Electroluminescent composition and electric device with high brightness

Abstract

The present invention is to provide a composition that can provide an electroluminescent device emitting light with high brightness. The present invention provides following: a composition including a polymer compound comprising one or more structural unit(s) selected from the group consisting of a structural unit represented by Formula (1), a structural unit represented by Formula (3), a structural unit represented by Formula (5), a structural unit represented by Formula (16), a structural unit represented by Formula (18), a structural unit represented by Formula (20), and a structural unit represented by Formula (22) and an ionic compound represented by Formula (23); an organic film and an electric device comprising the composition. ##STR00001##

Claims

1. A composition comprising: a polymer compound comprising one or more structural unit(s) selected from the group consisting of a structural unit represented by Formula (16), a structural unit represented by Formula (18), a structural unit represented by Formula (20), and a structural unit represented by Formula (22); and an ionic compound represented by Formula (23); wherein the structural unit represented by Formula (16) is: ##STR00382## wherein: R.sup.7 is a monovalent group comprising a group represented by Formula (17); Ar.sup.4 is a (2+n7)-valent aromatic group that optionally has a substituent other than R.sup.7; n7 is an integer of 1 or more; when a plurality of R.sup.7 are present, each R.sup.7 may be the same as or different from each other; and wherein the structural unit represented by Formula (17) is: ##STR00383## wherein: R.sup.8 is a (1+m4+m5)-valent organic group; Q.sup.1 is a divalent organic group; Q.sup.3 is a divalent organic group; Y.sup.1 is CO.sub.2.sup., SO.sub.3.sup., SO.sub.2.sup., PO.sub.3.sup.2, OR B(R.sup.).sub.3.sup.; R.sup. is an alkyl group having 1 to 30 carbon atoms that optionally have a substituent or an aryl group having 6 to 50 carbon atoms that optionally has a substituent; each R.sup. may be the same as or different from each other; M.sup.1 is a metallic cation or an ammonium cation that optionally has a substituent; Y.sup.3 is a cyano group or a group represented by either of Formulas (7) to (15); n2 is an integer of 0 or more; a1 is an integer of 1 or more and is selected so that the charge of the group represented by Formula (17) is zero; n6 is an integer of 0 or more; m4 and m5 are each independently an integer of 1 or more; when a plurality of Q.sup.1 are present, each Q.sup.1 may be the same as or different from each other; when a plurality of Q.sup.3 are present, each Q.sup.3 may be the same as or different from each other; when a plurality of Y.sup.1 are present, each Y.sup.1 may be the same as or different from each other; when a plurality of M.sup.1 are present, each M.sup.1 may be the same as or different from each other; when a plurality of Y.sup.3 are present, each Y.sup.3 may be the same as or different from each other; when a plurality of n2 are present, each n2 may be the same as or different from each other; when a plurality of a1 are present, each a1 may be the same as or different from each other; and when a plurality of n6 are present, each n6 may be the same as or different from each other; wherein Formulas (7) to (15) are:
O(RO).sub.a3R(7) ##STR00384##
S(RS).sub.a4R(9)
C(O)(RC(O)).sub.a4R(10)
C(S)(RC(S)).sub.a4R(11)
N{(R).sub.a4R}.sub.2(12)
C(O)O(RC(O)O).sub.a4R(13)
C(O)O(RO).sub.a4R(14)
NHC(O)(RNHC(O)).sub.a4R(15) wherein: R is a divalent hydrocarbon group that optionally has a substituent; R is a hydrogen atom, a monovalent hydrocarbon group that optionally has a substituent, a carboxyl group, a sulfo group, a hydroxyl group, a mercapto group, NR.sup.C.sub.2, a cyano group, or C(O)NR.sup.C.sub.2; R is a trivalent hydrocarbon group that optionally has a substituent; a3 is an integer of 1 or more; a4 is an integer of 0 or more; R.sup.c is an alkyl group having 1 to 30 carbon atoms that optionally has a substituent or an aryl group having 6 to 50 carbon atoms that optionally has a substituent; each R.sup.c may be the same as or different from each other; when a plurality of R are present, each R may be the same as or different from each other; when a plurality of R are present, each R may be the same as or different from each other; and when a plurality of a4 are present, each a4 may be the same as or different from each other; wherein the structural unit represented by Formula (18) is: ##STR00385## wherein: R.sup.9 is a monovalent group comprising a group represented by Formula (19); Ar.sup.5 is a (2+n8)-valent aromatic group that optionally has a substituent other than R.sup.9; n8 is an integer of 1 or more; when a plurality of R.sup.9 are present, each R.sup.9 may be the same as or different from each other; and wherein the group represented by Formula (19) is: ##STR00386## wherein: R.sup.10 is a (1+m6+m7)-valent organic group; Q.sup.3, and n6 are the same as the corresponding definitions above; Q.sup.2 is a divalent organic group; Y.sup.2 is a carbocation, an ammonium cation, a phosphonium cation, a sulfonium cation, or an iodonium cation; M.sup.2 is F.sup., Cl.sup., Br.sup., I.sup., OH.sup., B(R.sup.b).sub.4.sup., R.sup.bSO.sub.3.sup., R.sup.bCOO.sup., ClO.sup., ClO.sub.2.sup., ClO.sub.3.sup., ClO.sub.4.sup., SCN.sup., CN.sup., NO.sub.3.sup., HSO.sub.4.sup., H.sub.2PO.sub.4.sup., BF.sub.4.sup., or PF.sub.6.sup.; R.sup.b is an alkyl group having 1 to 30 carbon atoms that optionally has a substituent or an aryl group having 6 to 50 carbon atoms that optionally has a substituent; when a plurality of R.sup.b are present, and each R.sup.b may be the same as or different from each other; n4 is an integer of 0 or more; a2 is 1; m6 and m7 are each independently an integer of 1 or more; and when a plurality of Q.sup.2 are present, each Q.sup.2 may be the same as or different from each other; when a plurality of Q.sup.3 are present, each Q.sup.3 may be the same as or different from each other; when a plurality of Y.sup.2 are present, each Y.sup.2 may be the same as or different from each other; when a plurality of M.sup.2 are present, each M.sup.2 may be the same as or different from each other; when a plurality of Y.sup.3 are present, each Y.sup.3 may be the same as or different from each other; when a plurality of n4 are present, each n4 may be the same as or different from each other; and when a plurality of n6 are present, each n6 may be the same as or different from each other; wherein the structural unit represented by Formula (20) is: ##STR00387## wherein: R.sup.11 is a monovalent group comprising a group represented by Formula (2) or a group represented by Formula (17); R.sup.12 is a monovalent group comprising a group represented by Formula (21); Ar.sup.6 is a (2+n9+n10)-valent aromatic group that optionally has a substituent other than either R.sup.11 or R.sup.12; n9 and n10 are each independently an integer of 1 or more; and when a plurality of R.sup.11 are present, each R.sup.11 may be the same as or different from each other; when a plurality of R.sup.12 are present, each R.sup.12 may be the same as or different from each other; and wherein the group represented by Formula (21) is:
R.sup.13-{(Q.sup.3).sub.n6-Y.sup.3}.sub.m8(21) wherein: R.sup.13 is a single bond or a (1+m8)-valent organic group; Q.sup.3, Y.sup.3, and n6 are the same as the corresponding definitions above; m8 is an integer of 1 or more, and when R.sup.13 is a single bond, m8 is 1; when a plurality of Q.sup.3 are present, each Q.sup.3 may be the same as or different from each other; when a plurality of Y.sup.3 are present, each Y.sup.3 may be the same as or different from each other; and when a plurality of n6 are present, each n6 may be the same as or different from each other; wherein the group represented by Formula (2) is:
R.sup.2-{(Q.sup.1).sub.n2-Y.sup.1(M.sup.1).sub.a1}.sub.m1(2) wherein: Q.sup.1, Y.sup.1, M.sup.1, n2, and a1 are the same as the corresponding definitions above; R.sup.2 is a single bond or a (1+m1) valent organic group; a1 is an integer of 1 or more and is selected so that the charge of the group represented by Formula (2) is zero; m1 is an integer of 1 or more, and when R.sup.2 is a single bond, m1 is 1; when a plurality of Q.sup.1 are present, each Q.sup.1 may be the same as or different from each other; when a plurality of Y.sup.1 are present, each Y.sup.1 may be the same as or different from each other; when a plurality of M.sup.1 are present, each M.sup.1 may be the same as or different from each other; when a plurality of n2 are present, each n2 may be the same as or different from each other; when a plurality of a1 are present, each a1 may be the same as or different from each other; wherein the structural unit represented by Formula (22) is: ##STR00388## wherein: R.sup.14 is a monovalent group comprising a group represented by Formula (4) or a group represented by Formula (19); R.sup.15 is a monovalent group comprising a group represented by Formula (21); Ar.sup.17 is a (2+n11+n12)-valent aromatic group that optionally has a substituent other than either R.sup.14 or R.sup.15; n11 and n12 are each independently an integer of 1 or more; when a plurality of R.sup.14 are present, each R.sup.14 may be the same as or different from each other; when a plurality of R.sup.15 are present, each R.sup.15 may be the same as or different from each other; and wherein the group represented by Formula (4) is:
R.sup.4-{(Q.sup.2).sub.n4-Y.sup.2(M.sup.2).sub.a2}.sub.m2(4) wherein: Q.sup.2, Y.sup.2, M.sup.2, n4, and a2 are the same as the corresponding definitions above; R.sup.4 is a single bond or a (1+m2)-valent organic group; m2 is an integer of 1 or more, and when R.sup.4 is a single bond, m2 is 1; when a plurality of Q.sup.2 are present, each Q.sup.2 may be the same as or different from each other; when a plurality of Y.sup.2 are present, each Y.sup.2 may be the same as or different from each other; when a plurality of M.sup.2 are present, each M.sup.2 may be the same as or different from each other; when a plurality of n4 are present, each n4 may be the same as or different from each other; wherein the group represented by Formula (23) is:
(M.sup.3).sub.a5(Z.sup.3).sub.b1(23) wherein: M.sup.3 is a metallic cation or an ammonium cation that optionally has a substituent; Z.sup.3 is F.sup., Cl.sup., Br.sup., I.sup., OH.sup., B(R.sup.P).sub.4.sup., R.sup.PSO.sub.3.sup., R.sup.PCOO.sup., R.sup.PO.sup., ClO.sup., ClO.sub.2.sup., ClO.sub.3.sup., ClO.sub.4.sup., SCN.sup., CN.sup., NO.sub.3.sup., CO.sub.3.sup.2, SO.sub.4.sup.2, HSO.sub.4.sup., PO.sub.4.sup.3, HPO.sub.4.sup.2, H.sub.2PO.sub.4.sup., BF.sub.4.sup., or PF.sub.6.sup.; a5 is an integer of 1 or more, b1 is an integer of 1 or more, and a5 and b1 are selected so that the charge of the ionic compound represented by Formula (23) is zero; R.sup.P is a monovalent organic group that optionally has a substituent; and when a plurality of R.sup.P are present, each R.sup.P may be the same as or different from each other.

