Compositions, organic films and electroluminescent devices

Abstract

Compositions, organic films, and electroluminescent devices are provided. The composition includes a copolymer including a structural unit A represented by Chemical Formula 2 and / or a structural unit B represented by Chemical Formula 3, and a structural unit represented by Chemical Formula 1, each of the structural unit represented by Chemical Formula 1, the structural unit A represented by Chemical Formula 2, and the structural unit B represented by Chemical Formula 3 is described herein, and a salt compound including an iodonium cation and a borate anion represented by Chemical Formula 4, the borate anion represented by Chemical Formula 4 is described herein, wherein an energy difference (ΔE) between an ionization potential of the copolymer and an electron affinity of the borate anion is greater than or equal to 0.75 eV.

Description

[0001] This application claims priority to Japanese Patent Application No. 2025-067072, filed on April 15, 2025, with the Japan Patent Office, and Korean Patent Application No. 10-2026-0005460, filed on January 12, 2026, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0002] The invention discloses compositions, organic films comprising cured materials prepared by curing the compositions, and electroluminescent devices comprising organic films. Background Technology

[0003] There is strong interest in the research and development of quantum dots for RGB light sources covering a wide range of colors, as well as electroluminescent devices with quantum dots in the light-emitting layer (hereinafter also referred to as quantum dot electroluminescent devices or QD-LEDs). Such quantum dots and devices are being actively developed as display devices (e.g., lighting devices with thin films and / or lightweight or with relatively low power consumption).

[0004] By using specific aging techniques, the luminous efficiency and device lifespan of QD-LEDs can be significantly improved (see Patent Document 1 and Patent Document 2).

[0005] [Patent Document 1] Japanese Patent Application No. 2016-540357

[0006] [Patent Document 2] U.S. Patent Application Publication No. 2024 / 0014358 Summary of the Invention

[0007] Based on our research and our understanding gained from it, we found that the hole injection layer degrades during aging by forming anions (e.g., acrylate anions), and consequently, the current density decreases (i.e., dedoping), which in turn leads to increased driving voltage, degraded luminous efficiency, and reduced device lifetime. Therefore, there is a technical trade-off between the device performance improvement caused by positive aging and the device performance degradation caused by the deterioration of the hole injection layer due to negative aging.

[0008] Furthermore, from the perspective of large-area optimization, manufacturing process efficiency, and cost reduction, there is a recent need to use coating methods to manufacture QD-LEDs. On the other hand, in a stacked structure comprising a lower layer (e.g., a hole injection layer or hole transport layer) and an upper layer (e.g., an emitter layer), when the lower layer is formed by coating, the material used for the lower layer is required to have low solubility (orthogonality) with the solvent used to form the upper layer. However, conventional hole injection materials (hole transport materials) do not possess this characteristic.

[0009] Through our recent efforts to provide layers resistant to solvents used to form adjacent layers, enhancing resistance to positive aging, reducing the driving voltage of electroluminescent devices, improving luminous efficiency, and extending device lifetime, we have found that one or more of the above-mentioned technical objectives can be achieved in the presence of compositions comprising copolymers and salt compounds.

[0010] The copolymer comprises structural unit A represented by Formula 2 and / or structural unit B represented by Formula 3, and structural unit represented by Formula 1, and the salt compound comprises an iodonium cation and a borate anion represented by Formula 4. In the composition, the energy difference (ΔE) between the ionization potential of the copolymer and the electron affinity of the borate anion is greater than or equal to 0.75 eV, and the ionization potential of the copolymer is deeper than that of the iodonium cation.

[0011] Chemical Formula 1

[0012]

[0013] In chemical formula 1,

[0014] Ar 1 Ar 2 Ar 4 and Ar 5 Each is independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0015] Ar 3 It is a substituted or unsubstituted carbazole, a substituted or unsubstituted fluorene, a substituted or unsubstituted benzene, or a substituted or unsubstituted biphenylene, wherein, when Ar 3 When it is a substituted or unsubstituted benzene, or a substituted or unsubstituted biphenylene, Ar 1 Not substituted or unsubstituted benzene and / or Ar 2 Not substituted or unsubstituted benzene, and Ar 4 Not substituted or unsubstituted benzene and / or Ar 5 Benzene that is neither substituted nor unsubstituted

[0016] n1 is an integer greater than or equal to 1 and less than or equal to 3.

[0017] m1 is an integer greater than or equal to 1 and less than or equal to 3, and

[0018] It is a combination position;

[0019] Chemical formula 2

[0020]

[0021] In chemical formula 2,

[0022] Ar 6 and Ar 7 Each is independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and Ar 6 and Ar 7 They can form a ring together.

[0023] R 1 It is a group represented by the chemical formula (2-a), and

[0024] It is a combination of positions,

[0025] Chemical formula (2-a)

[0026]

[0027] In chemical formula (2-a),

[0028] L 1 It is a single bond or a group represented by the chemical formula (2-b).

[0029] Ar 8 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0030] Among them, when L 1 When it is a single bond, Ar 6 Ar 7 and Ar 8 At least one of them is not a substituted or unsubstituted benzene, and Ar 8 Can be used with Ar 6 and Ar 7 At least one of them together forms a ring,

[0031] n² is an integer greater than or equal to 2 and less than or equal to 5, and

[0032] It is a combination of positions,

[0033] Chemical formula (2-b)

[0034]

[0035] In chemical formula (2-b),

[0036] Ar 9 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and Ar is bound to the nitrogen atom. 9 Can be used with Ar 6 and Ar 7 At least one of them together forms a ring,

[0037] m2 is an integer greater than or equal to 1 and less than or equal to 5, and when m2 is an integer greater than or equal to 2, each Ar 9 Same or different, and

[0038] It is a combination position;

[0039] Chemical formula 3

[0040]

[0041] In chemical formula 3,

[0042] Ar 10 and Ar 11 Each is independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and Ar 10 and Ar 11 They can form a ring together.

[0043] R 2 It is a group represented by chemical formula (3-a) or chemical formula (3-b), and

[0044] It is a combination of positions,

[0045] Chemical formula (3-a)

[0046]

[0047] In chemical formula (3-a),

[0048] L 2 It is a single bond or a group represented by the chemical formula (3-c).

[0049] Ar 12 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0050] Among them, when L 2 When it is a single bond, Ar 12 Can be used with Ar 10 and Ar 11 At least one of them together forms a ring,

[0051] n3 is an integer greater than or equal to 2 and less than or equal to 5, and

[0052] It is a combination of positions,

[0053] Chemical formula (3-b)

[0054]

[0055] In chemical formula (3-b),

[0056] L 3 It is a single bond or a group represented by the chemical formula (3-c).

[0057] Ar 13 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0058] Among them, when L 3 When it is a single bond, Ar 13 Can be used with Ar 10 and Ar 11 At least one of them together forms a ring,

[0059] n4 is an integer greater than or equal to 2 and less than or equal to 5, and

[0060] It is a combination of positions,

[0061] Chemical formula (3-c)

[0062]

[0063] In the chemical formula (3-c),

[0064] Ar 14 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and Ar is bound to the nitrogen atom. 14 Can be used with Ar 10 and Ar 11 At least one of them together forms a ring,

[0065] m3 is an integer greater than or equal to 1 and less than or equal to 5, and when m3 is an integer greater than or equal to 2, each Ar 14 Same or different, and

[0066] It is a combination position;

[0067] Chemical Formula 4

[0068]

[0069] In chemical formula 4,

[0070] R 31 To R 34 Each is independently a hydrogen atom, a fluorine atom, or a group represented by the chemical formula (4-a).

[0071] Chemical formula (4-a)

[0072]

[0073] In chemical formula (4-a),

[0074] L 4 It is a single bond or a group represented by the chemical formula (4-b).

[0075] Ar 15 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0076] X is a fluorine atom or a group selected from group (4-1).

[0077] n5 is an integer greater than or equal to 1 and less than or equal to 5.

[0078] n6 is an integer that is either 0 or 1.

[0079] When multiple groups represented by the chemical formula (4-a) are present, each L 4 Same or different,

[0080] When multiple groups represented by the chemical formula (4-a) are present, each Ar 15 Same or different,

[0081] When multiple groups represented by the chemical formula (4-a) are present, the individual X groups may be the same or different.

[0082] When multiple groups represented by the chemical formula (4-a) are present, each n5 may be the same or different.

[0083] When multiple groups represented by the chemical formula (4-a) are present, each n6 may be the same or different.

[0084] When n5 is an integer greater than or equal to 2, each X is either the same or different, and

[0085] It is a combination of positions,

[0086] Chemical formula (4-b)

[0087]

[0088] In chemical formula (4-b),

[0089] Ar 16 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0090] m4 is an integer greater than or equal to 1 and less than or equal to 5, and when m4 is greater than or equal to 2, each Ar 16 Same or different, and

[0091] It is a combination of positions,

[0092] Group (4-1)

[0093]

[0094] In group (4-1),

[0095] It is a combination position.

[0096] According to an embodiment, an organic film includes: a carboxyl-containing compound and a cured material obtained by curing the composition.

[0097] According to an embodiment, an electroluminescent device includes: a first electrode for supplying holes; a second electrode for supplying electrons; and an organic layer disposed between the first electrode and the second electrode. At least one layer of the organic layer may include an organic film.

[0098] According to an embodiment, a means is provided that can improve resistance to solvents used to form adjacent layers and resistance to positive aging, reduce driving voltage, enhance luminous efficiency, and improve the device lifetime of electroluminescent devices. Attached Figure Description

[0099] Figure 1 This is a schematic diagram of an electroluminescent device according to an embodiment. Detailed Implementation

[0100] The composition according to the embodiments may include a copolymer and a salt compound, the copolymer comprising at least one structural unit selected from structural unit A represented by chemical formula 2 and / or structural unit B represented by chemical formula 3, and a structural unit represented by chemical formula 1, the salt compound comprising an iodonium cation and a borate anion represented by chemical formula 4, wherein, in the composition, the energy difference (ΔE) between the ionization potential of the copolymer and the electron affinity of the borate anion is greater than or equal to 0.75 eV, and the ionization potential of the copolymer is deeper than that of the iodonium cation.

[0101] Chemical Formula 1

[0102]

[0103] In chemical formula 1,

[0104] Ar 1 Ar 2 Ar 4 and Ar 5 Each can be an independently substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0105] Ar 3It can be substituted or unsubstituted carbazole, substituted or unsubstituted fluorene, substituted or unsubstituted benzene, or substituted or unsubstituted biphenylene, wherein, when Ar 3 When it is a substituted or unsubstituted benzene, or a substituted or unsubstituted biphenylene, Ar 1 Not substituted or unsubstituted benzene and / or Ar 2 Not substituted or unsubstituted benzene, and Ar 4 Not substituted or unsubstituted benzene and / or Ar 5 Benzene that is neither substituted nor unsubstituted

[0106] n1 can be an integer greater than or equal to 1 and less than or equal to 3.

[0107] m1 can be an integer greater than or equal to 1 and less than or equal to 3, and

[0108] It is a combination position;

[0109] Chemical formula 2

[0110]

[0111] In chemical formula 2,

[0112] Ar 6 and Ar 7 Each can be independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and Ar 6 and Ar 7 They can form a ring together.

[0113] R 1 It can be a group represented by the chemical formula (2-a), and

[0114] It is a combination of positions,

[0115] Chemical formula (2-a)

[0116]

[0117] In chemical formula (2-a)

[0118] L 1 It can be a single bond or a group represented by the chemical formula (2-b).

[0119] Ar 8 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0120] Among them, when L 1 When it is a single bond, Ar 6 Ar 7and Ar 8 At least one of them is not a substituted or unsubstituted benzene, and Ar 8 Can be used with Ar 6 and Ar 7 At least one of them together forms a ring,

[0121] n2 can be an integer greater than or equal to 2 and less than or equal to 5, and

[0122] It is a combination of positions,

[0123] Chemical formula (2-b)

[0124]

[0125] In chemical formula (2-b),

[0126] Ar 9 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and the Ar atom is bound to the nitrogen atom. 9 Can be used with Ar 6 and Ar 7 At least one of them together forms a ring,

[0127] m2 can be an integer greater than or equal to 1 and less than or equal to 5, and when m2 is an integer greater than or equal to 2, each Ar 9 They can be the same or different, and

[0128] It is a combination position;

[0129] Chemical formula 3

[0130]

[0131] In chemical formula 3,

[0132] Ar 10 and Ar 11 Each can be independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and Ar 10 and Ar 11 They can form a ring together.

[0133] R 2 It can be a group represented by chemical formula (3-a) or chemical formula (3-b), and

[0134] It is a combination of positions,

[0135] Chemical formula (3-a)

[0136]

[0137] In chemical formula (3-a),

[0138] L 2 It can be a single bond or a group represented by the chemical formula (3-c).

[0139] Ar 12 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0140] Among them, when L 2 When it is a single bond, Ar 12 Can be used with Ar 10 and Ar 11 At least one of them together forms a ring,

[0141] n3 can be an integer greater than or equal to 2 and less than or equal to 5, and

[0142] It is a combination of positions,

[0143] Chemical formula (3-b)

[0144]

[0145] In chemical formula (3-b),

[0146] L 3 It can be a single bond or a group represented by the chemical formula (3-c).

[0147] Ar 13 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0148] Among them, when L 3 When it is a single bond, Ar 13 Can be used with Ar 10 and Ar 11 At least one of them together forms a ring,

[0149] n4 can be an integer greater than or equal to 2 and less than or equal to 5, and

[0150] It is a combination of positions,

[0151] Chemical formula (3-c)

[0152]

[0153] In the chemical formula (3-c),

[0154] Ar 14It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and the Ar atom is bound to the nitrogen atom. 14 Can be used with Ar 10 and Ar 11 At least one of them together forms a ring,

[0155] m3 can be an integer greater than or equal to 1 and less than or equal to 5, and when m3 is an integer greater than or equal to 2, each Ar 14 Same or different, and

[0156] It is a combination position;

[0157] Chemical Formula 4

[0158]

[0159] In chemical formula 4,

[0160] R 31 To R 34 Each of these can be an independent hydrogen atom, a fluorine atom, or a group represented by the chemical formula (4-a).

[0161] Chemical formula (4-a)

[0162]

[0163] In chemical formula (4-a),

[0164] L 4 It can be a single bond or a group represented by the chemical formula (4-b).

[0165] Ar 15 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0166] X can be a fluorine atom or a group selected from group (4-1).

[0167] n5 can be an integer greater than or equal to 1 and less than or equal to 5.

[0168] n6 can be an integer of 0 or 1.

[0169] When multiple groups represented by the chemical formula (4-a) are present, each L 4 Same or different,

[0170] When multiple groups represented by the chemical formula (4-a) are present, each Ar 15 Same or different,

[0171] When multiple groups represented by the chemical formula (4-a) are present, the individual X groups may be the same or different.

[0172] When multiple groups represented by the chemical formula (4-a) are present, each n5 may be the same or different.

[0173] When multiple groups represented by the chemical formula (4-a) are present, each n6 may be the same or different.

[0174] When n5 is an integer greater than or equal to 2, each X is either the same or different, and

[0175] It is a combination of positions,

[0176] Chemical formula (4-b)

[0177]

[0178] In chemical formula (4-b),

[0179] Ar 16 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0180] m4 can be an integer greater than or equal to 1 and less than or equal to 5, and when m4 is greater than or equal to 2, each Ar 16 Same or different, and

[0181] It is a combination of positions,

[0182] Group (4-1)

[0183]

[0184] In group (4-1),

[0185] It is a combination position.

[0186] In the following description, polymers comprising at least one structural unit represented by structural unit A of chemical formula 2 and / or structural unit B of chemical formula 3, as well as structural units represented by chemical formula 1, may be simply referred to as "copolymers" or "copolymers according to the embodiments". Furthermore, salt compounds comprising iodonium cations and borate anions represented by chemical formula 4 are simply referred to as "salt compounds" or "salt compounds according to the embodiments".

[0187] The inventors hypothesize that the mechanism by which the objective is achieved through the embodiments is as follows.

[0188] In hole injection layers, it is known that hole injection characteristics can be improved by forming charge transfer complexes. If cations and anions do not form charge transfer complexes, it is highly likely that hole injection characteristics may degrade. Compared to the difference between the ionization potential of the hole injection material and the electron affinity of the acid anions generated by positive aging, the difference between the ionization potential of the hole injection material in the hole injection layer and the electron affinity of the borate anion (dopant) is relatively small. Therefore, exchange occurs between borate anions and acid anions generated by positive aging, the formed charge transfer complex collapses, and the cations and acid anions that have not formed charge transfer complexes bind together. Consequently, the conductivity of the hole injection layer deteriorates, and characteristics such as driving voltage, luminous efficiency, and device lifetime may deteriorate.

[0189] Furthermore, in the composition according to the embodiment, the composition may have a difference between the ionization potential of the copolymer as a hole injection material and the electron affinity of the borate anion (dopant) included in the salt compound, which is greater than the difference between the ionization potential of the copolymer and the electron affinity of the anion generated by positive aging, and the ionization potential of the copolymer is deeper than the ionization potential of the iodonium cation included in the salt compound. Therefore, even with positive aging, it is believed that the collapse of the charge transfer complex of the borate anion of the salt compound and the copolymer can be suppressed, the conductivity of the hole injection layer can be maintained, and the degradation of various characteristics (e.g., driving voltage, luminous efficiency, device lifetime, etc.) can be suppressed.

[0190] Furthermore, the copolymers according to the embodiments include multiple crosslinking groups in the structural units represented by chemical formula 2 or chemical formula 3. Therefore, the cured material obtained by curing the composition according to the embodiments has a high crosslinking density, which results in good resistance to solvents used to form adjacent layers.

[0191] The above mechanism is based on speculation, and its accuracy does not affect the scope of the invention. Similarly, the accuracy of other speculative matters in this specification does not affect the scope of the invention.

[0192] Embodiments of the present invention will be described below. The embodiments are not limited to the following embodiments and can be modified differently within the scope of the claims. Furthermore, the embodiments described herein can be arbitrarily combined to form other embodiments. Additionally, the various drawings are exaggerated for ease of explanation, and the size ratios of the constituent components in the various drawings may differ from reality.

[0193] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” are otherwise intended to include the plural forms containing “at least one,” unless the content clearly indicates otherwise. Thus, a reference to “the” following a reference to an element in a claim includes one element as well as multiple elements.

[0194] "At least one" should not be construed as limiting "one" or "a single one". "Or" means "and / or". As used herein, the term "and / or" includes any and all combinations of one or more of the relevant listed items.

[0195] It will be further understood that when the terms “comprising” and / or “including” or “containing” and / or “comprises” are used in this specification, they specify the presence of stated features, areas, integrals, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, areas, integrals, steps, operations, elements, components and / or groups thereof.

[0196] As used herein, “about” or “approximately” includes stated values ​​and means within an acceptable range of deviation from the specific value as determined by one of ordinary skill in the art, taking into account the measurement in question and the errors associated with the measurement of the specific value (i.e., the limitations of the measurement system). For example, “about” may mean within one or more standard deviations, or within ±10% or ±5% of the stated value.

[0197] Unless otherwise defined, all terms used herein (including technical and scientific terms) shall have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. It will be further understood that terms (such as those defined in common dictionaries) shall be interpreted as having the same meaning as they have in the relevant field and in the context of this disclosure, and shall not be interpreted in an idealized or overly formal sense unless clearly defined herein. In this specification, unless otherwise specifically stated, treatments and measurements of physical properties are performed at room temperature (greater than or equal to 20°C and less than or equal to 25°C) and relative humidity between 40% and 50% RH.

[0198] In this specification, "x and y are independent" means that x and y may be the same or different.

[0199] In this specification, groups derived from or originating from "compound z" indicate unsaturated groups, meaning that when "compound z" is made into a cyclic compound, hydrogen atoms directly bonded to the cyclic atoms are removed from the ring structure according to their valence.

[0200] In this specification, the number of cyclic atoms refers to the number of atoms in the corresponding ring itself of a compound (e.g., monocyclic compounds, fused-ring compounds, cross-linked compounds, carbocyclic compounds, and heterocyclic compounds) that has a structure in which atoms are bonded together to form a ring (e.g., monocyclic, fused-ring, ring assembly, etc.). The number of atoms that do not form a ring (e.g., hydrogen atoms terminating the bonds of the ring-forming atoms) or the number of atoms included in a substituent when the ring is replaced by a substituent is not included in the number of cyclic atoms. Unless otherwise stated, the number of cyclic atoms described below is assumed to be the same.

[0201] For example, the benzene ring has 6 cyclic atoms, the naphthalene ring has 10 cyclic atoms, the pyridine ring has 6 cyclic atoms, and the furan ring has 5 cyclic atoms.

[0202] When a benzene ring is substituted with a substituent (e.g., an alkyl group), the number of carbon atoms in the alkyl group is not included in the number of cyclic atoms of the benzene ring. Therefore, the number of cyclic atoms in a benzene ring substituted with this alkyl group is 6. Similarly, when a naphthalene ring is substituted with an alkyl group, for example, the number of atoms in the alkyl group is not included in the number of cyclic atoms of the naphthalene ring. Therefore, the number of cyclic atoms in a naphthalene ring substituted with this alkyl group is 10.

[0203] For example, the number of hydrogen atoms bonded to the pyridine ring or the number of atoms constituting substituents is not included in the number of cyclic atoms of the pyridine ring. Therefore, the number of cyclic atoms of the pyridine ring to which the hydrogen atom or substituent is bonded is 6.

[0204] In this specification, unless specifically defined, "substituted" means substituted with alkyl, cycloalkyl, hydroxyalkyl, alkoxy, alkoxyalkyl, cycloalkoxy, alkenyl, alkynyl, primary amino (-NH2), secondary amino (-NH(R)). 1 ):R 1 It is an alkyl or aryl group, a tertiary amino group (-N(R)). 1 (R) 2 ):R 1 and R 2 Each is independently alkyl or aryl, and in this case, R 1 and R 2Substitution can be achieved by forming rings, aryl groups, aryloxy groups, alkylthio groups, cycloalkylthio groups, arylthio groups, alkoxycarbonyl groups, aryloxycarbonyl groups, hydroxyl groups (-OH), carboxyl groups (-COOH), thiols (-SH), cyano groups (-CN), halogen atoms (fluorine, chlorine, bromine, or iodine), or combinations thereof. On the other hand, when the group is a substituent, the form of the group included in the definition of a substituent does not include forms further substituted by that group. For example, when the substituent is an alkyl group, the alkyl group is not further substituted by an alkyl group. However, this does not apply in some cases when heterosubstituents are introduced. For example, when an alkyl group is substituted by an aromatic hydrocarbon group, the aromatic hydrocarbon group may also be substituted by an alkyl group.

[0205] Here, the alkyl group used as a substituent can be a straight-chain or branched alkyl group (e.g., a straight-chain alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 30 carbon atoms). Specifically, the alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, 1,3-dimethylbutyl, 1-isopropylpropyl, 1,2-dimethylbutyl, n-heptyl, 1,4-dimethylpentyl, 3-ethylpentyl, 2-methyl-1-isopropylpropyl, 1-ethyl-3-methylpropyl Butyl, n-octyl, 2-ethylhexyl, 3-methyl-1-isopropylbutyl, 2-methyl-1-isopropylbutyl, 1-tert-butyl-2-methylpropyl, n-nonyl, 3,5,5-trimethylhexyl, n-decyl, isodeyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, nonadecanyl, eicosyl, etc.

