METHODS FOR CONTROLLING THE PHASE OF SELF-ASSEMBLED IONIC LIQUID CRYSTAL (ILC) STRUCTURES

Abstract

Embodiments of improved methods are provided to form ordered structures on a surface of a substrate using direct self-assembly (DSA) of ionic liquid crystals (ILCs). More specifically, various embodiments of methods are provided to control the phase of an ordered structure formed on a substrate surface via self-assembly of ILCs having cation head groups, alkyl tail groups having a plurality of hydrocarbons and anions. In the embodiments disclosed herein, the phase of the ordered structure is controlled by replacing the hydrogen (H) atoms of the hydrocarbons included the alkyl chain with larger sized functional groups. Adding larger sized functional groups to the alkyl chain changes the phase of the ordered structure by: (a) increasing the separation between the hydrophilic (cation) and hydrophobic (alkyl tail) groups of the ILCs, and (b) changing the orientation of alkyl tails within the tail groups of the self-assembled ILCs.

Claims

1. A method to control a phase of a self-assembled ionic liquid crystal (ILC) structure formed on a substrate, the method comprising: providing a solution comprising ionic liquid crystals (ILCs) having cation head groups, anions and alkyl tail groups, each alkyl tail group comprising a chain of hydrocarbons; depositing the solution onto a surface of the substrate, wherein the ILCs self-assemble on the surface of the substrate to form an ordered structure having alternating head groups and tail groups, wherein the cation head groups and the anions of the ILCs segregate to the head groups and the alkyl tail groups segregate to the tail groups; and controlling the phase of the ordered structure by replacing hydrogen (H) atoms within the chain of hydrocarbons with larger functional groups prior to depositing the solution onto the surface of the substrate.

2. The method of claim 1, wherein the cation head groups comprise an imidazolium, pyrazolium, pyrrolidinium, pyridinium, piperidinium, morpholinium, ammonium, phosphonium, sulphonium or cholinium-based cation head group.

3. The method of claim 1, wherein the cation head groups comprise an imidazolium-based cation head group of the form: 1-R.sub.1-3-R.sub.2-imidazolium, where R.sub.1 is an alkyl chain with a chain length ranging from 8-18 hydrocarbons, and R.sub.2 is a hydrogen, methyl, ethyl, propyl, butyl, substituted or unsubstituted phenyl, or other hydrocarbon group.

4. The method of claim 3, wherein the cation head groups comprise 1-dodecyl-3-methylimidazolium.

5. The method of claim 3, wherein the anions comprise tetrafluoroborate (BF.sub.4.sup.), chloride (Cl.sup.), acetate (CH.sub.3COO.sup.), hexafluorophosphate (PF.sub.6.sup.), trifluoromethyl acetate (C.sub.3H.sub.3F.sub.3O.sub.2.sup.), nitrate (NO.sub.3.sup.), dicyanamide (C.sub.2HN.sub.3.sup.), tetracyanoborate (B(CN).sub.4.sup.), trifluoromethane sulfonate (CF.sub.3O.sub.3S.sup.), bis((trifluoromethyl)sulfonyl)imdide ([(CF.sub.3SO.sub.2).sub.2N]), tetrachloroaluminate ([AlCl.sub.4]), heptachlorodialuminate ([Al.sub.2Cl.sub.7]), decachlorotrialuminate ([Al.sub.3Cl.sub.10]), tridecachlorotetraaluminate ([Al.sub.4Cl.sub.13]), tetrachloroferrate (Cl.sub.4Fe), trichlorostannate ([SnCl.sub.3]), pentachlorodistannate ([Sn.sub.2Cl.sub.5]), tetrachloroindate ([InCl.sub.4]), nonachlorodititanate ([Ti.sub.2Cl.sub.9]), nonachlorodizirconate ([Zr.sub.2Cl.sub.9]), nonachlorodihafnate ([Hf.sub.2Cl.sub.9]), tetrachloroaurate ([AuCl.sub.4]), tetrachlorogallate ([GaCl.sub.4]), heptachlorodigallate ([Ga.sub.2Cl.sub.7]), decachlorotrigallate ([Ga.sub.3Cl.sub.10]), trichloroplumbate ([PbCl.sub.3]), pentachloridoindate ([InCl.sub.5].sup.2), tetrachlorozincate ([ZnCl.sub.4].sup.2), hexachlorodizincate ([Zn.sub.2Cl.sub.6].sup.2), hexachlorotitanate ([TiCl.sub.6].sup.2), hexachlorozirconate ([ZrCl.sub.6].sup.2), decachlorodizirconate ([Zr.sub.2Cl.sub.10].sup.2), hexachlorohafnate ([HfCl.sub.6].sup.2), decachlorodihafnate ([Hf.sub.2Cl.sub.10].sup.2), tetrachloromanganate ([MnCl.sub.4].sup.2), tetrachloroferrate ([FeCl.sub.4].sup.2), tetrachlorocobaltate ([CoCl.sub.4].sup.2), tetrachloronicklate ([NiCl.sub.4].sup.2), tetrachloropaladate ([PdCl.sub.4].sup.2), tetrachloroplatinate ([PtCl.sub.4].sup.2), tetrachlorocuprate ([CuCl.sub.4].sup.2), octachlorotrizincate ([Zn.sub.3Cl.sub.8].sup.2), decachlorotetrazincate ([Zn.sub.4Cl.sub.10].sup.2), tetrachlorocadmate ([CdCl.sub.4].sup.2), hexachlorodicadmate ([Cd.sub.2Cl.sub.6].sup.2), tetrachloromercurate ([HgCl.sub.4].sup.2), or tetrachloroplumbate ([PbCl.sub.4].sup.2).

6. The method of claim 3, wherein said controlling the phase of the ordered structure comprises replacing the hydrogen (H) atoms with methyl (CH.sub.3) groups prior to depositing the solution onto the surface of the substrate.

7. The method of claim 6, wherein said replacing the hydrogen (H) atoms with the methyl (CH.sub.3) groups changes the phase of the ordered structure by: (a) increasing a separation between the alkyl tail groups in the tail groups of the ordered structure, and (b) changing an orientation of the alkyl tail groups in the tail groups of the ordered structure.

8. The method of claim 7, wherein the ILCs self-assemble on the surface of the substrate to form a nanopore/rod structure having alternating head groups and tail groups, wherein the cation head groups and the anions segregate to the head groups to form a plurality of rods within the nanopore/rod structure, with the alkyl tail groups oriented around the plurality of rods.

