Diazirine compounds and compositions derived therefrom

1. A method of forming a film for the fabrication of a microelectronic or optoelectronic device comprising:

coating a suitable substrate with a photoimageable composition to form a film;

patterning the film with a mask by exposing to a suitable radiation;

developing the film after exposure to form a photo-pattern; and

curing the film by heating to a suitable temperature;

wherein said composition comprising:

a polymer capable of reacting with a carbene to form a carbene inserted product;

a compound of the formula (IA), (II) or (IIA):

wherein,

A is a carbon, silicon, oxygen or nitrogen central core moiety;

L is a bond or a divalent linking or a spacer group selected from: —C(O)O—R 4 —OC(O)—, —C(O)O—R 4 —, —R 4 —OC(O)—R 4 —, —C(O)—R 4 —OC(O)—, —C(O)—R 4 —, —R 4 —C(O)—R 4 —, —O—R 4 —OC(O)—, —O—R 4 —O—, —O—R 4 —, —R 4 —O—R 4 —, —C(O)NR 5 —R 4 —OC(O)—, —C(O)NR 5 —R 4 —NR 5 C(O)—, —C(O)NR 5 —R 4 —, —R 4 —NR 5 C(O)—R 4 —, —C(O)—R 4 —NR 5 C(O)—, —NR 5 —R 4 —OC(O)—, —NR 5 —R 4 —NR 5 C(O)—, —NR 5 —R 4 —, —R 4 —NR 5 —R 4 —, —NR 5 —R 4 —NR 5 —, —R 4 —, and

 where each occurrence of R 4 may be the same or different which is a divalent group independently selected from (C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )aryl, (C 6 -C 12 )aryl(C 1 -C 12 )alkyl, (C 6 -C 10 )heteroaryl, (C 6 -C 10 )heteroaryl(C 1 -C 12 )alkyl, —(CH 2 —CH 2 —O) a —, where a is an integer from 1 to 10, provided that when R 4 is —(CH 2 —CH 2 —O) a — then the oxygen end of said group is linked only with either carbon or silicon containing linking group, which are optionally substituted with a group selected from halogen, —OH, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 6 -C 10 )aryl, (C 6 -C 10 )aryloxy, (C 6 -C 12 )alkyl and (C 6 -C 12 )aralkyloxy; and R 5 is hydrogen, (C 1 -C 6 )alkyl, (C 6 -C 10 )aryl or (C 6 -C 10 )aralkyl;

R 1 , R 2 , R 3 and R 3a are the same or different and each is independently selected from (C 1 -C 12 )alkyl, where portions of hydrogen on alkyl are replaced with fluorine, (C 1 -C 12 )perfluoroalkyl, (C 6 -C 12 )aryl, (C 6 -C 12 )aryl(C 1 -C 12 )alkyl, where portions of hydrogen on alkyl are replaced with fluorine, and (C 6 -C 12 )arylperfluoro(C 1 -C 12 )alkyl; and

Ar 1 , Ar 2 ,Ar 3 and Ar 3a are the same or different and each is independently selected from (C 6 -C 12 )arylene or (C 6 -C 12 )heteroarylene group optionally substituted with a group selected from halogen, —OH, (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 6 -C 10 )aryl, (C 6 -C 12 )aryloxy, (C 6 -C 12 )aryl(C 1 -C 4 )alkyl and (C 6 -C 12 )aryl(C 1 -C 4 )alkyloxy; and a carrier solvent.

2. The method of claim 1 , wherein the polymer is selected from the group consisting of:

a polycycloolefinic polymer;

a polyacrylate;

polyvinyl butyral;

polyvinyl trimethylsilane (PVTMS);

hydrogenated styrenic block copolymer;

ethyl cellulose; and

poly(4-tert-butyl-styrene).

3. The method of claim 1 , wherein the polymer is a polycycloolefinic polymer comprising at least one repeat unit represented by formula (IIIA), said repeat unit is derived from a monomer of formula (III):

wherein:

denotes a place of bonding with another repeat unit;

p is an integer 0, 1 or 2;

R 6 , R 7 , R 8 and R 9 are the same or different and each independently of one another is selected from hydrogen, linear or branched (C 1 -C 16 )alkyl, (C 1 -C 16 )alkenyl, hydroxy(C 1 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 3 -C 6 )alkyl, di(C 1 -C 2 )alkylmaleimide(C 2 -C 6 )alkoxy(C 1 -C 2 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 1 -C 12 )alkoxy(C 1 -C 8 )alkyl, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, (C 1 -C 6 )acyloxy, (C 1 -C 6 )acyloxy, oxiranyl(C 0 -C 8 )alkyl, oxiranyl(CH 2 ) c O(CH 2 ) d —, halogen or a group of formula (A):

