parameter of the composition containing Compound B is higher than those of the other compositions.

(17) The dry etching rate of the resin formed by curing the composition (Composition 3) containing 95 percent by weight of Compound C and 5 percent by weight of the radical initiator is 134 for oxygen plasma while the dry etching rate is 114 for fluorine plasma.

(18) The pattern profile of the resin formed by curing the composition (Composition 4) containing 95 percent by weight of Compound D and 5 percent by weight of the radical initiator is c, which means that the resin does not exhibit adequate formability.

(19) The resin formed by curing the composition (Composition 5) containing 95 percent by weight of Compound E and 5 percent by weight of the radical initiator exhibits adequate formability. However, the filling times are longer.

(20) The resin formed by curing the composition (Composition 6) containing 95 percent by weight of Compound F and 5 percent by weight of the radical initiator exhibits adequate formability. However, the filling times are longer.

(21) The resin formed by curing the composition (Composition 1) containing 95 percent by weight of Compound A and 5 percent by weight of the radical initiator does not adequate formability.

(22) TABLE-US-00002 TABLE 2 Constituents (ratio by weight) of compositions and characteristic values Compositions 7 8 9 10 11 12 13 Compound A Compound B Compound C Compound D 90 70 60 50 45 40 35 Compound E 5 25 35 45 50 55 60 Compound F Compound G Compound H Initiator A 5 5 5 5 5 5 5 Initiator B Surfactant A Surfactant B Surfactant C 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Surfactant D Ohnishi Parameter 2.56 2.54 2.53 2.82 2.52 2.52 2.51 Viscosity (mPa .Math. s) 18 100 190 550 1,700 2,600 4,200 Spin coating e e e e e e e Adhesion to substrate g g g g g g g Filling time (100 nm) 1 min 1 min 1 min 1 min 1 min 5 min 5 min Filling time (1000 nm) 1 min 1 min 1 min 1 min 1 min 1 min 1 min Pattern profile f f f f f f f Dry etching rate O.sub.2 gas 130 113 114 107 110 113 112 (nm/min) C.sub.3F.sub.8 gas 123 122 122 110 106 101 101 Ratio of dry etching O.sub.2 gas 0.695 0.604 0.610 0.572 0.588 0.604 0.599 rate C.sub.3F.sub.8 gas 0.641 0.635 0.635 0.573 0.552 0.526 0.526 Compositions 14 15 16 17 18 Compound A Compound B Compound C Compound D 30 25 20 15 5 Compound E 65 70 95 80 90 Compound F Compound G Compound H Initiator A 5 5 5 5 5 Initiator B Surfactant A Surfactant B Surfactant C 0.05 0.05 0.05 0.05 0.05 Surfactant D Ohnishi Parameter 2.5 2.5 2.49 2.49 2.48 Viscosity (mPa .Math. s) 6,800 16,500 35,100 81,100 >100,000 Spin coating e e e e e Adhesion to substrate g g g g g Filling time (100 nm) 10 min 15 min 15 min 15 min 15 min Filling time (1000 nm) 1 min 5 min 5 min 10 min 15 min Pattern profile f f f f f Dry etching rate O.sub.3 gas 111 113 110 106 104 (nm/min) C.sub.3 F.sub.8 gas 101 101 100 100 100 Ratio of dry etching O.sub.3 gas 0.594 0.604 0.588 0.567 0.556 rateC.sub.3 F.sub.8 gas 0.526 0.526 0.521 0.521 0.521 e: excellent; g: good; f: fine; c: cohesive failure; u: uncured

(23) The dry etching rate of Composition 7 is 130 nm/min for oxygen plasma while the dry etching rate is 123 for fluorine plasma. The dry etching rate of Composition 18 is 104 nm/min for oxygen plasma while the dry etching rate of Composition 18 is 100 nm/min for fluorine plasma. Compositions 7-18 show relative low etching rate for both oxygen plasma and fluorine plasma, which means that the compositions are suitable for forming etch-resistant resins. Since Compositions 7-17 show relatively short filling time in addition to the low dry etching rates, the compositions are especially suitable for nanoimprint technology. Since Compositions 7-11 show short filling time irrespective of pattern size, the compositions have general versatility in nanoimprint technology.

(24) It is more preferred that the dry etching rate for oxygen plasma ranges from 105 to 115 while the dry etching rate for fluorine plasma ranges from 100 to 122 to ensure compatibility between high etch-resistance and general versatility in nanoimprint technology. Alternatively, it is more preferred that Ohnishi parameter of the composition ranges from 2.49 to 2.54 to attain the compatibility.

