Gate insulator layer for organic electronic devices
View Patent ↗Embodiments in accordance with the present invention provide for the use of polycycloolefins in electronic devices and more specifically to the use of such polycycloolefins as gate insulator layers used in the fabrication of electronic devices, the electronic devices that encompass such polycycloolefin gate insulator and processes for preparing such polycycloolefin gate insulator layers and electronic devices encompassing such layers.
1. A gate insulator layer that is in direct contact with an organic semiconductor layer in an organic electronic device, said gate insulator layer consisting essentially of a polycycloolefinic polymer said polycycloolefinic polymer comprising a first type of repeating unit of formula I:
where Z is selected from —CH 2 —, —CH 2 —CH 2 — or —O—,
m is an integer from 0 to 5, and
each of R 1 , R 2 , R 3 and R 4 are independently selected from H, a C 1 to C 25 hydrocarbyl, a C 1 to C 25 halohydrocarbyl or a C 1 to C 25 perhalocarbyl group or one of R 1 , R 2 , R 3 and R 4 has a pendant crosslinkable group.
2. The gate insulator layer of claim 1 , wherein m is 0 or 1.
3. The gate insulator layer of claim 1 , wherein one of R 1 , R 2 , R 3 and R 4 has a pendent crosslinkable group.
4. The gate insulator layer of claim 3 , wherein the pendent crosslinkable group is a latent crosslinkable group.
5. The gate insulator layer of claim 3 , wherein the pendent crosslinkable group comprises a substituted or unsubstituted maleimide portion, an epoxide portion, a vinyl portion, a cinnamate portion or a coumarin portion.
6. The gate insulator layer of claim 3 , where the first type of repeating unit is derived from any one of the following monomers:
wherein
n is an integer from 1 to 8,
Q 1 and Q 2 are each independently of one another —H or —CH 3 , and
R 1 is —H or —OCH 3 .
7. The gate insulator layer of claim 1 , wherein the polycycloolefinic polymer further comprises a second type of repeating unit, such second type being distinct from the first type.
8. The gate insulator layer of claim 1 , wherein the polycycloolefinic polymer further comprises one or more types of repeating units in accordance with formula II
wherein
Z is selected from —CH 2 —, —CH 2 —CH 2 — or —O—,
m is an integer from 0 to 5,
each of R 5 , R 6 , R 7 and R 8 are independently selected from H, a C 1 to C 25 hydrocarbyl, a C 1 to C 25 halohydrocarbyl or a C 1 to C 25 perhalocarbyl group, the repeating units of formula II being distinct from the repeating units of formula I.
9. The gate insulator layer of claim 1 , comprising a blend of a first polycycloolefinic polymer and a second polycycloolefinic polymer.
10. The gate insulator layer of claim 9 , wherein the first polycycloolefinic polymer comprises one or more types of repeating units of formula I, and the second polycycloolefinic polymer comprises one or more types of repeating units of formula II
wherein
Z is selected from —CH 2 —, —CH 2 —CH 2 — or —O—,
m is an integer from 0 to 5,
each of R 1 , R 2 , R 3 and R 4 and R 5 , R 6 , R 7 and R 8 are independently selected from H,
a C 1 to C 25 hydrocarbyl, a C 1 to C 25 halohydrocarbyl or a C 1 to C 25 perhalocarbyl group, and wherein the repeating units of formula I are distinct from the repeating units of formula II.
11. The gate insulator layer of claim 1 , wherein the layer is formed from a polymer composition comprising the polycycloolefinic polymer and one or more of a solvent, a crosslinking agent, an adhesion promoter, an optional reactive solvent, a stabilizer, a UV sensitizer and a thermal sensitizer.
12. The gate insulator layer of claim 11 , wherein the adhesion promoter is represented by formula III
G-A′-P III
wherein
G is a surface-active group,
A′ is a spacer group or a single bond, and
P is a crosslinkable group.
13. The gate insulator layer of claim 12 , wherein the surface active group is a silane group, having the formula —SiR 12 R 13 R 14 , or a silazane group having the formula —NH—SiR 12 R 13 R 14 , wherein R 12 , R 13 and R 14 independently are selected from halogen, silazane, C 1 -C 12 -alkoxy, C 1 -C 12 -alkylamino, optionally substituted C 5 -C 20 -aryloxy and optionally substituted C 2 -C 20 -heteroaryloxy, and wherein one or two of R 12 , R 13 and R 14 may also denote C 1 -C 12 -alkyl, optionally substituted C 5 -C 20 -aryl and optionally substituted C 2 -C 20 -heteroaryl.
14. The gate insulator layer of claim 12 , wherein the crosslinkable group comprises a substituted or unsubstituted maleimide portion, an epoxide portion, a vinyl portion, a cinnamate portion or a coumarin portion.
15. The gate insulator layer of claim 13 , wherein the adhesion promoter is represented by structure A1
wherein
R 12 , R 13 and R 14 independently are selected from halogen, silazane, C 1 -C 12 -alkoxy, C 1 -C 12 -alkylamino, optionally substituted C 5 -C 20 -aryloxy and optionally substituted C 2 -C 20 -heteroaryloxy, and wherein one or two of R 12 , R 13 and R 14 may also denote C 1 -C 12 -alkyl, optionally substituted C 5 -C 20 -aryl and optionally substituted C 2 -C 20 -heteroaryl,
A′ is a spacer group or a single bond, and
R 10 and R 11 are each independently H or a C 1 -C 6 alkyl group.