2. The composition according to claim 1, wherein the (2+n7)-valent aromatic group represented by Ar.sup.4 is a group in which (2+n7) hydrogen atoms are removed from a ring represented by any one of Formulas 1 to 4, 6, 13 to 15, 19, 21, 23, 31 to 33, 43, 46, 47, and 51: ##STR00389## ##STR00390##

3. The composition according to claim 1, wherein the (2+n7)-valent aromatic group represented by Ar.sup.4 is a group in which n7 hydrogen atom is removed from a group represented by any one of Formulas 1, 3, 6, 13 to 15, 21, 23, 33, 43, 46, and 47: ##STR00391## ##STR00392##

4. The composition according to claim 1, wherein the (2+n8)-valent aromatic group represented by Ar.sup.5 is a group in which (2+n8) hydrogen atoms are removed from a ring represented by any one of Formulas 1 to 4, 6, 13 to 15, 19, 21, 23, 31 to 33, 43, 46, 47, and 51: ##STR00393## ##STR00394##

5. The composition according to claim 1, wherein the (2+n8)-valent aromatic group represented by Ar.sup.5 is a group in which n8 hydrogen atom is removed from a group represented by any one of Formulas 1, 3, 6, 13 to 15, 21, 23, 33, 43, 46, and 47: ##STR00395## ##STR00396##

6. The composition according to claim 1, wherein the (2+n9+n10)-valent aromatic group represented by Ar.sup.6 is a group in which (2+n9+n10) hydrogen atoms are removed from a ring represented by any one of Formulas 1 to 4, 13 to 15, 19, 21, 23, 31 to 33, 43, 46, 47, and 51: ##STR00397## ##STR00398##

7. The composition according to claim 1, wherein the (2+n9+n10)-valent aromatic group represented by Ar.sup.6 is a group in which (n9+n10) hydrogen atoms are removed from a group represented by any one of Formulas 1, 3, 13 to 15, 21, 23, 33, 43, 46, and 47: ##STR00399## ##STR00400##

8. The composition according to claim 1, wherein the (2+n11+n12)-valent aromatic group represented by Ar.sup.7 is a group in which (2+n11+n12) hydrogen atoms are removed from a ring represented by any one of Formulas 1 to 4, 13 to 15, 19, 21, 23, 31 to 33, 43, 46, 47, and 51: ##STR00401## ##STR00402##

9. The composition according to claim 1, wherein the (2+n11+n12)-valent aromatic group represented by Ar.sup.7 is a group in which (n11+n12) hydrogen atoms are removed from a group represented by any one of Formulas 1, 3, 13 to 15, 21, 23, 33, 43, 46, and 47: ##STR00403## ##STR00404##

10. The composition according to claim 1, wherein M.sup.3 is an alkali metal cation or an alkaline earth metal cation.

11. The composition according to claim 1, wherein the proportion of the ionic compound represented by Formula (23) comprised in the composition is 0.1 to 100% by weight to the weight of a polymer compound comprised in the composition.

12. An organic film comprising the composition according to claim 1.

13. An electric device comprising: a first electrode; a second electrode; a light emitting layer or a charge separation layer placed between the first electrode and the second electrode; and a layer comprising the compound according to claim 1 placed between the first electrode and any one of the light emitting layer or the charge separation layer.

14. The electric device according to claim 13, wherein the first electrode is a cathode.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described more specifically based on Examples and Comparative Example. The present invention, however, is not limited to the following Examples.

(2) Weight average molecular weights (Mw) and number average molecular weights (Mn) of polymer compounds were determined as polystyrene-equivalent weight average molecular weights and polystyrene-equivalent number average molecular weights by using a gel permeation chromatography (GPC) (manufactured by Tosoh Corporation: HLC-8220GPC). Samples that were measured were dissolved in THF to be about 0.5% by weight, and 50 L of the solution was injected into GPC. THF was used as a mobile phase of GPC, and the sample was flown in a flow rate of 0.5 mL/minute.

(3) Structural analysis of compounds and polymer compounds was carried out by .sup.1H-NMR analysis using a 300-MHz NMR spectrometer manufactured by Varian Inc. Measurement was carried out in a manner that a sample was dissolved in deuterated solvent (a solvent in which hydrogen atom(s) is(are) substituted with deuterium atom(s)) that was capable of dissolving the sample at a concentration of 20 mg/mL.

(4) An orbital energy of a highest occupied molecular orbital (HOMO) of a polymer compound was determined by measuring an ionization potential of the polymer compound and the obtained ionization potential was defined as the orbital energy.

(5) An orbital energy of a lowest unoccupied molecular orbital (LUMO) of the polymer compound was determined by calculating energy difference between HOMO and LUMO, and a sum of the value and the ionization potential measured above was defined as the orbital energy. A photoelectron spectrometer (manufactured by Riken Keiki Co., Ltd.: AC-2) was used for measurement of the ionization potential. An absorption spectrum of the polymer compound was measured by using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by Varian Inc.: Cary 5E) and energy difference between HOMO and LUMO was determined from absorption end of the absorption spectrum. Film samples of the polymer compounds having a thickness of about 100 nm that were formed on quartz substrates were used for these measurements.

Preparation Example 1

Synthesis of 2,7-dibromo-9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-fluorene (Compound A)

(6) 2,7-dibromo-9-fluorenone (52.5 g), ethyl salicylate (154.8 g), and mercaptoacetic acid (1.4 g) were poured in a 300 ml flask and the gas in the flask was replaced with nitrogen. Methanesulfonic acid (630 mL) was added, and the mixture was stirred overnight at 75 C. The mixture was allowed to cool, added to ice water, and stirred for 1 hour. The generated solid was filtered and washed with heated acetonitrile. The washed solid was dissolved in acetone. A solid was recrystallized from the obtained acetone solution and filtered. The obtained solid (62.7 g), 2-[2-(2-methoxyethoxy)ethoxy]ethyl p-toluenesulfonate (86.3 g), potassium carbonate (62.6 g), and 18-crown-6 (7.2 g) were dissolved in N,N-dimethylformamide (DMF) (670 mL) and the solution was transferred to a flask and stirred overnight at 105 C. The obtained mixture was allowed to cool to room temperature, added to ice water, and stirred for 1 hour. The reaction liquid was separately extracted by adding chloroform and the solution was concentrated, thus obtaining 2,7-dibromo-9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-fluorene (Compound A) (51.2 g).

(7) ##STR00335##

Preparation Example 2

Synthesis of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-fluorene (Compound B)

(8) Under a nitrogen atmosphere, Compound A (15 g), bis(pinacolato)diboron (8.9 g), [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium (II) dichloromethane complex (0.8 g), 1,1-bis(diphenylphosphino)ferrocene (0.5 g), potassium acetate (9.4 g), and dioxane (400 mL) were mixed. The reaction solution was heated to 110 C. and refluxed for 10 hours. After the reaction solution was allowed to cool, the reaction liquid was filtered and the filtrate was concentrated under reduced pressure. The reaction mixture was washed with methanol three times. A precipitate was dissolved in toluene. Activated carbon was added to the solution and the solution was stirred. Subsequently, the mixture was filtered and the filtrate was concentrated under reduced pressure, thus obtaining 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-fluorene (Compound B) (11.7 g).

(9) ##STR00336##

Preparation Example 3

Synthesis of poly[9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-fluorene] (Polymer Compound A) by Suzuki Coupling

(10) Under an inert atmosphere, Compound A (0.55 g), Compound B (0.61 g), triphenylphosphine palladium (0.01 g), methyltrioctylammonium chloride (manufactured by Sigma-Aldrich Co., trade name Aliquat 336 (registered trademark)) (0.20 g), and toluene (10 mL) were mixed and the reaction solution was heated to 105 C. To the reaction liquid, 2M sodium carbonate aqueous solution (6 mL) was added dropwise and the mixture was refluxed for 8 hours. To the reaction liquid, 4-tert-butylphenyl boronic acid (0.01 g) was added and the mixture was refluxed for 6 hours. Subsequently, sodium diethyldithiacarbamate aqueous solution (10 mL, concentration: 0.05 g/ml) was added and the mixed solution was stirred for 2 hours. After the mixed solution was added dropwise into methanol and the mixture was stirred for 1 hour, a deposited precipitate was filtered, dried for 2 hours under reduced pressure, and dissolved in THF. After the obtained solution was added dropwise into a mixed solvent of methanol and 3% by weight acetic acid aqueous solution and the mixture was stirred for 1 hour, a deposited precipitate was filtered and dissolved in THF. After thus obtained solution was added dropwise into methanol and the mixture was stirred for 30 minutes, a deposited precipitate was filtered, thus obtaining a solid. The obtained solid was dissolved in THF and purified through an alumina column and a silica gel column. After the THF solution recovered from the columns was concentrated, the solution was added dropwise into methanol and a deposited solid was filtered and dried. A yield of the obtained poly[9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-fluorene] (Polymer Compound A) was 520 mg.