9. The method of claim 8, wherein the plurality of rods are evenly distributed within the nanopore/rod structure with equal spacing between each of the plurality of rods.

10. A method to form a self-assembled ionic liquid crystal (ILC) structure on a substrate, the method comprising: providing a solution comprising ionic liquid crystals (ILCs) having imidazolium-based cation head groups, anions and alkyl tail groups, each alkyl tail group comprising a chain of hydrocarbons, and wherein each hydrocarbon in the chain of hydrocarbons comprises a plurality of methyl groups (CH.sub.3) bound to a carbon (C) atom; and depositing the solution onto a surface of the substrate, wherein the ILCs self-assemble on the surface of the substrate to form a nanopore/rod structure having alternating head groups and tail groups, wherein the imidazolium-based cation head groups and the anions of the ILCs segregate to the head groups to form a plurality of rods within the nanopore/rod structure, with the alkyl tail groups oriented around the plurality of rods.

11. The method of claim 10, wherein the imidazolium-based cation head groups are of the form: 1-R.sub.1-3-R.sub.2-imidazolium, where R.sub.1 is an alkyl chain with a chain length ranging from 8-18 hydrocarbons, and R.sub.2 is a hydrogen, methyl, ethyl, propyl, butyl, substituted or unsubstituted phenyl, or other hydrocarbon group.

12. The method of claim 10, wherein the imidazolium-based cation head groups comprise 1-dodecyl-3-methylimidazolium.

13. The method of claim 10, wherein the anions comprise tetrafluoroborate (BF.sub.4.sup.), chloride (Cl.sup.), acetate (CH.sub.3COO.sup.), hexafluorophosphate (PF.sub.6.sup.), trifluoromethyl acetate (C.sub.3H.sub.3F.sub.3O.sub.2), nitrate (NO.sub.3.sup.), dicyanamide (C.sub.2HN.sub.3.sup.), tetracyanoborate(B(CN).sub.4.sup.), trifluoromethane sulfonate (CF.sub.3O.sub.3S.sup.), bis((trifluoromethyl)sulfonyl)imdide ([(CF.sub.3SO.sub.2).sub.2N].sup.), tetrachloroaluminate ([AlCl.sub.4].sup.), heptachlorodialuminate ([Al.sub.2Cl.sub.7].sup.), decachlorotrialuminate ([Al.sub.3Cl.sub.10].sup.), tridecachlorotetraaluminate ([Al.sub.4Cl.sub.13].sup.), tetrachloroferrate (Cl.sub.4Fe.sup.), trichlorostannate ([SnCl.sub.3]), pentachlorodistannate ([Sn.sub.2Cl.sub.5].sup.), tetrachloroindate ([InCl.sub.4]), nonachlorodititanate ([Ti.sub.2Cl.sub.9]), nonachlorodizirconate ([Zr.sub.2Cl.sub.9]), nonachlorodihafnate ([Hf.sub.2Cl.sub.9]), tetrachloroaurate ([AuCl.sub.4]), tetrachlorogallate ([GaCl.sub.4]), heptachlorodigallate ([Ga.sub.2Cl.sub.7]), decachlorotrigallate ([Ga.sub.3Cl.sub.10]), trichloroplumbate ([PbCl.sub.3]), pentachloridoindate ([InCl.sub.5].sup.2), tetrachlorozincate ([ZnCl.sub.4].sup.2), hexachlorodizincate ([Zn.sub.2Cl.sub.6].sup.2), hexachlorotitanate ([TiCl.sub.6].sup.2), hexachlorozirconate ([ZrCl.sub.6].sup.2), decachlorodizirconate ([Zr.sub.2Cl.sub.10].sup.2), hexachlorohafnate ([HfCl.sub.6].sup.2), decachlorodihafnate ([Hf.sub.2Cl.sub.10].sup.2), tetrachloromanganate ([MnCl.sub.4].sup.2), tetrachloroferrate ([FeCl.sub.4].sup.2), tetrachlorocobaltate ([CoCl.sub.4].sup.2), tetrachloronicklate ([NiCl.sub.4].sup.2), tetrachloropaladate ([PdCl.sub.4].sup.2), tetrachloroplatinate ([PtCl.sub.4].sup.2), tetrachlorocuprate ([CuCl.sub.4].sup.2), octachlorotrizincate ([Zn.sub.3Cl.sub.8].sup.2), decachlorotetrazincate ([Zn.sub.4Cl.sub.10].sup.2), tetrachlorocadmate ([CdCl.sub.4].sup.2), hexachlorodicadmate ([Cd.sub.2Cl.sub.6].sup.2), tetrachloromercurate ([HgCl.sub.4].sup.2), or tetrachloroplumbate ([PbCl.sub.4].sup.2).

14. The method of claim 10, wherein the ILCs comprise 1-dodecyl-3-methylimidazolium tetrafluoroborate.

15. The method of claim 14, wherein the plurality of rods are evenly distributed within the nanopore/rod structure with equal spacing between each of the plurality of rods.

16. The method of claim 15, wherein the equal spacing between each of the plurality of rods is approximately 3 nm.

17. The method of claim 15, wherein a diameter of each rod is approximately 1 nm.

18. A self-assembled ionic liquid crystal (ILC) structure formed on a substrate via self-assembly of ionic liquid crystals (ILCs), wherein: the ILCs have imidazolium-based cation head groups, anions and alkyl tail groups, wherein the alkyl tail groups each comprise a chain of hydrocarbons, and wherein each hydrocarbon in the chain of hydrocarbons comprises a plurality of methyl groups (CH.sub.3) bound to a carbon (C) atom; and the ILCs self-assemble on a surface of the substrate to form a nanopore/rod structure having alternating head groups and tail groups, wherein the imidazolium-based cation head groups and the anions of the ILCs segregate to the head groups to form a plurality of rods within the nanopore/rod structure, with the alkyl tail groups oriented around the plurality of rods.

19. The self-assembled ILC structure of claim 18, wherein the imidazolium-based cation head groups are of the form: 1-R.sub.1-3-R.sub.2-imidazolium, where R.sub.1 is an alkyl chain with a chain length ranging from 8-18 hydrocarbons, and R.sub.2 is a hydrogen, methyl, ethyl, propyl, butyl, substituted or unsubstituted phenyl, or other hydrocarbon group.