[0206] As substituents, cycloalkyl groups may include, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0207] The hydroxyalkyl group can be an alkyl group (e.g., hydroxymethyl, hydroxyethyl) that is substituted with one to three (e.g., one or two, and one, for example) hydroxyl groups.

[0208] The alkoxy group used as a substituent can be a straight-chain or branched alkoxy group, but it is desirable to be a straight-chain alkoxy group having 1 to 20 carbon atoms or a branched alkoxy group having 3 to 20 carbon atoms. For example, the alkoxy group can be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy, tetradecoxy, pentadecoxy, hexadecoxy, heptadecanoxy, octadecoxy, 2-ethylhexoxy, 3-ethylpentoxy, etc.

[0209] The hydroxyalkyl group can be an alkyl group (e.g., hydroxymethyl, hydroxyethyl) that is substituted with one to three (e.g., one or two, and one, for example) hydroxyl groups.

[0210] The cycloalkoxy group used as a substituent can be, for example, cyclopropoxy, cyclobutyloxy, cyclopentoxy, cyclohexyloxy, etc.

[0211] Alkenyl groups that can be used as substituents may include, for example, vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 5-heptenyl, 1-octenyl, 3-octenyl, 5-octenyl, etc.

[0212] Alkynyl groups that can be used as substituents may include, for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 1-hepynyl, 2-hepynyl, 5-hepynyl, 1-octyynyl, 3-octyynyl, 5-octyynyl, etc.

[0213] Secondary amino groups that are substituents may include, for example, alkylamino groups having 1 to 10 carbon atoms (such as methylamino, ethylamino, n-propylamino, n-butylamino, isobutylamino, etc.) and monoarylamino groups (such as monophenylamino, mononaphthylamino, etc.).

[0214] Tertiary amino groups that are substituents may include, for example, dialkylamino groups having 2 to 20 carbon atoms (such as dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino and methylethylamino) and diarylamino groups (such as diphenylamino and dinaphthylamino).

[0215] Examples of aryl groups as substituents may include, for example, aryl groups having 6 to 30 carbon atoms. For example, aryl groups may include phenyl, naphthyl, diphenyl, fluorenyl, anthraceneyl, pyrene, azulel, acenaphthene, triphenyl, and phenanthrene.

[0216] Examples of aryloxy groups as substituents may include phenoxy and naphthoxy.

[0217] Examples of alkylthio groups as substituents may include methylthio, ethylthio, propanethio, pentylthio, hexylthio, octylthio, and dodecylthio.

[0218] Examples of cycloalkylthio groups as substituents include cyclopentylthio, cyclohexylthio, etc.

[0219] Examples of arylthio groups as substituents may include phenylthio and naphthio.

[0220] Examples of alkoxycarbonyl groups as substituents may include methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octoxycarbonyl, and dodecyloxycarbonyl.

[0221] Examples of aryloxycarbonyl groups as substituents may include phenoxycarbonyl and naphthoxycarbonyl.

[0222] In this specification, unless otherwise stated, substituents may include positional isomers. For example, the naphthyl group may be 1-naphthyl and / or 2-naphthyl, and the diphenyl group may be at least one of (1,1'-diphenyl)-2-yl, (1,1'-diphenyl)-3-yl, and (1,1'-diphenyl)-4-yl.

[0223] In this specification, unless otherwise specifically stated, the term "number of carbons" in relation to groups that may have substituents refers to the number of carbons excluding the substituents.

[0224] In the chemical formulas in this specification, unless otherwise defined, if a chemical bond is not shown at a position where a chemical bond should be indicated, it means that a hydrogen atom is bonded at that position.

[0225] In this specification, "substituent is a hydrogen atom" means that it has not been substituted.

[0226] In this specification, the text or chemical formulas containing " The asterisk (") symbol indicates the binding site with another atom.

[0227] <Copolymer>

[0228] The copolymer according to the embodiments may include at least one structural unit represented by structural unit A represented by chemical formula 2 and / or structural unit B represented by chemical formula 3, as well as a structural unit represented by chemical formula 1.

[0229] Chemical Formula 1

[0230]

[0231] In chemical formula 1,

[0232] Ar 1 Ar 2 Ar 4 and Ar 5 Each can be an independently substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0233] Ar 3 It can be a substituted or unsubstituted carbazole, a substituted or unsubstituted fluorene, a substituted or unsubstituted benzene, or a substituted or unsubstituted biphenylene, wherein, when Ar 3When it is a substituted or unsubstituted benzene, or a substituted or unsubstituted biphenylene, Ar 1 Non-substituted or unsubstituted benzene and / or Ar 2 Not substituted or unsubstituted benzene, and Ar 4 Non-substituted or unsubstituted benzene and / or Ar 5 Not substituted or unsubstituted benzene,

[0234] n1 can be an integer greater than or equal to 1 and less than or equal to 3.

[0235] m1 can be an integer greater than or equal to 1 and less than or equal to 3, and

[0236] It is a combination position;

[0237] Chemical formula 2

[0238]

[0239] In chemical formula 2,

[0240] Ar 6 and Ar 7 Each can be independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, or Ar 6 and Ar 7 They can form a ring together.

[0241] R 1 It can be a group represented by the chemical formula (2-a), and

[0242] It is a combination of positions,

[0243] Chemical formula (2-a)

[0244]

[0245] In chemical formula (2-a)

[0246] L 1 It can be a single bond or a group represented by the chemical formula (2-b).

[0247] Ar 8 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0248] Among them, when L 1 When it is a single bond, Ar 6 Ar 7 and Ar 8 At least one of them is not a substituted or unsubstituted benzene, and Ar 8 Can be used with Ar6 and Ar 7 At least one of them together forms a ring,

[0249] n2 can be an integer greater than or equal to 2 and less than or equal to 5, and

[0250] It is a combination of positions,

[0251] Chemical formula (2-b)

[0252]

[0253] In chemical formula (2-b),

[0254] Ar 9 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, wherein the Ar atom bound to the nitrogen atom 9 Can be used with Ar 6 and Ar 7 At least one of them together forms a ring,

[0255] m2 can be an integer greater than or equal to 1 and less than or equal to 5.

[0256] When m2 is an integer greater than or equal to 2, each Ar 9 Same or different,

[0257] It is a combination of positions, and

[0258] Among them, when L 1 When it is a single bond, Ar 6 Ar 7 and Ar 8 At least one of them is not a substituted or unsubstituted benzene ring;

[0259] Chemical formula 3

[0260]

[0261] In chemical formula 3,

[0262] Ar 10 and Ar 11 Each can be independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and Ar 10 and Ar 11 They can form a ring together.

[0263] R 2 It can be a group represented by chemical formula (3-a) or chemical formula (3-b), and

[0264] It is a combination of positions,

[0265] Chemical formula (3-a)

[0266]

[0267] In chemical formula (3-a),

[0268] L 2 It can be a single bond or a group represented by the chemical formula (3-c).

[0269] Ar 12 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0270] Among them, when L 2 When it is a single bond, Ar 12 Can be used with Ar 10 and Ar 11 At least one of them together forms a ring,

[0271] n3 can be an integer greater than or equal to 2 and less than or equal to 5, and

[0272] It is a combination of positions,

[0273] Chemical formula (3-b)

[0274]

[0275] In chemical formula (3-b),

[0276] L 3 It can be a single bond or a group represented by the chemical formula (3-c).

[0277] Ar 13 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0278] Among them, when L 3 When it is a single bond, Ar 13 Can be used with Ar 10 and Ar 11 At least one of them together forms a ring,

[0279] n4 can be an integer greater than or equal to 2 and less than or equal to 5, and

[0280] It is a combination of positions,

[0281] Chemical formula (3-c)

[0282]

[0283] In the chemical formula (3-c),

[0284] Ar 14 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, wherein the Ar atom bound to the nitrogen atom 14 Can be used with Ar 10 and Ar 11 At least one of them together forms a ring,

[0285] m3 can be an integer greater than or equal to 1 and less than or equal to 5, and when m3 is an integer greater than or equal to 2, each Ar 14 Same or different, and

[0286] It is a combination position.

[0287] The structural unit of the copolymer represented by Formula 1 may be included individually or in combination of two or more types of structural units.

[0288] When a copolymer comprises two or more types of structural units represented by chemical formula 1, the two or more types of structural units may be arranged in block, random, alternating or periodic form.

[0289] In chemical formula 1, Ar 1 Ar 2 Ar 4 and Ar 5 Each can be an substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, independently.

[0290] Aromatic cycloalkanes can represent groups derived from hydrocarbon rings that are all or partly aromatic. If two or more aromatic (partially or entirely aromatic) rings are present, these rings can be linked together by single bonds or fused together. The number of cycloatomic atoms in an aromatic cycloalkane can be greater than or equal to 6 and less than or equal to 14. Examples of aromatic cycloalkanes include phenylcycloalkanes, diphenylcycloalkanes, naphthylcycloalkanes, fluorenecycloalkanes, anthracenecycloalkanes, phenanthrenecycloalkanes, perylenecycloalkanes, tetraphenylcycloalkanes, pyrenecycloalkanes, benzo[a]pyrenecycloalkanes, terylcycloalkanes, triphenylenecycloalkanes, acenaphthenecycloalkanes, fluoranthenecycloalkanes, etc.

[0291] Aromatic heterocyclic groups refer to groups derived from aromatic heterocycles. In this specification, an aromatic heterocycle refers to a heterocycle that is partially or wholly aromatic. When a portion of an aromatic heterocycle is aromatic, the aromaticity may originate from the heterocyclic portion of the ring or from the hydrocarbon portion of the ring. An aromatic heterocycle may include aromatic rings without particular limitation, but may, for example, have one or more heteroatoms (e.g., nitrogen (N), oxygen (O), phosphorus (P), sulfur (S), silicon (Si), etc.) as cyclic atoms, while the remaining cyclic atom is a carbon atom (C). Furthermore, there exists a case where the carbon atom forming the ring structure is part of a ketone group (C=O), a thionone group (C=S), or a C=NH group, or where the sulfur atom forming the ring structure is part of a sulfinyl group (S=O) or a sulfonyl group (O=S=O), indicating that the atom forming the ring structure can be bonded to an atom outside the ring via a double bond. In this case, in this specification, the atom outside the ring that forms a double bond with the atom constituting the ring structure is considered part of the aromatic heterocycle. Furthermore, when an outer ring atom forming a double bond is bonded to a hydrogen atom via a single bond, that hydrogen atom is also considered part of an aromatic heterocycle.

[0292] Examples of aromatic heterocycles may include, for example, pyridine rings, pyrazine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings, isoquinoline rings, quinoxaline rings, quinazoline rings, naphthidine rings, acridine rings, phenazine rings, benzo[a]quinoline rings, benzo[a]isoquinoline rings, phenanthridine rings, phenanthrene rings, benzoquinone rings, coumarin rings, anthraquinone rings, fluorenone rings, furan rings, thiophene rings, benzo[a]furan rings, benzo[a]thiophene rings, dibenzo[a]furan rings, dibenzo[a]thiophene rings, pyrrole rings, indole rings, carbazole rings, indolecarbazole rings, imidazole rings, and benzimidazole rings. Pyrazole ring, indazole ring, oxazole ring, isoxazole ring, benzoxazole ring, benzoisoxazole ring, thiazole ring, isothiazole ring, benzothiazole ring, benzoisothiazole ring, imidazolinone ring, benzimidazolinone ring, imidazopyridine ring, imidazopyrimidine ring, imidazophenin ring, benzimidazolinin ring, azadibenzofuran ring, azacarbazole ring, azadibenzothiophene ring, diazadibenzofuran ring, diazacarbazole ring, diazadibenzothiophene ring, oxanthone ring, thioxanone ring, or combinations thereof.

[0293] When an aromatic heterocyclic group comprises two or more aromatic heterocycles, these rings can be bonded to each other by single bonds or can be fused together. Furthermore, when a monovalent aromatic heterocyclic group comprises two or more aromatic heterocycles, the atoms can act as cyclizing atoms of any of these rings.

[0294] The number of cyclic atoms (the sum of cyclic carbon atoms and cyclic heteroatoms) in an aromatic heterocyclic group is not particularly limited, but can be greater than or equal to 3 and less than or equal to 30. For example, from the same perspective, the number of cyclic atoms in an aromatic heterocyclic group can be greater than or equal to 5 and less than or equal to 20, or for example, greater than or equal to 6 and less than or equal to 14. The number of cyclic heteroatoms in an aromatic heterocycle is not particularly limited, but can be greater than or equal to 1 and less than or equal to 10. Furthermore, from the same perspective, the number of cyclic heteroatoms in an aromatic heterocycle can be greater than or equal to 1 and less than or equal to 5, or for example, greater than or equal to 1 and less than or equal to 3. As mentioned above, a cyclic atom refers to an atom that directly forms a ring structure. Therefore, in the case of an exocyclic atom that forms a double bond with an atom constituting the ring structure, the aforementioned atom is not included among the cyclic atoms.

[0295] Among the aforementioned aromatic heterocyclic groups, from the perspective of further improving the effects of the embodiments, Ar 1 Ar 2 Ar 4 and Ar 5 Each can be independently a dibenzofuran cyclogroup or a dibenzothiophene cyclogroup.

[0296] In chemical formula 1, Ar 3 It can be a substituted or unsubstituted carbazole ring group, a substituted or unsubstituted fluorene ring group, a substituted or unsubstituted benzene ring group, or a substituted or unsubstituted biphenyl ring group. In this case, when Ar 3 When it is a substituted or unsubstituted benzene ring group, or a substituted or unsubstituted biphenyl ring group, Ar 1 Not substituted or unsubstituted benzene ring groups and / or Ar 2 Not a substituted or unsubstituted benzene ring group, and Ar 4 Not substituted or unsubstituted benzene ring groups and / or Ar 5 It is neither a substituted nor an unsubstituted benzene ring group.

[0297] In the embodiments, the structural unit represented by chemical formula 1 may be selected from the structural units represented in groups (1-1) to (1-3):

[0298] Group (1-1)

[0299] Group (1-2)

[0300] Groups (1-3)

[0301] In groups (1-1) to (1-3),

[0302] R4 To R 6 R 71 To R 76 and R 81 To R 84 Each can be an independent hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0303] Each n1 can represent an integer greater than or equal to 1 and less than or equal to 3.

[0304] Each m1 can represent an integer greater than or equal to 1 and less than or equal to 3, and

[0305] It is a combination position.

[0306] For R 4 To R 6 R 71 To R 76 Or R 81 To R 84 Examples of hydrocarbon groups may include alkyl, cycloalkyl, alkenyl, ynyl, or aryl. These examples of hydrocarbon groups are the same as those exemplified in the substituents section above.

[0307] In addition to the structural unit represented by Formula 1, the copolymer according to the embodiments may also include at least one of structural unit A represented by Formula 2 and structural unit B represented by Formula 3:

[0308] Chemical formula 2

[0309]

[0310] In chemical formula 2,

[0311] Ar 6 and Ar 7 Each can be independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and Ar 6 and Ar 7 They can form a ring together.

[0312] R 1 It can be a group represented by the chemical formula (2-a), and

[0313] It is a combination of positions,

[0314] Chemical formula (2-a)

[0315]

[0316] In chemical formula (2-a),

[0317] L1 It can be a single bond or a group represented by the chemical formula (2-b).

[0318] Ar 8 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0319] Among them, when L 1 When it is a single bond, Ar 6 Ar 7 and Ar 8 At least one of them is not a substituted or unsubstituted benzene ring, and Ar 8 Can be used with Ar 6 and Ar 7 At least one of them together forms a ring,

[0320] n2 can be an integer greater than or equal to 2 and less than or equal to 5, and

[0321] It is a combination of positions,

[0322] Chemical formula (2-b)

[0323]

[0324] In chemical formula (2-b),

[0325] Ar 9 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and when Ar 9 When Ar combines with a nitrogen atom, 9 Can be used with Ar 6 and Ar 7 At least one of them forms a ring,

[0326] m2 can be an integer greater than or equal to 1 and less than or equal to 5, and when m2 is an integer greater than or equal to 2, each Ar 9 They can be the same or different.

[0327] It is a combination of positions, and

[0328] When L 1 When it is a single bond, Ar 6 Ar 7 and Ar 8 At least one of them is not a substituted or unsubstituted benzene ring;

[0329] Chemical formula 3

[0330]

[0331] In chemical formula 3,

[0332] Ar 10 and Ar 11 Each can be independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, or Ar 10 and Ar 11 They can form a ring together.

[0333] R 2 It can be a group represented by chemical formula (3-a) or chemical formula (3-b), and

[0334] It is a combination of positions,

[0335] Chemical formula (3-a)

[0336]

[0337] In chemical formula (3-a),

[0338] L 2 It can be a single bond or a group represented by the chemical formula (3-c).

[0339] Ar 12 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and

[0340] Among them, when L 2 When it is a single bond, Ar 12 Can be used with Ar 10 and Ar 11 At least one of them together forms a ring,

[0341] n3 can be an integer greater than or equal to 2 and less than or equal to 5, and

[0342] It is a combination of positions,

[0343] Chemical formula (3-b)

[0344]

[0345] In chemical formula (3-b),

[0346] L 3 It can be a single bond or a group represented by the chemical formula (3-c).

[0347] Ar 13 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0348] Among them, when L 3 When it is a single bond, Ar 13 Can be used with Ar10 and Ar 11 At least one of them together forms a ring,

[0349] n4 can be an integer greater than or equal to 2 and less than or equal to 5, and

[0350] It is a combination of positions,

[0351] Chemical formula (3-c)

[0352]

[0353] In the chemical formula (3-c),

[0354] Ar 14 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and when Ar 14 When Ar combines with a nitrogen atom, 14 Can be used with Ar 10 and Ar 11 At least one of them forms a ring,

[0355] m3 can be an integer greater than or equal to 1 and less than or equal to 5, where, when m3 is an integer greater than or equal to 2, each Ar 14 They can be the same or different, and

[0356] It is a combination position.

[0357] Ar of chemical formula 2 6 and Ar 7 Ar with chemical formula (2-a) 8 Ar with chemical formula (2-b) 9 Ar of chemical formula 3 10 and Ar 11 Ar with chemical formula (3-a) 12 Ar with chemical formula (3-b) 13 And Ar with chemical formula (3-c) 14 The definitions and examples of aromatic hydrocarbon cyclic groups and aromatic heterocyclic groups are the same as those described in Chemical Formula 1.

[0358] When the chemical formula (2-a) L 1 When it is a single bond, Ar 6 Ar 7 and Ar 8 At least one of them may not be a substituted or unsubstituted benzene ring.

[0359] Structural unit A, represented by chemical formula 2, may be included alone or in combination of two or more types of structural units. Similarly, structural unit B, represented by chemical formula 3, may be included alone or in combination of two or more types of structural units.

[0360] When the copolymer comprises two or more types of structural units A represented by Chemical Formula 2, the two or more types of structural units A may be arranged in a block, random, alternating, or periodic form. Similarly, when the copolymer comprises two or more types of structural units B represented by Chemical Formula 3, the two or more types of structural units B may be arranged in a block, random, alternating, or periodic form. Furthermore, when the copolymer comprises both structural units A and structural units B represented by Chemical Formula 2 and Chemical Formula 3 respectively, structural units A and structural units B may be arranged in a block, random, alternating, or periodic form.

[0361] Furthermore, at least one of the structural units A and B, as well as the structural unit represented by chemical formula 1, can be arranged in block form, random form, alternating form, or periodic form.

[0362] Structural unit A represented by chemical formula 2 can be represented by structural units represented in group 2, and is not limited thereto:

[0363] Group 2 .

[0364] Structural unit B, represented by chemical formula 3, can be represented by structural units in group 3, but is not limited to them:

[0365] Group 3 .

[0366] Based on the total number of moles of structural units represented by Formula 1, structural unit A represented by Formula 2, and structural unit B represented by Formula 3 in the copolymer, the molar ratio of structural units represented by Formula 1 can be greater than or equal to about 20 mol% and less than or equal to about 99 mol% (e.g., greater than or equal to about 50 mol% and less than or equal to about 95 mol%).

[0367] Based on the total number of moles of structural units represented by Formula 1, structural unit A represented by Formula 2, and structural unit B represented by Formula 3 in the copolymer, the molar ratio of at least one of structural unit A represented by Formula 2 and structural unit B represented by Formula 3 may be greater than or equal to about 1 mol% and less than or equal to about 80 mol% (e.g., greater than or equal to about 5 mol% and less than or equal to about 50 mol%).

[0368] Examples of copolymers in the embodiments are shown below, but are not limited thereto.

[0369] In the above chemical formulas, each It is a combination position.

[0370] The weight-average molecular weight (Mw) of the copolymers according to the embodiments is not particularly limited, as long as the desired effect of the embodiments is achieved. The weight-average molecular weight (Mw) of the copolymers can be, for example, greater than or equal to about 8000 Da and less than or equal to about 500000 Da, for example, greater than or equal to about 12000 Da and less than or equal to about 400000 Da, greater than or equal to about 15000 Da and less than or equal to about 300000 Da, greater than or equal to about 18000 Da and less than or equal to about 200000 Da, or for example, greater than or equal to about 20000 Da and less than or equal to about 100000 Da. Within the above-mentioned range of the weight-average molecular weight of the copolymers, layers with uniform thickness (e.g., hole injection layers, hole transport layers, etc.) can be prepared by adjusting the viscosity of a coating solution containing the copolymer.

[0371] The number-average molecular weight (Mn) of the copolymers according to the embodiments is not particularly limited, as long as the desired effect of the embodiments is achieved. The number-average molecular weight of the copolymers can be, for example, greater than or equal to about 3000 Da and less than or equal to about 250000 Da, for example, greater than or equal to about 4000 Da and less than or equal to about 200000 Da, greater than or equal to about 5000 Da and less than or equal to about 150000 Da, greater than or equal to about 6000 Da and less than or equal to about 100000 Da, or for example, greater than or equal to about 8000 Da and less than or equal to about 100000 Da. Within the above-mentioned range of the number-average molecular weight of the copolymers, layers with uniform thickness (e.g., hole injection layers, hole transport layers, etc.) can be prepared by adjusting the viscosity of a coating solution containing the copolymer.

[0372] Furthermore, the polydispersity (Mw / Mn) of the copolymer may be, for example, greater than or equal to about 1.2 and less than or equal to about 6.0, for example, greater than or equal to about 1.2 and less than or equal to about 4.0, or for example, greater than or equal to about 1.5 and less than or equal to about 3.5.

[0373] In this specification, there are no particular limitations on the measurement of number-average molecular weight (Mn) and weight-average molecular weight (Mw), and known methods or known methods with appropriate modifications can be used. In this specification, the number-average molecular weight and weight-average molecular weight are values ​​measured by the following methods. Furthermore, the polydispersity of the copolymer (Mw / Mn) can be calculated by dividing the weight-average molecular weight measured by the following methods by the number-average molecular weight measured by the following methods.

[0374] (Measurement of number-average molecular weight (Mn) and weight-average molecular weight (Mw))

[0375] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the copolymer were measured by SEC (size exclusion chromatography) using polystyrene as a standard under the following conditions:

[0376] (SEC measurement conditions)

[0377] Analytical Equipment (SEC): Shimadzu Corporation, Prominence (registered trademark)

[0378] Column: Polymer Laboratories, PLgel MIXED-B

[0379] Column temperature: 40℃

[0380] Flow rate: 1.0 mL / min

[0381] Sample solution injection volume: 20 μL (copolymer concentration: approximately 0.05% by weight)

[0382] Eluent: Tetrahydrofuran (THF)

[0383] Detector (UV-VIS detector): Shimadzu Corporation

[0384] Standard sample: polystyrene.