16. The gate insulator layer of claim 11 , where the crosslinking agent comprises two or more crosslinkable functional groups that are capable of reacting with the crosslinkable group of the said repeating unit of the polycycloolefinic polymer.
17. The gate insulator layer of claim 16 , wherein the crosslinking agent is represented by formula IV1 or IV2
P-X-P IV1
H 4-m C(A″-P) m IV2
where X is A″-X′-A″,
X′ is, O, S, NH, or a single bond,
A″ is a single bond or a connecting, spacer or bridging group,
P is a crosslinkable group, and m is 2, 3 or 4.
18. The gate insulator layer of claim 17 , wherein the crosslinkable group comprises a substituted or unsubstituted maleimide portion, an epoxide portion, a vinyl portion, a cinnamate portion or a coumarin portion.
19. The gate insulator layer of claim 16 , wherein the crosslinking agent is represented by formula C1:
wherein
R 10 and R 11 are independently of each other H or a C 1 -C 6 alkyl group, and
A″ is a single bond or a connecting, spacer or bridging group as defined in claim 17 and additionally selected from (CZ 2 ) n , (CH 2 ) n —(CH═CH) p —(CH 2 ) n , (CH 2 ) n —O, (CH 2 ) n —O—(CH 2 ) n , (CH 2 ) n —C 6 Q 10 -(CH 2 ) n , and C(O)—O, where
each n is independently an integer from 0 to 12,
p is an integer from 1-6,
Z is independently H or F, C 6 Q 10 is cyclohexyl that is substituted with Q,
Q is independently H, F, CH 3 , CF 3 or OCH 3 .
20. The gate insulator layer of claim 11 , wherein the solvent has orthogonal solubility properties with respect to an organic semiconductor layer.
21. The gate insulator layer of claim 1 , wherein the polycycloolefinic polymer further comprises one or more repeat units derived from a monomer selected from the following:
EONB
28
MGENB
29
DMMIMeNB
34
DMMIEtNB
35
DMMIPrNB
36
DMMIBuNB
37
DMMIHxNB
38
EtPhIndNB
49
PhIndNB
50 and
TESNB
53.
22. The gate insulator layer of claim 1 , wherein the polycycloolefinic polymer further comprises one or more repeat units derived from a monomer selected from the following:
NB
1
MeNB
2
BuNB
3
HexNB
4
OctNB
5
DecNB
6
PENB
7
MeOAcNB
9
NBC 4 F 9
15
NBCH 2 C 6 F 5
16 and
PPVENB
26.
23. A gate insulator layer that is in direct contact with an organic semiconductor layer in an organic electronic device, said gate insulator layer consisting essentially of a norbornene-type polymer formed from one or more norbornene-type monomers selected from the following formulae
NB
1
MeNB
2
BuNB
3
HexNB
4
OctNB
5
DecNB
6
PENB
7
TD
8
MeOAcNB
9
NBXOH
10
NBCH 2 GlyOAc
11
NBCH 2 GlyOH
12
NBTON
13
NBTODD
14
NBC 4 F 9
15
NBCH 2 C 6 F 5
16
NBC 6 F 5
17
NBCH 2 C 6 F 2
18
NBCH 2 C 6 H 4 CF 3
19
NBalkylC 6 F 5
20
FPCNB
21
FHCNB
22
FOCHNB
23
FPCHNB
24
C 8 PFAcNB
25
PPVENB
26
DCPD
27
EONB
28
MGENB
29
AkSiNB
30
ArSiNB
31
MCHMNB
32
NPCHMNB
33
DMMIMeNB
34
DMMIEtNB
35
DMMIPrNB
36
DMMIBuNB
37
DMMIHxNB
38
EtPhDMMINB
39
MMIMeNB
40
MINB
41
MIENB
42
DHNMINB
43
MeOCinnNB
44
CinnNB
45
EtMeOCinnNB
46
MeCoumNB
47
EtCoumNB
48
EtPhIndNB
49
PhIndNB
50
DiOxoTCNB
51
PFBTCNB
52
TESNB
53 and
PMNB
54
wherein “Me” means methyl, “Et” means ethyl, “OMe-p” means para-methoxy, “Ph” and “C 6 H 5 ” means phenyl, “C 6 H 4 ” means phenylene, “C 6 F 5 ” means pentafluorophenyl, “OAc” means acetate, “PFAc” means —OC(O) p —C 7 F 15 , and for each of the above subformulae having a methylene bridging group, such methylene bridging group is inclusive of a covalent bond or —(CH 2 ) p — where p is an integer from 1 to 6.
24. The gate insulator layer of claim 23 , wherein the polycycloolefinic polymer further comprises one or more repeat units derived from a monomer selected from the following:
EONB
28
MGENB
29
DMMIMeNB
34
DMMIEtNB
35
DMMIPrNB
36
DMMIBuNB
37
DMMIHxNB
38
EtPhIndNB
49
PhIndNB
50 and
TESNB
53.
25. The gate insulator layer of claim 23 , wherein the polycycloolefinic polymer further comprises one or more repeat units derived from a monomer selected from the following:
NB
1
MeNB
2
BuNB
3
HexNB
4
OctNB
5
DecNB
6
PENB
7
MeOAcNB
9
NBC 4 F 9
15
NBCH 2 C 6 F 5
16 and
PPVENB
26.