20. The self-assembled ILC structure of claim 18, wherein the anions comprise tetrafluoroborate (BF.sub.4.sup.), chloride (Cl.sup.), acetate (CH.sub.3COO.sup.), hexafluorophosphate (PF.sub.6.sup.), trifluoromethyl acetate (C.sub.3H.sub.3F.sub.3O.sub.2.sup.), nitrate (NO.sub.3.sup.), dicyanamide (C.sub.2HN.sub.3.sup.), tetracyanoborate (B(CN).sub.4.sup.), trifluoromethane sulfonate (CF.sub.3O.sub.3S.sup.), bis((trifluoromethyl)sulfonyl)imdide ([(CF.sub.3SO.sub.2).sub.2N].sup.), tetrachloroaluminate ([AlCl.sub.4].sup.), heptachlorodialuminate ([Al.sub.2Cl.sub.7].sup.), decachlorotrialuminate ([Al.sub.3Cl.sub.10]), tridecachlorotetraaluminate ([Al.sub.4Cl.sub.13]), tetrachloroferrate (Cl.sub.4Fe), trichlorostannate ([SnCl.sub.3].sup.), pentachlorodistannate ([Sn.sub.2Cl.sub.5].sup.), tetrachloroindate ([InCl.sub.4]), nonachlorodititanate ([Ti.sub.2Cl.sub.9]), nonachlorodizirconate ([Zr.sub.2Cl.sub.9]), nonachlorodihafnate ([Hf.sub.2Cl.sub.9]), tetrachloroaurate ([AuCl.sub.4]), tetrachlorogallate ([GaCl.sub.4]), heptachlorodigallate ([Ga.sub.2Cl.sub.7]), decachlorotrigallate ([Ga.sub.3Cl.sub.10]), trichloroplumbate ([PbCl.sub.3]), pentachloridoindate ([InCl.sub.5].sup.2), tetrachlorozincate ([ZnCl.sub.4].sup.2), hexachlorodizincate ([Zn.sub.2Cl.sub.6].sup.2), hexachlorotitanate ([TiCl.sub.6].sup.2), hexachlorozirconate ([ZrCl.sub.6].sup.2), decachlorodizirconate ([Zr.sub.2Cl.sub.10].sup.2), hexachlorohafnate ([HfCl.sub.6].sup.2), decachlorodihafnate ([Hf.sub.2Cl.sub.10].sup.2), tetrachloromanganate ([MnCl.sub.4].sup.2), tetrachloroferrate ([FeCl.sub.4].sup.2), tetrachlorocobaltate ([CoCl.sub.4].sup.2), tetrachloronicklate ([NiCl.sub.4].sup.2), tetrachloropaladate ([PdCl.sub.4].sup.2), tetrachloroplatinate ([PtCl.sub.4].sup.2), tetrachlorocuprate ([CuCl.sub.4].sup.2), octachlorotrizincate ([Zn.sub.3Cl.sub.8].sup.2), decachlorotetrazincate ([Zn.sub.4Cl.sub.10].sup.2), tetrachlorocadmate ([CdCl.sub.4].sup.2), hexachlorodicadmate ([Cd.sub.2Cl.sub.6].sup.2), tetrachloromercurate ([HgCl.sub.4].sup.2), or tetrachloroplumbate ([PbCl.sub.4].sup.2).

21. The self-assembled ILC structure of claim 18, wherein the ILCs comprise 1-dodecyl-3-methylimidazolium tetrafluoroborate.

22. The self-assembled ILC structure of claim 21, wherein the plurality of rods are evenly distributed within the nanopore/rod structure with equal spacing between each of the plurality of rods.

23. The self-assembled ILC structure of claim 22, wherein the equal spacing between each of the plurality of rods is approximately 3 nm.

24. The self-assembled ILC structure of claim 22, wherein a diameter of each rod is approximately 1 nm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0030] A more complete understanding of the present inventions and advantages thereof may be acquired by referring to the following description taken in conjunction with the accompanying drawings, in which like reference numbers indicate like features. It is to be noted, however, that the accompanying drawings illustrate only exemplary embodiments of the disclosed concepts and are therefore not to be considered limiting of the scope, for the disclosed concepts may admit to other equally effective embodiments.

[0031] FIG. 1A is a mapping of coarse grain particles of an example ionic liquid crystal (ILC) molecule.

[0032] FIG. 1B illustrates one example of an ordered structure (i.e., a layered structure) formed by direct self-assembly (DSA) of the ILC molecules shown in FIG. 1A.

[0033] FIG. 2 is a flowchart diagram illustrating a method that may be used to control a phase of a self-assembled ILC structure formed on a substrate in accordance with one embodiment of the present disclosure.

[0034] FIG. 3A depicts the chemical structure of an example ILC molecule (e.g., [C.sub.12mim][BF.sub.4.sup.]: 1-dodecyl-3-methylimidazolium tetrafluoroborate).

[0035] FIG. 3B provides a course-grain simulation of an ordered structure (i.e., a layered structure) formed by DSA of the ILC molecule shown in FIG. 3A.

[0036] FIG. 4A depicts the chemical structure of the ILC molecule shown in FIG. 3A after replacing the hydrogen (H) atoms in the alkyl chain with methyl (CH.sub.3) groups.

[0037] FIG. 4B provides a course-grain simulation of an ordered structure (i.e., a nanopore/rod structure) formed by DSA of the ILC molecule shown in FIG. 4A.

[0038] FIGS. 5A-5B provide a top view (FIG. 5A) and side view (FIG. 5B) of the nanopore/rod structure formed by DSA of the ILC molecule shown in FIG. 4A.

[0039] FIGS. 5C-5D provide additional views of the plurality of rods included within the nanopore/rod structure shown in FIGS. 5A-5B.

[0040] FIG. 5E provides a top view of the nanopores included within the nanopore/rod structure shown in FIGS. 5A-5B.

[0041] FIG. 5F provides a top view of the nanopore/rod structure shown in FIG. 5B, illustrating the even distribution of a plurality of rods formed via self-assembly of the ILCs shown in FIG. 4A.

[0042] FIG. 6 is a flowchart diagram illustrating a method that may be used to form a self-assembled ILC structure formed on a substrate in accordance with one embodiment of the present disclosure.

DETAILED DESCRIPTION

[0043] Ionic liquid crystals (ILCs) self-assemble into solid (crystalline phase) ordered structures at or near room temperature. The difference in polarity between the cation head groups and the alkyl tail groups of the ILCs promote direct self-assembly of ILC molecules by segregating the head and tail groups into ordered structures, with the cation head groups and anions segregating to the head groups and the alkyl tail groups segregating to the tail groups. It is generally well-known that the orientation and pitch of an ordered structure can be controlled by controlling the deposition temperature, the chain length of the alkyl tail groups included within the ILCs used to form the ordered structure and the hydrophobicity of the guide surface(s) upon which the ILCs are deposited, such as the underlying substrate surface and/or the sidewalls of a larger template pattern.