[0385] The ends of the main chain of the copolymer according to the embodiments are not particularly limited and are appropriately defined according to the type of raw materials used, but are generally hydrogen atoms.

[0386] The copolymers according to the embodiments can be used alone or in combination of two or more types of copolymers. Furthermore, the copolymers according to the embodiments can be synthesized using known synthetic methods. For example, the copolymers of the embodiments can be synthesized by those skilled in the art with reference to examples described later. For example, in the methods described in the examples, the copolymers can be synthesized by changing the raw materials or reaction conditions, adding or omitting some steps, or appropriately combining known synthetic methods.

[0387] There are no particular limitations on the methods used to determine the structure of the monomers or copolymers according to the embodiments. The structure of the monomers or copolymers can be determined, for example, by known methods (e.g., NMR, LC-MS, etc.).

[0388] With regard to the difference in electron affinity with the borate anion within a specific range, and from the perspective of further improving resistance to positive aging, the ionization potential of the copolymer can, for example, be greater than or equal to about 4.60 eV and less than or equal to about 5.70 eV. For example, the ionization potential of the copolymer can be greater than or equal to about 4.70 eV and less than or equal to about 5.60 eV (e.g., greater than or equal to about 4.80 eV and less than or equal to about 5.50 eV). The ionization potential can be controlled by adjusting the HOMO energy levels of the copolymer via the introduction of electron-donating groups. Furthermore, the ionization potential can be calculated by molecular orbital calculations, and can be calculated, for example, by the methods described in the examples.

[0389] The amount of copolymer in the composition according to the embodiments may be greater than or equal to about 30 wt% and less than or equal to about 99 wt%, for example greater than or equal to about 50 wt% and less than or equal to about 95 wt%, or for example greater than or equal to about 70 wt% and less than or equal to about 90 wt%.

[0390] <Salt compounds>

[0391] The composition according to the embodiments includes a salt compound comprising an iodonium cation and a borate anion represented by chemical formula 4:

[0392] Chemical Formula 4

[0393]

[0394] In chemical formula 4,

[0395] R 31 To R 34 Each is independently a hydrogen atom, a fluorine atom, or a group represented by the chemical formula (4-a).

[0396] Chemical formula (4-a)

[0397]

[0398] In chemical formula (4-a),

[0399] L 4 Each is independently a single bond or a group represented by the chemical formula (4-b).

[0400] Ar 15 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0401] X is a fluorine atom or a group represented in group (4-1).

[0402] n5 is an integer greater than or equal to 1 and less than or equal to 5, and

[0403] n6 is an integer of 0 or 1, where,

[0404] When multiple groups represented by the chemical formula (4-a) are present, each L 4 They can be the same or different.

[0405] When multiple groups represented by the chemical formula (4-a) are present, each Ar 15 They can be the same or different.

[0406] When multiple groups represented by the chemical formula (4-a) are present, each X may be the same or different.

[0407] When multiple groups represented by the chemical formula (4-a) are present, the individual n5 groups may be the same or different.

[0408] When multiple groups represented by the chemical formula (4-a) are present, each n6 may be the same or different.

[0409] When n5 is an integer greater than or equal to 2, the X values ​​can be the same or different, and

[0410] It is a combination of positions,

[0411] Chemical formula (4-b)

[0412]

[0413] In chemical formula (4-b),

[0414] Ar 16 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0415] m4 is an integer greater than or equal to 1 and less than or equal to 5, and when m4 is an integer greater than or equal to 2, each Ar 16 They can be the same or different, and

[0416] It is a combination of positions,

[0417] Group (4-1)

[0418]

[0419] In group (4-1),

[0420] It is a combination position.

[0421] Ar with chemical formula (4-a) 15 And Ar with chemical formula (4-b) 16 The aromatic and aromatic heterocyclic groups are the same as those described in the description of Formula 1, and therefore, detailed explanations are omitted here.

[0422] In terms of further improving resistance to solvents, R in formula 4 31 To R 34 At least one of them can be a group represented by chemical formula (4-a).

[0423] R in chemical formula 4 31 To R 34 Each of these can be an independent hydrogen atom, a fluorine atom, or a group represented by chemical formula (4-a). Among them, R in chemical formula 4... 31 To R 34 Each can be an independent fluorine atom or a group represented by the chemical formula (4-a).

[0424] In chemical formula (4-a), L 4 It can be a single bond or a group represented by chemical formula (4-b). When multiple groups represented by chemical formula (4-a) are present, each L... 4 They can be the same or different.

[0425] In chemical formula (4-b), Ar 16 It can be a substituted or unsubstituted aromatic group or an aromatic heterocyclic group. Among them, Ar 16 It can be a substituted or unsubstituted benzene ring group, or, for example, a benzene ring group substituted with a fluorine atom. The aromatic hydrocarbon ring group can be, for example, any of a benzene ring group and a fluorene ring group, or, for example, a benzene ring group, but is not limited thereto.

[0426] In chemical formula (4-b), m4 can be an integer greater than or equal to 1 and less than or equal to 5. In the embodiments, m4 can be an integer of 1 or 2, or for example, it can be 1.

[0427] In chemical formula (4-a), Ar 15 It can be a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group. When multiple groups represented by chemical formula (4-a) are present, each Ar 15 They can be the same or different. Among them, Ar 15 It can be, for example, a substituted or unsubstituted benzene ring group, or a benzene ring group substituted with a fluorine atom. The aromatic hydrocarbon ring group can be, for example, any of a benzene ring group and a fluorene ring group, or it can be, for example, a benzene ring group.

[0428] In chemical formula (4-a), X can be a fluorine atom or a group represented in group (4-1). When multiple groups represented by chemical formula (4-a) are present, the individual X's can be the same or different. Among them, X can be a group represented in group (4-1) in terms of resistance to positive aging. When n5 is greater than or equal to 2, the individual X's can be the same or different.

[0429] In chemical formula (4-a), n5 can be an integer greater than or equal to 1 and less than or equal to 5. When multiple groups represented by chemical formula (4-a) are present, the individual n5s can be the same or different. In the embodiments, n5 can be an integer of 1 or 2, or for example, it can be 1.

[0430] In chemical formula (4-a), n6 can be an integer of 0 or 1. When multiple groups represented by chemical formula (4-a) are present, the individual n6s can be the same or different. In the embodiments, n6 can be an integer of 0 or 1; for example, n6 can be an integer of 0 or an integer of 1.

[0431] In chemical formula (4-a), when L 4 When it is a single bond and n6 is an integer of 0, n5 can be an integer of 1, and X can be directly attached to a carbon atom of the benzene ring of chemical formula 4.

[0432] The borate anion may include, but is not limited to, at least one anion selected from the following: .

[0433] The borate anion may be included alone or in combination of two or more types.

[0434] Among borate anions, for example, borate anions can be represented by the anions shown below.

[0435] Regarding the difference in electron affinity with the copolymer within a specific range, and from the perspective of further improving resistance to positive aging, the electron affinity of the borate anion according to the embodiments may, for example, be greater than or equal to about 5.50 eV and less than or equal to about 6.50 eV, for example, greater than or equal to about 5.60 eV and less than or equal to about 6.40 eV, or for example, greater than or equal to about 5.70 eV and less than or equal to about 6.30 eV. The electron affinity can be controlled by adjusting the LUMO energy level of the borate anion via the introduction of electron-withdrawing groups. Furthermore, the electron affinity can be calculated using molecular orbital calculations, and for example, by the methods described in the examples.

[0436] In the embodiments, the energy difference (ΔE) between the ionization potential of the copolymer and the electron affinity of the borate anion can be greater than or equal to 0.75 eV, and the ionization potential of the copolymer can be at a level deeper than the ionization potential of the iodonium cation of the salt compound. If the energy difference (ΔE) is less than 0.75 eV, anion exchange between the acid and the borate anion occurs due to positive aging, and no charge transfer complex is formed, thus losing the conductivity of the electroluminescent device. Furthermore, if the ionization potential of the copolymer is shallower than or equal to the ionization potential of the iodonium cation, doping does not occur, and a charge transfer complex may not form. The energy difference (ΔE) can be greater than or equal to 0.80 eV (e.g., greater than or equal to 0.83 eV). A larger energy difference (ΔE) is better, but it is typically less than or equal to 1.50 eV.

[0437] The salt compound according to the embodiments includes a borate anion and an iodonium cation as a counter ion of the borate anion.

[0438] Examples of iodonium cations may include, for example, difuranyliodonium cation, dithienyliodonium cation, bis(4,5-dimethyl-2-furanyl)iodonium cation, bis(5-chloro-2-thienyl)iodonium cation, bis(5-cyano-2-furanyl)iodonium cation, bis(5-nitro-2-thienyl)iodonium cation, bis(5-acetyl-2-furanyl)iodonium cation, bis(5-carboxy-2-thienyl)iodonium cation, bis(5-methyl 5-phenyl-2-furanyl)iodonium cation, bis(5-phenyl-2-furanyl)iodonium cation, bis(5-(p-methoxyphenyl)-2-thienyl)iodonium cation, bis(5-vinyl-2-furanyl)iodonium cation, bis(5-ethynyl-2-thienyl)iodonium cation, bis(5-cyclohexyl-2-furanyl)iodonium cation, bis(5-hydroxy-2-thienyl)iodonium cation, bis(5-phenoxy-2-furanyl)iodonium Cations, bis(5-mercapto-2-thienyl)iodonium cation, bis(5-butyro-2-thienyl)iodonium cation, bis(5-phenylthio-2-thienyl)iodonium cation, diphenyliodonium cation, bis(p-tolyl)iodonium cation, bis(p-octylphenyl)iodonium cation, bis(p-octadecylphenyl)iodonium cation, bis(p-octyloxyphenyl)iodonium cation, bis(p-octadecyloxyphenyl)iodonium cation, phenyl(p-octadecyloxyphenyl)iodonium cation Phylene iodonium cation, 4-isopropyl-4'-methyldiphenyliodonium cation, (4-isobutylphenyl)-p-tolyliodonium cation, bis(1-naphthyl)iodonium cation, bis(4-phenylthioalkylphenyl)iodonium cation, phenyl(6-benzoyl-9-ethyl-9H-carbazole-3-yl)iodonium cation, (7-methoxy-2-oxo-2H-chromene-3-yl)-4'-isopropylphenyliodonium cation, etc., and not limited to these.

[0439] Iododon cations may be included alone or may be used in combination of two or more types.

[0440] Among the iodonium cations, diphenyliodonium cation, 4-isopropyl-4'-methyldiphenyliodonium cation, bis(p-tolyl)iodonium cation and (4-isobutylphenyl)(4'-tolyl)iodonium cation can be used.

[0441] There are no particular restrictions on the value of the ionization potential of the iodine cation, provided that the ionization potential of the copolymer is deeper than that of the iodine cation. The ionization potential of the iodine cation can, for example, be greater than or equal to about 4.00 eV and less than or equal to about 4.95 eV, for example, greater than or equal to about 4.10 eV and less than or equal to about 4.90 eV, or for example, greater than or equal to about 4.20 eV and less than or equal to about 4.85 eV. The ionization potential of the iodine cation can be calculated from molecular orbitals, or, for example, by the method described in the examples.

[0442] In addition to iodonium cations, the salt compounds according to the embodiments may also include other cations. Other cations may include, for example, ononium cations (such as sulfonium cations, sulfonium oxide cations, phosphonium cations, etc.).

[0443] Examples of sulfonium cations may include, for example, dimethylphenylsulfonium cation, dimethyl(o-fluorophenyl)sulfonium cation, dimethyl(m-chlorophenyl)sulfonium cation, dimethyl(p-bromophenyl)sulfonium cation, dimethyl(p-cyanophenyl)sulfonium cation, dimethyl(m-nitrophenyl)sulfonium cation, dimethyl(2,4,6-tribromophenyl)sulfonium cation, dimethyl(pentafluorophenyl)sulfonium cation, dimethyl(p-(trifluoromethyl)phenyl)sulfonium cation, dimethyl(p-hydroxyphenyl)sulfonium cation, and dimethyl(p-mercaptophenyl)sulfonium cation. Sulfonium cation, dimethyl(p-methylsulfinylphenyl)sulfonium cation, dimethyl(p-methylsulfonylphenyl)sulfonium cation, dimethyl(o-acetylphenyl)sulfonium cation, dimethyl(o-benzoylphenyl)sulfonium cation, dimethyl(p-methylphenyl)sulfonium cation, dimethyl(p-isopropylphenyl)sulfonium cation, dimethyl(p-octadecylphenyl)sulfonium cation, dimethyl(p-cyclohexylphenyl)sulfonium cation, dimethyl(p-methoxyphenyl)sulfonium cation, dimethyl(o-methoxycarbonylphenyl)sulfonium cation Dimethyl(p-phenylthioalkylphenyl)sulfonium cation, (7-methoxy-2-oxo-2H-chromen-4-yl)dimethylsulfonium cation, (4-methoxynaphthyl-1-yl)dimethylsulfonium cation, dimethyl(p-isopropoxycarbonylphenyl)sulfonium cation, dimethyl(2-naphthyl)sulfonium cation, dimethyl(9-anthrayl)sulfonium cation, diethylphenylsulfonium cation, methylethylphenylsulfonium cation, methyldiphenylsulfonium cation, triphenylsulfonium cation, diisopropylphenylsulfonium cation, diphenyl( 4-Phenylacetyl-phenyl)sulfonium cation, 4,4'-bis(diphenylsulfonium)diphenyl sulfide cation, 4,4'-bis[bis[(4-(2-hydroxy-ethoxy)-phenyl)]sulfonium diphenyl sulfide cation, 4,4'-bis(diphenylsulfonium)biphenylene cation, diphenyl(o-fluorophenyl)sulfonium cation, diphenyl(m-chlorophenyl)sulfonium cation, diphenyl(p-bromophenyl)sulfonium cation, diphenyl(p-cyanophenyl)sulfonium cation, diphenyl(m-nitrophenyl)sulfonium cation, diphenyl(2,4,6-Tribromophenyl)sulfonium cation, diphenyl(pentafluorophenyl)sulfonium cation, diphenyl(p-(trifluoromethyl)phenyl)sulfonium cation, diphenyl(p-hydroxyphenyl)sulfonium cation, diphenyl(p-mercaptophenyl)sulfonium cation, diphenyl(p-methylsulfinylphenyl)sulfonium cation, diphenyl(p-methylsulfonylphenyl)sulfonium cation, diphenyl(o-acetylphenyl)sulfonium cation, diphenyl(o-benzoylphenyl)sulfonium cation, diphenyl(p-methylphenyl)sulfonium cation, diphenyl(p-isopropylphenyl)sulfonium cation, diphenyl(p-octadecylphenyl)sulfonium cation, diphenyl(p-cyclohexylphenyl)sulfonium cation, diphenyl(p-methoxyphenyl)sulfonium cation, diphenyl(o-methoxycarbonylphenyl)sulfonium cation, diphenyl Examples of sulfonyl(p-phenylthioalkylphenyl) cations include, but are not limited to, diphenyl(2-naphthyl)sulfonium cations, (7-methoxy-2-oxo-2H-chromen-4-yl)diphenylsulfonium cations, (4-methoxynaphth-1-yl)diphenylsulfonium cations, diphenyl(p-isopropoxycarbonylphenyl)sulfonium cations, diphenyl(2-naphthyl)sulfonium cations, diphenyl(9-anthrayl)sulfonium cations, ethyldiphenylsulfonium cations, methylethyl(o-tolyl)sulfonium cations, methyldi(p-tolyl)sulfonium cations, tri(p-tolyl)sulfonium cations, diisopropyl(4-phenylthioalkylphenyl)sulfonium cations, diphenyl(2-thienyl)sulfonium cations, diphenyl(2-furanyl)sulfonium cations, and diphenyl(9-ethyl-9H-carbazole-3-yl)sulfonium cations.

[0444] Examples of sulfonium oxide cations may include, for example, dimethylphenylsulfonium oxide cation, dimethyl(o-fluorophenyl)sulfonium oxide cation, dimethyl(m-chlorophenyl)sulfonium oxide cation, dimethyl(p-bromophenyl)sulfonium oxide cation, dimethyl(p-cyanophenyl)sulfonium oxide cation, dimethyl(m-nitrophenyl)sulfonium oxide cation, dimethyl(2,4,6-tribromophenyl)sulfonium oxide cation, dimethyl(pentafluorophenyl)sulfonium oxide cation, dimethyl(p-(trifluoromethyl)phenyl)sulfonium oxide cation, dimethyl(p-hydroxyphenyl)sulfonium oxide cation, dimethyl(p-thiol)sulfonium oxide cation, and dimethyl(p-thiol)sulfonium oxide cation. dimethyl(p-methylsulfinylphenyl) sulfonium oxide cation, dimethyl(p-methylsulfonylphenyl) sulfonium oxide cation, dimethyl(o-acetylphenyl) sulfonium oxide cation, dimethyl(o-benzoylphenyl) sulfonium oxide cation, dimethyl(p-methylphenyl) sulfonium oxide cation, dimethyl(p-isopropylphenyl) sulfonium oxide cation, dimethyl(p-octadecylphenyl) sulfonium oxide cation, dimethyl(p-cyclohexylphenyl) sulfonium oxide cation, dimethyl(p-methoxyphenyl) sulfonium oxide cation, dimethyl(o-methoxycarbonylphenyl) Sulfonium oxide cation, dimethyl (p-phenylthioalkylphenyl)sulfonium oxide cation, (7-methoxy-2-oxo-2H-chromen-4-yl)dimethylsulfonium oxide cation, (4-methoxynaphth-1-yl)dimethylsulfonium oxide cation, dimethyl (p-isopropoxycarbonylphenyl)sulfonium oxide cation, dimethyl (2-naphthyl)sulfonium oxide cation, dimethyl (9-anthrayl)sulfonium oxide cation, diethylphenylsulfonium oxide cation, methyl ethylphenylsulfonium oxide cation, methyl diphenylsulfonium oxide cation, triphenylsulfonium oxide cation, diisopropylphenylsulfonium oxide Cationic, diphenyl(4-phenylthioalkyl-phenyl)-sulfonium oxide cation, 4,4'-bis(diphenylsulfonium oxide)diphenyl sulfide, 4,4'-bis[bis[(4-(2-hydroxy-ethoxy)-phenyl)]sulfonium oxide]diphenyl sulfide, 4,4'-bis(diphenylsulfonium oxide)biphenylene, diphenyl(o-fluorophenyl)sulfonium oxide cation, diphenyl(m-chlorophenyl)sulfonium oxide cation, diphenyl(p-bromophenyl)sulfonium oxide cation, diphenyl(p-cyanophenyl)sulfonium oxide cation, diphenyl(m-nitrophenyl)sulfonium oxide cation, diphenyl(2,4,6-Tribromophenyl)sulfonium oxide cation, diphenyl(pentafluorophenyl)sulfonium oxide cation, diphenyl(p-(trifluoromethyl)phenyl)sulfonium oxide cation, diphenyl(p-hydroxyphenyl)sulfonium oxide cation, diphenyl(p-mercaptophenyl)sulfonium oxide cation, diphenyl(p-methylsulfinylphenyl)sulfonium oxide cation, diphenyl(p-methylsulfonylphenyl)sulfonium oxide cation, diphenyl(o-acetylphenyl)sulfonium oxide cation, diphenyl(o-benzoylphenyl)sulfonium oxide cation, diphenyl(p-methylphenyl)sulfonium oxide cation, diphenyl(p-isopropylphenyl)sulfonium oxide cation, diphenyl(p-octadecylphenyl)sulfonium oxide cation, diphenyl(p-cyclohexylphenyl)sulfonium oxide cation, diphenyl(p-methoxyphenyl)sulfonium oxide cation, diphenyl(o-methoxycarbonylphenyl)sulfonium oxide cation, di Phosphine (p-phenylthioalkylphenyl)sulfonium oxide cation, (7-methoxy-2-oxo-2H-chromen-4-yl)diphenylsulfonium oxide cation, (4-methoxynaphth-1-yl)diphenylsulfonium oxide cation, diphenyl (p-isopropoxycarbonylphenyl)sulfonium oxide cation, diphenyl (2-naphthyl)sulfonium oxide cation, diphenyl (9-anthrayl)sulfonium oxide cation, ethyl diphenylsulfonium oxide cation, methyl ethyl (o-tolyl)sulfonium oxide cation, methyl di (p-tolyl)sulfonium oxide cation, tri (p-tolyl)sulfonium oxide cation, diisopropyl (4-phenylthioalkylphenyl)sulfonium oxide cation, diphenyl (2-thienyl)sulfonium oxide cation, diphenyl (2-furanyl)sulfonium oxide cation, diphenyl (9-ethyl-9Hcarbazole-3-yl)sulfonium oxide cation, etc., and not limited to these.

[0445] Examples of phosphonium cations may include, for example, trimethylphenylphosphonium cation, triethylphenylphosphonium cation, tetraphenylphosphonium cation, triphenyl(p-fluorophenyl)phosphonium cation, triphenyl(o-chlorophenyl)phosphonium cation, triphenyl(m-bromophenyl)phosphonium cation, triphenyl(p-cyanophenyl)phosphonium cation, triphenyl(m-nitrophenyl)phosphonium cation, triphenyl(p-phenylthioalkylphenyl)phosphonium cation, (7-methoxy-2-oxo-2H-chromene-4-yl)triphenylphosphonium cation, and triphenyl(o-hydroxyphenyl)phosphonium cation. Phosphorus cations include, but are not limited to, triphenyl(o-acetylphenyl)phosphonium cations, triphenyl(m-benzoylphenyl)phosphonium cations, triphenyl(p-methylphenyl)phosphonium cations, triphenyl(p-isopropoxyphenyl)phosphonium cations, triphenyl(o-methoxycarbonylphenyl)phosphonium cations, triphenyl(1-naphthyl)phosphonium cations, triphenyl(9-anthrayl)phosphonium cations, triphenyl(2-thienyl)phosphonium cations, triphenyl(2-furanyl)phosphonium cations, and triphenyl(9-ethyl-9H-carbazole-3-yl)phosphonium cations.

[0446] Other cations may be used alone or in combination of two or more types.

[0447] In order to further improve the effects of the embodiments, the salt compounds according to the embodiments may include, but are not limited to, the compounds shown below.

[0448] Salt compounds can be used alone or in combination of two or more types. Salt compounds can be commercially available products or synthetic products. There are no particular limitations on the methods for synthesizing salt compounds; for example, salt compounds can be synthesized based on knowledge of known synthetic methods. For example, salt compounds can be synthesized using the methods described in the examples or according to the methods described in the examples. For example, in the methods described in the examples, salt compounds can be synthesized by changing the starting materials or reaction conditions, adding or omitting some steps, or appropriately combining known synthetic methods.

[0449] Based on the total weight of the copolymer and salt compound according to the embodiment, the amount of salt compound in the composition according to the embodiment may be greater than or equal to about 1 wt% and less than or equal to about 70 wt%, for example greater than or equal to about 5 wt% and less than or equal to about 50 wt%, or for example greater than or equal to about 10 wt% and less than or equal to about 30 wt%.