(11) The polystyrene-equivalent number average molecular weight of Polymer Compound A was 5.210.sup.4. Polymer Compound A is made of the structural unit represented by Formula (A).

(12) ##STR00337##

Preparation Example 4

Synthesis of poly[9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]phenyl]-fluorene] (Polymer Compound A) by Yamamoto Polymerization

(13) Under an inert atmosphere, Compound A (1.31 g), 2,2-bipyridine (0.48 g), bis(1,5-cyclooctadiene) nickel (0.84 g), and THF (150 mL) were mixed and the mixture was stirred for 5 hours at 55 C. After the mixture was cooled to room temperature, the reaction solution was added dropwise into a mixture of methanol, water, and 15% by weight aqueous ammonia. After a generated precipitate was collected by filtration, dried under reduced pressure, and redissolved in THF. After the solution was filtered using celite, the filtrate was concentrated under reduced pressure. Methanol was added dropwise into the concentrated solution and a generated precipitate was collected by filtration and then dried under reduced pressure, thus obtaining Polymer Compound A (970 mg). The polystyrene-equivalent number average molecular weight of Polymer Compound A was 1.510.sup.5.

Preparation Example 5

Synthesis of Cesium Salt of Polymer Compound A (Conjugated Polymer Compound 1)

(14) Polymer Compound A (200 mg) synthesized in the method described in Preparation Example 3 was placed in a 100 mL flask and the gas in the flask was replaced with nitrogen. THF (20 mL) and ethanol (20 mL) were added and the mixture was heated to 55 C. An aqueous solution in which cesium hydroxide monohydrate (200 mg) was dissolved in water (2 mL) was added to the mixture and the obtained mixture was stirred for 6 hours at 55 C. After the mixture was cooled to room temperature, the reaction solvent was removed by distillation under reduced pressure. A generated solid was washed with water and dried under reduced pressure, thus obtaining a light yellow solid (150 mg). From NMR spectrum, complete disappearance of the signal derived from ethyl groups at the ethyl ester portion in Polymer Compound A was confirmed. The obtained cesium salt of Polymer Compound A is called Conjugated Polymer Compound 1. Conjugated Polymer Compound 1 is made of a structural unit represented by Formula (B).

(15) ##STR00338##

(16) An orbital energy of HOMO of Conjugated Polymer Compound 1 was 5.5 eV and an orbital energy of LUMO was 2.7 eV.

Preparation Example 6

Synthesis of Potassium Salt of Polymer Compound A (Conjugated Polymer Compound 2)

(17) Polymer Compound A (200 mg) synthesized in the method described in Preparation Example 3 was placed in a 100 mL flask and the gas in the flask was replaced with nitrogen. THF (20 mL) and methanol (10 mL) were mixed and an aqueous solution in which potassium hydroxide (400 mg) was dissolved in water (2 mL) was added to the mixed solution. The obtained mixture was stirred for 1 hour at 65 C. To the reaction solution, 50 mL of methanol was added and the mixture was further stirred for 4 hours at 65 C. After the mixture was cooled to room temperature, the reaction solvent was removed by distillation under reduced pressure. A generated solid was washed with water and dried under reduced pressure, thus obtaining a light yellow solid (131 mg).

(18) From NMR spectrum, complete disappearance of the signal derived from ethyl groups at the ethyl ester portion in Polymer Compound A was confirmed. The obtained potassium salt of Polymer Compound A is called Conjugated Polymer Compound 2. Conjugated Polymer Compound 2 made of a structural unit represented by Formula (C).

(19) ##STR00339##

(20) An orbital energy of HOMO of Conjugated Polymer Compound 2 was 5.5 eV and an orbital energy of LUMO was 2.7 eV.

Preparation Example 7

Synthesis of Sodium Salt of Polymer Compound A (Conjugated Polymer Compound 3)

(21) Polymer Compound A (200 mg) synthesized in the method described in Preparation Example 3 was placed in a 100 mL flask and the gas in the flask was replaced with nitrogen. THF (20 mL) and methanol (10 mL) were mixed and an aqueous solution in which sodium hydroxide (260 mg) was dissolved in water (2 mL) was added to the mixed solution. The obtained mixture was stirred for 1 hour at 65 C. To the reaction solution 30 mL of methanol was added and the mixture was further stirred for 4 hours at 65 C. After the mixture was cooled to room temperature, the reaction solvent was removed by distillation under reduced pressure. A generated solid was washed with water and dried under reduced pressure, thus obtaining a light yellow solid (123 mg). From NMR spectrum, complete disappearance of the signal derived from ethyl groups at the ethyl ester portion in Polymer Compound A was confirmed. The obtained sodium salt of Polymer Compound A is called Conjugated Polymer Compound 3. Conjugated Polymer Compound 3 is made of a structural unit represented by Formula (D).

(22) ##STR00340##

(23) An orbital energy of HOMO of Conjugated Polymer Compound 3 was 5.6 eV and an orbital energy of LUMO was 2.8 eV.

Preparation Example 8

Synthesis of Ammonium Salt of Polymer Compound A (Conjugated Polymer Compound 4)

(24) Polymer Compound A (200 mg) synthesized in the method described in Preparation Example 3 was placed in a 100 mL flask and the gas in the flask was replaced with nitrogen. THF (20 mL) and methanol (15 mL) were mixed and an aqueous solution in which tetramethylammonium hydroxide (50 mg) was dissolved in water (1 mL) was added to the mixed solution. The obtained mixture was stirred for 6 hours at 65 C. To the reaction solution, an aqueous solution in which tetramethylammonium hydroxide (50 mg) was dissolved in water (1 mL) was added and the mixture was further stirred for 4 hours at 65 C. After the mixture was cooled to room temperature, the reaction solvent was removed by distillation under reduced pressure. A generated solid was washed with water and dried under reduced pressure, thus obtaining a light yellow solid (150 mg). From NMR spectrum, 90% of disappearance of the signal derived from ethyl groups at the ethyl ester portion in Polymer Compound A was confirmed. The obtained ammonium salt of Polymer Compound A is called Conjugated Polymer Compound 4. Conjugated Polymer Compound 4 is made of a structural unit represented by Formula (E).

(25) ##STR00341##

(26) An orbital energy of HOMO of Conjugated Polymer Compound 4 was 5.6 eV and an orbital energy of LUMO was 2.8 eV.

Preparation Example 9

Synthesis of Polymer Compound B

(27) Under an inert atmosphere, Compound A (0.40 g), Compound B (0.49 g), N,N-bis(4-bromophenyl)-N,N-bis(4-tert-butyl-2,6-dimethylphenyl)1,4-phenylenediamine (35 mg), triphenylphosphine palladium (8 mg), methyltrioctylammonium chloride (manufactured by Sigma-Aldrich Corp., trade name Aliquat 336 (registered trademark)) (0.20 g), and toluene (10 mL) were mixed and the reaction solution was heated to 105 C. To the reaction liquid, 2M sodium carbonate aqueous solution (6 mL) was added dropwise and the mixture was refluxed for 8 hours. Phenylboronic acid (0.01 g) was added to the reaction liquid, and the mixture was refluxed for 6 hours.

(28) Subsequently, sodium diethyldithiacarbamate aqueous solution (10 mL, concentration: 0.05 g/mL) was added and the mixture was stirred for 2 hours. After the mixed solution was added dropwise into methanol and the mixture was stirred for 1 hour, a deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in THF. After the obtained solution was added dropwise into a mixed solvent of methanol and 3% by weight acetic acid aqueous solution and the mixture was stirred for 1 hour, a deposited precipitate was filtered and dissolved in THF. After thus obtained solution was added dropwise into methanol and the mixture was stirred for 30 minutes, a deposited precipitate was filtered, thus obtaining a solid. The obtained solid was dissolved in THF and purified through an alumina column and a silica gel column. After the THF solution recovered from the columns was concentrated, the concentrated solution was added dropwise into methanol and a deposited solid was filtered and dried. A yield of obtained Polymer Compound B was 526 mg.

(29) The polystyrene-equivalent number average molecular weight of Polymer Compound B was 3.610.sup.4. Polymer Compound B is made of a structural unit represented by Formula (F).

(30) ##STR00342##

(31) N,N-bis(4-bromophenyl)-N,N-bis(4-tert-butyl-2,6-dimethylphenyl)1,4-phenylenediamine can be synthesized by, for example, the method described in Japanese Patent Application Laid-open No. 2008-74917.

Preparation Example 10

Synthesis of Cesium Salt of Polymer Compound B (Conjugated Polymer Compound 5)

(32) Polymer Compound B (200 mg) was placed in a 100 mL flask and the gas in the flask was replaced with nitrogen. THF (20 mL) and methanol (20 mL) were added and mixed. To the mixed solution, an aqueous solution in which cesium hydroxide (200 mg) was dissolved in water (2 mL) was added, and the obtained mixture was stirred for 1 hour at 65 C. To the reaction solution, 30 mL of methanol was added and the mixture was further stirred for 4 hours at 65 C. After the mixture was cooled to room temperature, the reaction solvent was removed by distillation under reduced pressure. A generated solid was washed with water and dried under reduced pressure, thus obtaining a light yellow solid (150 mg). From NMR spectrum, complete disappearance of the signal derived from ethyl groups at the ethyl ester portion in Polymer Compound B was confirmed. The obtained cesium salt of Polymer Compound B is called Conjugated Polymer Compound 5. Conjugated Polymer Compound 5 is made of a structural unit represented by Formula (G).