[0044] As noted above in the Background section, ILCs are known to self-assemble into a wide variety of ordered phases (or mesophases), including nematic (N), smectic (Sm), columnar (Col) and cubic (Cub) phases. A mesophase is an intermediate state between the perfectly ordered crystalline and the disordered liquid state. Mesophase formation in ILCs is thought to be primarily controlled by van der Walls interactions between the alkyl chains, dipole-dipole, cation-TT interactions, IT-TT stacking, as well as the hydrogen bonding between the anions and cations of the ILCs. Mesophase formation has been observed in a wide variety of ILCs by choosing an alkyl chain, which is long enough to enhance the van der Walls forces between the alkyl tails and induce mesophase formation. For example, it has been found that imidazolium-based ILCs exhibit a mesophase when at least one sufficiently long alkyl chain is attached to a nitrogen (N) atom on the imidazolium cation. Specifically, imidazolium-based ILCs are known to exhibit SmA mesophases comprising periodic stacks of two-dimensional (2D) alternating layers of head group layers and tail group layers. In addition to alkyl chain length, the choice of anion has also been shown to affect the mesogenic properties of the self-assembled ILC structure.

[0045] New methods are provided in the present disclosure for controlling the phase of an ordered structure formed on a substrate surface via self-assembly of ILCs. In the disclosed embodiments, the phase of an ordered structure is controlled by replacing the hydrogen (H) atoms of the hydrocarbons included the alkyl chain with larger sized functional groups. Adding larger sized functional groups to the alkyl chain changes the phase of the ordered structure by: (a) increasing the separation between the hydrophilic (cation) and hydrophobic (alkyl tail) groups of the ILCs, and (b) changing the orientation of alkyl tails within the tail groups of the self-assembled ILCs.

[0046] In some embodiments, the methods disclosed herein can be used to change the phase of an ordered structure formed on a substrate surface via self-assembly of 1-dodecyl-3-methylimidazolium tetrafluoroborate ([C.sub.12mim][BF.sub.4.sup.]) ILCs. By replacing the H atoms in the alkyl chain of [C.sub.12mim][BF.sub.4.sup.] ILCs with CH.sub.3 groups, the techniques described herein randomize the orientation of alkyl tails within the tail groups of the self-assembled ILCs to change the phase of the ordered structure, thereby changing the ordered structure from a layered structure to nanopore/rod structure. It is noted, however, that the methods disclosed herein are not limited to [C.sub.12mim][BF.sub.4.sup.] ILCs and may be used to control the phase of ordered structures formed via self-assembly of other ILCs, possibly having different cations, anions and/or alkyl tail groups.

[0047] FIG. 2 illustrates one embodiment of a method 200 that uses the techniques disclosed herein to control a phase of a self-assembled ILC structure formed on a substrate. It will be recognized that the embodiment of the method 200 shown in FIG. 2 is merely exemplary and additional methods may utilize the techniques described herein. Further, additional processing steps may be added to the method 200 shown in FIG. 2 as the steps described are not intended to be exclusive. Moreover, the order of the steps is not limited to the order shown in the figure as different orders may occur and/or various steps may be performed in combination or at the same time.

[0048] The method 200 includes providing a solution comprising ionic liquid crystals (ILCs) having cation head groups, anions and alkyl tail groups, each alkyl tail group comprising a chain of hydrocarbons (in step 210) and depositing the solution onto a surface of a substrate (in step 220). Once deposited in step 210, the ILCs self-assemble on the surface of the substrate to form an ordered structure having alternating head groups and tail groups, with the cation head groups and the anions of the ILCs segregated to the head groups and the alkyl tail groups segregated to the tail groups. The method 200 further includes controlling the phase of the ordered structure by replacing the hydrogen (H) atoms within the chain of hydrocarbons with larger molecules (in step 230) before the solution is deposited onto the surface of the substrate (in step 220).

[0049] The ILCs used in the method 200 may include a wide variety of cation head groups. For example, the ILCs may include imidazolium, pyrazolium, pyrrolidinium, pyridinium, piperidinium, morpholinium, ammonium, phosphonium, sulphonium or cholinium-based cation head groups. In some embodiments, the ILCs may include an imidazolium-based cation head group of the form: 1-R.sub.1-3-R.sub.2-imidazolium, where R.sub.1 is an alkyl chain with a chain length ranging from 8-18 hydrocarbons, and R.sub.2 is a hydrogen, methyl, ethyl, propyl, butyl, substituted or unsubstituted phenyl, or other hydrocarbon group.

[0050] In one example embodiment, the ILCs used in the method 200 may include a 1-dodecyl-3-methylimidazolium-based cation head group (otherwise referred to as C12mim), which is a monovalent cation (i.e., a cation having a +1 charge) head group having an aromatic ring with an alkyl chain of 12 hydrocarbons covalently bound to the N1 position and a methyl group covalently bound to the N3 position of the aromatic ring. It is noted, however, that ILCs having imidazolium-based cation head groups with different alkyl chain lengths can also be provided within the solution. For example, imidazolium-based ILCs having anywhere from 8 hydrocarbons (C8mim) to 18 hydrocarbons (C18mim) in the alkyl chain can be used. It is further noted that ILCs with other cation head groups with potentially different valences and/or alkyl chain lengths may also be provided within the solution.

[0051] The ILCs used in the method 200 may also include a wide variety of anions, including monovalent anions (i.e., anions having a 1 charge), divalent anions (i.e., anions having a 2 charge) or trivalent anions (i.e., anions having a 3 charge). The anions included within the ILCs may be organic anions or metalate anions.