—(CH 2 ) c —(OCH 2 —CH 2 ) d —OR  (A)

wherein:

c is an integer 0, 1, 2, 3 or 4;

d is an integer 0, 1, 2, 3 or 4; and

R is linear or branched (C l -C 6 )alkyl, (C 5 -C 8 )cycloalkyl, (C 6 -C l0 )aryl or (C 7 -C 12 )aralkyl; where each of the aforementioned substituents are optionally substituted with a group selected from halogen or hydroxy.

4. The method of claim 3 , wherein the polymer comprises one or more repeat units derived from the corresponding monomers selected from the group consisting of:

bicyclo[2.2.1]hept-2-ene (NB);

5-butylbicyclo[2.2.1]hept-2-ene (BuNB);

5-hexylbicyclo[2.2.1]hept-2-ene (HexNB);

5-octylbicyclo[2.2.1]hept-2-ene (OctNB);

5-decylbicyclo[2.2.1]hept-2-ene (DecNB);

5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (1-ButenylNB);

5-(but-2-en-1-yl)bicyclo[2.2.1]hept-2-ene (2-ButenylNB);

5-(but-1-en-1-yl)bicyclo[2.2.1]hept-2-ene (3-ButenyINB);

5-perfluoroethylbicyclo[2.2.1]hept-2-ene (C 2 F 5 NB);

5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C 4 F 9 NB);

5-perfluorohexylbicyclo[2.2.1]hept-2-ene (C 6 F 13 NB);

norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);

3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid (NBEtCOOH);

1-(3-(bicyclo[2.2.1]hept-5-en-2-yl)propyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);

1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);

1-(6-(bicyclo[2.2.1]hept-5-en-2-yl)hexyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);

5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene (NBTON);

bicyclo[2.2.1]hept-5-en-2-yl(ethoxy)dimethylsilane (NBSiMe 2 (OEt);

bicyclo[2.2.1]hept-5-en-2-ylmethyl acetate (MeOAcNB); and

bicyclo[2.2.1]hept-5-en-2-ylmethanol (MeOHNB).

5. The method of claim 3 , wherein the polymer comprises one or more repeat units derived from the corresponding monomers selected from the group consisting of:

bicyclo[2.2.1]hept-2-ene (NB);

5-butylbicyclo[2.2.1]hept-2-ene (BuNB);

5-hexylbicyclo[2.2.1]hept-2-ene (HexNB);

5-octylbicyclo[2.2.1]hept-2-ene (OctNB); and

5-decylbicyclo[2.2.1]hept-2-ene (DecNB).

6. The method of claim 3 , wherein the polymer comprises one or more repeat units derived from the corresponding monomers selected from the group consisting of:

5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (1-ButenylNB);

5-(but-2-en-1-yl)bicyclo[2.2.1]hept-2-ene (2-ButenylNB); and

5-(but-1-en-1-yl)bicyclo[2.2.1]hept-2-ene (3-ButenylNB).

7. The method of claim 3 , wherein the polymer comprises one or more repeat units derived from the corresponding monomers selected from the group consisting of:

5-perfluoroethylbicyclo[2.2.1]hept-2-ene (C 2 F 5 NB);

5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene (C 4 F 9 NB);

5-perfluorohexylbicyclo[2.2.1]hept-2-ene (C 6 F 13 NB);

norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB); and

3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid (NBEtCOOH).

8. The method of claim 3 , wherein the polymer comprises one or more repeat units derived from the corresponding monomers selected from the group consisting of:

1-(3-(bicyclo[2.2.1]hept-5-en-2-yl)propyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);

1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);

1-(6-(bicyclo[2.2.1]hept-5-en-2-yl)hexyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);

5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene (NBTON);

bicyclo[2.2.1]hept-5-en-2-yl(ethoxy)dimethylsilane (NBSiMe 2 (OEt);

bicyclo[2.2.1]hept-5-en-2-ylmethyl acetate (MeOAcNB); and

bicyclo[2.2.1]hept-5-en-2-ylmethanol (MeOHNB).

9. The method of claim 3 , wherein the polymer is a copolymer of maleic anhydride and at least one repeat unit of formula (IIIA).

