Photosensitive compositions, preparation methods thereof, and quantum dot polymer composite pattern produced therefrom

1. A photosensitive composition comprising:

a plurality of quantum dots comprising an organic ligand on a surface thereof;

a photoinitiator system;

a binder comprising a carboxylic acid group;

a photopolymerizable monomer comprising a carbon-carbon double bond; and

a solvent,

wherein the photoinitiator system comprises a first photoinitiator comprising an oxime compound and a second photoinitiator comprising a phosphine oxide compound, an amino ketone compound, or a combination thereof, and

wherein the composition further comprises a reactive compound comprising at least two thiol groups and represented by Chemical Formula 2:

wherein in Chemical Formula 2,

R 1 is selected from hydrogen; a substituted or unsubstituted C1 to C30 linear or branched alkyl group; a substituted or unsubstituted C6 to C30 aryl group; a substituted or unsubstituted C3 to C30 heteroaryl group; a substituted or unsubstituted C3 to C30 cycloalkyl group; a substituted or unsubstituted C3 to C30 heterocycloalkyl group; a C1 to C10 alkoxy group; a hydroxy group; —NH 2 ; a substituted or unsubstituted C1 to C30 amine group (—NRR′, wherein R and R′ are each independently hydrogen or a C1 to C30 linear or branched alkyl group); an isocyanate group; a halogen; —ROR′ (wherein R is a substituted or unsubstituted C1 to C20 alkylene group and R′ is hydrogen or a C1 to C20 linear or branched alkyl group); acyl halide (—RC(═O)X, wherein R is a substituted or unsubstituted alkylene group and X is a halogen); —C(═O)OR′ (wherein R′ is hydrogen or a C1 to C20 linear or branched alkyl group); —CN; or —C(═O)ONRR′ (wherein R and R′ are each independently hydrogen or a C1 to C20 linear or branched alkyl group),

L 1 is a carbon atom, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C6 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C6 to C30 heteroarylene group, wherein at least one of non-adjacent methylene (—CH 2 —) groups of the substituted C1 to C30 alkylene group is replaced by a sulfonyl group (—SO 2 —), a carbonyl group (—CO—), an ether group (—O—), a sulfide group (—S—), a sulfoxide group (—SO—), an ester group (—C(═O)O—), an amide group (—C(═O)NR—) (wherein R is hydrogen or a C1 to C10 alkyl group), or a combination thereof,

Y 1 is a single bond; a substituted or unsubstituted C1 to C30 alkylene group; a substituted or unsubstituted C2 to C30 alkenylene group; a substituted C1 to C30 alkylene group or a C2 to C30 alkenylene group wherein at least one methylene (—CH 2 —) group is replaced by a sulfonyl group (—S(═O) 2 —), a carbonyl group (—C(═O)—), an ether group (—O—), a sulfide group (—S—), a sulfoxide group (—S(═O)—), an ester group (—C(═O)O—), an amide group (—C(═O)NR—) (wherein R is hydrogen or a C1 to C10 linear or branched alkyl group), an imine group (—NR—) (wherein R is hydrogen or a C1 to C10 linear or branched alkyl group) or a combination thereof,

m is an integer of 1 or more,

k1 is 0 or an integer of 1 or more,

k2 is an integer of 1 or more, and

a sum of m and k2 is an integer of 3 or more,

provided that when Y 1 is not a single bond, m does not exceed the valence of Y 1 , and provided that a sum of k1 and k2 does not exceed the valence of L 1 ,

wherein a weight ratio of the first photoinitiator and the second photoinitiator is about 1:1 to 1:0.1;

wherein an amount of the quantum dot is greater than or equal to about 10 weight % and an amount of the reactive compound is greater than 10 weight % and less than or equal to about 40 weight %, based on a total weight of the composition, and

wherein the photosensitive composition is configured to maintain a blue light photoconversion rate of greater than or equal to about 40% of an initial value thereof after being exposed to light, developed, and heated at 180° C. for 30 minutes.