[0450] Solvent

[0451] In addition to copolymers and salt compounds, the compositions according to the embodiments may also include solvents.

[0452] The solvent can be, for example (but not limited to), a solvent having a boiling point greater than or equal to about 100°C and less than or equal to about 350°C at atmospheric pressure (101.3 kPa, 1 atm). The boiling point of the solvent at atmospheric pressure can, for example, be greater than or equal to about 150°C and less than or equal to about 320°C, or for example, greater than or equal to about 180°C and less than or equal to about 300°C. If the boiling point of the solvent at atmospheric pressure is within the above range, the film-forming properties and processability in wet film-forming methods (such as inkjet methods) can be improved. There are no particular limitations on solvents having a boiling point greater than or equal to about 100°C and less than or equal to about 350°C at atmospheric pressure, and commonly known solvents can be appropriately used. Below, a solvent having a boiling point greater than or equal to about 100°C and less than or equal to about 350°C at atmospheric pressure is given as an example, but it is not limited thereto.

[0453] Hydrocarbon solvents may include, but are not limited to, octane, nonane, decane, undecane, dodecane, etc.

[0454] Aromatic hydrocarbon solvents may include, but are not limited to, toluene, xylene, ethylbenzene, n-propylbenzene, isopropylbenzene, mesitylene, n-butylbenzene, sec-butylbenzene, 1-phenylpentane, 2-phenylpentane, 3-phenylpentane, phenylcyclopentane, phenylcyclohexane, 2-ethylbiphenyl, 3-ethylbiphenyl, etc.

[0455] Ether solvents may include, but are not limited to, 1,4-dioxane, 1,2-diethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, anisole, ethoxybenzene, 3-methyl anisole, m-dimethoxybenzene, etc.

[0456] Ketone solvents may include, but are not limited to, 2-hexanone, 3-hexanone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, cycloheptanone, etc.

[0457] Ester solvents may include, but are not limited to, butyl acetate, butyl propionate, butyl butyrate, propylene carbonate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, etc.

[0458] Nitrile solvents may include, but are not limited to, benzonitrile, 3-methylbenzonitrile, etc.

[0459] Amide solvents may include, but are not limited to, N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone.

[0460] Solvents can be used alone or in combination of two or more types.

[0461] The amount of solvent in the composition according to the examples is not particularly limited. For example, from the perspective of ease of application, the solids concentration (total concentration of copolymer and salt compound) of the composition may be, for example, greater than or equal to about 0.1% (0.1 wt%) and less than or equal to about 10 wt%, or, for example, greater than or equal to about 0.5 wt% and less than or equal to about 5 wt%.

[0462] There are no particular limitations on the method for preparing the composition according to the examples. For example, methods include sequentially adding and mixing the copolymer and the salt compound in a solvent; adding and mixing the copolymer and the salt compound in a solvent at one time; and preparing solutions of the copolymer and the salt compound separately and then mixing them. There are also no particular limitations on the temperature and mixing time during mixing.

[0463] Another embodiment provides an organic film comprising a carboxyl-containing compound and a cured material obtained by curing the composition according to the embodiment.

[0464] [Electroluminescent devices]

[0465] In the following, the electroluminescent device according to the embodiment will be described in detail with reference to the accompanying drawings. Figure 1 This is a schematic diagram illustrating an electroluminescent device according to an embodiment. In this specification, "electroluminescent device" may be abbreviated as "EL device".

[0466] like Figure 1 As shown, the EL device 100 according to an embodiment includes a substrate 110, a first electrode 120 on the substrate 110, a hole injection layer 130 on the first electrode 120, a hole transport layer 140 on the hole injection layer 130, an emission layer (or light-emitting layer) 150 on the hole transport layer 140, an electron transport layer 160 on the emission layer 150, an electron injection layer 170 on the electron transport layer 160, and a second electrode 180 on the electron injection layer 170.

[0467] The substrate 110 can be a substrate used as a conventional EL device. For example, the substrate 110 can be a semiconductor substrate such as, for example, a glass substrate, a silicon substrate, or a transparent plastic substrate.

[0468] A first electrode 120 is formed on a substrate 110. The first electrode 120 may provide holes and can be an anode, and may be formed from a metal, alloy, conductive compound, or the like with a high work function. For example, the first electrode 120 can be formed as a transparent electrode using indium tin oxide (In₂O₃-SnO₂:ITO), indium zinc oxide (In₂O₃-ZnO), tin oxide (SnO₂), or zinc oxide (ZnO), which have excellent transparency and conductivity. Furthermore, the first electrode 120 can be formed as a reflective electrode by stacking magnesium (Mg), aluminum (Al), or the like on a transparent conductive film. After forming the first electrode 120 on the substrate 110, it can be washed and subjected to UV-ozone treatment if necessary.

[0469] Hole injection layer 130 may be formed on first electrode 120. Hole injection layer 130 may be a layer that promotes the injection of holes from first electrode 120, and specifically, may be formed to have a thickness of, for example, from about 10 nm to about 1000 nm, or for example, from about 20 nm to about 50 nm (dry film thickness; the same applies hereinafter).

[0470] According to an embodiment, the hole injection layer 130 may include a curing material formed by curing the composition according to the embodiment (curing material obtained by curing the composition according to the embodiment, curing material of the composition according to the embodiment). Hereinafter, the curing material formed by curing the composition according to the embodiment (curing material obtained by curing the composition according to the embodiment, curing material of the composition according to the embodiment) will be simply referred to as "curing material according to the embodiment".

[0471] According to an embodiment, the hole injection layer 130 may include a curing material according to an embodiment and a carboxyl-containing compound used in positive aging as described below.

[0472] The pre-cured film comprising the composition according to the embodiments can be formed by a coating method (solution coating method). For example, the pre-cured film can be formed using solution coating methods (such as spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spraying, screen printing, flexographic printing, offset printing, inkjet printing, etc.).

[0473] The film formed by the coating method is then cured. There are no particular limitations on the curing method, and the curing method can be heat curing. Heat curing can be carried out in an air atmosphere or an inert gas atmosphere. There are no particular limitations on the temperature used for heat curing, but for example, the temperature used for heat curing can be greater than or equal to 80°C, greater than or equal to 100°C, greater than or equal to 130°C, greater than or equal to 150°C, or greater than or equal to 200°C. Furthermore, the temperature used for heat curing can be, for example, less than or equal to 250°C, less than or equal to 230°C, less than or equal to 200°C, less than or equal to 180°C, or less than or equal to 150°C. There are no particular limitations on the heat curing time, and it can be, for example, 5 minutes or longer, 10 minutes or longer, 15 minutes or longer, 20 minutes or longer, or 30 minutes or longer. Furthermore, the heat curing time can be, for example, 70 minutes or less, 60 minutes or less, 50 minutes or less, 30 minutes or less, or 20 minutes or less. In this way, the cured product according to the embodiment can be obtained. Furthermore, in this way, a layer containing the cured product according to the embodiment can be obtained.

[0474] In addition to the cured product (and, if desired, a carboxyl compound) according to the embodiments, or when any layer other than the hole injection layer 130 of the EL device 100 contains the cured product (and, if desired, a carboxyl compound) according to the embodiments, the hole injection layer 130 may be formed to include a known hole injection material. The hole injection layer 130 may be formed using a known hole injection material. Known hole injection materials forming the hole injection layer 130 may include, for example, poly(ether ketone)-containing triphenylamine (TPAPEK), 4-isopropyl-4'-methyldiphenyliodonium tetra(pentafluorophenyl)borate (PPBI), N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-diphenyl-4,4'-diamine (DNTPD), copper phthalocyanine, and 4,4',4"-tris(3-methylphenylphenylamino)triphenylamine (m-MTDA). TA), N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (NPB), 4,4',4"-tris(diphenylamino)triphenylamine (TDATA), 4,4',4"-tris(N,N-2-naphthylphenylamino)triphenylamine (2-TNATA), polyaniline / dodecylbenzenesulfonic acid, poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate): PEDOT / PSS, or polyaniline / 10-camphorsulfonic acid, but not limited to these.

[0475] A hole transport layer 140 may be formed on the hole injection layer 130. The hole transport layer 140 may be a layer with the function of transporting holes, and may be formed with a thickness of, for example, from about 10 nm to about 150 nm, or, for example, from about 20 nm to about 50 nm. The hole transport layer 140 may be formed by solution coating using the composition according to the embodiment. According to this method, the durability (luminescence lifetime) of the EL device 100 may be extended. Furthermore, the current efficiency of the EL device 100 may be improved and the driving voltage reduced. Moreover, since the hole transport layer may be formed by solution coating, a large-area film can be effectively formed.

[0476] In an embodiment, hole transport layer 140 may include a curing material according to an embodiment. According to an embodiment, hole transport layer 140 may include a curing material according to an embodiment and a carboxyl-containing compound for positive aging described below. Specific examples of coating and curing methods are the same as those described for hole injection layer 130.

[0477] In addition to the cured product (and, if desired, a carboxyl compound) according to the embodiments, or when any layer other than the hole transport layer 140 of the EL device 100 includes the cured product (and, if desired, a carboxyl compound) according to the embodiments, the hole transport layer 140 may be formed to include a known hole transport material. Known hole transport materials may include, for example, carbazole derivatives such as 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), N-phenylcarbazole and polyvinylcarbazole, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-diphenyl]-4,4'-diamine (TPD), 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA), or N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (NPB), and are not limited thereto.

[0478] The light-emitting layer 150 can be formed on the hole transport layer 140. The light-emitting layer 150 can be a layer that emits light through fluorescence, phosphorescence, or the like, and can be formed using vacuum deposition, spin coating, inkjet printing, or the like. The light-emitting layer 150 can be formed with a thickness, for example, greater than or equal to about 10 nm and less than or equal to about 60 nm, or for example, greater than or equal to about 20 nm and less than or equal to about 50 nm. Any known light-emitting material can be used as the light-emitting material for the light-emitting layer 150. However, the light-emitting material included in the light-emitting layer 150 can be a light-emitting material capable of emitting light from triplet excitons (i.e., phosphorescence). In this case, the driving lifetime of the EL device 100 can be further improved.

[0479] The light-emitting layer 150 is not particularly limited and may have a known structure. For example, the light-emitting layer includes at least one of semiconductor nanocrystal particles and / or organometallic complexes. That is, in embodiments, the organic film may have a light-emitting layer including at least one of semiconductor nanocrystal particles and organometallic complexes. In embodiments, the organic film may include a light-emitting layer comprising semiconductor nanocrystal particles. When the light-emitting layer includes semiconductor nanocrystal particles, the EL device may be a quantum dot electroluminescent device (QLED), a quantum dot light-emitting device, or a quantum dot light-emitting diode. Furthermore, when the light-emitting layer includes an organometallic complex, the EL device may be an organic light-emitting device (OLED).

[0480] In the form of a light-emitting layer comprising semiconductor nanocrystal particles (QLED), the light-emitting layer is a single layer or multiple layers of semiconductor nanocrystal particles (quantum dots). Here, the semiconductor nanocrystal particles (quantum dots) are particles of a specific size that exhibit quantum confinement effects. The diameter of the semiconductor nanocrystal particles (quantum dots) is not particularly limited, but can be approximated to approximately 1 nm to approximately 10 nm.

[0481] Semiconductor nanocrystal particles (quantum dots) arranged in the light-emitting layer can be synthesized through wet chemical processes, organometallic chemical vapor deposition, molecular beam epitaxy, or other similar processes. Among these, the wet chemical process is a method of growing particles by adding precursor materials to an organic solvent.

[0482] In wet chemical processes, organic solvents naturally distribute onto the surface of quantum dot crystals during crystal growth, acting as dispersants to control crystal growth. Therefore, wet chemical processes offer a more convenient and cost-effective way to control the growth of semiconductor nanocrystal particles compared to vapor deposition methods such as metal-organic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE).

[0483] Semiconductor nanocrystal particles (quantum dots) can have their band gaps controlled by manipulating their size, thereby allowing light of various wavelengths to be emitted from the light-emitting layer (quantum dot light-emitting layer). Therefore, by using multiple quantum dots of different sizes, displays that emit light of multiple wavelengths can be fabricated. The size of the quantum dots can be selected to emit red, green, or blue light, enabling the construction of color displays. Furthermore, the sizes of the quantum dots can be combined to emit white light of various colors.

[0484] Semiconductor materials selected from group II-VI semiconductor compounds, group III-V semiconductor compounds, group IV-VI semiconductor compounds, group IV elements or compounds, or combinations thereof, can be used as semiconductor nanocrystal particles (quantum dots).

[0485] There are no particular limitations on the II-VI group semiconductor compounds, and examples may include: binary compounds selected from CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe and mixtures thereof; ternary compounds selected from CdSeS, CdSeTe, CdSTe, ZnSeS, ZnTeSe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe and mixtures thereof; and quaternary compounds selected from CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe and mixtures thereof.

[0486] There are no particular limitations on III-V semiconductor compounds, and examples may include: binary compounds selected from GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb and mixtures thereof; ternary compounds selected from GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP and mixtures thereof; and quaternary compounds selected from GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb and mixtures thereof.

[0487] There are no particular limitations on IV-VI group semiconductor compounds, and examples may include: binary compounds selected from SnS, SnSe, SnTe, PbS, PbSe, PbTe and mixtures thereof; ternary compounds selected from SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe and mixtures thereof; and quaternary compounds selected from SnPbSSe, SnPbSeTe, SnPbSTe and mixtures thereof.

[0488] There are no particular limitations on group IV elements or compounds, and examples may include: a single element selected from Si or Ge; or a binary element compound selected from SiC, SiGe, or mixtures thereof.

[0489] Semiconductor nanocrystal particles (quantum dots) can have a homogeneous single structure or a core-shell dual structure. The core and shell can be made of different materials. The materials constituting the core and shell can each be composed of different semiconductor compounds. However, the band gap of the shell material can be larger than that of the core material. For example, the structure can be ZnTeSe / ZnSe / ZnS, InP / ZnSe / ZnS, CdSe / ZnS, InP / ZnS, etc.

[0490] For example, a process for fabricating quantum dots with a core (CdSe) / shell (ZnS) structure is described. First, using TOPO (trioctylphosphine oxide) as a surfactant, a core (CdSe) precursor material (such as (CH3)2Cd (dimethylcadmium)) and TOPSe (trioctylphosphine selenide) are infused into an organic solvent to form a crystal. Then, after holding the crystal at a high temperature for a specific time to allow it to grow to a specific size, a precursor material (ZnS) for the shell is infused to form a shell on the surface of the already formed core. This allows for the fabrication of TOPO-coated CdSe / ZnS quantum dots.

[0491] Furthermore, in the form of an OLED comprising an organometallic complex, the emitting layer 150 may include (as a host material) such as 6,9-diphenyl-9'-(5'-phenyl-[1,1':3',1"-triphenyl]-3-yl)3,3'-di[9H-carbazole], 3,9-diphenyl-5-(3-(4-phenyl-6-(5'-phenyl-[1,1':3',1"-triphenyl]-3-yl)-1,3,5-triazin-2-yl)phenyl)-9H-carbazole, 9,9'-diphenyl-3,3'-di[9H-carbazole], tri( 8-Hydroxyquinoline aluminum (Alq3), 4,4'-bis(carbazole-9-yl)biphenyl (CBP), poly(N-vinylcarbazole) (PVK), 9,10-bis(naphthyl-2-yl)anthracene (ADN), 4,4',4"-tris(N-carbazole)triphenylamine (TCTA), 1,3,5-tris(N-phenyl-benzimidazole-2-yl)benzene (TPBI), 3-tert-butyl-9,10-bis(naphthyl-2-yl)anthracene (TBADN), bis-stilbene (DSA), 4-4'-bis(9-carbazole)-2,2'-dimethyl-biphenyl (dmCBP), etc.

[0492] Furthermore, the luminescent layer 150 may include (as dopant materials) such as dinoxyphenylene and its derivatives, rubrene and its derivatives, coumarin and its derivatives, 4-dicyanomethylene-2-(p-dimethylaminostyryl)-6-methyl-4H-pyran (DCM) and its derivatives, bis[2-(4,6-difluorophenyl)pyridine]pyridinecarboxylic acid iridium(III) (FIrpic), bis(1-phenylisoquinoline)(acetylacetone)iridium(III) (Ir(piq)2(acac)), tris(2-phenylpyridine)iridium(III) (Ir(ppy)3), iridium (Ir) complexes (such as, for example, tris(2-(3-p-xylene)phenyl)pyridineiridium(III)), osmium (Os) complexes, platinum complexes, etc. Among these, for example, the luminescent material may be a luminescent organometallic complex compound.

[0493] There are no particular limitations on the method used to form the light-emitting layer. The light-emitting layer can be formed by coating a coating solution comprising at least one of semiconductor nanocrystal particles and organometallic complexes (solution coating method). In this case, the solvent constituting the coating solution can be selected as a solvent that does not dissolve the material in the hole transport layer (such as, for example, a hole transport material).

[0494] An electron transport layer 160 may be formed on the light-emitting layer 150. The electron transport layer 160 may be a layer that functions to transport electrons, and may be formed using methods such as vacuum deposition, spin coating, and inkjet printing. The electron transport layer 160 may be formed to have a thickness of, for example, greater than or equal to about 15 nm and less than or equal to about 50 nm.

[0495] The electron transport layer 160 may be formed of a known electron transport material. Examples of known electron transport materials may include lithium (8-hydroxyquinoline) (lithium quinoline, Liq), tris(8-hydroxyquinoline)aluminum (Alq3), or compounds having a nitrogen-containing aromatic ring. Examples of compounds having a nitrogen-containing aromatic ring may include: compounds containing a pyridine ring (such as, for example, 1,3,5-tris[(3-pyridyl)-benzene-3-yl]benzene), compounds containing a triazine ring (such as, for example, 2,4,6-tris(3'-(pyridin-3-yl)diphenyl-3-yl)-1,3,5-triazine), or compounds containing an imidazole ring (such as, for example, 2-(4-(N-phenylbenzimidazolyl-1-yl-phenyl)-9,10-dinaphthylanthracene or 1,3,5-tris(N-phenyl-benzimidazol-2-yl)benzene (TPBI)). The electron transport material may be used alone or as a mixture of two or more types.

[0496] An electron injection layer 170 may be formed on the electron transport layer 160. The electron injection layer 170 may be a layer that facilitates the injection of electrons from the second electrode 180. The electron injection layer 170 may be formed using a vacuum deposition method or the like. The electron injection layer 170 may be formed to have a thickness, for example, greater than or equal to about 0.1 nm and less than or equal to about 5 nm, or for example, greater than or equal to about 0.3 nm and less than or equal to about 2 nm. Any known material may be used as the material for forming the electron injection layer 170. For example, the electron injection layer 170 may be formed from lithium compounds (such as, for example, lithium (8-hydroxyquinoline) (lithium quinoline, Liq) and lithium fluoride (LiF)), sodium chloride (NaCl), cesium fluoride (CsF), lithium oxide (Li₂O), or barium oxide (BaO).

[0497] The second electrode 180 may be formed on the electron injection layer 170. The second electrode 180 may be formed using a vacuum deposition method or the like. The second electrode 180 may provide electrons and may be, for example, a cathode, and may be formed of a metal, alloy, or conductive compound having a small work function. For example, the second electrode 180 may be formed as a reflective electrode using a metal (such as lithium (Li), magnesium (Mg), aluminum (Al), calcium (Ca)) or an alloy (such as aluminum-lithium (Al-Li), magnesium-indium (Mg-In), or magnesium-silver (Mg-Ag)). The second electrode 180 may be formed with a thickness of, for example, from about 10 nm to about 200 nm (e.g., from about 50 nm to about 150 nm). Alternatively, the second electrode 180 may be formed as a transparent electrode using a thin film of metallic material having a thickness of 20 nm or less, or a transparent conductive film (such as, for example, indium tin oxide (In2O3-SnO2) or indium zinc oxide (In2O3-ZnO)).

[0498] There are no particular limitations on the film-forming method for layers other than the organic film containing the cured product (and, if desired, a carboxyl compound) according to the embodiments. Layers other than the organic film containing the cured product (and, if desired, a carboxyl compound) according to the embodiments can be formed, for example, by vacuum deposition or by solution coating.

[0499] <Positive aging and carboxyl-containing compounds>

[0500] As described above, the unique technology of QD-LEDs is positive aging induced by acid compounds, which improves the luminous efficiency and device lifetime of QD-LEDs. An electroluminescent device (e.g., a QD-LED) according to an embodiment may include an organic layer comprising a curing material according to an embodiment. Therefore, even when positive aging is performed using acid compounds, a reduction in driving voltage and improvements in durability (luminous lifetime) and luminous efficiency (current efficiency) can be achieved. Therefore, the electroluminescent device (e.g., a QD-LED) according to an embodiment can exhibit excellent performance.

[0501] The acidic compounds used in positive aging may include, for example, carboxyl-containing compounds, sulfinic acid-containing compounds, and sulfonic acid-containing compounds. Among these, carboxyl-containing compounds may be used, for example.

[0502] Carboxyl-containing compounds may include at least one selected from the following: for example, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, (meth)acrylic acid, poly(meth)acrylic acid, benzoic acid, hexahydrobenzoic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, citric acid, malic acid, 3-isopropylmalic acid, itaconic acid, or citraconic acid, but not limited thereto.

[0503] There are no particular limitations on the positive aging method. For example, after manufacturing a QD-LED, a resin containing an acid compound or a solution containing an acid compound (e.g., a solution using an alcohol as a solvent) is placed or applied to the first or second electrode of the QD-LED, and then irradiated with an active energy beam to form an acid compound layer. Positive aging can then be performed under heating conditions. In this case, the acid compound can be a compound containing a carboxyl group.

[0504] In addition to the solvents described herein, alcohol solvents (e.g., ethanol, n-propanol, isopropanol, butanol, methyl cellosolve, ethylene glycol monobutyl ether, or propylene glycol monomethyl ether) may also be used as solvents in solutions containing the aforementioned compounds. The aforementioned solvents may be used alone or in combination of two or more different solvents. The concentration of the solution containing the acid compound is not particularly limited, for example, it may be about 0.5% or more by weight and about 30% or less by weight (e.g., about 1% or more by weight and about 20% or less by weight).

[0505] The active energy rays used may include ultraviolet light, such as gamma rays (436 nm), hamma rays (405 nm), iamma rays (365 nm), etc. Additionally, wavelengths less than or equal to 300 nm (such as KrF rays (248 nm), ArF rays (193 nm), etc.) may also be used. The cumulative luminous flux of the active energy rays may, for example, be greater than or equal to about 5 mJ / cm². 2 And less than or equal to approximately 20 mJ / cm 2 .