[0052] In some embodiments, ILCs having monovalent cation head groups and monovalent anions may be used in the method 200 to provide the ILCs with a 1:1 cation/anion charge ratio. Examples of monovalent anions that may be included within the ILCs include, but are not limited to, tetrafluoroborate (BF.sub.4.sup.), chloride (Cl), acetate (CH.sub.3COO.sup.), hexafluorophosphate (PF.sub.6.sup.), trifluoromethyl acetate (C.sub.3H.sub.3F.sub.3O.sub.2), nitrate (NO.sub.3.sup.), dicyanamide (C.sub.2HN.sub.3.sup.), tetracyanoborate (B(CN).sub.4.sup.), trifluoromethane sulfonate (CF.sub.3O.sub.3S), bis((trifluoromethyl)sulfonyl)imdide ([(CF.sub.3SO.sub.2).sub.2N].sup.), tetrachloroaluminate ([AlCl.sub.4].sup.), heptachlorodialuminate ([Al.sub.2Cl.sub.7].sup.), decachlorotrialuminate ([Al.sub.3Cl.sub.10].sup.), tridecachlorotetraaluminate ([Al.sub.4Cll.sub.3].sup.), tetrachloroferrate (Cl.sub.4Fe.sup.), trichlorostannate ([SnCl.sub.3].sup.), pentachlorodistannate ([Sn.sub.2Cl.sub.5].sup.), tetrachloroindate ([InCl.sub.4]), nonachlorodititanate ([Ti.sub.2Cl.sub.9]), nonachlorodizirconate ([Zr.sub.2Cl.sub.9]), nonachlorodihafnate ([Hf.sub.2Cl.sub.9]), tetrachloroaurate ([AuCl.sub.4]), tetrachlorogallate ([GaCl.sub.4]), heptachlorodigallate ([Ga.sub.2Cl.sub.7]), decachlorotrigallate ([GasCl.sub.10]), and trichloroplumbate ([PbCl3]).

[0053] In other embodiments, ILCs having monovalent cation head groups and divalent anions (or trivalent anions) may be used in the method 200 to provide the ILCs with a 1:2 cation/anion charge ratio (or a 1:3 cation/anion charge ratio). Examples of divalent anions that may be included within the ILCs include, but are not limited to, pentachloridoindate ([InCl.sub.5].sup.2), tetrachlorozincate ([ZnCl.sub.4].sup.2), hexachlorodizincate ([Zn.sub.2Cl.sub.6].sup.2), hexachlorotitanate ([TiCl.sub.6].sup.2), hexachlorozirconate ([ZrCl.sub.6].sup.2), decachlorodizirconate ([Zr.sub.2Cl.sub.10].sup.2), hexachlorohafnate ([HfCl.sub.6].sup.2), decachlorodihafnate ([Hf.sub.2Cl.sub.10].sup.2), tetrachloromanganate ([MnCl.sub.4].sup.2), tetrachloroferrate ([FeCl.sub.4].sup.2), tetrachlorocobaltate ([CoCl.sub.4].sup.2), tetrachloronicklate ([NiCl.sub.4].sup.2), tetrachloropaladate ([PdCl.sub.4].sup.2), tetrachloroplatinate ([PtCl.sub.4].sup.2), tetrachlorocuprate ([CuCl.sub.4].sup.2), octachlorotrizincate ([Zn.sub.3Cl.sub.8].sup.2), decachlorotetrazincate ([Zn.sub.4Cl.sub.10].sup.2), tetrachlorocadmate ([CdCl.sub.4].sup.2), hexachlorodicadmate ([Cd.sub.2Cl.sub.6].sup.2), tetrachloromercurate ([HgCl.sub.4].sup.2), and tetrachloroplumbate ([PbCl.sub.4].sup.2). Hexachloridoindate ([InCl.sub.6].sup.3) is one example of a trivalent anion that may be included within the ILCs. In some cases, ILCs having monovalent cation head groups and divalent anions (or trivalent anions) may be used in the method 200 to increase the pitch of the ordered structure formed in step 220 by preventing the alkyl tail groups from interdigitating within the tail groups of the ordered structure.

[0054] In yet other embodiments, the ILCs used in the method 200 may be metalate salt ILCs having metalate anions. As known in the art, a metalate anion (or metalate) is a complex anion containing a metal ligated to several atoms or small groups. A metalate anion can include any metal and a wide variety of ligands. Examples of metals that may be included within a metalate anion include transition metals (such as, e.g., iron (Fe), copper (Cu), cobalt (Co), Zinc (Zn), Cadmium (Cd), etc.), post-transition metals (such as, e.g., aluminum (Al), indium (In), tin (Sn), lead (Pb), bismuth (Bi), etc.) and lanthanides (such as, e.g., cerium (Ce), neodymium (Nd), samarium (Sm), etc.). Examples of ligands that may be included within a metalate anion include oxo, halo, cyano (CN), thiocyano (SCN), nitrato, sulfato, phosphato, phosphine, trifluoromethane sulfonate, sulfo and carbonato ligands. In some embodiments, chlorometalate anions may be used to form metalate salt ILCs. Examples of chlorometalate anions that may be used to form metalate salt ILCs include, but are not limited to, chloroaluminate anions (such as, e.g., [AlCl.sub.4], [Al.sub.2Cl.sub.7], [Al.sub.3Cl.sub.10], [Al.sub.4Cl.sub.13], etc.), chloroferrate anions (such as, e.g., Cl.sub.4Fe), chlorostannate anions (such as, e.g., [SnCl.sub.3], [Sn.sub.2Cl.sub.5], etc.), chloroindate anions (such as, e.g., [InCl.sub.6].sup.3, ([InCl.sub.5].sup.2, [InCl.sub.4], etc.), and chlorozincate anions (such as, e.g., [ZnCl.sub.4].sup.2, [Zn.sub.2Cl.sub.6].sup.2, [Zn.sub.3Cl.sub.8].sup.2, etc.).

[0055] As noted above, the phase of the ordered structure is controlled in step 230 by replacing hydrogen (H) atoms within the chain of hydrocarbons with larger functional groups prior to depositing the solution onto the surface of the substrate in step 220. In some embodiments, the phase of the ordered structure may be controlled in step 230 by replacing the H atoms with methyl (CH.sub.3) groups prior to depositing the solution onto the surface of the substrate in step 220. Replacing the H atoms with larger CH.sub.3 groups adds bulk to the alkyl chain and prevents the alkyl tail groups from interdigitating within the tail groups of the ordered structure. In addition to increasing the separation between the alkyl tail groups, adding CH.sub.3 groups to the alkyl chain changes the orientation of the alkyl tail groups within the tail groups of the ordered structure, which changes the phase of the ordered structure.

[0056] A wide variety of techniques can be used to replace the H atoms with CH.sub.3 groups in step 230. For example, it is generally well known that imidazolium molecules can be synthesized by reacting methylimidazole with an alkyl bromide (such as, e.g., [BF.sub.4.sup.]) at elevated temperature to produce 1-alkyl-3-methylimidazolium bromide. Ion exchange can be used to make imidazolium salts with other anions. To synthesize an ILC having CH.sub.3 functional groups in the alkyl chain, instead of hydrogen atoms, methylimidazole can be reacted with a methylated alkyl bromide (such as, e.g. 2-bromo-2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-icosihenamethyltridecane) at elevated temperature to produce an ILC-CH.sub.3 based off of C.sub.12mim.

