Direct photopatterning of robust and diverse materials

Patent metadata

Field	Value
Publication number	US-2015118188-A1
Application number	US-201414505824-A
Country	US
Kind code	A1
Filing date	Oct 3, 2014
Priority date	Oct 30, 2013
Publication date	Apr 30, 2015
Grant date	—

Abstract

The present invention relates to methods of metathesizing olefins using catalysts previously considered to be practically inactive. The present invention further relates to novel photosensitive compositions, their use as photoresists, and methods related to patterning polymer layers on substrates. Further, modifications to the compositions and method provide for an unprecedented functionalization of the compositions, useful for example in the preparation of sensors, drug delivery systems, and tissue scaffolds. The novel compositions and associated methods also provide for the opportunity to prepare 3-dimensional objects which provide new access to critically dimensioned devices, including for example photonic devices.

First claim

What is claimed:

1 . A photosensitive composition comprising a ruthenium carbene metathesis catalyst of Formula (II):

admixed within a polymerizable material matrix comprising at least one unsaturated organic precursor;
wherein
L 1 , and L 2 are independently neutral electron donor ligands, linked by a hydrocarbylene linking group such as an alkylene, substituted alkylene, heteroalkylene, substituted heteroalkene, arylene, substituted arylene, heteroarylene, or substituted heteroarylene linkage, such that when taken together with the Ru to which they are bound or coordinated, form a 5, 6, or 7-membered ring;
X 1 and X 2 are independent anionic ligands;
Y is O, N—R 1 , or S, preferably O; and
Q is a two-atom linkage having the structure —CR 11 R 12 —CR 13 R 14 — or —CR 11 ═CR 13 —, preferably —CR 11 R 12 —CR 13 R 14 —, wherein R 11 , R 12 , R 13 , and R 14 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups.
R 1 and R 2 are independently hydrogen, optionally substituted hydrocarbyl, optionally substituted heteroatom-containing hydrocarbyl, functional groups, or may be linked to form a cyclic group, which may be aliphatic or aromatic, and may contain substituents and/or heteroatoms; and
R 3 and R 4 are independently optionally substituted hydrocarbyl, or optionally substituted heteroatom-containing hydrocarbyl, and may contain substituents and/or heteroatoms.

2 . The photosensitive composition of claim 1 , wherein the Ru═C(R 1 )(Y—R 2 ) moiety where R 2 is C 1-6 alkyl.

3 . The photosensitive composition of claim 1 , wherein Q is —CH 2 —CH 2 — and either R 3 or R 4 , or both R 3 and R 4 are phenyl groups, optionally substituted in the 2,6 positions with independent C 1-6 alkyl groups.

4 . The photosensitive composition of claim 1 , wherein Q is —CH 2 —CH 2 — and R 3 and R 4 are independently mesityl or optionally substituted adamantyl.

5 . The photosensitive composition of claim 1 , wherein

is a phenanthroline, optionally substituted with electron-withdrawing or electron-donating groups.

6 . The photosensitive composition of claim 5 , where the metathesis catalyst comprises a compound having a structure:

7 . The photosensitive composition of claim 1 , wherein the ruthenium carbene catalyst, upon activation by irradiation of light of at at least one wavelength in a range of from about 150 nm to about 800 nm can crosslink or polymerize at least one of the unsaturated organic precursor.

8 . The photosensitive composition of claim 1 , wherein the unsaturated organic precursor comprises a mono-unsaturated cyclic olefin; a monocyclic diene; or a bicyclic or polycyclic olefin.

9 . The photosensitive composition of claim 8 , herein the unsaturated organic precursor comprises a compound having a structure:

or a mixture thereof, wherein
Ra, R b , R c , R d , R e , and R f are independently H or alkyl (preferably C 1-20 alkyl, more preferably C 1-10 alkyl.

10 . A method of patterning a polymeric image on a substrate, said method comprising;
(a) depositing a layer of a photosensitive composition of claim 1 on a substrate; (b) irradiating a portion of the layer of photosensitive composition with a light comprising at least one wavelength in a range of from about 150 to about 800 nm, so as to polymerize the irradiated portion of the layer, thereby providing polymerized and unpolymerized regions in the layer.