(25) TABLE-US-00003 TABLE 3 Constituents (ratio by weight) of compositions and characteristic values Compositions 19 20 21 22 23 24 Compound A Compound B Compound C 90 70 65 60 55 50 Compound D Compound E 5 25 30 35 40 45 Compound F Compound G Compound H Initiator A 5 5 5 5 5 5 Initiator B Surfactant A Surfactant B Surfactant C 0.05 0.05 0.05 0.05 0.05 0.05 Surfactant D Ohnishi Parameter 2.59 2.56 2.56 2.54 2.54 2.54 Viscosity (mPa .Math. s) 190 770 1,400 1,700 2,800 4,000 Spin coating e e e e e e Adhesion to substrate g g g g g g Filling time (100 nm) 1 min 1 min 1 min 1 min 5 min 5 min Filling time (1000 nm) 1 min 1 min 1 min 1 min 1 min 1 min Pattern profile f f f f f f Dry etching rate (nm/min) O.sub.2 gas 131 120 109 109 109 109 C.sub.3F.sub.8 gas 140 138 138 137 137 137 Ratio of dry etching rate O.sub.2 gas 0.701 0.642 0.583 0.583 0.583 0.583 C.sub.3F.sub.8 gas 0.729 0.719 0.719 0.714 0.714 0.714 Compositions 25 26 27 28 29 Compound A Compound B Compound C 45 35 25 20 5 Compound D Compound E 50 60 70 75 90 Compound F Compound G Compound H Initiator A 5 5 5 5 5 Initiator B Surfactant A Surfactant B Surfactant C 0.05 0.05 0.05 0.05 0.05 Surfactant D Ohnishi Parameter 2.53 2.52 2.51 2.5 2.48 Viscosity (mPa .Math. s) 6,800 19,200 62,300 104,800 >110,000 Spin coating e e e e e Adhesion to substrate g g g g g Filling time (100 nm) 10 min 15 min 15 min 15 min 15 min Filling time (1000 nm) 1 min 5 min 5 min 10 min 15 min Pattern profile f f f f f Dry etching rate O.sub.2 gas 108 107 107 106 104 (nm/min) C.sub.3F.sub.8 gas 136 136 135 135 134 Ratio of dry etching O.sub.2 gas 0.578 0.572 0.572 0.567 0.556 rate C.sub.3F.sub.8 gas 0.708 0.708 0.703 0.708 0.635 e: excellent; g: good; f: fine; c: cohesive failure; u: uncured

(26) The dry etching rate of Composition 19 for oxygen plasma is 131 nm/min while the dry etching rate of Composition 19 for fluorine plasma is 140 nm/min. The dry etching rate of Composition 29 for oxygen plasma is 104 nm/min while the dry etching rate of Composition 29 for fluorine plasma is 134 nm/min. Compositions 19-29 show relative low etching rate, which means that the compositions are suitable for forming etch-resistant resins. Since Compositions 19-28 also show relatively short filling time in addition to the low dry etching rates, the compositions are especially suitable for nanoimprint technology. Since Composition 19-22 show short filling time irrespective of pattern size, the compositions have general versatility in nanoimprint technology.

(27) It is more preferred that the dry etching rate of the composition for oxygen plasma ranges from 105 to 115 while the dry etching rate of the composition for fluorine plasma ranges from 135 to 140 to ensure compatibility between high etch-resistance and general versatility in nanoimprint technology. Alternatively, it is more preferred that Ohnishi parameter of the composition ranges from 2.49 to 2.54 to attain the compatibility.

(28) It is more preferred that at least one of polymerizable compounds contained in compositions has only one polymerizable group like Compound C and Compound D while another of the polymerizable compounds has at least two polymerizable groups like Compound E.

(29) TABLE-US-00004 TABLE 4 Constituents (ratio by weight) of compositions containing at least one surfactant and characteristic values Compositions 30 31 32 33 34 35 36 37 38 39 40 41 Compound A Compound B Compound C Compound D 50 50 50 50 50 60 50 50 40 60 50 40 Compound E 45 45 45 45 45 35 45 45 55 5 15 25 Compound F 30 30 30 Compound G 5 5 5 5 5 5 5 5 5 Compound H 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Initiator A Initiator B 5 5 5 5 5 5 5 5 5 5 5 5 Surfactant A 0.05 0.05 0.05 Surfactant B 0.5 1.2 1.5 1.2 1.2 1.2 1.2 Surfactant C Surfactant D 1 1.5 0.05 0.01 0.05 0.05 Ohnishi Parameter 2.57 2.57 2.57 2.57 2.57 2.58 2.57 2.57 2.56 2.48 2.47 2.46 Viscosity (mPa .Math. s) <550 <550 <550 <550 <550 <190 <550 <550 <2,600 >190 >550 >2,600 Spin coating g g g g g e e e e e e e Adhesion to substrate e e e e e e e e e e e e Filling time (100 nm) <1 min <1 min <1 min <1 min <1 min <1 min <1 min <1 min <5 min <1 min <5 min >15 min Filling time (1000 nm) <1 min <1 min <1 min <1 min <1 min <1 min <1 min <1 min <1 min <1 min <5 min <10 min Patten profile f f f f f f f f f f f f Dry etching O.sub.2 gas 110 110 110 110 110 111 110 110 110 106 106 106 rate (nm/min) C.sub.3F.sub.8 gas 117 117 117 117 117 112 117 117 110 118 113 112 Ratio of dry O.sub.2 gas 0.588 0.588 0.588 0.588 0.588 0.594 0.588 0.588 0.588 0.567 0.567 0.567 etching rate C.sub.3F.sub.8 gas 0.609 0.609 0.609 0.609 0.609 0.583 0.609 0.609 0.573 0.615 0.589 0.583 e: excellent; g: good; f: fine; c: cohesive failure; u: uncured