2. The photosensitive composition of claim 1 , wherein the organic ligand comprises RCOOH, RNH 2 , R 2 NH, R 3 N, RSH, R 3 PO, R 3 P, ROH, RCOOR′, RPO(OH) 2 , R 2 POOH (wherein R and R′ are each independently a C5 to C24 aliphatic hydrocarbon group or a C6 to C20 aromatic hydrocarbon group), a polymer organic ligand, or a combination thereof.

3. The photosensitive composition of claim 1 , wherein the quantum dot further comprises a Group II-VI compound, a Group III-V compound, a Group 1-III-VI compound, a Group I-II-IV-VI compound, or a combination thereof.

4. The photosensitive composition of claim 3 , wherein

the Group II-VI compound comprises:

a binary compound of SnS, SnSe, SnTe, PbS, PbSe, PbTe, or a combination thereof;

a ternary compound of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, or a combination thereof; or

a quaternary compound of SnPbSSe, SnPbSeTe, SnPbSTe, or a combination thereof;

the Group III-V compound comprises

a binary compound of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, or a combination thereof;

a ternary compound of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, or a combination thereof; and

a quaternary compound of GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, or a combination thereof;

the Group 1-II-VI compound comprises CuInSe 2 , CuInS 2 , CuInGaSe, or CuInGaS; and

the Group I-II-IV-VI compound comprises CuZnSnSe or CuZnSnS.

5. The photosensitive composition of claim 3 , wherein

the Group II-VI compound further comprises a Group III metal or the Group III-V compound further comprises a Group II metal.

6. The photosensitive composition of claim 1 , wherein the first photoinitiator has a wavelength of maximum absorption (λ max ) of about 250 nanometers to about 350 nanometers, and the second photoinitiator has a wavelength of maximum absorption (λ max ) of about 310 nanometers to about 400 nanometers.

7. The photosensitive composition of claim 1 ,

wherein the oxime compound comprises an arylthioaryl group, an acyl group RC(═O)— (wherein R is a C1 to C30 alkyl group, a C6 to C30 aryl group, or a C6 to C30 cycloalkyl group), C3 to C30 cycloalkyl group, an alkanedione group, or a combination thereof,

wherein the aminoketone compound comprises a dialkylamino group, a morpholinylphenyl group, an acetophenone group, or a combination thereof, and

wherein the phosphine oxide compound comprises acylphosphine oxide.

8. The photosensitive composition of claim 7 ,

wherein the oxime compound is an oxime compound having an arylthioaryl moiety,

wherein the aminoketone compound comprises 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and

wherein the phosphine oxide compound comprises a mixture of monoacyl phosphine oxide compound and a bisacylphosphine oxide compound.

9. The photosensitive composition of claim 1 , wherein an amount of the photoinitiator system is less than or equal to about 5 weight %, based on a total weight of the composition.

10. The photosensitive composition of claim 1 , wherein the binder has an acid value of greater than or equal to about 50 milligrams of KOH per gram of the binder.

11. The photosensitive composition of claim 1 , wherein the binder comprises:

a copolymer, which is a reaction product of a monomer composition comprising:

a first monomer comprising a carboxylic acid group and a carbon-carbon double bond,

a second monomer comprising a carbon-carbon double bond and a hydrophobic moiety and not comprising a carboxylic acid group, and optionally,

a third monomer comprising a carbon-carbon double bond and a hydrophilic moiety, and not comprising a carboxylic acid group;

a polymer comprising a main chain comprising a carboxylic acid group and a backbone structure incorporated in the main chain, wherein the backbone structure comprises a quaternary carbon atom, which is a part of a cyclic group, and two aromatic rings bound to the quaternary carbon atom; or

a combination thereof.