(33) ##STR00343##

(34) An orbital energy of HOMO of Conjugated Polymer Compound 5 was 5.3 eV and an orbital energy of LUMO was 2.6 eV.

Preparation Example 11

Synthesis of Polymer Compound C

(35) Under an inert atmosphere, Compound A (0.55 g), Compound B (0.67 g), N,N-bis(4-bromophenyl)-N,N-bis(4-tert-butyl-2,6-dimethylphenyl)1,4-phenylenediamine (0.038 g), 3,7-dibromo-N-(4-n-butylphenyl) phenoxazine (0.009 g), triphenylphosphine palladium (0.01 g), methyltrioctylammonium chloride (manufactured by Sigma-Aldrich Co., trade name Aliquat 336 (registered trademark)) (0.20 g), and toluene (10 mL) were mixed, and the mixture was heated to 105 C. To the reaction liquid, 2M sodium carbonate aqueous solution (6 mL) was added dropwise and the mixture was refluxed for 2 hours. Phenylboronic acid (0.004 g) was added to the reaction liquid, and the mixture was refluxed for 6 hours. Subsequently, sodium diethyldithiacarbamate aqueous solution (10 mL, concentration: 0.05 g/mL) was added and the mixture was stirred for 2 hours. After the mixed solution was added dropwise into methanol and the mixture was stirred for 1 hour, a deposited precipitate was filtered and dried under reduced pressure for 2 hours. The obtained solid was dissolved in THF. After the obtained solution was added dropwise into a mixed solvent of methanol and 3% by weight of acetic acid aqueous solution and the mixture was stirred for 1 hour, a deposited precipitate was filtered and dissolved in THF. After thus obtained solution was added dropwise into methanol and the mixture was stirred for 30 minutes, a deposited precipitate was filtered, thus obtaining a solid. The obtained solid was dissolved in THF and purified through an alumina column and a silica gel column. After the THF solution recovered from the columns was concentrated, the concentrated solution was added dropwise into methanol and a deposited solid was filtered and dried. A yield of obtained Polymer Compound C was 590 mg.

(36) The polystyrene-equivalent number average molecular weight of Polymer Compound C was 2.710.sup.4. Polymer Compound C is made of a structural unit represented by Formula (H).

(37) ##STR00344##

(38) 3,7-dibromo-N-(4-n-butylphenyl)phenoxazine was synthesized by the method described in Japanese Patent Application Laid-open No. 2004-137456.

Preparation Example 12

Synthesis of Cesium Salt of Polymer Compound C (Conjugated Polymer Compound 6)

(39) Polymer Compound C (200 mg) was placed in a 100 mL flask and the gas in the flask was replaced with nitrogen. THF (15 mL) and methanol (10 mL) were mixed. To the mixed solution, an aqueous solution in which cesium hydroxide (360 mg) was dissolved in water (2 mL) was added, and the obtained mixture was stirred for 3 hours at 65 C. To the reaction solution, 10 mL of methanol was added and the mixture was further stirred for 4 hours at 65 C. After the mixture was cooled to room temperature, the reaction solvent was removed by distillation under reduced pressure. A generated solid was washed with water and dried under reduced pressure, thus obtaining a light yellow solid (210 mg). From NMR spectrum, complete disappearance of the signal derived from ethyl groups at the ethyl ester portion in Polymer Compound C was confirmed. The obtained cesium salt of Polymer Compound C is called Conjugated Polymer Compound 6. Conjugated Polymer Compound 6 is made of a structural unit represented by Formula (I).

(40) ##STR00345##

(41) An orbital energy of HOMO of Conjugated Polymer Compound 6 was 5.3 eV and an orbital energy of LUMO was 2.4 eV.

Preparation Example 13

Synthesis of Polymer Compound D

(42) Under an inert atmosphere, Compound A (0.37 g), Compound B (0.82 g), 1,3-dibromobenzene (0.09 g), triphenylphosphine palladium (0.01 g), methyltrioctylammonium chloride (manufactured by Sigma-Aldrich Co., trade name Aliquat 336 (registered trademark)) (0.20 g), and toluene (10 mL) were mixed and the reaction solution was heated to 105 C. To the reaction liquid, 2M sodium carbonate aqueous solution (6 mL) was added dropwise and the reaction solution was refluxed for 7 hours. Phenylboronic acid (0.002 g) was added to the reaction liquid, and the reaction solution was refluxed for 10 hours. Subsequently, sodium diethyldithiacarbamate aqueous solution (10 mL, concentration: 0.05 g/mL) was added and the mixed solution was stirred for 1 hour. After the mixed solution was added dropwise into 300 mL of methanol and the mixture was stirred for 1 hour, a deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 20 mL of THF. After the obtained solution was added dropwise into a mixed solvent of methanol and 3% by weight acetic acid aqueous solution and the mixture was stirred for 1 hour, a deposited precipitate was filtered and dissolved in THF. After thus obtained solution was added dropwise into methanol and the mixture was stirred for 30 minutes, a deposited precipitate was filtered, thus obtaining a solid. The obtained solid was dissolved in THF and purified through an alumina column and a silica gel column. After the THF solution recovered from the columns was concentrated, the concentrated solution was added dropwise into methanol and a deposited solid was filtered and dried. A yield of obtained Polymer Compound D was 293 mg.

(43) The polystyrene-equivalent number average molecular weight of Polymer Compound D was 1.810.sup.4. Polymer Compound D is made of the structural unit represented by Formula (J).

(44) ##STR00346##

Preparation Example 14

Synthesis of Cesium Salt of Polymer Compound D (Conjugated Polymer Compound 7)

(45) Polymer Compound D (200 mg) was placed in a 100 mL flask and the gas in the flask was replaced with nitrogen. THF (10 mL) and methanol (5 mL) were mixed. To the mixed solution, an aqueous solution in which cesium hydroxide (200 mg) was dissolved in water (2 mL) was added, and the reaction solution was stirred for 2 hours at 65 C. To the reaction solution, 10 mL of methanol was added and the mixture was further stirred for 5 hours at 65 C. After the mixture was cooled to room temperature, the reaction solvent was removed by distillation under reduced pressure. A generated solid was washed with water and dried under reduced pressure, thus obtaining a light yellow solid (170 mg). From NMR spectrum, complete disappearance of the signal derived from ethyl groups at the ethyl ester portion in Polymer Compound D was confirmed. The obtained cesium salt of Polymer Compound D is called Conjugated Polymer Compound 7. Conjugated Polymer Compound 7 is made of a structural unit represented by Formula (K).

(46) ##STR00347##

(47) An orbital energy of HOMO of Conjugated Polymer Compound 7 was 5.6 eV and an orbital energy of LUMO was 2.6 eV.

Preparation Example 15

Synthesis of Polymer Compound E

(48) Under an inert atmosphere, Compound B (1.01 g), 1,4-dibromo-2,3,5,6-tetrafluorobenzene (0.30 g), triphenylphosphine palladium (0.02 g), methyltrioctylammonium chloride (manufactured by Sigma-Aldrich Co., trade name Aliquat 336 (registered trademark)) (0.20 g), and toluene (10 mL) were mixed and the reaction solution was heated to 105 C. To the reaction liquid, 2M sodium carbonate aqueous solution (6 mL) was added dropwise and the reaction solution was refluxed for 4 hours. Phenylboronic acid (0.002 g) was added to the reaction liquid, and the mixture was refluxed for 4 hours. Subsequently, sodium diethyldithiacarbamate aqueous solution (10 mL, concentration: 0.05 g/mL) was added and the mixture was stirred for 1 hour. After the mixed solution was added dropwise into methanol and the mixture was stirred for 1 hour, a deposited precipitate was filtered and dried under reduced pressure for 2 hours. The obtained solid was dissolved in THF. After the obtained solution was added dropwise into a mixed solvent of methanol and 3% by weight of acetic acid aqueous solution and the mixture was stirred for 1 hour, a deposited precipitate was filtered and dissolved in THF. After thus obtained solution was added dropwise into methanol and the mixture was stirred for 30 minutes, a deposited precipitate was filtered, thus obtaining a solid. The obtained solid was dissolved in a mixed solvent of THF/ethyl acetate (1/1 (volume ratio)) and purified through an alumina column and a silica gel column. After the THF solution recovered from the columns was concentrated, the concentrated solution was added dropwise into methanol and a deposited solid was filtered and dried. A yield of obtained Polymer Compound E was 343 mg.

(49) The polystyrene-equivalent number average molecular weight of Polymer Compound E was 6.010.sup.4. Polymer Compound E is made of a structural unit represented by Formula (L).

(50) ##STR00348##

Preparation Example 16

Synthesis of Cesium Salt of Polymer Compound E (Conjugated Polymer Compound 8)

(51) Polymer Compound E (150 mg) was placed in a 100 mL flask and the gas in the flask was replaced with nitrogen. THF (10 mL) and methanol (5 mL) were mixed. To the mixed solution, an aqueous solution in which cesium hydroxide (260 mg) was dissolved in water (2 mL) was added, and the obtained reaction solution was stirred for 2 hours at 65 C. To the reaction solution, 10 mL of methanol was added and the mixture was further stirred for 5 hours at 65 C. After the mixture was cooled to room temperature, the reaction solvent was removed by distillation under reduced pressure. A generated solid was washed with water and dried under reduced pressure, thus obtaining a light yellow solid (130 mg). From NMR spectrum, complete disappearance of the signal derived from ethyl groups at the ethyl ester portion in Polymer Compound E was confirmed. The obtained cesium salt of Polymer Compound E is called Conjugated Polymer Compound 8. Conjugated Polymer Compound 8 is made of a structural unit represented by Formula (M).

(52) ##STR00349##

(53) An orbital energy of HOMO of Conjugated Polymer Compound 8 was 5.9 eV and an orbital energy of LUMO was 2.8 eV.

