Dendritic compounds, photoresist compositions and methods of making electronic devices

1. A dendritic compound, comprising:

an anionic dendron comprising a focal point comprising an anionic group and a linking group; and

a photoreactive cation;

wherein the dendritic compound is of general formula (I):

wherein:

L is a substituted or unsubstituted branched C 1-30 aliphatic group, C 5-30 aromatic group or C 6-30 aralkyl group, having two or more branches with a functional group on each branch, wherein the functional groups are independently chosen from amine, ether, carbonyl, ester, amide, sulfate, sulfonate, sulfonimide, or a combination comprising at least one of the foregoing groups;

X is a substituted or unsubstituted C 1-30 alkyl, C 1-30 fluoroalkyl, C 3-30 cycloalkyl or C 3-30 fluorocycloalkyl group, optionally comprising an ether, ester, carbonate, amine, amide, urea, sulfate, sulfonate, or sulfonamide containing group;

T is a terminal group comprising a substituted or unsubstituted, C 5 or greater cyclic, polycyclic, or fused polycyclic aliphatic group, aromatic group, acid labile group or cyclic lactone, wherein one or more carbon atom in the terminal group can be substituted with a heteroatom;

n is a generation number chosen from integers of 2 or more;

y is the number of linking groups L within a given dendritic generation n and is chosen from integers of 1 or more;

w is the number of terminal branches of linking groups L within the final dendritic generation n and is chosen from integers of 2 or more;

wherein for a first generation (n=1), L is covalently linked to X, and for any subsequent generation (n=2 or greater), L of the subsequent generation is connected to a group L of the previous generation (n−1), and each terminal branch of linking groups L within the final dendritic generation terminates in a terminal group T; and

Z + is a photoreactive cation.

2. The dendritic compound of claim 1 , wherein one or more terminal group T comprises an acid labile group.

3. The dendritic compound of claim 1 , wherein one or more terminal group T comprises an unprotected group.

4. The dendritic compound of claim 1 , wherein Z + is a cation of general formula (V):

wherein each R 1 is independently a substituted or unsubstituted C 1-20 alkyl, C 1-20 fluoroalkyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 5-20 heteroaryl, C 7-20 aralkyl, C 7-20 fluoroaralkyl, C 6-20 heteroaralkyl, and Ar is a C 5-30 aromatic-containing group, wherein the R 1 groups together or an R 1 group together with the Ar group may form a ring together with the sulfur atom, the ring with the sulfur atom optionally including a heteroatom or a carbonyl group.

5. The dendritic compound of claim 1 , wherein Z+ is a cation of the formula VIa, VIb, VIc, VId or VIe:

wherein:

each R 1 is independently substituted or unsubstituted C 1-20 alkyl, C 1-20 fluoroalkyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 5-20 heteroaryl, C 7-20 aralkyl, C 7-20 fluoroaralkyl, or C 6-20 heteroaralkyl, wherein R 1 is independently unsubstituted or further substituted to include an acid-labile group, a base-labile group, or a base-soluble group, wherein each R 1 is separate or is connected to the other R 1 and/or to an aromatic group of the cation; and

R 2 is H, a halogen atom, C 1-20 alkyl, C 1-20 fluoroalkyl, C 1-20 alkoxy, C 1-20 fluoroalkoxy, C 1-20 thioalkoxy, C 1-20 fluorothioalkoxy, C 1-20 alkoxycarbonyl, C 1-20 fluoroalkoxycarbonyl, C 1-20 thioalkoxycarbonyl, C 1-20 fluorothioalkoxycarbonyl, C 3-20 cycloalkyl, C 3-20 fluorocycloalkyl, C 3-20 cycloalkoxy, C 3-20 fluorocycloalkoxy, C 2-20 alkenyl, C 2-20 fluoroalkenyl, C 6-20 aryl, C 6-20 fluoroaryl, C 6-20 aryloxy, C 6-20 fluoroaryloxy, C 5-20 heteroaryl, C 5-20 heteroaryloxy, C 5-20 heteroaryloxy, C 7-20 aralkyl, C 7-20 fluoroaralkyl, C 7-20 aralkyloxy C 7-20 fluoroaralkyloxy, or C 6-20 heteroaralkyl, or C 6-20 heteroaralkyloxy, wherein R 2 is unsubstituted or substituted to include an acid-labile group, a base-labile group or a base-soluble group, and w is an integer of 1 to 5.