[0506] There is no particular limitation on the thickness of the oxide compound layer; for example, the thickness can be greater than or equal to about 10 nm, greater than or equal to about 30 nm, greater than or equal to about 50 nm, greater than or equal to about 70 nm, greater than or equal to about 90 nm, greater than or equal to about 100 nm, greater than or equal to about 120 nm, greater than or equal to about 140 nm, greater than or equal to about 160 nm, greater than or equal to about 180 nm, greater than or equal to about 200 nm, greater than or equal to about 250 nm, greater than or equal to about 300 nm, or greater than or equal to about 10 nm. Equal to about 350nm, greater than or equal to about 400nm, greater than or equal to about 450nm, greater than or equal to about 500nm, greater than or equal to about 550nm, greater than or equal to about 600nm, greater than or equal to about 650nm, greater than or equal to about 700nm, greater than or equal to about 750nm, greater than or equal to about 800nm, greater than or equal to about 850nm, greater than or equal to about 900nm, greater than or equal to about 950nm, greater than or equal to about 1μm, or greater than or equal to about 1.5μm. Furthermore, the thickness of the oxide compound layer may be, for example, less than or equal to about 100 μm, less than or equal to about 90 μm, less than or equal to about 80 μm, less than or equal to about 70 μm, less than or equal to about 60 μm, less than or equal to about 50 μm, less than or equal to about 40 μm, less than or equal to about 30 μm, less than or equal to about 20 μm, less than or equal to about 10 μm, less than or equal to about 9 μm, less than or equal to about 8 μm, less than or equal to about 7 μm, less than or equal to about 6 μm, less than or equal to about 5 μm, less than or equal to about 4 μm, less than or equal to about 3 μm, less than or equal to about 2 μm, or less than or equal to about 1 μm.

[0507] The QD-LED device in which the oxide compound layer has been formed can be kept at a predetermined temperature for a predetermined period of time for positive aging. The positive aging period can be, for example, 12 hours or longer, 20 hours or longer, 24 hours or longer, 2 days or longer, or 3 days or longer. In addition, the positive aging period can be, for example, 30 days or less, 20 days or less, 10 days or less, or 7 days or less, and these examples are not limiting.

[0508] Temperatures used for positive aging can be, for example, greater than or equal to about 30°C, greater than or equal to about 35°C, greater than or equal to about 40°C, greater than or equal to about 50°C, greater than or equal to about 55°C, greater than or equal to about 60°C, or greater than or equal to about 65°C.

[0509] After positive aging, the cured material and carboxyl-containing compound according to the embodiments may be included in any of the layers (organic layers) disposed between, for example, the first electrode 120 and the second electrode 180. That is, according to the embodiments, an organic layer comprising the cured product and the carboxyl-containing compound according to the embodiments (hereinafter also referred to as "the organic layer according to the embodiments") may be provided. According to another embodiment, an electroluminescent device is provided, the electroluminescent device comprising a first electrode layer supplying holes, a second electrode layer supplying electrons, and at least one organic layer disposed between the first electrode layer and the second electrode layer, wherein at least one layer of the at least one organic layer comprises an organic film comprising the cured product and the carboxyl-containing compound according to the embodiments.

[0510] According to embodiments, the cured product and carboxyl-containing compound may be included in the hole injection layer 130 as a hole injection material, in the hole transport layer 140 as a hole transport material, or in the light-emitting layer 150 as a light-emitting material (substrate). For example, the cured product and carboxyl-containing compound according to embodiments may be included in the hole injection layer 130 as a hole injection material, or in the hole transport layer 140 as a hole transport material. For example, the cured material and carboxyl-containing compound according to embodiments may be included in the hole injection layer 130 as a hole injection material. That is, in embodiments, at least one layer selected from the hole transport layer, the hole injection layer, or the light-emitting layer may include an organic film according to embodiments. In embodiments, at least one layer selected from the hole transport layer or the hole injection layer may include an organic film according to embodiments. In embodiments, the hole injection layer may include an organic film according to embodiments.

[0511] The cured material of the copolymer according to the embodiments exhibits good resistance to solvents used in the coating solution for forming adjacent layers of the hole injection layer and / or hole transport layer. Solvents used to form adjacent layers may include, for example, cyclohexane, hexane, octane, decane, tetradecane, hexadecane, indane, butanol, octanol, cyclohexylbenzene, dodecylbenzene, o-dichlorobenzene, etc., but are not limited thereto. Therefore, the cured material of the copolymer according to the embodiments exhibits good resistance to solvents.

[0512] In this specification, the assessment of the solvent resistance of the cured copolymer material can be performed based on the retention rate calculated by the following method.

[0513] <Resistance to solvents (retention rate)>

[0514] The solvent resistance of the copolymer curing material was evaluated using the method described below. Specifically, the copolymer was dissolved in xylene (the solvent) at a concentration of 1 wt% to prepare a copolymer coating solution. Next, the copolymer coating solution was applied to a quartz substrate using spin coating and dried (cured) at 230°C for 30 minutes to form a film with a dried thickness of 25 nm. The absorption spectrum of the formed film (before solvent impregnation) was then measured using a UV-Vis spectrophotometer (manufactured by Shimadzu Corporation, UV-1800). The wavelength of the peak at the longest wavelength side of the absorption spectrum was used as the reference wavelength.

[0515] Subsequently, the same film (the film before solvent impregnation) on the quartz substrate was immersed in the solvent cyclohexylbenzene (CHB) for 20 minutes, removed from the solvent, and dried (cured) at 230°C for 30 minutes. The absorption spectrum of the dried film (the film after solvent impregnation) was measured using a UV-Vis spectrophotometer in the same manner as described above. For this absorption spectrum, the retention rate (%) was defined as the ratio of the intensity at the reference wavelength of the absorption spectrum after solvent impregnation to the intensity at the reference wavelength of the absorption spectrum before solvent impregnation {(“intensity at the reference wavelength of the absorption spectrum after solvent impregnation” / “intensity at the reference wavelength of the absorption spectrum before solvent impregnation”) × 100 (%)}, and this ratio was evaluated.

[0516] For example, the retention rate obtained above can be greater than or equal to 80%, or for example, greater than or equal to 90%. When the retention rate is greater than or equal to 80%, it can be considered that the cured product equivalent to the copolymer is insoluble in the solvent used to form the adjacent layer (e.g., it has high solvent resistance). If the retention rate is less than 80%, mixing can occur between the hole injection layer or hole transport layer and the adjacent layer, which can lead to performance degradation of the electroluminescent device.

[0517] In summary, an EL device 100 according to an embodiment has been described as an example of an electroluminescent device according to an embodiment. The EL device 100 according to an embodiment may include an organic layer (e.g., a hole transport layer or a hole injection layer) comprising a curable material according to an embodiment and a carboxyl-containing compound. Therefore, the EL device can exhibit excellent resistance to positive aging, improved durability (luminescence lifetime), and luminous efficiency (current efficiency), resulting in an EL device with a reduced drive voltage. Furthermore, the EL device 100 according to an embodiment can have good resistance to solvents used to form adjacent layers.

[0518] The stack-up structure of the EL device 100 according to the embodiment is not limited to the example described above. The EL device 100 according to the embodiment can be formed with other known stack-up structures. For example, in the EL device 100, one or more of the hole injection layer 130, hole transport layer 140, electron transport layer 160, and electron injection layer 170 may be omitted, and other layers may be provided. Furthermore, each layer of the EL device 100 may be formed as a single layer or multiple layers.

[0519] For example, the EL device 100 may also include a hole blocking layer between the hole transport layer 140 and the light-emitting layer 150 to prevent excitons or holes from diffusing into the electron transport layer 160. The hole blocking layer may be formed of, for example, an oxadiazole derivative, a triazole derivative, or a phenanthroline derivative.

[0520] Furthermore, the compositions according to the embodiments can be applied to electroluminescent devices other than QD-LEDs or OLEDs. There are no particular limitations on other electroluminescent devices to which the compositions according to the embodiments can be applied, but for example, organic-inorganic perovskite light-emitting devices may be included.

[0521] Although examples have been described in detail with reference to embodiments, these are descriptive and exemplary, not limiting, and it is clear that the scope of the embodiments should be interpreted in accordance with the appended claims.

[0522] The above examples include the following embodiments.

[0523] 1. A composition comprising:

[0524] The copolymer includes structural unit A represented by chemical formula 2 and / or structural unit B represented by chemical formula 3, and structural unit represented by chemical formula 1; and

[0525] Salt compounds, including iodonium cations and borate anions represented by formula 4,

[0526] The energy difference (ΔE) between the ionization potential of the copolymer and the electron affinity of the borate anion is greater than or equal to about 0.75 eV, and the ionization potential of the copolymer is deeper than that of the iodonium cation.

[0527] Chemical Formula 1

[0528]

[0529] In chemical formula 1,

[0530] Ar 1 Ar 2 Ar 4 and Ar 5Each is independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0531] Ar 3 It is a substituted or unsubstituted carbazole, a substituted or unsubstituted fluorene, a substituted or unsubstituted benzene, or a substituted or unsubstituted biphenylene.

[0532] Among them, when Ar 3 When it is a substituted or unsubstituted benzene, or a substituted or unsubstituted biphenylene, Ar 1 Not substituted or unsubstituted benzene and / or Ar 2 Not substituted or unsubstituted benzene, and Ar 4 Not substituted or unsubstituted benzene and / or Ar 5 Benzene that is neither substituted nor unsubstituted

[0533] n1 is an integer greater than or equal to 1 and less than or equal to 3.

[0534] m1 is an integer greater than or equal to 1 and less than or equal to 3, and

[0535] It is a combination position;

[0536] Chemical formula 2

[0537]

[0538] In chemical formula 2,

[0539] Ar 6 and Ar 7 Each is independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, or Ar 6 and Ar 7 Together they form a ring.

[0540] R 1 It is a group represented by the chemical formula (2-a).

[0541] Chemical formula (2-a)

[0542]

[0543] In the chemical formula (2-a),

[0544] L 1 It is a single bond or a group represented by the chemical formula (2-b).

[0545] Ar 8 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0546] Among them, L1 It's a single bond, Ar 6 Ar 7 and Ar 8 At least one of them is not a substituted or unsubstituted phenyl, or Ar 8 Optional with Ar 6 and Ar 7 At least one of them together forms a ring,

[0547] n² is an integer greater than or equal to 2 and less than or equal to 5, and

[0548] It is a combination of positions,

[0549] Chemical formula (2-b)

[0550]

[0551] In the chemical formula (2-b),

[0552] Ar 9 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, or an Ar atom bound to a nitrogen atom. 9 Optional with Ar 6 and Ar 7 At least one of them together forms a ring,

[0553] m2 is an integer greater than or equal to 2 and less than or equal to 5, where, when m2 is an integer greater than or equal to 2, each Ar 9 Same or different, and

[0554] It is a combination position;

[0555] Chemical formula 3

[0556]

[0557] In chemical formula 3,

[0558] Ar 10 and Ar 11 Each is independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, or Ar 10 and Ar 11 They can optionally form a ring together.

[0559] R 2 It is a group represented by chemical formula (3-a) or chemical formula (3-b), and

[0560] It is a combination of positions,

[0561] Chemical formula (3-a)

[0562]

[0563] In the chemical formula (3-a),

[0564] L 2 It is a single bond or a group represented by the chemical formula (3-c).

[0565] Ar 12 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0566] Among them, when L 2 When it is a single bond, Ar 12 Optional with Ar 10 and Ar 11 At least one of them together forms a ring,

[0567] n3 is an integer greater than or equal to 2 and less than or equal to 5, and

[0568] It is a combination of positions,

[0569] Chemical formula (3-b)

[0570]

[0571] In the chemical formula (3-b),

[0572] L 3 It is a single bond or a group represented by the chemical formula (3-c).

[0573] Ar 13 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0574] Among them, when L 3 When it is a single bond, Ar 13 Optional with Ar 10 and Ar 11 At least one of them together forms a ring,

[0575] n4 is an integer greater than or equal to 2 and less than or equal to 5, and

[0576] It is a combination of positions,

[0577] Chemical formula (3-c)

[0578]

[0579] In the chemical formula (3-c),

[0580] Ar 14 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, or an Ar atom bound to a nitrogen atom. 14 Optional with Ar 10 and Ar 11 At least one of them together forms a ring,

[0581] m3 is an integer greater than or equal to 1 and less than or equal to 5, and when m3 is an integer greater than or equal to 2, each Ar 14 Same or different, and

[0582] It is a combination position;

[0583] Chemical Formula 4

[0584]

[0585] In chemical formula 4,

[0586] R 31 To R 34 Each is independently a hydrogen atom, a fluorine atom, or a group represented by the chemical formula (4-a):

[0587] Chemical formula (4-a)

[0588]

[0589] In the chemical formula (4-a),

[0590] L 4 It is a single bond or a group represented by the chemical formula (4-b).

[0591] Ar 15 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0592] X is a fluorine atom or a group selected from group (4-1).

[0593] n5 is an integer greater than or equal to 1 and less than or equal to 5.

[0594] n6 is an integer of 0 or 1, where,

[0595] When multiple groups represented by the chemical formula (4-a) are present, each L 4 Same or different,

[0596] When multiple groups represented by the chemical formula (4-a) are present, each Ar 15 Same or different,

[0597] When multiple groups represented by the chemical formula (4-a) are present, the individual X groups may be the same or different.

[0598] When multiple groups represented by the chemical formula (4-a) are present, each n5 may be the same or different.

[0599] When multiple groups represented by the chemical formula (4-a) are present, each n6 may be the same or different.

[0600] When n5 is an integer greater than or equal to 2, each X is either the same or different, and

[0601] It is a combination of positions,

[0602] Chemical formula (4-b)

[0603]

[0604] In the chemical formula (4-b),

[0605] Ar 16 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group.

[0606] m4 is an integer greater than or equal to 1 and less than or equal to 5, and when m4 is greater than or equal to 2, each Ar 16 Same or different, and

[0607] It is a combination of positions,

[0608] Group (4-1)

[0609]

[0610] In group (4-1),

[0611] It is a combination position.

[0612] 2. The composition according to claim 1, wherein the borate anion is selected from the groups represented below: .

[0613] 3. A composition according to any one of items 1 and 2, wherein the structural unit represented by chemical formula 1 is selected from the groups represented in groups (1-1) to (1-3):

[0614] Group (1-1)

[0615] Group (1-2)

[0616] Groups (1-3)

[0617] Among them, in groups (1-1) to (1-3),

[0618] R 4 To R 6 R 71 To R 76 and R 81 To R 84 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0619] Each n1 represents an integer greater than or equal to 1 and less than or equal to 3.

[0620] Each m1 represents an integer greater than or equal to 1 and less than or equal to 3, and

[0621] It is a combination position.

[0622] 4. A composition according to any one of items 1 to 3, wherein the structural unit A represented by chemical formula 2 is selected from the groups represented in group 2:

[0623] Group 2 .

[0624] Among them, in the chemical formula of group 2, It is a combination position.

[0625] 5. A composition according to any one of items 1 to 4, wherein the structural unit B represented by chemical formula 3 is selected from the groups represented in group 3:

[0626] Group 3

[0627] Among them, in the chemical formula of group 3, It is a combination position.

[0628] 6. The composition according to any one of items 1 to 5, wherein the copolymer is selected from copolymers represented by the following chemical formulas:

[0629] Wherein, in the chemical formula, It is a combination position.

[0630] 7. The composition according to any one of items 1 to 6, wherein, based on the total number of moles of structural units represented by chemical formula 1, structural unit A represented by chemical formula 2 and structural unit B represented by chemical formula 3 in the copolymer, the molar ratio of structural units represented by chemical formula 1 is greater than or equal to about 20 mol% and less than or equal to about 99 mol%.

[0631] 8. The composition according to any one of items 1 to 7, wherein, based on the total number of moles of the structural unit represented by chemical formula 1, structural unit A represented by chemical formula 2 and structural unit B represented by chemical formula 3 in the copolymer, the molar ratio of at least one of the structural unit A represented by chemical formula 2 and structural unit B represented by chemical formula 3 is greater than or equal to about 1 mol% and less than or equal to about 80 mol%.

[0632] 9. The composition according to any one of items 1 to 8, wherein the weight-average molecular weight (Mw) of the copolymer is greater than or equal to about 8,000 Da and less than or equal to about 500,000 Da.

[0633] 10. The composition according to any one of items 1 to 9, wherein, based on the total weight of the copolymer and the salt compound, the amount of the salt compound in the composition is greater than or equal to about 1 wt% and less than or equal to about 70 wt%.

[0634] 11. The composition according to any one of claims 1 to 10, wherein the electron affinity of the borate anion is greater than or equal to about 5.50 eV and less than or equal to about 6.50 eV.

[0635] 12. The composition according to any one of claims 1 to 11, wherein the iodonium cation is any one of the following: difuranyliodonium cation, dithienyliodonium cation, bis(4,5-dimethyl-2-furanyl)iodonium cation, bis(5-chloro-2-thienyl)iodonium cation, bis(5-cyano-2-furanyl)iodonium cation, bis(5-nitro-2-thienyl)iodonium cation, bis(5-acetyl-2-furanyl)iodonium cation, bis(5-carboxyl-2-... bis(5-methoxycarbonyl-2-furanyl)iodonium cation, bis(5-phenyl-2-furanyl)iodonium cation, bis(5-(p-methoxyphenyl)-2-thienyl)iodonium cation, bis(5-vinyl-2-furanyl)iodonium cation, bis(5-ethynyl-2-thienyl)iodonium cation, bis(5-cyclohexyl-2-furanyl)iodonium cation, bis(5-hydroxy-2-thienyl)iodonium cation, bis(5-phenoxy-2- Furanyl)iodonium cation, bis(5-mercapto-2-thienyl)iodonium cation, bis(5-butthio-2-thienyl)iodonium cation, bis(5-phenylthio-2-thienyl)iodonium cation, diphenyliodonium cation, bis(p-tolyl)iodonium cation, bis(p-octylphenyl)iodonium cation, bis(p-octadecylphenyl)iodonium cation, bis(p-octyloxyphenyl)iodonium cation, bis(p-octadecyloxyphenyl)iodonium cation, phenyl(p-octadecyloxyphenyl)iodonium Onion cations, 4-isopropyl-4'-methyldiphenyliodonium cations, (4-isobutylphenyl)-p-tolyliodonium cations, bis(1-naphthyl)iodonium cations, bis(4-phenylthioalkylphenyl)iodonium cations, phenyl(6-benzoyl-9-ethyl-9H-carbazole-3-yl)iodonium cations, (7-methoxy-2-oxo-2H-chromene-3-yl)-4'-isopropylphenyliodonium cations, and combinations of any two or more of the iodonium cations listed above.

[0636] 13. The composition according to any one of claims 1 to 12, wherein the ionization potential of the iodonium cation is greater than or equal to about 4.00 eV and less than or equal to about 4.95 eV.

[0637] 14. The composition according to any one of claims 1 to 13, wherein the salt compound further comprises a sulfonium cation, a sulfonium oxide cation, a phosphonium cation, or a combination thereof.

[0638] 15. An organic membrane comprising: a carboxyl-containing compound and a cured material obtained by curing a composition according to any one of claims 1 to 14.

[0639] 16. The organic membrane according to item 15, wherein the carboxyl-containing compound is acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, (meth)acrylic acid, poly(meth)acrylic acid, benzoic acid, hexahydrobenzoic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, citric acid, malic acid, 3-isopropylmalic acid, itaconic acid, citraconic acid, or combinations thereof.

[0640] 17. An electroluminescent device, comprising:

[0641] The first electrode supplies holes.

[0642] The second electrode supplies electrons; and

[0643] An organic layer is disposed between the first electrode and the second electrode.

[0644] At least one of the organic layers comprises an organic membrane according to item 15 or item 16.

[0645] 18. The electroluminescent device according to item 17, wherein the at least one organic layer comprising the organic film is a hole injection layer.

[0646] 19. The electroluminescent device according to claim 17 or 18, wherein the organic layer comprises: a light-emitting layer comprising semiconductor nanoparticles, organometallic complexes, or combinations thereof.

[0647] 20. An electroluminescent device according to any one of claims 17 to 19, wherein the organic layer comprises: a light-emitting layer comprising semiconductor nanoparticles.

[0648] Example

[0649] The present disclosure is described in more detail using the following examples and comparative examples. However, the technical scope of the present disclosure is not limited to the following examples. In the following examples, unless specifically described, the various operations are performed at room temperature (25°C). Furthermore, unless specifically stated otherwise, “%” and “parts” mean “weight %” and “parts by weight”, respectively.

[0650] The ionization potential of the copolymer, the electron affinity of the salt compound, and the ionization potential of the iodonium cation are calculated as follows. Here, ΔE is obtained by subtracting the ionization potential of the copolymer from the electron affinity of the salt compound.

[0651] <Calculation Method>

[0652] The ionization potentials of the copolymer, the electron affinity of the salt compound, and the ionization potential of the iodonium cation were determined by density functional theory (DFT) using Gaussian 16 (Gaussian Inc.) as the calculation software and as the functional B3LYP and the basis function 6-31G(d, p).

[0653] Synthesis Example 1: Synthesis of Compound M-1

[0654] Compound M-1, represented by the following chemical formula, was synthesized using the same method as in Synthesis Example 3 disclosed in Japanese Patent Application Publication No. 2021-138915.

[0655]

[0656] Synthesis Example 2: Synthesis of Compound M-2

[0657] Except for replacing 4-chloro-N-(4-chlorophenyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)phenyl)aniline with 4-bromo-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)phenyl)aniline, the compound M-2 represented by the following chemical formula was synthesized by the same method as in Synthesis Example 4 disclosed in Japanese Patent Application Publication No. 2021-138915.

[0658]

[0659] Synthesis Example 3: Synthesis of Compound CL-1

[0660] According to reaction scheme 1, compound CL-1 was synthesized as follows:

[0661] Reaction Scheme 1

[0662] To a 500 mL argon-purified four-necked flask, 2,7-dichloro-9H-carbazole (25.0 g), 1,3-dibromo-5-fluorobenzene (40.3 g), cesium carbonate (69.0 g), and N,N-dimethylformamide (DMF) (510 mL) were added, and the mixture was stirred at 170 °C (bath temperature) for 8 hours. After cooling to room temperature, the aqueous layer was separated and extracted with toluene (200 mL × 2). The organic layer was washed with water (200 mL × 2) and dried over magnesium sulfate. The solvent was removed under reduced pressure, and the residue was recrystallized from toluene / ethanol to give compound CL-1-1 (41.3 g).

[0663] Under an argon atmosphere, the above-obtained compound CL-1-1 (40.0 g), bis(pinacolyl)diboron (86.4 g), potassium acetate (KOAc) (41.7 g), [1,1'-bis(diphenylphosphine)ferrocene]palladium(II) chloride (PdCl2(dppf)) (3.1 g) and 1,4-dioxane (400 mL) were added to a 1000 mL three-necked flask, and the mixture was stirred at 110 °C (bath temperature) for 3 hours. The mixture was cooled to room temperature, and insoluble matter was removed by filtration using diatomaceous earth as a filter aid. The solvent was removed by distillation under reduced pressure, and the residue was dissolved in a mixed solvent of toluene (100 mL) and hexane (100 mL), with activated carbon (40.0 g) added, and the mixture was refluxed for 30 minutes. Insoluble matter was filtered using diatomaceous earth as a filter aid. The solvent was removed by distillation under reduced pressure, and the residue was crystallized and purified by adding a toluene / ethanol mixture to give compound CL-1-2 (32.6 g).

[0664] To a 1000 mL argon-purified four-necked flask, the above-obtained compound CL-1-2 (30.0 g), 3-bromocyclo[4.2.0]octyl-1,3,5-triene (19.5 g), sodium carbonate (16.9 g), tetrakis(triphenylphosphine)palladium(0)(Pd(PPh3)4) (1.5 g), and solvent (i.e., toluene (300 mL), ethanol (120 mL), and water (120 mL)) were added, and the mixture was stirred at 100 °C (bath temperature) for 3 hours. After cooling to room temperature, the aqueous layer was separated and extracted with toluene (100 mL × 2). The organic layer was washed with water (100 mL × 2) and dried over magnesium sulfate. The solvent was removed under reduced pressure, and the residue was added toluene (200 mL) and refluxed at 60 °C for 1 hour, then the solid was filtered and dried. The solvent was removed under reduced pressure, and the resulting residue was recrystallized and purified by adding a toluene / ethanol mixed solvent to provide compound CL-1-3 (37.6 g).