Preparation Example 17

Synthesis of 1,3-dibromo-5-ethoxycarbonyl-6-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]benzene

(54) Under an inert atmosphere, 3,5-dibromosalicylic acid (20 g), ethanol (17 mL), concentrated sulfuric acid (1.5 mL), and toluene (7 mL) were mixed and the reaction solution was heated and stirred for 20 hours at 130 C. After the reaction solution was allowed to cool, the reaction solution was added to ice water (100 mL). The obtained mixture was separately extracted with chloroform and the obtained solution was concentrated. The obtained solid was dissolved in isopropanol and the solution was added dropwise into distilled water. The obtained deposit was filtered, thus obtaining a solid (18 g). Under an inert atmosphere, the obtained solid (1 g), 2-[2-(2-methoxyethoxy)ethoxy]ethyl p-toluenesulfonate (1.5 g), potassium carbonate (0.7 g), and DMF (15 mL) were mixed and the reaction solution was heated and stirred for 4 hours at 100 C. After the reaction solution was allowed to cool, the reaction solution was separately extracted with chloroform, and the solution was concentrated. The concentrated product was dissolved in chloroform and purified through a silica gel column. The solution was concentrated, thus obtaining 1,3-dibromo-5-ethoxycarbonyl-6-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]benzene (1.0 g).

Preparation Example 18

Synthesis of Polymer Compound F

(55) Under an inert atmosphere, Compound A (0.2 g), Compound B (0.5 g), 1,3-dibromo-5-ethoxycarbonyl-6-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]benzene (0.1 g), triphenylphosphine palladium (30 mg), tetrabutylammonium bromide (4 mg), and toluene (19 mL) were mixed and the reaction solution was heated to 105 C. To the reaction liquid, 2M sodium carbonate aqueous solution (5 mL) was added dropwise and the reaction solution was refluxed for 5 hours. Phenylboronic acid (6 mg) was added to the reaction liquid, and the mixture was refluxed for 14 hours. Subsequently, sodium diethyldithiacarbamate aqueous solution (10 mL, concentration: 0.05 g/mL) was added and the mixture was stirred for 2 hours. The water layer was removed, and the organic layer was washed with distilled water. The organic layer was concentrated, and the obtained solid was dissolved in chloroform and purified through an alumina column and a silica gel column. The eluted solution from the column was concentrated and dried. A yield of obtained Polymer Compound F was 0.44 g.

(56) The polystyrene-equivalent number average molecular weight of Polymer Compound F was 3.610.sup.4. Polymer Compound F is made of a structural unit represented by Formula (N).

(57) ##STR00350##

Preparation Example 19

Synthesis of Cesium Salt of Polymer Compound F (Conjugated Polymer Compound 9)

(58) Polymer Compound F (200 mg) was placed in a 100 mL flask and the gas in the flask was replaced with nitrogen. THF (14 mL) and methanol (7 mL) were added and mixed. To the mixed solution, an aqueous solution in which cesium hydroxide (90 mg) was dissolved in water (1 mL) was added, and the reaction solution was stirred for 1 hour at 65 C. To the reaction solution, 5 mL of methanol was added and the mixture was further stirred for 4 hours at 65 C. After the mixture was cooled to room temperature, the reaction solvent was removed by distillation under reduced pressure. A generated solid was washed with water and dried under reduced pressure, thus obtaining a light yellow solid (190 mg). From NMR spectrum, complete disappearance of the signal derived from ethyl groups at the ethyl ester portion in Polymer Compound F was confirmed. The obtained cesium salt of Polymer Compound F is called Conjugated Polymer Compound 9. Conjugated Polymer Compound 9 is made of a structural unit represented by Formula (O).

(59) ##STR00351##

(60) An orbital energy of HOMO of Conjugated Polymer Compound 9 was 5.6 eV and an orbital energy of LUMO was 2.8 eV.

Preparation Example 20

Synthesis of Compound C

(61) Under a nitrogen atmosphere, 2,7-dibromo-9-fluorenone (92.0 g, 272 mmol) and diethyl ether (3.7 L) were mixed and cooled to 0 C., and 1 mol/L of methyl iodide magnesium-diethyl ether solution (0.5 L, 545 mmol) was added dropwise. The reaction mixture was stirred for 3 hours. An ammonium chloride aqueous solution was added to the reaction mixture and the water layer was removed. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography, thus obtaining Compound C (92.81 g, 262 mmol, and yield 96%).

(62) ##STR00352##

Preparation Example 21

Synthesis of Compound D

(63) Under a nitrogen atmosphere, Compound C (83.0 g, 234 mmol), p-toluenesulfonic acid monohydrate (4.49 g, 23.6 mmol), and chloroform (2.5 L) were refluxed for 1 hour. An ammonium chloride aqueous solution was added to the reaction mixture and the water layer was removed. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure, thus obtaining Compound D (73.6 g, 219 mmol, and yield 93%).

(64) ##STR00353##

Preparation Example 22

Synthesis of Compound E

(65) Under a nitrogen atmosphere, Compound D (70.0 g, 208 mmol), ethyl salicylate (104 g, 625 mmol), mercaptoacetic acid (4.20 g, 45.6 mmol), and methane sulfonic acid (1214 g) were stirred for 8 hours at 70 C. The reaction mixture was added dropwise into ice water and a deposited solid was recovered by filtration. The solid was washed with methanol. The crude product was purified by silica gel column chromatography, thus obtaining Compound E (52.14 g, 104 mmol, and yield 50%).

(66) ##STR00354##

Preparation Example 23

Synthesis of Compound F

(67) Under a nitrogen atmosphere, Compound E (41.2 g, 82.0 mmol), 2-[2-(2-methoxyethoxy)ethoxy]-ethyl-p-toluenesulfonate (75.8 g, 238 mmol), dimethylformamide (214 g), potassium carbonate (54.4 g, 394 mmol), and 18-crown-6 (4.68 g, 18 mmol) were stirred for 2 hours at 105 C. Water was added to the reaction mixture and the obtained mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography, thus obtaining Compound F (40.2 g, 62.0 mmol, and yield 76%).

(68) .sup.1H NMR (400 MHz, CDCl.sub.3, rt): (ppm)=1.37 (3H), 1.84 (3H), 3.36 (3H), 3.53 (2H), 3.58-3.79 (6H), 3.73 (2H), 4.12 (2H), 4.34 (2H), 6.80 (1H), 6.90 (1H), 7.28 (2H), 7.48 (2H), 7.58 (2H), 7.70 (1H).

(69) ##STR00355##

Preparation Example 24

Synthesis of Compound G

(70) Under a nitrogen atmosphere, Compound F (28.4 g, 43.8 mmol), bis(pinacolato)diboron (24.30 g, 95.7 mol), dichloromethane adduct of [1,1-bis(diphenylphosphino)ferrocene]palladium (II) dichloride (0.35 g, 0.4 mmol), 1,1-bis(diphenylphosphino)ferrocene (0.24 g, 0.4 mmol), potassium acetate (25.60 g, 260 mmol), and 1,4-dioxane (480 mL) were stirred for 17 hours at 120 C., and the reaction mixture was filtered and washed with ethyl acetate. The filtrate was concentrated under reduced pressure and purified by silica gel column chromatography. Subsequently, the product was purified by recrystallization, thus obtaining Compound G (18.22 g, 24.5 mmol, and yield 56%).

(71) .sup.1H NMR (400 MHz, CDCl.sub.3, rt): (ppm)=1.30-1.47 (27H), 1.88 (3H), 3.35 (3H), 3.53 (2H), 3.60-3.69 (4H), 3.73 (2H), 3.84 (2H), 4.10 (2H), 4.34 (2H), 6.74 (1H), 6.87 (1H), 7.58 (2H), 7.72-7.89 (5H).

(72) ##STR00356##

Preparation Example 25

Synthesis of Polymer Compound G

(73) Under an argon atmosphere, Compound F (0.47 g), Compound G (0.48 g), dichloro bis(triphenylphosphine) palladium (0.6 mg), tetrabutylammonium bromide (6 mg), toluene (6 mL), and 2 mol/L sodium carbonate aqueous solution (2 mL) were stirred for 6 hours at 105 C. Subsequently, phenylboronic acid (35 mg) was added and the reaction mixture was stirred for 14 hours at 105 C. Sodium diethyldithiocarbamate trihydrate (0.65 g) and water (13 mL) were added to the reaction mixture, and the obtained mixture was stirred for 2 hours at 80 C. The mixture was added dropwise into methanol, and the deposit was recovered by filtration and dried. The solid was dissolved in chloroform and purified by alumina and silica gel column chromatography. The eluted solution was added dropwise into methanol, and the deposit was recovered by filtration and dried, thus obtaining Polymer Compound G (0.57 g).

(74) The polystyrene-equivalent number average molecular weight of Polymer Compound G was 2.010.sup.4. Polymer Compound G is made of a structural unit represented by Formula (P).

(75) ##STR00357##

Preparation Example 26

Synthesis of Cesium Salt of Polymer Compound G (Conjugated Polymer Compound 10)

(76) Under an argon atmosphere, Polymer Compound G (0.20 g), THF (18 mL), methanol (9 mL), cesium hydroxide monohydrate (97 mg), and water (1 mL) were stirred for 2 hours at 65 C. Subsequently, methanol (52 mL) was added and the reaction mixture was stirred for 6 hours at 65 C. The reaction mixture was concentrated and dried. Methanol was added to the solid and the mixture was filtered. The filtrate was added dropwise into isopropanol, and the solid was recovered by filtration, thus obtaining a cesium salt of Polymer Compound G (0.20 g). The obtained cesium salt of Polymer Compound G is called Conjugated Polymer Compound 10. Conjugated Polymer Compound 10 is made of a structural unit represented by Formula (Q).

(77) ##STR00358##

(78) An orbital energy of HOMO of Conjugated Polymer Compound 10 was 5.51 eV and an orbital energy of LUMO was 2.64 eV.