10. The method of claim 9 , wherein the maleic anhydride ring of the copolymer is at least partially opened with an alcohol.

11. The method of claim 10 , wherein the polymer is selected from the group consisting of:

a copolymer containing repeating units derived from bicyclo[2.2.1]hept-2-ene and maleic anhydride ring opened with n -butanol; and

a copolymer containing repeating units derived from 5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene and maleic anhydride ring opened with n-butanol.

12. The method of claim 1 , wherein the polymer is selected from the group consisting of:

poly(5-hexylbicyclo[2.2.1]hept-2-ene) (poly(HexNB));

poly(5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene) (poly(1-ButenylNB));

poly(5-n-perfluorobutylbicyclo[2.2.1]hept-2-ene) (poly(C 4 F 9 NB));

a copolymer of bicyclo[2.2.1]hept-2-ene (NB) and bicyclo[2.2.1]hept -5-en-2-yl(ethoxy)dimethylsilane (NBSiMe 2 (OEt);

a copolymer of norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB) and bicyclo[2.2.1]hept-5-en-2-ylmethanol (MeOHNB); and

a copolymer containing repeating units derived from bicyclo[2.2.1]hept-2-ene and maleic anhydride ring opened with n-butanol.

13. The method of claim 1 comprising the compound of formula (IA), which is selected from the group consisting of:

methylene bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate);

ethane-1,2-diyl bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate);

propane-1,3-diyl bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate);

butane-1,4-diyl bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate);

3,3′-((oxybis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl) -3H-diazirine);

3,3′-((oxybis(ethane-2,1-diyl))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine);

3-(trifluoromethyl)-3-(4-(3-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)propyl)phenyl)-3H-diazirine;

3-(trifluoromethyl)-3-(4-(2-((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl)oxy)ethyl)phenyl)-3H-diazirine;

4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzyl 4-(3-(trifluoromethyl) -3H-diazirin-3-yl)benzoate;

4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenethyl 2-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)acetate;

2-oxo-2-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)ethyl 3-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate;

1,3-bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)propan-1-one;

1,3-bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenyl)propan-2-one;

(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenoxy)methyl 3-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate;

1,2-bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenoxy)ethane;

3-(trifluoromethyl)-3-(4-(3-(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)phenoxy)propyl)phenyl)-3H-diazirine;

(N-methyl-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamido)methyl 4-(3-(trifluoromethyl)3H-diazirin3-yl)benzoate; and

N,N′-methylenebis(N-methyl-4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzamide).

14. The method of claim 1 comprising the compound of formula (II) or (IIA), which is selected from the group consisting of:

2-ethyl-2-(((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoyl)oxy)methyl)propane-1,3-diyl bis(4-(3-(trifluoromethyl)-3H -diazirin-3-yl)benzoate);

2-(perfluoroethyl)-2-(((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoyl)oxy)methyl)propane-1,3-diyl bis(4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzoate);

3,3′-((((2-ethyl-2-(((4-(3-(trifluoromethyl)-3H-diazirin-3yl) benzyl)oxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(4,1-phenylene)) bis(3-(trifluoromethyl)-3H-diazirine); and

3,3′-((((2-(perfluoroethyl)-2-(((4-(3-(trifluoromethyl)-3H-diazirin-3-yl)benzypoxy)methyppropane-1,3-diyl)bis(oxy))bis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine).

15. The method of claim 1 wherein said carrier solvent is selected from the group consisting of: ethanol, isopropanol, acetone, cyclohexanone, cyclopentanone, decane, toluene, p-menthane, benzyl acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), N-methyl-2-pyrrolidone (NMP), gamma-butyrolactone (GBL), N,N-dimethylacetamide, N,N-dimethylformamide, anisole, methyl 3-methoxypropionate, tetrahydrofuran (THF), 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-(trifluoromethyl)hexane (HFE-7500), 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane, 1,1,1,2,2,3,4,4,4-nonafluoro-3-methoxybutane and mixtures in any combination thereof.

16. The method of claim 1 , where said developing is performed by an aqueous developer.

17. The method of claim 1 , where said developing is performed by a solvent.

18. The method of claim 1 , where the substrate is first softbaked before said curing at a temperature of from about 70° C. to about 130° C. for 2 minutes to 10 minutes.

19. The method of claim 1 , where said curing is performed at a temperature of from about 120° C. to about 250° C. for about 20 minutes to about 180 minutes.