[0665] In a 1000 mL three-necked flask purged with argon, the above-obtained compound CL-1-3 (20.0 g), bis(pinacolyl)diboron (39.3 g), potassium acetate (13.3 g), [1,1'-bis(diphenylphosphine)ferrocene]dichloropalladium(II)dichloromethane adduct (PdCl2(dppf)·CH2Cl2) (3.1 g), XPhos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl) (1.84 g), and 1,4-dioxane (200 mL) were added, and the mixture was stirred at 110 °C (bath temperature) for 3 hours. The mixture was cooled to room temperature, and insoluble matter was removed using diatomaceous earth as a filter aid. The solvent was removed by distillation under reduced pressure, and the residue was dissolved in a mixed solvent of toluene (100 mL) and hexane (100 mL), followed by the addition of activated carbon (20.0 g) and reflux for 30 minutes. Insoluble matter was filtered using diatomaceous earth as a filter aid. The solvent was removed by distillation under reduced pressure, and the resulting residue was purified by recrystallization using a toluene / ethanol mixture to provide compound CL-1 (16.3 g).

[0666] Synthesis Example 4: Synthesis of Compound CL-2

[0667] According to reaction scheme 2, compound CL-2 was synthesized:

[0668] Reaction Scheme 2

[0669] To a 2000 mL three-necked flask purged with argon, 60 g of 4-chloroaniline, 94.5 g of 1-bromo-4-chlorobenzene, 67.8 g of sodium tert-butoxide (t-BuONa), and 940 mL of toluene were added and dispersed under a nitrogen atmosphere. Then, 19.2 g of the [1,1'-bis(diphenylphosphine)ferrocene]dichloropalladium(II)dichloromethane complex (PdCl2(dppf)·CH2Cl2) was added, and the mixture was stirred at 90 °C for 9 hours. After the reaction was complete, the mixture was cooled to room temperature and filtered through diatomaceous earth. The resulting solution was concentrated and purified by silica gel column chromatography (eluent: toluene / hexane). The solid obtained after solvent removal was purified by recrystallization from a toluene / hexane mixed solvent. It was then dried under vacuum (50 °C, 16 hours) to give compound CL-2-1 (79.7 g).

[0670] In a 2000 mL three-necked flask purged with argon, the obtained compound CL-2-1 (25.0 g), 1,3-dibromo-5-iodobenzene (57.0 g), sodium tert-butoxide (20.2 g), and toluene (525 mL) were added and dispersed under a nitrogen atmosphere. Next, the [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)dichloromethane complex (2.57 g) was added, and the mixture was stirred at 90 °C for 9 hours. After the reaction was complete, the mixture was cooled to room temperature, and the base was filtered off using diatomaceous earth. The resulting solution was concentrated and purified by silica gel column chromatography (eluent: toluene / hexane). The solvent was removed, and the resulting solid was purified by recrystallization using a toluene / methanol mixture. The solid was then dried under vacuum (50 °C, 16 hours) to give compound CL-2-2 (31.9 g).

[0671] In a 500 mL three-necked flask purged with argon, the previously obtained compound CL-2-2 (15.0 g), 4-vinylphenylboronic acid (14.1 g), and dimethoxyethane (DME) (159 mL) were added and dissolved. Next, an aqueous solution of tripotassium phosphate (80 mL) (95.34 mmol, 20.2 g) was added, and nitrogen was bubbled through the mixture for 30 minutes. Then, tetrakis(triphenylphosphine)palladium (0) (1.84 g) was added, and the mixture was stirred at 90 °C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature and separated by ethyl acetate and water. The organic layer was dried over magnesium sulfate to remove the solvent. The crude product was purified by silica gel column chromatography (eluent: toluene / hexane). The solid obtained after solvent removal was further purified by recrystallization from n-hexane. Subsequently, it was dried under vacuum (50 °C, 16 hours) to give compound CL-2-3 (11.6 g).

[0672] To a 500 mL argon-purified three-necked flask, the previously obtained compound CL-2-3 (11.0 g), bis(pinacol)diboron (21.6 g), potassium acetate (112.2 g), and 1,4-dioxane (212 mL) were added and dissolved under a nitrogen atmosphere. Next, palladium acetate (0.48 g) and XPhos (1.01 g) were added, and the mixture was stirred under reflux for 6 hours. After the reaction was complete, the mixture was cooled to room temperature, and the base was filtered off using diatomaceous earth as a filter aid. The resulting solution was concentrated and purified by silica gel column chromatography (eluent: toluene / ethanol). The crude product was obtained by washing with acetonitrile to remove the solvent. The solid recovered by filtration was further purified by recrystallization using a toluene / hexane mixed solvent. Subsequently, it was dried under vacuum (50 °C, 16 h) to give compound CL-2 (8.7 g).

[0673] Synthesis Example 5: Synthesis of Compound M-3

[0674] According to reaction scheme 3, compound M-3 was synthesized:

[0675] Reaction scheme 3

[0676] In a 200 mL three-necked flask purged with argon, N,N'-bis(p-tolyl)benzidine (10.0 g), 2-bromo-9,9-dihexyl-7-iodo-9H-fluorene (31.1 g), cuprous(I) iodide (0.5 g), phenanthroline (1.5 g), sodium tert-butoxide (7.9 g), and 1,4-dioxane (30 mL) were added, and the mixture was stirred at 110 °C (bath temperature) for 3 hours. The mixture was cooled to room temperature, and the insoluble material was filtered off using diatomaceous earth as a filter aid. The solvent was removed by distillation under reduced pressure, and the residue was dissolved in a mixed solvent of toluene (100 mL) and hexane (100 mL), with activated carbon (20.0 g) added, and the mixture was refluxed for 30 minutes. Insoluble material was filtered out using diatomaceous earth as a filter aid, the solvent was removed by distillation under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / hexane) to obtain compound M-3-1 (22.1 g).

[0677] To a 500 mL three-necked flask purged with argon, compound M-3-1 (20.0 g), p-toluidine (3.8 g), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)dichloromethane adduct (0.5 g), sodium tert-butoxide (4.8 g), and toluene (170 mL) were added, and the mixture was stirred at 120 °C (bath temperature) for 12 hours. The mixture was cooled to room temperature, and insoluble matter was removed by filtration through diatomaceous earth as a filter aid. The solvent was removed by distillation under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / hexane) to give compound M-3-2 (13.0 g).

[0678] To a 100 mL three-necked flask purged with argon, add the above-obtained compound M-3-2 (10.0 g), 2-bromo-9,9-dimethyl-7-iodo-9H-fluorene (6.8 g), cuprous(I) iodide (0.2 g), phenanthroline (0.3 g), sodium tert-butoxide (2.3 g), and 1,4-dioxane (10 mL), and stir the mixture at 110 °C (bath temperature) for 18 hours. After cooling to room temperature, remove insoluble matter by filtration using diatomaceous earth as a filter aid. Remove the solvent by distillation under reduced pressure, and dissolve the residue in a mixed solvent of toluene (100 mL) and hexane (100 mL), add activated carbon (20.0 g), and reflux for 30 minutes. Filter the insoluble matter using diatomaceous earth as a filter aid. The solvent was removed by distillation under reduced pressure, and the residue was purified by silica gel column chromatography (elution: toluene / hexane) to obtain compound M-3 (10.3 g).

[0679] Synthesis Example 6: Synthesis of Compound M-4

[0680] According to reaction scheme 4, compound M-4 was synthesized:

[0681] Reaction scheme 4

[0682]

[0683] To a 500 mL three-necked flask purged with argon, add dibromo-9,9-dihexylfluorene (10.0 g), 9,9-dimethyl-9H-fluorene-2-amine (8.9 g), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)dichloromethane adduct (0.3 g), sodium tert-butoxide (5.9 g), and toluene (200 mL), and stir the mixture at 120 °C (bath temperature) for 6 hours. Cool the mixture to room temperature and remove insoluble material by filtration using diatomaceous earth as a filter aid. Remove the solvent under reduced pressure and purify the residue by silica gel column chromatography (eluent: toluene / hexane) to give compound M-4-1 (19.8 g).

[0684] In a 100 mL three-necked flask purged with argon, compound M-4-1 (15.0 g), 1-bromo-4-iodobenzene (11.9 g), cuprous(I) iodide (CuI) (0.4 g), phenanthroline (0.7 g), sodium tert-butoxide (5.7 g), and 1,4-dioxane (20 mL) obtained above were added, and the mixture was stirred at 110 °C (bath temperature) for 18 hours. The mixture was cooled to room temperature, and insoluble matter was removed by filtration using diatomaceous earth as a filter aid. The solvent was removed by distillation under reduced pressure, and the residue was dissolved in a mixed solvent of toluene (100 mL) and hexane (100 mL), with activated carbon (20.0 g) added and refluxed for 30 minutes. Insoluble matter was filtered using diatomaceous earth as a filter aid. The solvent was removed by distillation under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / hexane) to give compound M-4 (10.6 g).

[0685] Synthesis Example 7: Synthesis of Compound M-5

[0686] According to reaction scheme 5, compound M-5 was synthesized:

[0687] Reaction scheme 5

[0688]

[0689] To a 500 mL three-necked flask purged with argon, add dibromo-9,9-dihexylfluorene (20.0 g), p-toluidine (9.1 g), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)dichloromethane adduct (0.7 g), sodium tert-butoxide (11.7 g), and toluene (250 mL), and stir the mixture at 120 °C (bath temperature) for 5 hours. Cool the reaction to room temperature and remove insoluble matter by diatomaceous earth filtration. Remove the solvent under reduced pressure and purify the residue by silica gel column chromatography (eluent: toluene / hexane) to give compound M-5-1 (15.1 g).

[0690] To a 100 mL three-necked flask purged with argon, add the above-obtained compound M-5-1 (10.0 g), 2-bromo-9,9-dimethyl-7-iodo-9H-fluorene (14.0 g), cuprous(I) iodide (0.3 g), phenanthroline (0.6 g), sodium tert-butoxide (4.8 g), and 1,4-dioxane (20 mL), and stir the mixture at 110 °C (bath temperature) for 18 hours. After cooling to room temperature, remove insoluble matter by filtration using diatomaceous earth as a filter aid. Remove the solvent by distillation under reduced pressure, and dissolve the residue in a mixed solvent of toluene (100 mL) and hexane (100 mL), add activated carbon (20.0 g), and reflux for 30 minutes. Filter out the insoluble matter using diatomaceous earth as a filter aid. The solvent was removed by distillation under reduced pressure, and the residue was purified by silica gel column chromatography (elution: toluene / hexane) to give compound M-5 (10.6 g).

[0691] Synthesis Example 8: Synthesis of Compound M-6

[0692] According to reaction scheme 6, compound M-6 was synthesized:

[0693] Reaction scheme 6

[0694]

[0695] To a 500 mL three-necked flask purged with argon, 2,7-dibromo-9,9-dihexyl-9H-fluorene (25.0 g), p-toluidine (11.4 g), and toluene (254 mL) were added and dissolved by stirring under nitrogen atmosphere. Next, sodium tert-butoxide (14.6 g) and [1,1'-bis(diphenylphosphine)ferrocene]dichloropalladium(II)dichloromethane adduct (1.24 g) were added, and the mixture was stirred under reflux for 2 hours. After the reaction was complete, the mixture was cooled to room temperature and filtered through the base using diatomaceous earth as a filter aid. The resulting solution was concentrated and purified by silica gel column chromatography (eluent: toluene / hexane). The solid obtained after solvent removal was dissolved in hexane by heating at 65 °C, slowly cooled, and purified by recrystallization. The resulting solid was dried under vacuum overnight to provide compound M-6-1 (22.0 g) (white solid).

[0696] In a 200 mL three-necked flask purged with argon, the previously obtained compound M-6-1 (36.0 g), 1-bromo-4-iodobenzene (56.1 g), sodium tert-butoxide (19.1 g), and 1,4-dioxane (66 mL) were added and dispersed, then purged with nitrogen. Next, cuprous iodide (I) (0.63 g) and trans-1,2-cyclohexanediamine (chxn) (1.51 g) were added, and the mixture was stirred under reflux for 21 hours. After the reaction was complete, toluene was added and the mixture was cooled to room temperature. The base was then filtered off using diatomaceous earth as a filter aid. The crude product was purified by silica gel column chromatography (eluent: toluene). The solid obtained after solvent removal was further purified by recrystallization (solvent: toluene / hexane). The obtained solid was dried under vacuum overnight to give a white solid compound M-6 (29.5 g).

[0697] Synthesis Example 9: Synthesis of Compound M-7

[0698] According to reaction scheme 7, compound M-7 was synthesized:

[0699] Reaction Scheme 7

[0700] In a 200 mL three-necked flask purged with argon, compound M-6 (13.6 g), bis(pinacolyl)diboron (16.2 g), potassium acetate (6.25 g), and 1,4-dioxane (73 mL) were added and dissolved under a nitrogen atmosphere. Next, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)dichloromethane adduct (0.39 g) was added, and the mixture was stirred under reflux for 4 hours. After the reaction was complete, the mixture was cooled to room temperature, and the base was filtered using diatomaceous earth as a filter aid. The resulting solution was concentrated and purified by silica gel column chromatography (eluent: toluene). The crude product obtained by solvent removal was washed with acetonitrile. The solid recovered by filtration was further purified by recrystallization (toluene / acetonitrile). The resulting solid was dried under vacuum (50 °C, 16 h) to provide compound M-7 (11.1 g).

[0701] Synthesis Example 10: Synthesis of Compound M-8

[0702] According to reaction scheme 8, compound M-8 was synthesized:

[0703] Reaction Scheme 8

[0704]

[0705] To a 300 mL four-necked flask purged with argon, 2,7-dibromo-9-phenylcarbazole (4.73 g), 4-butylaniline (3.68 g), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)dichloromethane adduct (286 mg), sodium tert-butoxide (3.37 g), and toluene (50 mL) were added, and the mixture was heated and stirred at 110 °C for 3 hours under an argon atmosphere. The reaction mixture was allowed to stand and cooled to room temperature, and the insoluble material was filtered through diatomaceous earth. The solvent was removed by distillation under reduced pressure. The resulting solid was then dissolved in toluene (100 mL) and purified by silica gel column chromatography (eluent: toluene / hexane) to give compound M-8-1 (4.81 g).

[0706] In a 200 mL argon-purified four-necked flask, the previously obtained compound M-8-1 (4.81 g), 1-bromo-4-iodobenzene (7.33 g), cuprous(I) iodide (0.164 g), sodium tert-butoxide (2.48 g), trans-1,2-cyclohexanediamine (0.196 g), and 1,4-dioxane (55 mL) were added, and the mixture was heated and stirred at 100 °C for 30 hours. The mixture was cooled to room temperature, then further cooled, and the insoluble matter was filtered off using diatomaceous earth. The solvent was removed by distillation under reduced pressure. The resulting solid was then dissolved in toluene (100 mL) and purified by silica gel column chromatography (elution: toluene / hexane) to give compound M-8 (3.16 g).

[0707] Synthesis Example 11: Synthesis of Compound M-9

[0708] According to reaction scheme 9, compound M-9 was synthesized:

[0709] Reaction Scheme 9

[0710]

[0711] In a 200 mL argon-purified four-necked flask, 2,7-dibromo-9-phenylcarbazole (5.50 g), 4-methylaniline (3.07 g), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)dichloromethane adduct (333 mg), sodium tert-butoxide (3.91 g), and toluene (58 mL) were added, and the mixture was heated and stirred at 110 °C for 3 hours under an argon atmosphere. The mixture was allowed to stand until room temperature, cooled, and the insoluble matter was filtered off using diatomaceous earth. The solvent was removed by distillation under reduced pressure. The resulting solid was then dissolved in toluene (100 mL) and purified by silica gel column chromatography (elution: toluene / hexane) to give compound M-9-1 (5.02 g).

[0712] In a 200 mL four-necked flask purged with argon, the previously obtained compound M-9-1 (4.30 g), 1-bromo-4-iodobenzene (8.03 g), cuprous(I) iodide (0.179 g), sodium tert-butoxide (2.71 g), trans-1,2-cyclohexanediamine (0.215 g), and 1,4-dioxane (60 mL) were added, and the mixture was heated and stirred at 100 °C for 30 hours under an argon atmosphere. The mixture was allowed to reach room temperature, cooled, and the insoluble material was filtered through diatomaceous earth. The solvent was removed by distillation under reduced pressure. The resulting solid was then dissolved in toluene (100 mL) and purified by silica gel column chromatography (eluent: toluene / hexane) to give compound M-9 (3.16 g).

[0713] Synthesis Example 12: Synthesis of Compound M-10

[0714] According to reaction scheme 10, compound M-10 was synthesized:

[0715] Reaction Scheme 10

[0716]

[0717] Compound M-10-1 was synthesized using the same method as in Synthesis Example 1 disclosed in Japanese Patent Application Publication No. 2021-138915.

[0718] To a 100 mL three-necked flask, compound M-10-1 (14.0 g), bis(pinacolyl)diboron (21.8 g), potassium acetate (8.25 g), and 1,4-dioxane (100 mL) were added and dissolved under a nitrogen atmosphere. Next, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)dichloromethane adduct (0.55 g) was added, and the mixture was stirred under reflux for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and the base was filtered using diatomaceous earth as a filter aid. The resulting solution was concentrated and purified by silica gel column chromatography (eluent: toluene). The crude product obtained by solvent removal was washed with acetonitrile. The solid recovered by filtration was further purified by recrystallization (solvent: toluene / acetonitrile). The resulting solid was dried under vacuum (50 °C, 16 h) to give compound M-10 (7.5 g).

[0719] Synthesis Example 13: Synthesis of Copolymer P-1

[0720] copolymer P-1

[0721]

[0722] Under a nitrogen atmosphere, compound M-1 (1.48 g), compound CL-2 (0.27 g), dibromo-9,9-dihexylfluorene (0.51 g), palladium acetate (3.3 mg), tris(2-methoxyphenyl)phosphine (31.6 mg), toluene (30 mL), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (7.60 g) were added to a four-necked flask and stirred at 85 °C for 6 hours. Then, phenylboronic acid (206 mg), bis(triphenylphosphine)palladium(II) dichloride (82.9 mg), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (7.10 g) were added, and the mixture was stirred at 85 °C for 6 hours. Afterward, sodium N,N-diethyldithiocarbamate trihydrate (4.6 g) dissolved in ion-exchanged water (50 mL) was added, and the mixture was stirred at 85 °C for 2 hours. The organic layer was separated from the aqueous layer. The solvent in the organic layer was distilled off under reduced pressure, and the residue was redeprecipitated with toluene / methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (30 mL), and alumina (20.0 g) and diatomaceous earth (5.0 g) were added, followed by stirring at 90 °C for 1 hour. The alumina and diatomaceous earth were filtered off, and 12N hydrochloric acid (20 mL) was added to the filtrate, followed by stirring at room temperature for 12 hours. The aqueous layer was separated, and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain copolymer P-1 (1.16 g). The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-1 were measured by SEC. Therefore, the weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-1 were 28300 Da and 2.24, respectively. Based on the monomer feed ratio, it is presumed that copolymer P-1 obtained in this manner is the copolymer represented by the above chemical formula. The ionization potential of copolymer P-1 is 5.34 eV.

[0723] Synthesis Example 14: Synthesis of Copolymer P-2

[0724] copolymer P-2

[0725]

[0726] Under a nitrogen atmosphere, compound M-2 (1.52 g), compound CL-2 (0.34 g), dibromo-9,9-dihexylfluorene (0.64 g), palladium acetate (5.5 mg), tris(2-methoxyphenyl)phosphine (52.0 mg), toluene (37 mL), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (8.90 g) were added to a four-necked flask and stirred at 85 °C for 6 hours. Then, phenylboronic acid (215 mg), bis(triphenylphosphine)palladium(II) dichloride (103.6 mg), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (8.90 g) were added, and the mixture was stirred at 85 °C for 6 hours. Subsequently, sodium N,N-diethyldithiocarbamate trihydrate (5.8 g) dissolved in deionized water (70 mL) was added, and the mixture was stirred at 85 °C for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was removed by distillation under reduced pressure, and the residue was redeprecipitated with toluene / methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (40 mL), and alumina (25.0 g) and diatomaceous earth (5.0 g) were added. The mixture was stirred at 90 °C for 1 hour. The alumina and diatomaceous earth were filtered, and 12N hydrochloric acid (30 mL) was added to the filtrate. The mixture was stirred at room temperature for 12 hours. The aqueous layer was removed, and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain copolymer P-2 (1.16 g). The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-2 were measured by SEC. The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-2 were 26000 Da and 2.56, respectively. Based on the monomer feed ratio, copolymer P-2 obtained in this manner is presumed to be the copolymer represented by the above chemical formula. The ionization potential of copolymer P-2 is 5.41 eV.

[0727] Synthesis Example 15: Synthesis of Copolymer P-3

[0728] copolymer P-3

[0729] Under a nitrogen atmosphere, compound M-3 (1.96 g), compound CL-2 (0.67 g), palladium acetate (2.5 mg), tris(2-methoxyphenyl)phosphine (23.3 mg), toluene (53 mL), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (5.68 g) were added to a four-necked flask and stirred at 85 °C for 6 hours. Then, phenylboronic acid (196 mg), bis(triphenylphosphine)palladium(II) dichloride (46.4 mg), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (5.68 g) were added and stirred at 85 °C for 6 hours. Subsequently, sodium trihydrate of N,N-diethyldithiocarbamate (3.7 g) dissolved in deionized water (70 mL) was added and stirred at 85 °C for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was removed by distillation under reduced pressure and reprecipitated with toluene / methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (40 mL), and alumina (20.0 g) and diatomaceous earth (5.0 g) were added. The mixture was stirred at 90 °C for 1 hour. The alumina and diatomaceous earth were filtered off, and 12N hydrochloric acid (30 mL) was added to the filtrate. The mixture was stirred at room temperature for 12 hours. The aqueous layer was removed, and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain copolymer P-3 (1.01 g). The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-3 were measured by SEC. The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-3 were 36000 Da and 2.24, respectively. Based on the monomer input ratio, copolymer P-3 obtained in this manner is presumed to be the copolymer represented by the above chemical formula. The ionization potential of copolymer P-3 is 4.90 eV.