12. The photosensitive composition of claim 11 , wherein in the monomer composition,

a content of the first monomer is greater than or equal to about 10 mole percent and less than or equal to about and 90 mole percent,

a content of the second monomer is greater than or equal to about 10 mole percent and less than or equal to about 90 mole percent, and

a content of the third monomer is less than or equal to about 20 mol %.

13. The photosensitive composition of claim 11 , wherein the backbone structure of the binder is represented by Chemical Formula A:

wherein in Chemical Formula A,

* indicates a portion linked to an adjacent atom of the main chain of the binder,

Z 1 is a linking moiety represented by Chemical Formulae A-1 to A-6, and

wherein in Chemical Formulae A-1 to A-6, * indicates a portion linked to an aromatic moiety:

wherein in Chemical Formula A-5, R a is a hydrogen atom, an ethyl group, C 2 H4 Cl, C 2 H 4 OH, CH 2 CH═CH 2 , or a phenyl group,

14. The photosensitive composition of claim 1 , wherein the photopolymerizable monomer comprises:

a main monomer comprising 1 to 6 (meth)acrylate groups; and optionally,

at least one of a first auxiliary monomer comprising 8 to 20 (meth)acrylate groups and a second auxiliary monomer represented by Chemical Formula 1:

R 1 O-(L 1 ) m -L 3 -A-L 4 -(L 2 ) n -OR 2   Chemical Formula 1

wherein in Chemical Formula 1,

A is a C1 to C40 aliphatic hydrocarbon group, a C6 to C40 aromatic hydrocarbon group, a moiety comprising at least two C6 to C40 aromatic hydrocarbon groups linked by a substituted or unsubstituted C1 to C10 alkylene group, an ether group or a combination thereof, or an ether group,

L 1 and L 2 are the same or different, and are each a C2 to C5 substituted or unsubstituted oxyalkylene group, and

m and n are each an integer ranging from 0 to 20, provided that m and n are not simultaneously 0,

L 3 and L 4 are the same or different, and are each a single bond, O—(CH 2 ) n —CH(OH)—CH 2 —, or —(CH 2 ) n —CH(OH)—CH 2 —, and

R 1 and R 2 are the same or different, and are each independently CR 2 ═CR— (wherein R is hydrogen or a methyl group) or CR 2 =CRC(═O)— (wherein R is hydrogen or a methyl group).

15. The photosensitive composition of claim 1 , wherein the reactive compound comprises ethoxylated pentaerythritol tetra(3-mercaptopropionate), trimethylolpropanetri(3-mercaptopropionate), trimethylolpropanetri(3-mercaptoacetate), glycol di-3-mercaptopropionate, polypropylene glycol di-3-mercaptopropionate, ethoxylated trimethylpropane tri(3-mercaptopropionate), glycol dimercaptoacetate, ethoxylated glycol dimercaptoacetate, 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropanetris(3-mercaptopropionate), tris[2-(3-mercaptopropinonyloxy)ethyl]isocyanurate, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), 1,6-hexanedithiol, 1,3-propanedithiol, 1,2-ethanedithiol, polyethylene glycol dithiol comprising 1 to 10 ethylene glycol structural units, or a combination thereof.

16. The photosensitive composition of claim 1 , wherein the photosensitive composition is developable with an alkali aqueous solution after exposure.

17. The photosensitive composition of claim 1 , wherein the photosensitive composition further comprises a light diffusing agent selected from a metal oxide particle, a metal particle, and a combination thereof.

18. The photosensitive composition of claim 1 , wherein the photosensitive composition comprises:

about 1 percent by weight to about 40 percent by weight of the quantum dot;

about 0.5 percent by weight to about 40 percent by weight of the binder;

about 1 percent by weight to about 30 percent by weight of the photopolymerizable monomer;

about 0.01 percent by weight to about 10 percent by weight of the photoinitiator system; and

a balance amount of the solvent based on the total weight of the composition.

19. The photosensitive composition of claim 1 , wherein the amount of the reactive compound is greater than or equal to about 15 weight %.