Preparation Example 27

Synthesis of Polymer Compound H

(79) Under an argon atmosphere, Compound F (0.528 g), Compound G (0.493 g), dichloro bis(triphenylphosphine) palladium (0.56 mg), N,N-bis(4-bromophenyl)-N,N-bis(4-tert-butyl-2,6-dimethylphenyl)1,4-phenylenediamine (35.8 mg), methyltrioctylammonium chloride (manufactured by Sigma-Aldrich Corp., trade name Aliquat 336 (registered trademark)) (8.10 mg, 0.0200 mmol), toluene (20 mL), and 2 mol/L sodium carbonate aqueous solution (10 mL) were stirred for 6 hours at 105 C. Subsequently, phenylboronic acid (35 mg) was added and the reaction mixture was stirred for 14 hours at 105 C. Sodium diethyldithiocarbamate trihydrate (0.72 g) and water (14 mL) were added to the reaction mixture, and the obtained mixture was stirred for 2 hours at 80 C. The mixture was added dropwise into methanol, and the deposit was recovered by filtration and dried. The solid was dissolved in chloroform and purified by alumina and silica gel column chromatography. The eluted solution was concentrated and dried. The concentrated product was dissolved in toluene and the solution was added dropwise into methanol. The deposit was recovered by filtration and dried, thus obtaining Polymer Compound H (0.31 g).

(80) The polystyrene-equivalent number average molecular weight of Polymer Compound H was 1.810.sup.4. Polymer Compound H is made of a structural unit represented by Formula (R).

(81) ##STR00359##

Preparation Example 28

Synthesis of Cesium Salt of Polymer Compound H (Conjugated Polymer Compound 11)

(82) Under an argon atmosphere, Polymer Compound H (0.15 g), THF (20 mL), methanol (10 mL), cesium hydroxide monohydrate (103 mg), and water (1 mL) were stirred for 2 hours at 65 C. Subsequently, methanol (20 mL) was added and the reaction mixture was stirred for 2 hours at 65 C. The reaction mixture was concentrated and dried. Methanol was added to the solid and the mixture was filtered. The filtrate was added dropwise into isopropanol, and the solid was recovered by filtration, thus obtaining a cesium salt of Polymer Compound H (0.15 g). The obtained cesium salt of Polymer Compound H is called Conjugated Polymer Compound 11. Conjugated Polymer Compound 11 is made of a structural unit represented by Formula (S).

(83) ##STR00360##

(84) An orbital energy of HOMO of Conjugated Polymer Compound 11 was 5.23 eV and an orbital energy of LUMO was 2.36 eV.

Preparation Example 29

Synthesis of 2,7-dibromo-9,9-bis(3,4-dihydroxy)-fluorene

(85) Under nitrogen gas stream, 2,7-dibromo-9-fluorenone (121.9 g), catechol (883.1 g), and 3-mercaptopropionic acid (4.87 g), and concentrated sulfuric acid (18.4 g) were mixed and stirred for 2 hours at 125 C. The mixture was allowed to cool and added to ice water. The generated solid was separated by filtration. The obtained solid was dissolved in ethanol, and the ethanol solution was added to hexane. The generated solid was separated by filtration, thus obtaining 2,7-dibromo-9,9-bis(3,4-dihydroxy)-fluorene (168.1 g) represented by the following formula.

(86) ##STR00361##

Preparation Example 30

Synthesis of Compound H

(87) Under nitrogen gas stream, 2,7-dibromo-9,9-bis(3,4-dihydroxy)-fluorene (138.4 g), 2-[2-(2-methoxyethoxy)ethoxy]-ethyl-p-toluenesulfonate (408.6 g), potassium carbonate (358.5 g), and acetonitrile (2.5 L) were mixed and the mixture was refluxed for 3 hours. After the reaction mixture was allowed to cool, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure. The concentrated filtrate was purified by silica gel column chromatography, thus obtaining Compound H (109.4).

(88) ##STR00362##

Preparation Example 31

Synthesis of Compound I

(89) Under a nitrogen atmosphere, Compound H (101.2 g), bis(pinacolato)diboron (53.1 g), dichloromethane complex of [1,1-bis(diphenylphosphino)ferrocene]dichloro-palladium (II) (3.7 g), 1,1-bis(diphenylphosphino)ferrocene (5.4 g), potassium acetate (90.6 g), and dioxane (900 mL) were mixed and the reaction solution was heated to 110 C. and reflexed for 8 hours. After allowed to cool, the reaction liquid was filtered and the filtrate was concentrated under reduced pressure. The concentrated filtrate was purified by silica gel column chromatography, thus obtaining Compound I (51.4 g).

(90) ##STR00363##

Preparation Example 32

Synthesis of Polymer Compound I

(91) Compound G (0.360 g), Compound I (0.273 g), Compound H (0.493 g), N,N-bis(4-bromophenyl)-N,N-bis(4-tert-butyl-2,6-dimethylphenyl)1,4-phenylenediamine (35.8 mg), aliquot 336 (8.10 mg), bis(triphenylphosphine)dichloro palladium (1.12 mg), 2 mol/L of sodium carbonate aqueous solution (15 mL), and toluene (20 mL) were stirred for 6 hours at 105 C. Subsequently, phenylboronic acid (39 mg) was added and the obtained mixture was stirred for 6 hours at 105 C. Sodium diethyldithiocarbamate trihydrate (0.72 g) and water (14 mL) were added to the reaction mixture, and the obtained mixture was stirred for 2 hours at 80 C. The mixture was added dropwise into methanol, and the deposit was recovered by filtration and dried. The solid was dissolved in chloroform and purified by alumina and silica gel column chromatography. The eluted solution was concentrated and dried. The concentrated product was dissolved in toluene and the solution was added dropwise into methanol. The deposit was recovered by filtration and dried, thus obtaining Polymer Compound I (0.41 g).

(92) The polystyrene-equivalent number average molecular weight of Polymer Compound I was 2.010.sup.4. Polymer Compound I is made of a structural unit represented by Formula (T).

(93) ##STR00364##

Preparation Example 33

Synthesis of Cesium Salt of Polymer Compound I (Conjugated Polymer Compound 12)

(94) Under an argon atmosphere, Polymer Compound I (0.15 g), THF (20 mL), methanol (10 mL), cesium hydroxide monohydrate (103 mg), and water (1 mL) were stirred for 2 hours at 65 C. Subsequently, methanol (20 mL) was added and the mixture was stirred for 2 hours at 65 C. The reaction mixture was concentrated and dried. Methanol was added to the solid and the mixture was filtered. The filtrate was added dropwise into isopropanol, and the solid was recovered by filtration and dried, thus obtaining a cesium salt of Polymer Compound I (0.17 g). The obtained cesium salt of Polymer Compound I is called Conjugated Polymer Compound 12. Conjugated Polymer Compound 12 is made of a structural unit represented by Formula (U).

(95) ##STR00365##

(96) An orbital energy of HOMO of Conjugated Polymer Compound 12 was 5.25 eV and an orbital energy of LUMO was 2.38 eV.

Preparation Example 34

Synthesis of Polymer Compound J

(97) Compound I (0.715 g), Compound F (0.426 g), methyltrioctylammonium chloride (manufactured by Sigma-Aldrich Co., trade name Aliquat 336 (trademark)) (6.60 mg), bis(triphenylphosphine)dichloro palladium (0.460 mg), 2 mol/L sodium carbonate aqueous solution (10 mL), and toluene (20 mL) were added and the mixture was stirred at 105 C. Toluene (20 ml) was stirred for 5 hours at 105 C. Subsequently, phenylboronic acid (32 mg) was added and the mixture was stirred for 6 hours at 105 C. Sodium diethyldithiocarbamate trihydrate (0.72 g) and water (14 mL) were added to the reaction mixture, and the obtained mixture was stirred for 2 hours at 80 C. The mixture was added dropwise into methanol, and the deposit was recovered by filtration and dried. The solid was dissolved in chloroform and purified by alumina and silica gel column chromatography. The eluted solution was concentrated and dried. The concentrated product was dissolved in toluene and the solution was added dropwise into methanol. The deposit was recovered by filtration and dried, thus obtaining Polymer Compound J (0.55 g).

(98) The polystyrene-equivalent number average molecular weight of Polymer Compound J was 2.310.sup.4. Polymer Compound J is made of a structural unit represented by Formula (V).

(99) ##STR00366##

Preparation Example 35

Synthesis of Cesium Salt of Polymer Compound J (Conjugated Polymer Compound 13)

(100) Under an argon atmosphere, Polymer Compound J (0.15 g), THF (20 mL), methanol (10 mL), cesium hydroxide monohydrate (103 mg), and water (1 mL) were stirred for 2 hours at 65 C. Subsequently, methanol (20 mL) was added and the mixture was stirred for 2 hours at 65 C. The reaction mixture was concentrated and dried, and methanol was added to the solid and the mixture was filtered. The obtained filtrate was concentrated and dried, and the obtained solid was dried after washed with water, thus obtaining a cesium salt of Polymer Compound J (0.14 g). The obtained cesium salt of Polymer Compound J is called Conjugated Polymer Compound 13. Conjugated Polymer Compound 13 is made of a structural unit represented by Formula (W).

(101) ##STR00367##

(102) An orbital energy of HOMO of Conjugated Polymer Compound 13 was 5.56 eV and an orbital energy of LUMO was 2.67 eV.

Preparation Example 36

Synthesis of Compound J

(103) Under a nitrogen atmosphere, 5-bromo-2-hydroxybenzoic acid (92.85 g), ethanol (1140 mL), and concentrated sulfuric acid (45 mL) were refluxed for 48 hours. After the mixture was concentered under reduced pressure, ethyl acetate was added and the organic layer was washed with water and 10% by weight sodium carbonate aqueous solution. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography, thus obtaining Compound J (95.38 g, yield 91%).