(30) Compositions 30-41 contain at least one surfactant. Surfactant A and Surfactant B are polymeric surfactants, while Surfactant C and Surfactant D contain at least one fluorine atom. Films obtained from all of such compositions show fine pattern profiles. Compositions 30-38 contain Compound G and Compound which are a silane coupling agent and a phosphoric acid, respectively.

(31) Compositions 30-38 show good coating properties and excellent adhesion to substrate. Compound G and Compound H can contribute to improvement of adhesion to substrate concertedly.

(32) Compositions 35-38, which contain two kinds of surfactants, show excellent coating properties and adhesion to substrate. This indicates that it is preferred that a polymeric surfactant and a surfactant containing at least one fluorine atom are added to compositions.

(33) It is preferred that one of the two surfactants has a polymeric moiety containing carbon atoms more than 20. More preferably, such surfactant may have a moiety represented by the following equation:

(34) ##STR00003##

(35) where R 1 is a hydrogen atom, a halogen atom, a substituent containing an oxygen atom, a sulfur atom, a carbon atom and a silicon atom; and R1 is a hydrogen atom, a halogen atom, a substituent containing an oxygen atom, a sulfur atom, a carbon atom and a silicon atom.

(36) Alternatively, such surfactant has the solubility parameter (SP) value ranging from 8.0 to 12.0. Preferably, the SP value may range from 9.5 to 10.0. The SP value is obtained by the following equation:

(37) $\begin{array}{cc}\mathrm{Formula}1& \\ \mathrm{Solubility}\mathrm{Parameter}={\left(\frac{{.Math.}_i{e}_i}{{.Math.}_i{v}_i}\right)}^{\frac{1}{2}}& \left(1\right)\end{array}$
where: e.sub.i is evaporation energy of atom or atomic group. v.sub.i is molar volume of atom or atomic group.

(38) It is preferred that the other kind of surfactants contains at least one fluorine atom. More preferably, such surfactant may have a moiety represented by the following equation:
Formula 2
F(CF.sub.2).sub.kZ(II)

(39) where: k is an integer which is equal to or greater than 1 and which is equal to or smaller than 20; and Z is a hydrogen atom, oxygen atom, carbon atom, sulfur atom or silicon atom.

(40) Compositions 39-41 contain three monomers selected from the group consisting of Compounds A-F. More concretely, such compositions show excellent coating properties and adhesion to substrate. Such compositions contain a compound having only one polymerizable group and an aromatic group and a compound having plural polymerizable groups and an aromatic group. It is preferred that such compositions contain at least two kinds of monomer each of which contains at least two polymerizable groups and at least one aromatic group.

(41) FIG. 1 shows a typical manufacturing process for a component utilizing a composition relating to an aspect of the disclosure.

(42) The manufacturing process is as follows:

(43) (A) A solution of a composition mentioned above is disposed on a substrate 2 by a spin-coating process to form a coating film 1 of the solution.

(44) (B) A solvent contained in the solution is removed by heating the solution disposed on the substrate 2 to form a coating film 3 of the composition. A typical heating temperature and time for the removal of solvent are around 80 degrees Celsius and 2 minutes, respectively.

(45) (C) The coating film 3 is sandwiched between a mold 4 and the substrate 2 by putting pressure upon at least one of the mold 4 and the substrate 2. A plurality of concave portions or a plurality of convex portions are formed in the mold 4.

(46) (D) A resin 5 is formed by an irradiation of the composition with a light transmitted through any one of the substrate 2 and the mold 4. The resin 5 has a plurality of thicker portions and a plurality of thinner portions. A typical light source for the light irradiation is a xenon lamp or UV lamp. The energy density of the irradiation light is typically ca. 1 J/cm.sup.2. It is preferred that the light irradiation is carried out typically under an inert gas atmosphere such as nitrogen atmosphere and argon atmosphere. After the resin 5 is formed, the mold 4 is separated from the resin 5.

(47) (E) Dry etching is carried out for removing the plurality of thinner portions.

(48) (F) After the dry etching process, the plurality of thicker portions are left on the substrate 2.

(49) (G) A plurality of portion of the substrate 2 on which the plurality of thinner portions of the resin have been formed are etched to form a plurality of grooves.

(50) (H) The plurality of thicker portions are removed by an ashing process to obtain a member 6 having a plurality of grooves. The member can be utilized for a component such as light guide plate and photomask.

(51) Such component can be a component contained in a device or a component utilized for manufacturing a device.