[0057] In some embodiments, the method 200 shown in FIG. 2 may be used to control the phase of an ordered structure formed via self-assembly of imidazolium-based ILCs. FIG. 3A illustrates the chemical structure of an example ILC 300 ([C.sub.12mim][BF.sub.4.sup.]) having an imidazolium cation head group 302 ([C.sub.12mim]) covalently bound to an alkyl chain of hydrocarbons 304 and a monovalent anion 306 ([BF.sub.4.sup.]). In the ILC 300, the imidazolium cation head group 302 comprises an aromatic ring with an alkyl chain of hydrocarbons 304 covalently bound to the N1 position, and a methyl (CH.sub.3) group covalently bound to the N3 position of the aromatic ring. In the example shown in FIG. 3A, the alkyl chain of hydrocarbons 304 includes 11 methylene (CH.sub.2) groups with covalent bonds between the carbon (C) atoms of the CH.sub.2 groups and one terminal methyl (CH.sub.3) group covalently bound through the carbon atom. Although 12 hydrocarbons are explicitly shown in FIG. 3A, imidazolium-based ILCs having different alkyl chain lengths (e.g., [C.sub.8mim] . . . [C.sub.18mim]) and/or different anions may also be used in the method 200.

[0058] FIG. 3B illustrates an ordered structure formed by direct self-assembly (DSA) of the ILCs 300 shown in FIG. 3A. As shown in FIG. 3B, the ILCs 300 self-assemble into a layered structure 350 having alternating layers of head group layers 352 and tail group layers 354, with the cation head groups and the anions of the ILCs segregated to the head group layers 352 and the alkyl tail groups segregated to the tail group layers 354. Pairing a monovalent anion (such as, e.g., [BF.sub.4.sup.]) with a monovalent cation head group of sufficient alkyl chain length (such as, e.g., [C.sub.12mim]) allows the self-assembled ILCs 300 to form a layered structure 350 having interdigitated alkyl tails in the tail group layers 354 and an SmA mesophase.

[0059] In some embodiments of the method 200, the H atoms in the alkyl chain of hydrocarbons 304 may be replaced with CH.sub.3 groups in step 230 to form an ILC 400 as shown in FIG. 4A. FIG. 4A illustrates the chemical structure of an example ILC 400 ([C.sub.12mim][CH.sub.3][BF.sub.4.sup.]) having an imidazolium cation head group 402 ([C.sub.12mim]) covalently bound to an alkyl chain of hydrocarbons 404 and a monovalent anion 406 ([BF.sub.4.sup.]). Like the ILC 300, the imidazolium cation head group 402 of the ILC 400 comprises an aromatic ring with an alkyl chain of hydrocarbons 404 covalently bound to the N1 position, and a CH.sub.3 group covalently bound to the N3 position of the aromatic ring. As noted above and described in more detail below, the CH.sub.3 groups added to the alkyl chain prevent the alkyl tails from interdigitating and change the orientation of alkyl tails during self-assembly of the ILCs 400.

[0060] FIG. 4B illustrates an ordered structure formed by direct self-assembly (DSA) of the ILCs 400 shown in FIG. 4A. As shown in FIG. 4B, the ILCs 400 self-assemble into a nanopore/rod structure 450 having alternating head groups 452 and tail groups 454, with the cation head groups and the anions of the ILCs 400 segregated to the head groups 452 to form the rods within the nanopore/rod structure 450. The alkyl tail groups of the ILCs 400 are segregated to the tail groups 454 and oriented around the rods.

[0061] FIGS. 5A-5B provide additional views of the nanopore/rod structure 450 formed by DSA of the ILCs 400 shown in FIG. 4A. In the top view shown in FIG. 5A, the nanopore/rod structure 450 is depicted as a three-dimensional (3D) structure with a plurality of rods 456 extending through the 3D structure. A side view of the nanopore/rod structure 450 is shown in FIG. 5B. As shown in FIGS. 5A-5B, the alkyl tails within the tail groups 454 of the nanopore/rod structure 450 are not interdigitated and aligned, as in the layered structure 350 shown in FIG. 3B. Instead, the alkyl tails within the tail groups 454 are separated and distributed somewhat randomly around the plurality of rods 456. FIGS. 5C-5E provide additional views of the plurality of rods 456 and nanopores 458 included within the nanopore/rod structure 450. As shown in FIGS. 5A-5D, the plurality of rods 456 are evenly distributed within the nanopore/rod structure 450 with equal spacing between each of the plurality of rods 456. The spacing between the rods is dependent, at least in part, on the alkyl chain length.

[0062] FIG. 5F provides a top view of the nanopore/rod structure 450 shown in FIG. 5B, illustrating the even distribution of the rods 456 formed via self-assembly of the [C.sub.12mim][CH.sub.3][BF.sub.4.sup.] ILCs 400 shown in FIG. 4A. When [C.sub.12mim][CH.sub.3][BF.sub.4.sup.] ILCs self-assemble on a substrate surface, the cation head groups and anions segregate to the head groups 452 to form a plurality of rods 456, which are evenly distributed within the nanopore/rod structure 450. In the embodiment shown in FIG. 5F, each of the plurality of rods 456 has a diameter of about 1.1 nm and are spaced about 3 nm apart. It is noted that the diameter of, and spacings between, the rods 456 shown in FIG. 5F are exemplary and that utilization other imidazolium-based ILCs having different alkyl chain lengths and/or different anions may result in alternative diameters and/or inter-rod spacings.

[0063] As shown in the comparison of FIG. 3B and FIGS. 5A-5F, replacing the hydrogen (H) atoms in the alkyl chain with methyl (CH.sub.3) groups in step 230 of the method 200 shown in FIG. 2 changes the phase of the ordered structure by: (a) increasing the separation between the alkyl tail groups in the tail groups of the ordered structure, and (b) changing the orientation of the alkyl tail groups in the tail groups of the ordered structure. Instead of forming a layered structure 350 exhibiting an SmA mesophase as shown in FIG. 3B, the addition of CH.sub.3 groups to the alkyl chain forms a nanopore/rod structure 450 as shown in FIGS. 5A-5F.