(104) ##STR00368##

Preparation Example 37

Synthesis of Compound K

(105) Under a nitrogen atmosphere, Compound J (95.0 g), bis(pinacolato)diboron (108.5 g), dichloromethane adduct of [1,1-bis(diphenylphosphino)ferrocene]palladium (II) dichloride (3.3 g), 1,1-bis(diphenylphosphino)ferrocene (2.2 g), potassium acetate (117.2 g), and 1,4-dioxane (1.3 L) were stirred for 22 hours at 105 C. The reaction mixture was filtered and washed with dioxane and toluene. The filtrate was concentrated under reduced pressure and ethyl acetate was added. The mixture was washed with saturated saline. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography, thus obtaining Compound K (90.1 g, 308 mmol).

(106) ##STR00369##

Preparation Example 38

Synthesis of Compound L

(107) Under a nitrogen atmosphere, 1,5-dihydroxynaphthalene (15.0 g), triethylamine (28.5 g), and chloroform (150 mL) were mixed and cooled to 0 C. Trifluoromethanesulfonic acid anhydride (68.7 g) was added dropwise, and the reaction mixture was stirred for 1 hour. Water and chloroform were added to the reaction mixture. The water layer was removed and the organic layer was washed with water. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was purified by recrystallization, thus obtaining Compound L (31.46 g). In the following formula, Tf represents a trifluoromethylsulfonyl group.

(108) ##STR00370##

Preparation Example 39

Synthesis of Compound M

(109) Under a nitrogen atmosphere, Compound L (16.90 g), Compound K (23.30 g), tetrakis(triphenylphosphine) palladium (0) (4.60 g), potassium phosphate (42.30 g), and 1,2-dimethoxyethane (340 mL) were stirred for 14 hours at 80 C., and the reaction mixture was filtered and washed with chloroform and methanol. The filtrate was concentrated under reduced pressure and the concentrate product was purified by silica gel column chromatography, thus obtaining Compound M (8.85 g).

(110) ##STR00371##

Preparation Example 40

Synthesis of Compound N

(111) Under a nitrogen atmosphere, Compound M (8.80 g), 2-[2-(2-methoxyethoxy)ethoxy]-ethyl-p-toluenesulfonate (12.52 g), dimethylformamide (380 mL), potassium carbonate (13.32 g), and 18-crown-6 (1.02 g) were stirred for 23 hours at 100 C. The reaction mixture was added to water and extracted with ethyl acetate. The organic layer was washed with a sodium chloride aqueous solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography, thus obtaining Compound N (7.38 g)

(112) ##STR00372##

Preparation Example 41

Synthesis of Compound O

(113) Under a nitrogen atmosphere, Compound N (5.53 g), bis(pinacolato)diboron (11.25 g), (1,5-cyclooctadiene) (methoxy) iridium (I) dimer (0.15 g, manufactured by Sigma-Aldrich Co., Ltd.), 4,4-di-tert-butyl-2,2-dipyridyl (0.12 g, manufactured by Sigma-Aldrich Co., Ltd.), and 1,4-dioxane (300 mL) were stirred for 19 hours at 110 C., and the reaction mixture was concentrated under reduced pressure. The crude product was purified by silica gel column chromatography, and subsequently, the product was purified by recrystallization, thus obtaining Compound O (5.81 g).

(114) .sup.1H NMR (400 MHz, CDCl.sub.3, rt): (ppm)=1.27-1.41 (30H), 3.39 (6H), 3.57 (4H), 3.66-3.75 (8H), 3.83 (4H), 3.99 (4H), 4.27-4.42 (8H), 7.13 (2H), 7.60 (2H), 7.76 (2H), 7.93 (2H), 8.30 (2H).

(115) ##STR00373##

Preparation Example 42

Synthesis of Polymer Compound K

(116) Under an argon atmosphere, Compound H (0.53 g), Compound O (0.43 g), dichlorobis(triphenylphosphine) palladium (0.3 mg), Aliquat 336 (5 mg, manufactured by Sigma-Aldrich Co., Ltd.), toluene (12 mL), and 2 mol/L sodium carbonate aqueous solution (1 mL) were stirred for 9 hours at 105 C. Subsequently, phenylboronic acid (23 mg) was added and the mixture was stirred for 14 hours at 105 C. Sodium diethyldithiocarbamate trihydrate (0.40 g) and water (8 mL) were added to the reaction mixture, and the obtained mixture was stirred for 2 hours at 80 C. The mixture was added dropwise into methanol, and the deposit was recovered by filtration and dried. The solid was dissolved in chloroform and purified by alumina and silica gel column chromatography. The eluted solution was added dropwise into methanol, and the deposit was recovered by filtration and dried, thus obtaining Polymer Compound K (0.56 g).

(117) The polystyrene-equivalent number average molecular weight of Polymer Compound K was 3.410.sup.4. Polymer Compound K is made of a structural unit represented by Formula (W).

(118) ##STR00374##

Preparation Example 43

Synthesis of Cesium Salt of Polymer Compound K (Conjugated Polymer Compound 14)

(119) Under an argon atmosphere, Polymer Compound K (0.25 g), THF (13 mL), methanol (6 mL), cesium hydroxide monohydrate (69 mg), and water (1 mL) were stirred for 6 hours at 65 C. The reaction mixture was concentrated and added dropwise into isopropanol, and the solid was recovered by filtration and dried. Methanol was added to the solid and the mixture was filtered. The filtrate was added dropwise into isopropanol, and the obtained solid was recovered by filtration and dried, thus obtaining a cesium salt of Polymer Compound K (0.19 g). The obtained cesium salt of Polymer Compound K is called Conjugated Polymer Compound 14. Conjugated Polymer Compound 14 is made of a structural unit represented by Formula (X).

(120) ##STR00375##

(121) An orbital energy of HOMO of Conjugated Polymer Compound 14 was 5.50 eV and an orbital energy of LUMO was 2.65 eV.

Preparation Example 44

Synthesis of Compound P

(122) Under a nitrogen atmosphere, Compound K (60.01 g), 1,4-dibromo-2-iodobenzene (111.61 g, synthesized by the method described in Angew. Chem. Int. Ed. 2008, 888-890), tetrakis(triphenylphosphine) palladium (0) (12.32 g), silver carbonate (84.95 g), and THF (1200 mL) were stirred for 11 hours at 65 C. The reaction mixture was filtered and washed with THF and toluene. The filtrate was concentrated under reduced pressure and the concentrated filtrate was purified by silica gel column chromatography, thus obtaining Compound P (36.82 g).

(123) ##STR00376##

Preparation Example 45

Synthesis of Compound Q

(124) Under a nitrogen atmosphere, Compound P (22.0 g), 2-[2-(2-methoxyethoxy)ethoxy]-ethyl-p-toluenesulfonate (17.8 g), dimethylformamide (370 mL), potassium carbonate (18.31 g), and 18-crown-6 (2.30 g) were stirred for 14 hours at 95 C. Water was added to the reaction mixture and extracted with ethyl acetate. The organic layer was washed with a saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography, thus obtaining Compound Q (26.30 g)

(125) .sup.1H NMR (400 MHz, CDCl.sub.3, rt): (ppm)=1.38 (3H), 3.38 (3H), 3.55 (2H), 3.62-3.71 (4H), 3.78 (2H), 3.93 (2H), 4.25 (2H), 4.36 (2H), 7.04 (1H), 7.32 (1H), 7.44-7.53 (3H), 7.80 (1H).

(126) ##STR00377##

Preparation Example 46

Synthesis of Polymer Compound L

(127) Under an argon atmosphere, Compound I (1.09 g), Compound Q (0.41 g), dichloro bis(triphenylphosphine) palladium (1.1 mg), methyltrioctylammonium chloride (manufactured by Sigma-Aldrich Co., Ltd., trade name Aliquat 336 (registered trademark)) (8 mg), toluene (18 mL), and 2 mol/L sodium carbonate aqueous solution (2 mL) were stirred for 23 hours at 105 C., and subsequently, phenylboronic acid (37 mg) was added and the mixture was stirred for 6 hours at 105 C. Water was added to the reaction mixture and the organic layer was concentrated under reduced pressure, thus obtaining Polymer Compound L (1.26 g).

(128) The polystyrene-equivalent number average molecular weight of Polymer Compound L was 810.sup.3. Polymer Compound L is made of a structural unit represented by Formula (Y).

(129) ##STR00378##

Preparation Example 47

Synthesis of Cesium Salt of Polymer Compound L (Conjugated Polymer Compound 15)

(130) Under an argon atmosphere, Polymer Compound L (0.20 g), THF (13 mL), methanol (6 mL), cesium hydroxide monohydrate (40 mg), and water (1 mL) were stirred for 4 hours at 70 C., and the reaction mixture was concentrated under reduced pressure. Water was added to the solid and the mixture was filtered. The solid was dried, thus obtaining a cesium salt of Polymer Compound L (0.19 g). The obtained cesium salt of Polymer Compound L is called Conjugated Polymer Compound 15. Conjugated Polymer Compound 15 is made of a structural unit represented by Formula (Z).

(131) ##STR00379##

(132) An orbital energy of HOMO of Conjugated Polymer Compound 15 was 5.67 eV and an orbital energy of LUMO was 2.59 eV.

Example 1

Preparation of Composition 1

(133) Conjugated Polymer Compound 1 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 1 made of Conjugated Polymer Compound 1 and cesium hydroxide.

Example 2

Preparation of Composition 2

(134) Conjugated Polymer Compound 2 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 2 made of Conjugated Polymer Compound 2 and cesium hydroxide.

Example 3

Preparation of Composition 3

(135) Conjugated Polymer Compound 3 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 3 made of Conjugated Polymer Compound 3 and cesium hydroxide.

Example 4

Preparation of Composition 4

(136) Conjugated Polymer Compound 4 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 4 made of Conjugated Polymer Compound 4 and cesium hydroxide.