6. A photoresist composition, comprising:

an acid-sensitive polymer, and

a dendritic compound of claim 1 .

7. A method of forming an electronic device, comprising:

(a) applying a layer of a photoresist composition of claim 6 on a substrate;

(b) patternwise exposing the photoresist composition layer to activating radiation; and

(c) developing the exposed photoresist composition layer to provide a resist relief image.

8. The method of claim 7 , wherein the activating radiation is EUV radiation.

9. The method of claim 7 , wherein the developing is conducted with an organic solvent developer.

10. The dendritic compound of claim 1 , wherein n=2.

11. The dendritic compound of claim 10 , wherein the dendritic compound is of the formula (IIb):

wherein:

each T is independently a C 5 or greater cyclic, polycyclic, or fused polycyclic aliphatic group, aromatic group, acid labile group, cyclic lactone, cyclic sultone, base-labile group, or base-soluble group, wherein T is optionally substituted with one or more hydroxyl group, cyano group, heteroatom, amine group, ether group or ester group;

each R 3 and R 4 is independently H, C 1-10 alkyl, C 3-10 cycloalkyl or C 3-10 fluorocycloalkyl;

each R 5 and R 6 is independently H, F, C 1-10 alkyl, C 1-10 fluoroalkyl, C 3-10 cycloalkyl or C 3-10 fluorocycloalkyl, wherein at least one of R 5 and R 6 contains F;

Z + is a cation; and

n and m are each independently an integer from 1 to 3.

12. The dendritic compound of claim 10 , wherein the dendritic compound is of the formula (IIIb):

wherein:

each R3 and R4 is independently H, C 1-10 alkyl, C 3-10 cycloalkyl or C 3-10 fluorocycloalkyl;

each R 5 and R 6 is independently H, F, C 1-10 alkyl, C 1-10 fluoroalkyl, C 3-10 cycloalkyl or C 3-10 fluorocycloalkyl; at least one R 5 and/or R 6 contains F;

each R 7 and R 8 is independently an alkyl, cycloalkyl or substituted cycloalky and together can be connected to form an aliphatic, aromatic or hetertoaromatic cyclic or polycyclic moiety; and

Z + is a cation.

13. The dendritic compound of claim 10 , wherein the dendritic compound is of the following formula:

wherein X is H or OH.

14. The dendritic compound of claim 10 , wherein the dendritic compound is of the following formula:

15. The dendritic compound of claim 1 , wherein n=3.

16. The dendritic compound of claim 15 , wherein the dendritic compound is of the formula (IIc):

wherein:

each T is independently a C 5 or greater cyclic, polycyclic, or fused polycyclic aliphatic group, aromatic group, acid labile group, cyclic lactone, cyclic sultone, base-labile group, or base-soluble group, wherein T is optionally substituted with one or more hydroxyl group, cyano group, heteroatom, amine group, ether group or ester group;

each R 3 and R 4 is independently H, C 1-10 alkyl, C 3-10 cycloalkyl or C 3-10 fluorocycloalkyl;

each R 5 and R 6 is independently H, F, C 1-10 alkyl, C 1-10 fluoroalkyl, C 3-10 cycloalkyl or C 3-10 fluorocycloalkyl, wherein at least one of R 5 and R 6 contains F;

Z + is a cation; and

n and m are each independently an integer from 1 to 3.

17. The dendritic compound of claim 15 , wherein the dendritic compound is of the formula (IIIc):

wherein:

each R3 and R4 is independently H, C 1-10 alkyl, C 3-10 cycloalkyl or C 3-10 fluorocycloalkyl;

each R 5 and R 6 is independently H, F, C 1-10 alkyl, C 1-10 fluoroalkyl, C 3-10 cycloalkyl or C 3-10 fluorocycloalkyl; at least one R 5 and/or R 6 contains F;

each R 7 and R 8 is independently an alkyl, cycloalkyl or substituted cycloalky and together can be connected to form an aliphatic, aromatic or hetertoaromatic cyclic or polycyclic moiety; and

Z + is a cation.

18. A dendritic compound chosen from the following compounds:

19. A photoresist composition, comprising:

an acid-sensitive polymer, and

a dendritic compound of claim 18 .

20. A method of forming an electronic device, comprising:

(a) applying a layer of a photoresist composition of claim 19 on a substrate;

(b) patternwise exposing the photoresist composition layer to activating radiation; and

(c) developing the exposed photoresist composition layer to provide a resist relief image.