[0064] FIG. 6 illustrates an embodiment of a method 600 that uses the techniques described herein to form a self-assembled ILC structure formed on a substrate. It will be recognized that the embodiment of the method 600 shown in FIG. 6 is merely exemplary and additional methods may utilize the techniques described herein. Further, additional processing steps may be added to the method 600 shown in FIG. 6 as the steps described are not intended to be exclusive. Moreover, the order of the steps is not limited to the order shown in the figure as different orders may occur and/or various steps may be performed in combination or at the same time.

[0065] The method 600 shown in FIG. 6 includes providing a solution comprising ionic liquid crystals (ILCs) having imidazolium-based cation head groups, anions and alkyl tail groups, each alkyl tail group comprising a chain of hydrocarbons (in step 610) and depositing the solution onto a surface of a substrate (in step 620). In the method 600, each hydrocarbon in the chain of hydrocarbons comprises a plurality of methyl groups (CH.sub.3) bound to a carbon (C) atom. Once deposited in step 620, the ILCs self-assemble on the surface of the substrate to form a nanopore/rod structure having alternating head groups and tail groups. An example of a nanopore/rod structure 450 is shown in FIGS. 5A-5F. As shown in FIGS. 5A-5F, the imidazolium-based cation head groups and the anions of the ILCs segregate to the head groups to form a plurality of rods 456 within the nanopore/rod structure 450, with the alkyl tail groups oriented around the plurality of rods.

[0066] Similar to the previous method, the ILCs used in the method 600 may include a wide variety of imidazolium-based cation head groups, anions and alkyl chain lengths. In some embodiments, the imidazolium-based cation head groups may be of the form: 1-R.sub.1-3-R.sub.2-imidazolium, where R.sub.1 is an alkyl chain with a chain length ranging from 8-18 hydrocarbons, and R.sub.2 is a hydrogen, methyl, ethyl, propyl, butyl, substituted or unsubstituted phenyl, or other hydrocarbon group. In one example embodiment, the imidazolium-based cation head groups may be 1-dodecyl-3-methylimidazolium (C.sub.12mim); however, imidazolium-based ILCs having anywhere from 8 hydrocarbons (C8mim) to 18 hydrocarbons (C18mim) in the alkyl chain can also be used. As noted above, the anions included within the ILCs may be organic or metalate anions having a variety of valences. Although certainly not limited to such, the ILCs used in the method 600 may tetrafluoroborate (BF.sub.4.sup.) anions in one embodiment.

[0067] The method 600 shown in FIG. 6 forms a nanopore/rod structure having a plurality of rods, which are evenly distributed within the nanopore/rod structure with equal spacing between each of the plurality of rods. When [C.sub.12mim][CH.sub.3][BF.sub.4.sup.] ILCs are used in the method 600 to form a nanopore/rod structure 450, as shown in FIG. 5F, the plurality of rods 456 are evenly distributed within the nanopore/rod structure 450 with a spacing of about 3 nm and a diameter of about 1.1 nm. Other ILCs having potentially different imidazolium-based cation head groups, anions and alkyl chain lengths may also be used in the method 600 to form nanopore/rod structure having different inter-rod spacings or diameters.

[0068] Various embodiments of methods are provided herein for forming self-assembled ILCs structures and for controlling the phase of self-assembled ILCs structures. In the disclosed embodiments, the phase of an ordered structure is controlled by replacing hydrogen (H) atoms within the chain of hydrocarbons with larger functional groups (e.g., methyl (CH.sub.3) groups) prior to depositing the solution onto the surface of the substrate. As noted above and shown in the drawings, replacing the H atoms with larger CH.sub.3 groups adds bulk to the alkyl chain and prevents the alkyl tail groups from interdigitating within the tail groups of the ordered structure. In addition to increasing the separation between the alkyl tail groups, adding CHs groups to the alkyl chain changes the orientation of the alkyl tail groups within the tail groups of the ordered structure, which changes the phase of the ordered structure.

[0069] The techniques described herein provide new methods for controlling the phase of ordered structures formed on a substrate surface via self-assembly of ILCs. In some embodiments, additional techniques can be combined with those described herein to: (a) tune the pitch of the ordered structures formed on the substrate surface, (b) tune the orientation of the ordered structures formed on a wide variety of substrate surfaces and/or (c) overcome the challenges faced when transferring the patterning information of the ordered structures to an underlying substrate.

[0070] Co-pending U.S. patent application Ser. No. 18/677,972, entitled Methods for Controlling the Pitch of Self-Assembled lonic Liquid Crystal (ILC) Structures, provides various methods for controlling the pitch of the self-assembled ILC structures. As noted in the co-pending application, the pitch (p) of an ordered structure (e.g., a layered structure) can be controlled by controlling a cation/anion charge ratio of the ILCs used to form the ordered structure. Depending on the valency of the cation head groups and anions included within the ILCs, the ILCs may self-assemble with interdigitated alkyl tail groups, alkyl tail groups aligned tail-to-tail, or alkyl tail groups that are spaced even further apart. In some embodiments, an ionic liquid (IL) may be added to the ILCs to further increase the pitch (p) of the ordered structures by increasing the width of the head group layers. In addition, minor pitch adjustments can be made by changing the alkyl chain length of the ILCs and/or the IL.

[0071] Co-pending U.S. patent application Ser. No. 18/388,240, entitled Methods for Forming Vertically Layered lonic Liquid Crystal (ILC) Structures on a Semiconductor Substrate, provides various methods for controlling the orientation of the self-assembled ILC structures. As noted in the co-pending application, a vertically oriented structure (e.g., a vertically layered structure) may be formed on a variety of substrate surfaces by exposing the ILC solution to a gas phase, non-polar solvent (such as, e.g., hexane gas) as the ILC solution is being deposited onto the substrate surface. Because the gas phase, non-polar solvent provides an ambient environment, which neither attracts nor repels the polar molecules of the ILCs, the gas phase, non-polar solvent enables the ILCs to orient themselves into a vertically layered structure on a periodic substrate surface and/or within features (e.g., trenches, holes, etc.) having a neutral bottom surface and hydrophilic sidewalls.

[0072] In some embodiments, a vertically oriented structure may be used to pattern a substrate surface. However, forming a vertically oriented structure on a substrate surface is only one challenge that must be overcome to enable self-assembled ILCs to be used for pattern transfer. After a vertically oriented pattern of self-assembled ILCs is formed on a substrate surface, additional challenges must be overcome to successfully transfer the vertically oriented pattern to an underlying surface. For example, removing the alkyl tail groups from the ILC film leaves an ionic liquid on the substrate surface. On the other hand, removing the cation head groups from the ILC film leaves the alkyl tail groups, which are also liquid at room temperature. The remaining group (e.g., the anions) within the ILC film is mobile in both of these options, so no patterning information will be maintained if one or more groups of the self-assembled ILC is removed.

