High internal free volume compositions for low-k dielectric and other applications
The present invention provides materials, devices, and methods involving new heterocyclic, shape-persistent monomeric units with internal free volume. In some cases, materials the present invention may comprise monomers, oligomers, or polymers that incorporate a heterocyclic, shape-persistent iptycene. The present invention may provide materials having low dielectric constants and improved stability at high operating temperatures due to the electron-poor character of materials. In addition, compositions of the invention may be easily synthesized and readily modified to suit a particular application.
1. A composition, comprising:
a polymer comprising a shape-persistent molecule having at least 20% free volume, wherein the shape-persistent molecule comprises a 5-membered, 6-membered, or 7-membered heteroaromatic ring comprising at least two heteroatom ring atoms, the polymer further comprising a metal, wherein the metal forms a bond with a heteroatom on a monomeric unit and wherein the polymer is substantially non-fluorescent in the visible region.
2. A composition as in claim 1 , wherein shape-persistent molecule comprises an iptycene.
3. A composition as in claim 1 , wherein the polymer comprises a first monomeric unit that forms a hydrogen bond with a second monomeric unit.
4. A composition as in claim 3 , wherein the hydrogen bond causes at least a portion of the polymer to adopt a planar structure.
5. A composition as in claim 1 , further comprising a metal, wherein the metal forms a first bond with a heteroatom on a first monomeric unit and a second bond with a second monomeric unit, wherein the second monomeric unit is adjacent to the first monomeric unit.
6. A composition as in claim 1 , arranged as a dielectric material in an electronic component.
7. A composition as in claim 1 which, in a solid state, has dielectric constant of about 3.0 or less.
8. A composition as in claim 1 , wherein the polymer has a structure comprising the formula,
wherein A and C can be the same or different and each comprises an aromatic group; B and D can be absent, heteroatom, alkene, alkyne, or substituted derivatives thereof; and n is less than about 10,000.
9. A composition as in claim 8 , wherein at least one of A and C comprises an iptycene moiety.
10. A composition as in claim 8 , wherein at least one of A and C comprises an iptycene and B and D are oxygen.
11. A composition as in claim 8 , wherein A, B, C and D are optionally substituted with R, and R can be hydrogen, halide, alkyl, heteroalkyl, aryl, heteroaryl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, alkoxy, aryloxy, aryl, cyano, nitro, hydroxyl, a carbonyl group, or substituted derivatives thereof.
12. A composition as in claim 8 , wherein the polymer has a structure,
further comprising a metal.
13. A composition as in claim 8 , wherein the polymer comprises a monomeric unit having the structure,
wherein Q 1 , Q 2 , Q 3 , and Q 4 can be the same or different and are selected from among carbon, heteroatom, or substituted derivatives thereof; Y 3 , Y 4 , Y 5 , and Y 6 can be absent, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, aralkyl, heteroaralkyl, heteroatom, or substituted derivatives thereof; each R can be the same or different and can be selected from among halide, alkyl, heteroalkyl, aryl, heteroaryl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, alkoxy, aryloxy, aryl, cyano, nitro, hydroxyl, a carbonyl group, or substituted derivatives thereof; and n can be 0, 1, 2, 3, or 4.
14. A composition as in claim 13 , wherein the polymer comprises the structure,
15. A composition as in claim 1 , comprising a shape persistent molecule containing bridgehead atoms, with molecular structures radiating from the bridgehead atoms in three directions and extending outwardly therefrom such that each defines a van der Waals contact of furthest point from the bridgehead atoms of no less than 3.5 Å.
16. A composition as in claim 1 , having an average molecular weight greater than 2000 daltons.