11 . The method of claim 10 , wherein the photosensitive composition is deposited by spin coating, dip coating, or spray coating or wherein photosensitive composition is a gelled, semi-solid or solid film and is deposited by laminating on the substrate.

12 . The method of claim 10 , wherein the irradiated portion is patterned through use of a photomask, by a direct writing application of light, or by interference, nanoimprint, or diffraction gradient lithography.

13 . The method of claim 10 , further comprising removing the unpolymerized region of the pattern.

14 . A patterned polymer layer prepared according to claim 12 , or an article containing said patterned polymer layer.

15 . The polymer layer of claim 14 , the polymer layer being resistant to aqueous HF, said patterned polymer being able to withstand exposure to aqueous HF at room temperatures for a period of 1 hour without measurable peeling from the substrate.

16 . A photosensitive composition comprising a Fischer-type carbene ruthenium metathesis catalyst admixed or dissolved within a polymerizable material matrix comprising at least one unsaturated organic precursor and at least one unsaturated tethered organometallic precursor, each organic and organometallic precursor having at least one alkene or one alkyne bond,
wherein the ruthenium carbene catalyst can be activated by irradiation by light having at least one wavelength in a range of from about 150 to about 800 nm.

17 . The photosensitive composition of claim 16 , wherein the at least one unsaturated organic precursor is a ROMP precursor.

18 . The photosensitive composition of claim 16 , wherein the organometallic moiety comprises a Group 3 to Group 12 transition metal, preferably Fe, Co, Ni, Ti, Al, Cu, Zn, Ru, Rh, Ag, Ir, Pt, Au, or Hg.

19 . The photosensitive composition of claim 18 , wherein the at least one unsaturated tethered organometallic precursor comprises an organometallic moiety comprises a catalyst capable of catalyzing metathesis or cross-coupling reactions or splitting water.

20 . The photosensitive composition of claim 18 , wherein the organometallic moiety is capable of catalyzing the oxidation or reduction of an organic substrate under oxidizing or reducing conditions.

21 . A photosensitive composition comprising a Fischer-type carbene ruthenium metathesis catalyst admixed or dissolved within a polymerizable material matrix comprising at least one unsaturated organic precursor, each organic having at least one alkene or one alkyne bond;
wherein the ruthenium carbene catalyst can be activated by irradiation by light having at least one wavelength in a range of from about 150 to about 800 nm; said at least one unsaturated organic precursor comprising a compound having a structure:

wherein
Z is —O— or C(R a )(R b );
R P is independently H; or C 1-6 alkyl optionally substituted at the terminus with —N(Ra)(R b ), —O—R a , —C(O)O—R a , —OC(O)—(C 1-6 alkyl), or —OC(O)—(C 6-10 aryl); or an optionally protected sequence of 3 to 10 amino acids (preferably including R-G-D or arginine-glycine-aspartic acid);
W is independently —N(Ra)(R b ), —O—R a , or —C(O)O—R a , —P(O)(OR a ) 2 , —SO 2 (OR a ), or SO 3 − ;
R a and R b are independently H or C 1-6 alkyl;
the C 6-10 aryl is optionally substituted with 1, 2, 3, 4, or 5 optionally protected hydroxyl groups (the protected hydroxyl groups preferably being benzyl); and
n is independently

Assignees

• California Inst Of Techn

Inventors

• Weitekamp Raymond
• Grubbs Robert H
• Atwater Harry A
• Fakonas James

Classifications

• C08G2261/94

  Applications in sensors, e.g. biosensors · CPC title

• G03F7/029

  Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur · CPC title

• C08G2261/1426

  containing carboxy groups (COOH) and/or -C(=O)O-moieties · CPC title

• C08G2261/1432

  containing amide groups · CPC title

• C08G2261/3342

  derived from cycloolefins containing heteroatoms · CPC title