[0073] Co-pending U.S. patent application Ser. No. 18/388,222, entitled Methods for Patterning a Semiconductor Substrate Using Metalate Salt lonic Liquid Crystals, overcomes the challenges faced when transferring the patterning information of self-assembled ILCs to an underlying substrate. The co-pending application discloses various methods to pattern a semiconductor substrate using direct self-assembly of metalate salt ILCs followed by oxidation of the self-assembled metalate salt ILC film to produce a robust metal oxide pattern, which can be transferred to an underlying layer of a semiconductor substrate.

[0074] As noted in the co-pending application, metalate salt ILCs can be synthesized by dissolving stoichiometric amounts of metal halides in imidazolium-based ILCs with a halide anion. A wide variety of metal halides and halide anions can be combined with imidazolium-based ILCs to synthesize metalate salt ILCs. For example, aluminum chloride (AlCl.sub.3) can be dissolved in 1-docecyl-3-methylimidazolium chloride to form 1-dodecyl-3-methylimidazolium tetrachloroaluminate. The metalate salt ILCs formed in such synthesis contain an imidazolium-based cation head group covalently bound to an elongated alkyl tail group and metalate anion (e.g., tetrachloroaluminate (AlCl.sub.4.sup.)). Other metalate salt ILCs can be formed by dissolving other metal halides in ionic liquid crystal (ILC) halide salts.

[0075] Similar to other ILCs, metalate salt ILCs can self-assemble into solid (crystalline phase) ordered structures at or near room temperature. The difference in polarity between the cation head groups and the metalate anions promote direct self-assembly of the metalate salt ILC molecules by segregating the head and tail groups into layered structures (or lamellar structures) with the cation head groups and metalate anions segregated to the head group layers and the alkyl tail groups segregated to the tail group layers. Similar to other ILCs, the orientation of the self-assembled metalate salt ILCs can be controlled by controlling the deposition temperature and the hydrophobicity of the surface(s) upon which the metalate salt ILCs are deposited. In some embodiments, the layer pitch of the self-assembled metalate salt ILCs can be controlled by: (a) controlling the cation/anion charge ratio of the cation head groups and anions included within the metalate salt ILCs, and/or (b) adding an ionic liquid to the metalate salt ILCs. For 1-dodecyl-3-methylimidazolium-based metalate salt ILCs, the layer pitch may be range between approximately 3-6 nm by performing one or more of the pitch control methods (a)-(b).

[0076] After self-assembly, an oxidation process (e.g., an oxygen plasma ashing, ultra-violet (UV) ozone, gas phase oxidation or solution phase oxidation process) can be used to oxidize the metalate salt ILC film and form a more robust pattern that can be transferred to the underlying substrate. The oxidation process removes the alkyl tail group layers from the vertically layered ILC structures by converting the organic material within the alkyl tail group layers into volatile carbon oxides, which are removed from the substrate surface during the oxidation process. However, the metalate anions within the head group layers are converted into non-volatile metal oxides, which are left on the substrate surface after oxidation. In doing so, the oxidation process volatizes the ionic liquid crystal layer, but leaves behind a metal oxide pattern where the metalate anions were concentrated. The metal oxide pattern left on the substrate surface is more robust than the ILC film, and as such, can be used as a hard mask for pattern transfer to underlying layer(s).

[0077] The term semiconductor substrate or substrate as used herein means and includes a base material or construction upon which materials are formed. It will be appreciated that the substrate may include a single material, a plurality of layers of different materials, a layer or layers having regions of different materials or different structures in them, etc. These materials may include semiconductors, insulators, conductors, or combinations thereof. For example, the substrate may be a semiconductor substrate, a base semiconductor layer on a supporting structure, a metal electrode or a semiconductor substrate having one or more layers, structures or regions formed thereon. The substrate may be a conventional silicon substrate or other bulk substrate comprising a layer of semi-conductive material. As used herein, the term bulk substrate means and includes not only silicon wafers, but also silicon-on-insulator (SOI) substrates, such as silicon-on-sapphire (SOS) substrates and silicon-on-glass (SOG) substrates, epitaxial layers of silicon on a base semiconductor foundation, and other semiconductor or optoelectronic materials, such as silicon-germanium, germanium, gallium arsenide, gallium nitride, and indium phosphide. The substrate may be doped or undoped.

[0078] The substrate may also include any material portion or structure of a device, particularly a semiconductor or other electronics device, and may, for example, be a base substrate structure, such as a semiconductor substrate or a layer on or overlying a base substrate structure. Thus, the term substrate is not intended to be limited to any particular base structure, underlying layer or overlying layer, patterned layer or unpatterned layer, but rather, is contemplated to include any such layer or base structure, and any combination of layers and/or base structures.

[0079] It is noted that reference throughout this specification to one embodiment or an embodiment means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention, but do not denote that they are present in every embodiment. Thus, the appearances of the phrases in one embodiment or in an embodiment in various places throughout this specification are not necessarily referring to the same embodiment of the invention. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments. Various additional layers and/or structures may be included and/or described features may be omitted in other embodiments.

[0080] One skilled in the relevant art will recognize that the various embodiments may be practiced without one or more of the specific details, or with other replacement and/or additional methods, materials, or components. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of various embodiments of the invention. Similarly, for purposes of explanation, specific numbers, materials, and configurations are set forth in order to provide a thorough understanding of the invention. Nevertheless, the invention may be practiced without specific details. Furthermore, it is understood that the various embodiments shown in the figures are illustrative representations and are not necessarily drawn to scale.

[0081] Further modifications and alternative embodiments of the methods described herein will be apparent to those skilled in the art in view of this description. It will be recognized, therefore, that the described methods are not limited by these example arrangements. It is to be understood that the forms of the methods herein shown and described are to be taken as example embodiments. Various changes may be made in the implementations. Thus, although the inventions are described herein with reference to specific embodiments, various modifications and changes can be made without departing from the scope of the present inventions. Accordingly, the specification and figures are to be regarded in an illustrative rather than a restrictive sense, and such modifications are intended to be included within the scope of the present inventions. Further, any benefits, advantages, or solutions to problems that are described herein with regard to specific embodiments are not intended to be construed as a critical, required, or essential feature or element of any or all the claims.