[0730] Synthesis Example 16: Synthesis of Copolymer P-4

[0731] copolymer P-4

[0732]

[0733] Under a nitrogen atmosphere, compound M-4 (1.78 g), compound CL-2 (1.18 g), palladium acetate (3.8 mg), tris(2-methoxyphenyl)phosphine (35.6 mg), toluene (59 mL), and a 20 wt% aqueous solution of tetrabutylammonium hydroxide (8.58 g) were added to a four-necked flask and stirred at 85 °C for 6 hours. Then, phenylboronic acid (301 mg), bis(triphenylphosphine)palladium(II) dichloride (71.4 mg), and a 20 wt% aqueous solution of tetrabutylammonium hydroxide (8.58 g) were added, and the mixture was stirred at 85 °C for 6 hours. Next, sodium N,N-diethyldithiocarbamate trihydrate (5.7 g) dissolved in deionized water (60 mL) was added, and the mixture was stirred at 85 °C for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was distilled off under reduced pressure, and the residue was reprecipitated with toluene / methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (40 mL), and alumina (20.0 g) and diatomaceous earth (5.0 g) were added. The mixture was then stirred at 90 °C for 1 hour. The alumina and diatomaceous earth were filtered off, and 12N hydrochloric acid (30 mL) was added to the filtrate. The mixture was stirred at room temperature for 12 hours. The aqueous layer was removed, and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain copolymer P-4 (1.42 g). The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-4 were measured by SEC. The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-4 were 28200 Da and 2.12, respectively. Based on the monomer feed ratio, copolymer P-4 obtained in this manner is presumed to be the copolymer represented by the above chemical formula. The ionization potential of copolymer P-4 is 5.02 eV.

[0734] Synthesis Example 17: Synthesis of Copolymer P-5

[0735] Copolymer P-5

[0736]

[0737] Under a nitrogen atmosphere, compound M-5 (1.34 g), compound CL-2 (0.87 g), palladium acetate (2.8 mg), tris(2-methoxyphenyl)phosphine (26.1 mg), toluene (45 mL), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (6.36 g) were added to a four-necked flask and stirred at 85 °C for 6 hours. Then, phenylboronic acid (220 mg), bis(triphenylphosphine)palladium(II) dichloride (52.0 mg), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (6.36 g) were added, and the mixture was stirred at 85 °C for 6 hours. Next, sodium diethyldithiocarbamate trihydrate (4.2 g) dissolved in ion-exchanged water (45 mL) was added, and the mixture was stirred at 85 °C for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was removed by distillation under reduced pressure, and the residue was reprecipitated with toluene / methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (35 mL), and alumina (15.0 g) and diatomaceous earth (5.0 g) were added. The mixture was then stirred at 90 °C for 1 hour. The alumina and diatomaceous earth were filtered off, and 12N hydrochloric acid (30 mL) was added to the filtrate. The mixture was stirred at room temperature for 12 hours. The aqueous layer was removed, and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain copolymer P-5 (1.01 g). The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-5 were measured by SEC. The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-5 were 34100 Da and 2.56, respectively. Based on the monomer feed ratio, copolymer P-5 obtained in this manner is presumed to be the copolymer represented by the above chemical formula. The ionization potential of copolymer P-5 is 5.02 eV.

[0738] Synthesis Example 18: Synthesis of Copolymer P-6

[0739] Copolymer P-6

[0740]

[0741] Under a nitrogen atmosphere, compound M-6 (1.12 g), compound CL-2 (0.92 g), palladium acetate (2.9 mg), tris(2-methoxyphenyl)phosphine (27.8 mg), toluene (41 mL), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (6.77 g) were added to a four-necked flask and stirred at 85 °C for 6 hours. Then, phenylboronic acid (234 mg), bis(triphenylphosphine)palladium(II) dichloride (55.3 mg), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (6.77 g) were added, and the mixture was stirred at 85 °C for 6 hours. Next, sodium diethyldithiocarbamate trihydrate (4.5 g) dissolved in deionized water (45 mL) was added, and the mixture was stirred at 85 °C for 2 hours. The organic layer was separated from the aqueous layer, and the solvent in the organic layer was removed under reduced pressure. The residue was then redeprecipitated with toluene / methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (35 mL), and alumina (15.0 g) and diatomaceous earth (5.0 g) were added. The mixture was then stirred at 90 °C for 1 hour. The alumina and diatomaceous earth were filtered off, and 12N hydrochloric acid (30 mL) was added to the filtrate. The mixture was stirred at room temperature for 12 hours. The aqueous layer was removed, and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to produce copolymer P-6 (0.97 g). The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-6 were measured by SEC. The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-6 were 20300 Da and 2.10, respectively. Based on the monomer feed ratio, copolymer P-6 obtained in this manner is presumed to be the copolymer represented by the above chemical formula. The ionization potential of copolymer P-6 is 5.04 eV.

[0742] Synthesis Example 19: Synthesis of Copolymer P-7

[0743] copolymer P-7

[0744]

[0745] Under a nitrogen atmosphere, compound M-10 (0.69 g), compound CL-2 (0.28 g), dibromo-9,9-dihexylfluorene (1.12 g), palladium acetate (2.9 mg), tris(2-methoxyphenyl)phosphine (27.8 mg), toluene (41 mL), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (6.77 g) were added to a four-necked flask and stirred at 85 °C for 6 hours. Then, phenylboronic acid (234 mg), bis(triphenylphosphine)palladium(II) dichloride (55.3 mg), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (6.77 g) were added, and the mixture was stirred at 85 °C for 6 hours. Subsequently, sodium diethyldithiocarbamate trihydrate (4.5 g) dissolved in deionized water (45 mL) was added, and the mixture was stirred at 85 °C for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was removed by distillation under reduced pressure, and the residue was redeprecipitated with toluene / methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (35 mL), alumina (15.0 g) and diatomaceous earth (5.0 g) were added, and the mixture was stirred at 90 °C for 1 hour. The alumina and diatomaceous earth were filtered, 12N hydrochloric acid (30 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The aqueous layer was removed, and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain copolymer P-7 (0.77 g). The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-7 were measured by SEC. The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-7 were 27100 Da and 2.43, respectively. Based on the monomer feed ratio, copolymer P-7 obtained in this manner is presumed to be the copolymer represented by the above chemical formula. The ionization potential of copolymer P-7 is 5.27 eV.

[0746] Synthesis Example 20: Synthesis of Copolymer P-8

[0747] Copolymer P-8

[0748] Under a nitrogen atmosphere, compound M-3 (1.72 g), compound CL-2 (0.20 g), compound M-7 (0.64 g), palladium acetate (2.2 mg), tris(2-methoxyphenyl)phosphine (20.4 mg), toluene (39 mL), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (4.98 g) were added to a four-necked flask and stirred at 85 °C for 6 hours. Then, phenylboronic acid (201 mg), bis(triphenylphosphine)palladium(II) dichloride (48.7 mg), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (4.98 g) were added, and the mixture was stirred at 85 °C for 6 hours. Next, sodium N,N-diethyldithiocarbamate trihydrate (4.0 g) dissolved in deionized water (41 mL) was added, and the mixture was stirred at 85 °C for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was removed by distillation under reduced pressure, and the residue was redeprecipitated with toluene / methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (35 mL), and alumina (13.0 g) and diatomaceous earth (4.0 g) were added, and the mixture was stirred at 90 °C for 1 hour. The alumina and diatomaceous earth were filtered, and 12N hydrochloric acid (30 mL) was added to the filtrate. The mixture was stirred at room temperature for 12 hours. The aqueous layer was removed, and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain copolymer P-8 (1.03 g). The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-8 were measured by SEC. The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-8 were 36000 Da and 2.24, respectively. Based on the monomer feed ratio, copolymer P-8 obtained in this manner is presumed to be the copolymer represented by the above chemical formula. The ionization potential of copolymer P-8 is 4.86 eV.

[0749] Synthesis Example 21: Synthesis of Copolymer P-9

[0750] Copolymer P-9

[0751] Under a nitrogen atmosphere, compound M-8 (1.06 g), compound CL-2 (0.35 g), compound M-1 (1.23 g), palladium acetate (3.8 mg), tris(2-methoxyphenyl)phosphine (35.6 mg), toluene (39 mL), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (8.68 g) were added to a four-necked flask and stirred at 85 °C for 6 hours. Then, phenylboronic acid (300 mg), bis(triphenylphosphine)palladium(II) dichloride (70.7 mg), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (8.68 g) were added, and the mixture was stirred at 85 °C for 6 hours. Next, sodium N,N-diethyldithiocarbamate trihydrate (60 mL, 6.7 g) dissolved in ion-exchanged water was added, and the mixture was stirred at 85 °C for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was removed by distillation under reduced pressure, and the residue was redeprecipitated with toluene / methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (45 mL), and alumina (20.0 g) and diatomaceous earth (10.0 g) were added, followed by stirring at 90 °C for 1 hour. The alumina and diatomaceous earth were filtered off, and 12N hydrochloric acid (40 mL) was added to the filtrate, which was then stirred at room temperature for 12 hours. The aqueous layer was removed, and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water, and then dried under vacuum to obtain copolymer P-9 (1.23 g). The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-9 were measured by SEC. The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-9 were 50000 Da and 2.42, respectively. Based on the monomer feed ratio, copolymer P-9 obtained in this manner is presumed to be the copolymer represented by the above chemical formula. The ionization potential of copolymer P-9 is 4.92 eV.

[0752] Synthesis Example 22: Synthesis of Copolymer P-10

[0753] Copolymer P-10

[0754] Under a nitrogen atmosphere, compound M-7 (1.38 g), compound CL-1 (0.11 g), compound M-6 (1.38 g), palladium acetate (3.6 mg), tris(2-methoxyphenyl)phosphine (34.2 mg), toluene (58 mL), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (8.34 g) were added to a four-necked flask and stirred at 85 °C for 6 hours. Then, phenylboronic acid (289 mg), bis(triphenylphosphine)palladium(II) dichloride (68.1 mg), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (8.34 g) were added, and the mixture was stirred at 85 °C for 6 hours. Next, sodium N,N-diethyldithiocarbamate trihydrate (5.9 g) dissolved in ion-exchanged water (60 mL) was added, and the mixture was stirred at 85 °C for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was removed by distillation under reduced pressure, and the mixture was reprecipitated with toluene / methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (45 mL), and alumina (20.0 g) and diatomaceous earth (10.0 g) were added, followed by stirring at 90 °C for 1 hour. The alumina and diatomaceous earth were filtered off, and 12N hydrochloric acid (40 mL) was added to the filtrate, followed by stirring at room temperature for 12 hours. The aqueous layer was removed, and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water, and then dried under vacuum to obtain copolymer P-10 (1.12 g). The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-10 were measured by SEC. The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-10 were 22800 Da and 2.89, respectively. Based on the monomer feed ratio, copolymer P-10 obtained in this manner is presumed to be the copolymer represented by the above chemical formula. The ionization potential of copolymer P-10 is 5.00 eV.

[0755] Synthesis Example 23: Synthesis of copolymer P-11

[0756] Copolymer P-11

[0757] Under a nitrogen atmosphere, compound M-9 (1.35 g), compound CL-1 (0.12 g), compound M-1 (1.29 g), palladium acetate (4.0 mg), tris(2-methoxyphenyl)phosphine (37.4 mg), toluene (55 mL), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (9.13 g) were added to a four-necked flask and stirred at 85 °C for 6 hours. Then, phenylboronic acid (316 mg), bis(triphenylphosphine)palladium(II) dichloride (70.7 mg), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (9.13 g) were added, and the mixture was stirred at 85 °C for 6 hours. Next, sodium N,N-diethyldithiocarbamate trihydrate (6.7 g) dissolved in deionized water (60 mL) was added, and the mixture was stirred at 85 °C for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was removed by distillation under reduced pressure, and the residue was redeprecipitated with toluene / methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (45 mL), and alumina (20.0 g) and diatomaceous earth (10.0 g) were added. The mixture was stirred at 90 °C for 1 hour. The alumina and diatomaceous earth were filtered, and 12N hydrochloric acid (40 mL) was added to the filtrate. The mixture was stirred at room temperature for 12 hours. The aqueous layer was removed, and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain copolymer P-11 (1.23 g). The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-11 were measured by SEC. The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer P-11 were 22600 Da and 2.11, respectively. Based on the monomer feed ratio, copolymer P-11 obtained in this manner is presumed to be the copolymer represented by the above chemical formula. The ionization potential of copolymer P-11 is 4.99 eV.

[0758] Synthesis Example 24: Synthesis of Compound D-1

[0759] Compound D-1, which is a salt compound including borate anions, was prepared according to reaction scheme 11.

[0760] Reaction Scheme 11

[0761] In a 100 mL four-necked flask purged with argon, 5.00 g of 1-bromo-2,3,5,6-tetrafluoro-4-vinylbenzene and 60 mL of diethyl ether (Et₂O) were added, and the mixture was stirred under an argon atmosphere and cooled to -78 °C. A hexane solution of n-butyllithium (n-BuLi) (1.6 mol / L, 14.3 mL) was added dropwise, and the mixture was stirred at -78 °C for 30 minutes. Next, a dichloromethane solution of 3-bromoborane (1 mol / L, 4.1 mL) was added dropwise to the reaction solution at -78 °C, and the mixture was stirred overnight. Water (35 mL) was then added to the resulting reaction mixture, and liquid-liquid extraction was performed. The resulting organic layer was concentrated to give a grayish-white solid (3.78 g). The solid was purified by column chromatography (dichloromethane / acetonitrile) to yield compound D-1-1 (2.09 g) as a white solid. The obtained compound D-1-1 and diphenyliodonium chloride (0.92 g) were dissolved in a mixed solvent of dichloromethane / methanol (MeOH) (dichloromethane:methanol = 10:1 (v / v), 40 mL) and stirred for 1 hour. Water (35 mL) was added to the resulting mixture, and the organic layer was washed. After removing the solvent by distillation, the mixture was purified by column chromatography (elution: dichloromethane / acetonitrile) to yield compound D-1 (1.63 g). The borate anion included in compound D-1 has an electron affinity of 5.75 eV.

[0762] Synthesis Example 25: Synthesis of Compound D-2

[0763] Compound D-2, which is a salt compound including borate anions, was prepared according to reaction scheme 12.

[0764] Reaction Scheme 12

[0765] To a 100 mL argon-purified four-necked flask, add 2.20 g of 4-bromo-2,2',3,3',5,5',6,6'-octafluoro-4"-vinyl-1,1':4',1"-terphenyl and 60 mL of diethyl ether, and stir the mixture under an argon atmosphere while cooling to -78 °C. Add dropwise a hexane solution of n-butyllithium (1.6 mol / L, 3.20 mL), and stir the mixture at -78 °C for 30 minutes. Then, add dropwise a dichloromethane solution of 3-bromoborane (1 mol / L, 0.99 mL) to the reaction solution at -78 °C, and stir the mixture overnight. Afterward, add 45 mL of water to the resulting reaction solution and perform liquid-liquid extraction. Concentrate the resulting organic layer to give a grayish-white solid. The solid was purified by column chromatography (eluent: dichloromethane / acetonitrile) to give compound D-2-1 (0.93 g) as a white solid. Compound D-2-1 and diphenyliodonium chloride (0.18 g) were dissolved in a mixed solvent of dichloromethane / methanol (dichloromethane:methanol = 10:1 (v / v), 20 mL) and stirred for 1 hour. Water (20 mL) was then added to the resulting reaction solution, and the organic layer was washed. After removing the solvent by distillation, the mixture was purified by column chromatography (dichloromethane / acetonitrile) to give compound D-2 (0.40 g). The electron affinity of the borate anion included in compound D-2 is 6.08 eV.

[0766] Synthesis Example 26: Synthesis of Compound D-3

[0767] Compound D-3, which is a salt compound including borate anions, was prepared according to reaction scheme 13.

[0768] Reaction Scheme 13

[0769] To a 100 mL argon-purified four-necked flask, add 1.00 g of 4-bromo-2,2',3,3',5,5',6,6'-octafluoro-4"-vinyl-1,1':4',1"-terphenyl (27 mL) and diethyl ether, and stir the mixture under argon atmosphere and cool to -78 °C. Add dropwise a hexane solution of n-butyllithium (1.6 mol / L, 1.4 mL), and stir the mixture at -78 °C for 30 minutes. Next, dissolve 0.942 g of tris(pentafluorophenyl)borane in dichloromethane (3.8 mL), add the solution dropwise at -78 °C, and stir the mixture overnight. Then, add 20 mL of water to the resulting reaction solution and perform liquid-liquid extraction. Concentrate the resulting organic layer to give a grayish-white solid. The solid was purified by column chromatography (eluent: dichloromethane / acetonitrile) to give compound D-3-1 (1.14 g) as a white solid. Next, compound D-3-1 and diphenyliodonium chloride (0.58 g) were dissolved in a mixed solvent of dichloromethane / methanol (dichloromethane:methanol = 10:1 (v / v), 20 mL) and stirred for 1 hour. Water (10 mL) was added to the resulting reaction solution, and the organic layer was washed. After removing the solvent by distillation, the solution was purified by column chromatography (eluent: dichloromethane / acetonitrile) to give compound D-3 (1.14 g). The electron affinity of the borate anion included in compound D-3 is 6.22 eV.

[0770] Synthesis Example 27: Synthesis of Compound D-4

[0771] Compound D-4, which is a salt compound including borate anions, was prepared according to reaction scheme 14.

[0772] Reaction Scheme 14

[0773] In a 100 mL four-necked flask purged with argon, 5.00 g of 4-bromo-2,2',3,3',5,5',6,6'-octafluoro-4"-vinyl-1,1'-biphenyl and 45 mL of diethyl ether were added, and the mixture was stirred under an argon atmosphere while cooling to -78 °C. A hexane solution of n-butyllithium (1.6 mol / L, 9.0 mL) was added dropwise, and the mixture was stirred at -78 °C for 30 minutes. Then, a dichloromethane solution of 3-bromoborane (1 mol / L, 2.57 mL) was added dropwise at -78 °C, and the mixture was stirred overnight. Water (22 mL) was then added to the resulting reaction solution, and the mixture underwent liquid-liquid extraction. The resulting organic layer was concentrated to obtain... A grayish-white solid. The solid obtained by column chromatography (eluent: dichloromethane / acetonitrile) was used to provide compound D-4-1 (2.21 g) as a white solid. Next, compound D-4-1 and diphenyliodonium chloride (0.53 g) were dissolved in a mixed solvent of dichloromethane / methanol (dichloromethane:methanol = 10:1 (v / v), 20 mL) and stirred for 1 hour. Water (10 mL) was added to the resulting reaction solution, and the organic layer was washed. After removing the solvent by distillation, the solution was purified by column chromatography (eluent: dichloromethane / acetonitrile) to give compound D-4 (1.73 g). The electron affinity of the borate anion included in compound D-4 is 6.17 eV.

[0774] Synthesis Example 28: Synthesis of Compound D-5

[0775] Compound D-5, which is a salt compound including borate anions, was prepared according to reaction scheme 15.

[0776] Reaction Scheme 15

[0777] To a 100 mL four-necked flask purged with argon, add 2.00 g of 4-bromo-2,2',3,3',5,5',6,6'-octafluoro-4"-vinyl-1,1'-biphenyl and 65 mL of diethyl ether, and stir the mixture under an argon atmosphere while cooling to -78 °C. Add dropwise a hexane solution of n-butyllithium (1.6 mol / L, 3.3 mL), stirring for approximately 30 minutes while maintaining the internal temperature. Then, dissolve 2.24 g of tris(pentafluorophenyl)borane in dichloromethane (mL) and add dropwise while maintaining the internal temperature, stirring the mixture overnight. Next, add water (30 mL) to the reaction mixture, perform liquid-liquid extraction, and concentrate the organic layer. A grayish-white solid was obtained. The solid underwent column chromatography using dichloromethane / acetonitrile as the eluent to provide a white solid compound D-5-1 (2.24 g). The white solid compound D-5-1 and diphenyliodonium chloride (0.83 g) were dissolved in a mixed solvent of dichloromethane / methanol (dichloromethane:methanol = 10:1 (v / v, 30 mL)) and stirred for 1 hour. Water (15 mL) was then added, and the organic layer was washed. After removing the solvent by distillation, silica gel column chromatography was performed using dichloromethane / acetonitrile as the eluent (eluent: dichloromethane / acetonitrile) to give compound D-5 (1.68 g). The electron affinity of the borate anion included in compound D-5 is 6.25 eV.

[0778] Example 1

[0779] Preparation of composition 1, fabrication of electroluminescent device 1, and positive aging

[0780] As the first electrode (anode), a glass substrate with a patterned indium tin oxide (ITO) film of 150 nm thickness is provided. The ITO-attached glass substrate is washed sequentially with a neutral detergent, deionized water, water, and isopropanol, and then treated with UV-ozone.

[0781] The copolymer P-1 prepared in Synthesis Example 13 was prepared by dissolving it at a concentration of 3 wt% in a mixed solvent of xylene and butyl benzoate (xylene:butyl benzoate = 100:10 by volume). Separately, another solution was prepared by dissolving 4-isopropyl-4'-methyldiphenyliodonium tetra(pentafluorophenyl)borate (PIPB, manufactured by Tokyo Kasei Kogyo Co., Ltd.) at a concentration of 3 wt% in a mixed solvent of xylene and butyl benzoate (xylene:butyl benzoate = 100:10 by volume). The two solutions were mixed such that the weight ratio of copolymer P-1 to PIPB was 90:10 to prepare composition 1 (coating solution 1 for forming a hole injection layer). The PIPB described above has an electron affinity of 6.29 eV for its borate anion.

[0782]

[0783] Next, on the glass substrate with ITO attached above, composition 1 (coating solution 1 for forming a hole injection layer) is applied to a thickness of 100 nm (dry film thickness) by spin coating, and then heated at 230°C for 30 minutes to form a hole injection layer with a thickness of 100 nm (dry film thickness).

[0784] Subsequently, a hole transport material (HTP-1 (polymer compound P-3 described in Japanese Patent Application Publication No. 2021-138915)) represented by the following chemical formula was dissolved in xylene (solvent) at a concentration of 1 wt% to prepare a coating solution for forming a hole transport layer. On the hole injection layer formed above, the coating solution for forming the hole transport layer was applied to a thickness of 25 nm (dry film thickness) by spin coating, and then heated at 230°C for 30 minutes to form a hole transport layer with a thickness of 25 nm (dry film thickness).

[0785]

[0786] Next, blue quantum dots (ZnTeSe / ZnSe / ZnS (core / shell / shell; average diameter = 10 nm)) were dispersed in octane at a concentration of 1.0 wt% to prepare a quantum dot dispersion. This quantum dot dispersion was then applied to a hole transport layer by spin coating to achieve a dry film thickness of 25 nm, followed by drying. This resulted in a light-emitting layer with a thickness of 25 nm (dry film thickness) on the hole transport layer. When ultraviolet light was irradiated onto the quantum dot dispersion, the emitted light exhibited a peak wavelength of 462 nm and a full width at half maximum (FWHM) of 30 nm.

[0787] The light-emitting layer is completely dried.

[0788] Next, a dispersion of ZnMgO (solvent: ethanol, concentration: 10 wt%) was spin-coated onto the heat-treated quantum dot emitting layer and heat-treated at 80 °C to form an electron transport layer with a thickness of 20 nm. Aluminum (Al) was vacuum-deposited onto the fabricated electron transport layer to form a second electrode with a thickness of 100 nm, resulting in a stacked structure and fabricating a quantum dot electroluminescent device 1.

[0789] LOCTITE® AA366 (manufactured by Henkel, containing methacrylate, acrylic acid, methacrylic acid, etc.) was applied to the second electrode of the stacked structure and irradiated with ultraviolet light (wavelength: 365 nm, cumulative flux: 10 mJ / cm²). 2 An acid compound layer (thickness: 1.5 μm) was formed to obtain the quantum dot electroluminescent device 1 before treatment (before positive aging treatment). It was placed in a constant temperature oven at 70 °C for 5 days to obtain the quantum dot electroluminescent device 1 after treatment (after positive aging treatment).

