Quantum dot device, film having multilayered structure, and electronic device

A method of manufacturing a quantum dot device, comprising

• coating a first composition comprising a perovskite compound represented by Chemical Formula 1 on a first electrode and then annealing to form a first hole transport layer,
• coating a second composition comprising a perovskite compound represented by Chemical Formula 2′ on the first hole transport layer, and then annealing to form a second hole transport layer,
• forming a quantum dot layer on the second hole transport layer, and
• forming a second electrode on the quantum dot layer to manufacture the quantum dot device,
• AMX3 Chemical Formula 1
• wherein, in Chemical Formula 1,
• A is an ammonium cation having a C1 or C2 alkyl group, an ammonium cation having a C1 or C2 haloalkyl group, an ammonium cation having a C1 or C2 cyanoalkyl group, an ammonium cation having a C1 or C2 alkoxy group, a formamidinium cation, a halogen-substituted formamidinium cation, an alkali metal ion, or a combination thereof,
• M is a transition metal, a rare earth metal, or a combination thereof, and
• X is a halide ion, a combination of two or more different halide ions, CNS−, PF6−, or BF4−,
• Chemical Formula 2′
• A′X′ wherein,
• in Chemical Formula 2′,
• A′ is an organic ammonium cation
• selected from the group consisting of a substituted or unsubstituted pyrrolidinium cation, a substituted or unsubstituted piperidinium cation, a substituted or unsubstituted pyridinium cation, pyridazinium cation, a substituted or unsubstituted pyrimidinium cation, a substituted or unsubstituted pyrazinium cation, a substituted or unsubstituted imidazolium cation, a substituted or unsubstituted pyrazolium cation, a substituted or unsubstituted thiazolium cation, a substituted or unsubstituted oxazolium cation, a substituted or unsubstituted triazolium cation, a substituted or unsubstituted piperazinium cation, a substituted or unsubstituted morpholinium cation, or a combination thereof, and
• X′ is a halide ion.

A quantum dot device, comprising

• a first electrode, a second electrode, a quantum dot layer disposed between the first electrode and the second electrode, and a hole transport layer disposed between the quantum dot layer and the first electrode,
• wherein the hole transport layer comprises a first hole transport layer including a three-dimensional structure perovskite thin film, and a second hole transport layer including a two-dimensional structure perovskite thin film,
• wherein the two-dimensional structure perovskite thin film comprises a perovskite compound represented by Chemical Formula 2:
• AA′MX(4-n)X′n Chemical Formula 2
• wherein, in Chemical Formula 2,
• A is an ammonium cation having a C1 or C2 alkyl group, an ammonium cation having a C1 or C2 haloalkyl group, an ammonium cation having a C1 or C2 cyanoalkyl group, an ammonium cation having a C1 or C2 alkoxy group, a formamidinium cation, a halogen-substituted formamidinium cation, an alkali metal ion, or a combination thereof,
• A′ is an amine cation, and the amine is selected from the group consisting of a primary amine, secondary amine, or a tertiary aliphatic amine,
• M is a transition metal, a rare earth metal, or a combination thereof,
• X is a halide ion, a combination of two or more different halide ions, CNS−, PF6−, or BF4−,
• X′ is a halide ion, and
• n is greater than 0 and less than 4,
• wherein the amine cation is at least one of:
• a cation represented by Chemical Formula 2a:
• wherein, in Chemical Formula 2a,
• R21, R22, R23, and R24 are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, or a substituted or unsubstituted C2 to C30 heteroaryl group, and
• at least one of R21, R22, R23, or R24 is a substituted or unsubstituted C3 to C30 alkyl group, a substituted or unsubstituted C3 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, or a substituted or unsubstituted C2 to C30 heteroaryl group;
• a cation represented by Chemical Formula 2aa:
• wherein, in Chemical Formula 2aa,
• R21a is a substituted or unsubstituted C3 to C30 alkyl group, a substituted or unsubstituted C3 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, or a substituted or unsubstituted C2 to C30 heteroaryl group;
• a cation represented by Chemical Formula 2b:
• wherein, in Chemical Formula 2b,
• R51 to R54 are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,
• R55 is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 aralkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heteroaryl group or NRxRy, wherein Rx to Ry are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group.

A quantum dot device, comprising

• a first electrode, a second electrode, a quantum dot layer disposed between the first electrode and the second electrode, and a hole transport layer disposed between the quantum dot layer and the first electrode,
• wherein the hole transport layer comprises a first hole transport layer including a three-dimensional structure perovskite thin film, and a second hole transport layer including a two-dimensional structure perovskite thin film,
• wherein the two-dimensional structure perovskite thin film comprises a perovskite compound represented by Chemical Formula 2:
• AA′MX(4-n)X′n Chemical Formula 2
• wherein, in Chemical Formula 2,
• A is an ammonium cation having a C1 or C2 alkyl group, an ammonium cation having a C1 or C2 haloalkyl group, an ammonium cation having a C1 or C2 cyanoalkyl group, an ammonium cation having a C1 or C2 alkoxy group, a formamidinium cation, a halogen-substituted formamidinium cation, an alkali metal ion, or a combination thereof,
• A′ is an amine cation, and the amine is an aromatic amine or a non-aromatic heterocyclic amine,
• M is a transition metal, a rare earth metal, or a combination thereof,
• X is a halide ion, a combination of two or more different halide ions, CNS−, PF6−, or BF4−,
• X′ is a halide ion, and
• n is greater than 0 and less than 4.