[0790] <Manufacturing MSM (Metal-Semiconductor-Metal) Devices 1, and Positive Aging>

[0791] As the first electrode (anode), a glass substrate with a patterned indium tin oxide (ITO) film of 150 nm thickness is provided. The ITO-attached glass substrate is washed sequentially with a neutral detergent, deionized water, water, and isopropanol, and then treated with UV-ozone.

[0792] The copolymer P-1 synthesized in Synthesis Example 13 was dissolved at a concentration of 3 wt% in a mixed solvent of xylene and butyl benzoate (xylene:butyl benzoate = 100:10 by volume). Separately, another solution was prepared by dissolving 4-isopropyl-4'-methyldiphenyliodonium tetra(pentafluorophenyl)borate (PIPB, manufactured by Tokyo Chemical Industry Co., Ltd., see the above chemical formula) at a concentration of 3 wt% in a mixed solvent of xylene and butyl benzoate (xylene:butyl benzoate = 100:10 by volume). The two solutions were mixed such that the mass ratio of copolymer P-1 to PIPB was 90:10 to prepare composition 1 (coating solution 1 for the hole injection layer).

[0793] Next, composition 1 (coating solution 1 for hole injection layer) is applied to the glass substrate to which ITO is attached by spin coating to a thickness of 100 nm (dry film thickness), and then heated at 230°C for 30 minutes to form a hole injection layer with a thickness of 100 nm (dry film thickness).

[0794] Using a vacuum deposition apparatus, a mixed film of silver and magnesium (hereinafter also referred to as "AgMg") is deposited on the hole injection layer formed above to form a second electrode (cathode) with a thickness of 20 nm, thereby fabricating MSM device 1.

[0795] Next, LOCTITE® AA366 (manufactured by Henkel, containing methacrylate, acrylic acid, methacrylic acid, etc.) was applied to the second electrode of the stacked structure and irradiated with ultraviolet light (wavelength: 365nm, total irradiation dose: 10mJ / cm²). 2 An acid compound layer (thickness: 1.5 μm) was formed to obtain the MSM device 1 before treatment (before positive aging treatment). It was then placed in a constant temperature oven at 70 °C for 5 days to obtain the MSM device 1 after treatment (after positive aging treatment).

[0796] Examples 2 to 11

[0797] Except for changing the types of copolymers and salt compounds as listed in Table 1 below, the same procedures as in Example 1 are followed to manufacture compositions 2 to 11, quantum dot electroluminescent devices 2 to 11, untreated quantum dot electroluminescent devices 2 to 11, treated quantum dot electroluminescent devices 2 to 11, MSM devices 2 to 11, untreated MSM devices 2 to 11, and treated MSM devices 2 to 11.

[0798] Comparison Example 1

[0799] Comparative composition 1, comparative electroluminescent device 1, comparative electroluminescent device 1 before treatment, comparative electroluminescent device 1 after treatment, comparative MSM device 1, comparative MSM device 1 before treatment, and comparative MSM device 1 after treatment were prepared in the same manner as in Example 1, except that the compound TFB shown below (i.e., poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine)]) was used instead of copolymer P-1.

[0800]

[0801] Comparison Example 2

[0802] Comparative composition 2, comparative electroluminescent device 2, comparative electroluminescent device 2 before treatment, comparative electroluminescent device 2 after treatment, comparative MSM device 2, comparative MSM device 2 before treatment, and comparative MSM device 2 after treatment were prepared in the same manner as in Example 4, except that compound HT-1, shown below, was used instead of copolymer P-3. See the description of the synthesis of compound HT-1 in ACS Materials Lett. 2023, 5, pp. 3184-3191.

[0803]

[0804] Comparison Example 3

[0805] Except that copolymer P-1 is synthesized according to synthesis example 29 described below and shown below, comparative composition 3, comparative electroluminescent device 3, comparative electroluminescent device 3 before treatment, comparative electroluminescent device 3 after treatment, comparative MSM device 3, comparative MSM device 3 before treatment and comparative MSM device 3 after treatment are manufactured following the same procedure as in example 1.

[0806]

[0807] Synthesis Example 29: Synthesis of copolymer HT-2

[0808] The copolymer HT-2 was synthesized according to reaction scheme 16.

[0809] Reaction Scheme 16

[0810]

[0811] In a 300 mL argon-purified three-necked flask, 10.0 g of 2,6-dibromo-4,4-dihexyl-4H-cyclopentadieno[2,1-b:3,4-b']dithiophene, 4.5 g of p-toluidine, 0.3 g of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II)dichloromethane adduct, 5.7 g of sodium tert-butoxide, and 200 mL of toluene were added, and the mixture was stirred at 120 °C (bath temperature) for 12 hours. After cooling to room temperature, the precipitate was removed by filtration using diatomaceous earth as a filter aid. The solvent was removed by distillation under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / hexane) to give compound HT-2-1 (7.5 g).

[0812] In a 300 mL argon-purified three-necked flask, the previously obtained compound HT-2-1 (5.0 g), 2-bromo-9,9-dimethyl-7-iodo-9H-fluorene (7.6 g), cuprous iodide (0.2 g), phenanthroline (0.3 g), sodium tert-butoxide (2.6 g), and 1,4-dioxane (10 mL) were added, and the mixture was stirred at 110 °C (bath temperature) for 18 hours. After cooling to room temperature, diatomaceous earth was used as a filter aid to remove insoluble matter. The solvent was removed by distillation under reduced pressure, and the residue was dissolved in a mixed solvent of toluene (100 mL) and hexane (100 mL), with activated carbon (5.0 g) added, and refluxed for 30 minutes. The insoluble matter was filtered using diatomaceous earth as a filter aid. The solvent was removed by distillation under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / hexane) to give compound HT-2-2 (8.3 g).

[0813] Under a nitrogen atmosphere, the above-obtained compound HT-2-2 (1.79 g), compound CL-2 (1.14 g), palladium acetate (3.7 mg), tris(2-methoxyphenyl)phosphine (34.3 mg), toluene (59 mL), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (8.68 g) were added to a four-necked flask, and the mixture was stirred at 85 °C for 6 hours. Then, phenylboronic acid (196 mg), bis(triphenylphosphine)palladium(II) dichloride (68.4 mg), and a 20 wt% aqueous solution of tetraethylammonium hydroxide (5.68 g) were added, and the mixture was stirred at 85 °C for 6 hours. Next, sodium N,N-diethyldithiocarbamate trihydrate (4.7 g) dissolved in deionized water (70 mL) was added, and the mixture was stirred at 85 °C for 2 hours. After separating the organic layer from the aqueous layer, the solvent in the organic layer was removed by distillation under reduced pressure, and the residue was redeprecipitated with toluene / methanol. The precipitated solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in toluene (40 mL), and alumina (20.0 g) and diatomaceous earth (5.0 g) were added. The mixture was stirred at 90 °C for 1 hour. The alumina and diatomaceous earth were filtered, and 12N hydrochloric acid (30 mL) was added to the filtrate. The mixture was stirred at room temperature for 12 hours. The aqueous layer was removed, and the organic layer was added dropwise to methanol. The precipitated solid was washed with methanol and water and dried under vacuum to obtain copolymer HT-2 (1.67 g). The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer HT-2 were measured by SEC. The weight-average molecular weight (Mw) and polydispersity (Mw / Mn) of copolymer HT-2 were 29000 Da and 2.56, respectively. Based on the monomer feed ratio, copolymer HT-2 obtained in this manner was presumed to be the copolymer represented by the above chemical formula. The ionization potential of copolymer HT-2 was 4.69 eV.

[0814] Evaluate

[0815] [Assessment of solubility (residual film rate)]

[0816] The solubility of the copolymer included in the composition was evaluated using the following method: The copolymer was dissolved in xylene as a solvent at a concentration of 1 wt% to prepare a copolymer coating solution. The copolymer coating solution was then spin-coated onto a quartz substrate and dried at 230°C for 30 minutes to form a film with a dried thickness of 25 nm. Subsequently, the absorption spectrum of the formed film (before solvent impregnation) was measured using a UV-Vis spectrophotometer (manufactured by Shimadzu Corporation, UV-1800). The wavelength of the peak at the longest wavelength in the absorption spectrum was measured and set as the reference wavelength.

[0817] Next, the same film (the film before solvent impregnation) on the quartz substrate was immersed in the solvent cyclohexylbenzene (CHB) for 20 minutes, then removed from the solvent and dried at 230°C for 30 minutes. The absorption spectrum of the dried film (the film after solvent impregnation) was measured using a UV-Vis spectrophotometer in the same manner as described above. For this absorption spectrum, the ratio of the intensity at the reference wavelength of the absorption spectrum after solvent impregnation to the intensity at the reference wavelength of the absorption spectrum before solvent impregnation {(“intensity at the reference wavelength of the absorption spectrum after solvent impregnation” / “intensity at the reference wavelength of the absorption spectrum before solvent impregnation”) × 100 (%)} was defined as the residual film rate (%). The obtained residual film rate (%) was evaluated according to the following criteria, and the uniformity of coating was also evaluated:

[0818] : Greater than or equal to 80%

[0819] Less than 80%

[0820] [Measurement of conductivity retention]

[0821] For each MSM device manufactured as described above, the conductivity retention rate is evaluated using the following method.

[0822] When a voltage is applied to the MSM device, current begins to flow at a certain voltage. Using a DC constant voltage power supply (manufactured by Kikusui Co., Ltd., source meter), a voltage was applied to the MSM device from 0V to 10V in increments of 0.2V, and the corresponding current values ​​were measured.

[0823] The current per unit area (current density) is calculated using the area of ​​the MSM device, and the conductivity retention rate is calculated by dividing the current density of the processed MSM device by the current density of the unprocessed MSM device, and evaluated based on the following criteria:

[0824] : Greater than or equal to 80%

[0825] : Greater than or equal to 60% and less than 80%

[0826] Less than 60%

[0827] The conductivity retention rate of Comparative Example 1 was not evaluated because it could not be laminated due to its solvent solubility. Furthermore, the conductivity retention rate of Comparative Example 3 was not evaluated because it could not form a charge-transfer complex.

[0828] Table 1

[0829] EA: Electron Affinity

[0830] Evaluation of quantum dot electroluminescent devices

[0831] The quantum dot electroluminescent device 13 fabricated in Example 13 and the comparative quantum dot electroluminescent device 2 fabricated in Comparative Example 2 were evaluated using the following methods: driving voltage (Op.V.: operating voltage), luminous efficiency (EQE (%)), and luminous lifetime (LT50 (hours)). The results are shown in Table 2 below.

[0832] (Operating voltage (Op.V.))

[0833] When a DC constant voltage power supply (manufactured by Kiensu Corporation, source material) is applied to each quantum dot electroluminescent device, current begins to flow at a constant voltage, and the quantum dot electroluminescent device emits light. A voltage of 5 mA / cm² is applied. 2 The voltage at the current density is used as the operating voltage "Op.V."

[0834] (Luminous Efficiency (EQE))

[0835] For each quantum dot electroluminescent device, when a voltage is applied, current begins to flow at a certain voltage, and the quantum dot electroluminescent device emits light. Using a DC constant voltage power supply (manufactured by KENX Corporation, source meter), the voltage was gradually increased for each device, and the current value was measured at this time. The brightness at the time of emission was measured using a brightness measurement device (manufactured by Topcon Techno House Corporation, SR-3). Here, the measurement was stopped at the point where the brightness began to decay.

[0836] Calculate the external quantum efficiency (EQE) at Op.V., assuming Lambertian emission, from the spectral radiation spectrum measured by a luminance measuring device.

[0837] (Luminescence lifetime (LT50))

[0838] A DC constant voltage power supply (manufactured by Kenus Co., Ltd., source meter) was used, and a specified voltage was applied to each quantum dot electroluminescent device to make each quantum dot electroluminescent device emit light. While measuring the emission of the quantum dot electroluminescent devices using a luminance measurement device (manufactured by Topcon TechnoHouse Co., Ltd., SR-3), the current was gradually increased, and the emission was measured until the luminance reached 650 nits (cd / m²). 2 When the brightness is gradually reduced as measured by the brightness measuring device, the time until the brightness reaches 50% of the initial brightness is defined as "LT50".

[0839] EQE and LT50 are expressed as relative values, with the value set to 1.0 for the quantum dot electroluminescent device 2.

[0840] Table 2

[0841] As shown in Table 2, the operating voltage (Op.V.) of the quantum dot electroluminescent device 13 is lower than that of the comparative quantum dot electroluminescent device 2, and the EQE and LT50 of the quantum dot electroluminescent device 13 are higher than those of the comparative quantum dot electroluminescent device 2.

[0842] It should be understood that the embodiments described herein should be considered descriptively only and not for limiting purposes. The description of features or aspects in each embodiment should be considered applicable to other similar features or aspects in other embodiments.

[0843] Although one or more embodiments have been described with reference to the accompanying drawings, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope defined by the appended claims.

Claims

1. A composition comprising: The copolymer includes structural unit A represented by chemical formula 2 and / or structural unit B represented by chemical formula 3, as well as structural unit represented by chemical formula 1; as well as Salt compounds, including iodonium cations and borate anions represented by formula 4, The energy difference between the ionization potential of the copolymer and the electron affinity of the borate anion is greater than or equal to 0.75 eV, and the ionization potential of the copolymer is deeper than that of the iodonium cation. Chemical Formula 1 In chemical formula 1, Ar 1 Ar 2 Ar 4 and Ar 5 Each is independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group. Ar 3 It is a substituted or unsubstituted carbazole, a substituted or unsubstituted fluorene, a substituted or unsubstituted benzene, or a substituted or unsubstituted biphenylene. Among them, when Ar 3 When it is a substituted or unsubstituted benzene, or a substituted or unsubstituted biphenylene, Ar 1 Not substituted or unsubstituted benzene and / or Ar 2 Not substituted or unsubstituted benzene, and Ar 4 Not substituted or unsubstituted benzene and / or Ar 5 Benzene that is neither substituted nor unsubstituted n1 is an integer greater than or equal to 1 and less than or equal to 3. m1 is an integer greater than or equal to 1 and less than or equal to 3, and It is a combination position; Chemical formula 2 In chemical formula 2, Ar 6 and Ar 7 Each is independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and / or Ar 6 and Ar 7 Together they form a ring. R 1 It is a group represented by the chemical formula (2-a), and It is a combination of positions, Chemical formula (2-a) In the chemical formula (2-a), L 1 It is a single bond or a group represented by the chemical formula (2-b). Ar 8 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group. Among them, when L 1 When it is a single bond, Ar 6 Ar 7 and Ar 8 At least one of them is not a substituted or unsubstituted phenyl group, and / or Ar 8 with Ar 6 and Ar 7 At least one of them together forms a ring, n² is an integer greater than or equal to 2 and less than or equal to 5, and It is a combination of positions, Chemical formula (2-b) In the chemical formula (2-b), Ar 9 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and / or an Ar atom bonded to a nitrogen atom. 9 Optional with Ar 6 and Ar 7 At least one of them together forms a ring, m2 is an integer greater than or equal to 1 and less than or equal to 5, where, when m2 is an integer greater than or equal to 2, each Ar 9 Same or different, and It is a combination position; Chemical formula 3 In chemical formula 3, Ar 10 and Ar 11 Each is independently a substituted or unsubstituted aromatic cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and / or Ar 10 and Ar 11 Together they form a ring. R 2 It is a group represented by chemical formula (3-a) or chemical formula (3-b), and It is a combination of positions, Chemical formula (3-a) In the chemical formula (3-a), L 2 It is a single bond or a group represented by the chemical formula (3-c). Ar 12 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group. Among them, when L 2 When it is a single bond, Ar 12 Optional with Ar 10 and Ar 11 At least one of them together forms a ring, n3 is an integer greater than or equal to 2 and less than or equal to 5, and It is a combination of positions, Chemical formula (3-b) In the chemical formula (3-b), L 3 It is a single bond or a group represented by the chemical formula (3-c). Ar 13 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group. Among them, when L 3 When it is a single bond, Ar 13 Optional with Ar 10 and Ar 11 At least one of them together forms a ring, n4 is an integer greater than or equal to 2 and less than or equal to 5, and It is a combination of positions, Chemical formula (3-c) In the chemical formula (3-c), Ar 14 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group, and / or an Ar atom bonded to a nitrogen atom. 14 Optional with Ar 10 and Ar 11 At least one of them together forms a ring, m3 is an integer greater than or equal to 1 and less than or equal to 5, and when m3 is an integer greater than or equal to 2, each Ar 14 Same or different, and It is a combination position; Chemical Formula 4 In chemical formula 4, R 31 To R 34 Each is independently a hydrogen atom, a fluorine atom, or a group represented by the chemical formula (4-a). Chemical formula (4-a) In the chemical formula (4-a), L 4 It is a single bond or a group represented by the chemical formula (4-b). Ar 15 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group. X is a fluorine atom or a group selected from group (4-1). n5 is an integer greater than or equal to 1 and less than or equal to 5. n6 is an integer of 0 or 1, where, When multiple groups represented by the chemical formula (4-a) are present, each L 4 Same or different, When multiple groups represented by the chemical formula (4-a) are present, each Ar 15 Same or different, When multiple groups represented by the chemical formula (4-a) are present, each X may be the same or different. When multiple groups represented by the chemical formula (4-a) are present, each n5 may be the same or different. When multiple groups represented by the chemical formula (4-a) are present, each n6 may be the same or different. When n5 is an integer greater than or equal to 2, each X is either the same or different, and It is a combination of positions, Chemical formula (4-b) In the chemical formula (4-b), Ar 16 It is a substituted or unsubstituted aromatic hydrocarbon cyclic group, or a substituted or unsubstituted aromatic heterocyclic group. m4 is an integer greater than or equal to 1 and less than or equal to 5, and when m4 is greater than or equal to 2, each Ar 16 Same or different, and It is a combination of positions, Group (4-1) In group (4-1), It is a combination position.

2. The composition according to claim 1, wherein, The borate anion is selected from the groups represented below: 。 3. The composition according to claim 1, wherein, The structural unit represented by chemical formula 1 is selected from the groups represented in groups (1-1) to (1-3): Group (1-1) Group (1-2) Groups (1-3) Among them, in groups (1-1) to (1-3), R 4 To R 6 R 71 To R 76 and R 81 To R 84 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Each n1 represents an integer greater than or equal to 1 and less than or equal to 3. Each m1 represents an integer greater than or equal to 1 and less than or equal to 3, and It is a combination position.

4. The composition according to claim 1, wherein, Structural unit A, represented by chemical formula 2, is selected from the groups represented in group 2: Group 2 Among them, in the chemical formula of group 2, It is a combination position.

5. The composition according to claim 1, wherein, Structural unit B, represented by chemical formula 3, is selected from the groups represented in group 3: Group 3 Among them, in the chemical formula of group 3, It is a combination position.

6. The composition according to claim 1, wherein, The copolymer is selected from copolymers represented by the following chemical formulas: Wherein, in the chemical formula, It is a combination position.

7. The composition according to claim 1, wherein, Based on the total number of moles of structural units represented by chemical formula 1, structural unit A represented by chemical formula 2, and structural unit B represented by chemical formula 3 in the copolymer, the molar ratio of structural units represented by chemical formula 1 is greater than or equal to 20 mol% and less than or equal to 99 mol%.

8. The composition according to claim 1, wherein, Based on the total number of moles of structural units represented by Formula 1, structural unit A represented by Formula 2, and structural unit B represented by Formula 3 in the copolymer, the molar ratio of structural units represented by Formula 1 is greater than or equal to 50 mol% and less than or equal to 95 mol%.

9. The composition according to claim 1, wherein, The weight-average molecular weight of the copolymer is greater than or equal to 8000 Da and less than or equal to 500000 Da.

10. The composition according to claim 1, wherein, Based on the total weight of the copolymer and the salt compound, the amount of the salt compound in the composition is greater than or equal to 1 wt% and less than or equal to 70 wt%.

11. The composition according to claim 1, wherein, The electron affinity of the borate anion is greater than or equal to 5.50 eV and less than or equal to 6.50 eV.

12. The composition according to claim 1, wherein, The iodonium cation is any one of the following: difuranyliodonium cation, dithienyliodonium cation, bis(4,5-dimethyl-2-furanyl)iodonium cation, bis(5-chloro-2-thienyl)iodonium cation, bis(5-cyano-2-furanyl)iodonium cation, bis(5-nitro-2-thienyl)iodonium cation, bis(5-acetyl-2-furanyl)iodonium cation, bis(5-carboxy-2-thien ... (-methoxycarbonyl-2-furanyl)iodonium cation, bis(5-phenyl-2-furanyl)iodonium cation, bis(5-(p-methoxyphenyl)-2-thienyl)iodonium cation, bis(5-vinyl-2-furanyl)iodonium cation, bis(5-ethynyl-2-thienyl)iodonium cation, bis(5-cyclohexyl-2-furanyl)iodonium cation, bis(5-hydroxy-2-thienyl)iodonium cation, bis(5-phenoxy-2-furanyl) Iodonium cation, bis(5-mercapto-2-thienyl)iodonium cation, bis(5-butthio-2-thienyl)iodonium cation, bis(5-phenylthio-2-thienyl)iodonium cation, diphenyliodonium cation, bis(p-tolyl)iodonium cation, bis(p-octylphenyl)iodonium cation, bis(p-octadecylphenyl)iodonium cation, bis(p-octyloxyphenyl)iodonium cation, bis(p-octadecyloxyphenyl)iodonium cation, phenyl(p-octadecyl) (Oxyphenyl)iodonium cation, 4-isopropyl-4'-methyldiphenyliodonium cation, (4-isobutylphenyl)-p-tolyliodonium cation, bis(1-naphthyl)iodonium cation, bis(4-phenylthioalkylphenyl)iodonium cation, phenyl(6-benzoyl-9-ethyl-9H-carbazole-3-yl)iodonium cation, (7-methoxy-2-oxo-2H-chromen-3-yl)-4'-isopropylphenyliodonium cation and combinations thereof.

13. The composition according to claim 1, wherein, The ionization potential of the iodonium cation is greater than or equal to 4.00 eV and less than or equal to 4.95 eV.

14. The composition according to claim 1, wherein, Salt compounds also include sulfonium cations, sulfonium oxide cations, phosphonium cations, or combinations thereof.

15. An organic membrane, comprising: Carboxyl-containing compounds and cured materials obtained by curing the composition according to any one of claims 1 to 14.

16. The organic membrane according to claim 15, wherein, The carboxyl-containing compound is any one of the following: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, (meth)acrylic acid, poly(meth)acrylic acid, benzoic acid, hexahydrobenzoic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, citric acid, malic acid, 3-isopropylmalic acid, itaconic acid, citraconic acid, and combinations thereof.

17. An electroluminescent device, comprising: The first electrode supplies holes. The second electrode supplies electrons; as well as An organic layer is disposed between the first electrode and the second electrode. Wherein, at least one organic layer comprises the organic membrane according to claim 15.

18. The electroluminescent device according to claim 17, wherein, The at least one layer of the organic layer comprising the organic membrane is a hole injection layer.

19. The electroluminescent device according to claim 17, wherein, The organic layer includes: The light-emitting layer includes semiconductor nanoparticles, organometallic complexes, or combinations thereof.

20. The electroluminescent device according to claim 17, wherein, The organic layer includes: The light-emitting layer includes semiconductor nanoparticles.

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