Example 5

Preparation of Composition 5

(137) Conjugated Polymer Compound 5 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 5 made of Conjugated Polymer Compound 5 and cesium hydroxide.

Example 6

Preparation of Composition 6

(138) Conjugated Polymer Compound 6 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 6 made of Conjugated Polymer Compound 6 and cesium hydroxide.

Example 7

Preparation of Composition 7

(139) Conjugated Polymer Compound 7 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 7 made of Conjugated Polymer Compound 7 and cesium hydroxide.

Example 8

Preparation of Composition 8

(140) Conjugated Polymer Compound 8 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 8 made of Conjugated Polymer Compound 8 and cesium hydroxide.

Example 9

Preparation of Composition 9

(141) Conjugated Polymer Compound 9 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 9 made of Conjugated Polymer Compound 9 and cesium hydroxide.

Example 10

Preparation of Composition 10

(142) Conjugated Polymer Compound 10 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 10 made of Conjugated Polymer Compound 10 and cesium hydroxide.

Example 11

Preparation of Composition 11

(143) Conjugated Polymer Compound 11 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 11 made of Conjugated Polymer Compound 11 and cesium hydroxide.

Example 12

Preparation of Composition 12

(144) Conjugated Polymer Compound 12 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 12 made of Conjugated Polymer Compound 12 and cesium hydroxide.

Example 13

Preparation of Composition 13

(145) Conjugated Polymer Compound 13 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 13 made of Conjugated Polymer Compound 13 and cesium hydroxide.

Example 14

Preparation of Composition 14

(146) Conjugated Polymer Compound 14 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 14 made of Conjugated Polymer Compound 14 and cesium hydroxide.

Example 15

Preparation of Composition 15

(147) Conjugated Polymer Compound 15 (2 mg) and cesium hydroxide monohydrate (0.2 mg) were mixed, thus obtaining Composition 15 made of Conjugated Polymer Compound 15 and cesium hydroxide.

Example 16

Preparation of Composition 16

(148) Conjugated Polymer Compound 10 (2 mg) and cesium hydroxide monohydrate (0.1 mg) were mixed, thus obtaining Composition 16 made of Conjugated Polymer Compound 10 and cesium hydroxide.

Example 17

Preparation of Composition 17

(149) Conjugated Polymer Compound 10 (2 mg) and cesium hydroxide monohydrate (0.4 mg) were mixed, thus obtaining Composition 17 made of Conjugated Polymer Compound 10 and cesium hydroxide.

Example 18

Preparation of Composition 18

(150) Conjugated Polymer Compound 10 (2 mg) and cesium hydroxide monohydrate (1 mg) were mixed, thus obtaining Composition 18 made of Conjugated Polymer Compound 10 and cesium hydroxide.

Example 19

Preparation of Composition 19

(151) Conjugated Polymer Compound 1 (2 mg) and cesium acetate (0.2 mg) were mixed, thus obtaining Composition 19 made of Conjugated Polymer Compound 1 and cesium acetate.

Example 20

Preparation of Composition 20

(152) Conjugated Polymer Compound 1 (2 mg) and cesium benzoate (0.2 mg) were mixed, thus obtaining Composition 20 made of Conjugated Polymer Compound 1 and cesium benzoate.

Example 21

Preparation of Composition 21

(153) Conjugated Polymer Compound 1 (2 mg) and sodium benzoate (0.2 mg) were mixed, thus obtaining Composition 21 made of Conjugated Polymer Compound 1 and sodium benzoate.

Preparation Example 48

Synthesis of Compound R

(154) Under a nitrogen atmosphere, ethyl salicylate (5.0 g), 2-[2-(2-methoxyethoxy)ethoxy]-ethyl-p-toluenesulfonate (10.1 g), potassium carbonate (6.24 g), and dimethylformamide (20 mL) were stirred for 3 hours at 100 C., and the reaction mixture was added to water and the obtained mixture was extracted with chloroform. The organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography, thus obtaining Compound R (8.78 g)

(155) ##STR00380##

Preparation Example 49

Synthesis of Compound S

(156) Under a nitrogen atmosphere, Compound R (1.00 g), methanol (5 mL), cesium hydroxide monohydrate (0.57 g), and water (2 mL) were stirred for 5 hours at 80 C., and the reaction mixture was concentrated under reduced pressure. The solid was dried, thus obtaining Compound S (1.36 g).

(157) ##STR00381##

Example 22

Preparation of Composition 22

(158) Conjugated Polymer Compound 1 (2 mg) and Compound S (0.2 mg) were mixed, thus obtaining Composition 22 made of Conjugated Polymer Compound 1 and Compound S.

Example 23

Preparation of Composition 23

(159) Conjugated Polymer Compound 1 (2 mg) and potassium methoxide (0.2 mg) were mixed, thus obtaining Composition 23 made of Conjugated Polymer Compound 1 and potassium methoxide.

Example 24

Preparation of Composition 24

(160) Conjugated Polymer Compound 1 (2 mg) and cesium carbonate (0.2 mg) were mixed, thus obtaining Composition 24 made of Conjugated Polymer Compound 1 and cesium carbonate.

Example 25

Preparation of Composition 25

(161) Conjugated Polymer Compound 1 (2 mg) and sodium tetraphenylborate (0.2 mg) were mixed, thus obtaining Composition 25 made of Conjugated Polymer Compound 1 and sodium tetraphenylborate.

Example 26

Preparation of Electroluminescent Device 1

(162) A hole injection material solution was applied onto an ITO anode (thickness: 45 nm) that was formed and patterned on a surface of a glass substrate by a spin coating method to form a film of a hole injection layer having a thickness of 60 nm. The glass substrate on which the film of the hole injection layer was formed was heated for 10 minutes at 200 C. under an inert atmosphere (under a nitrogen atmosphere) to insolubilize the hole injection layer. The substrate was naturally cooled to room temperature, thus obtaining a substrate on which the hole injection layer was formed.

(163) Here, as the hole injection material solution, AQ-1200 being a polythiophene-sulfonic acid-based hole injection material obtained from Plextronics Inc. was used.

(164) Subsequently, Hole Transport Polymer Material A and xylene were mixed, thus obtaining Hole Transport Layer Forming Composition A including 0.7% by weight of Hole Transport Polymer Material A.

(165) Here, Hole Transport Polymer Material A was synthesized by the following method.

(166) Under an inert gas atmosphere, 2,7-dibromo-9,9-di(octyl)fluorene (1.4 g), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-di(octyl)fluorene (6.4 g), N,N-bis(4-bromophenyl)-N,N-bis(4-butylphenyl)-1,4-phenylenediamine (4.1 g), bis(4-bromophenyl)benzocyclobuteneamine (0.6 g), tetraethylammonium hydroxide (1.7 g), palladium acetate (4.5 mg), tri(2-methoxy-phenyl)phosphine (0.03 g), and toluene (100 mL) were mixed and the mixture was heated and stirred for 2 hours at 100 C. Subsequently, phenylboronic acid (0.06 g) was added and the obtained mixture was stirred for 10 hours. After the mixture was allowed to cool, the water layer was removed. After sodium diethyldithiocarbamate aqueous solution was added and stirred, the water layer was removed and the organic layer was washed with water and 3% by weight acetic acid aqueous solution. After the organic layer was poured to methanol to precipitate a polymer, the polymer separated by filtration was dissolved in toluene again. The solution was flown though columns of silica gel and alumina. The eluted toluene solution including the polymer was recovered, and the recovered toluene solution was poured to methanol to precipitate the polymer. The precipitated polymer was separated by filteration and dried under vacuum at 50 C., thus obtaining Hole Transport Polymer Material A. The polystyrene-equivalent weight average molecular weight of Hole Transport Polymer Material A was 3.010.sup.5.

(167) Onto the above-obtained hole injection layer on the substrate on which the hole injection layer was formed, Hole Transport Layer Forming Composition A was applied by the spin coating method, thus obtaining a coating film having a thickness of 20 nm. After the substrate having the coating film was heated for 60 minutes at 180 C. under an inert atmosphere (a nitrogen atmosphere) to insolubilize the coating film, the substrate was naturally cooled to room temperature, thus obtaining the substrate on which a hole transport layer was formed.

(168) Subsequently, Light Emitting Polymer Material A and xylene were mixed, thus obtaining Light Emitting Layer Forming Composition A including 1.4% by weight of Light Emitting Polymer Material A.

(169) Here, Light Emitting Polymer Material A was synthesized by the following method.

(170) Under an inert gas atmosphere, 2,7-dibromo-9,9-di(octyl)fluorene (9.0 g), N,N-bis(4-bromophenyl)-N,N-bis(4-tert-butyl-2,6-dimethylphenyl)1,4-phenylenediamine (1.3 g), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-di(4-hexylphenyl)fluorene (13.4 g), tetraethylammonium hydroxide (43.0 g), palladium acetate (8 mg), tri(2-methoxyphenyl)phosphine (0.05 g), and toluene (200 mL) were mixed and the mixture was heated and stirred for 8 hours at 90 C. Subsequently, phenylboronic acid (0.22 g) was added and the obtained mixture was stirred for 14 hours. After the mixture was allowed to cool, the water layer was removed. After sodium diethyldithiocarbamate aqueous solution was added and stirred, the water layer was removed and the organic layer was washed with water and 3% by weight acetic acid aqueous solution. After the organic layer was poured to methanol to precipitate a polymer, the polymer separated by filtration was dissolved in toluene again. The solution was flown though columns of silica gel and alumina. The eluted toluene solution including the polymer was recovered, and the recovered toluene solution was poured to methanol to precipitate the polymer. The precipitated polymer was dried under vacuum at 50 C., thus obtaining Light Emitting Polymer Material A (12.5 g). According to gel permeation chromatography, the polystyrene-equivalent weight average molecular weight of Light Emitting Polymer Material A was 3.110.sup.5.

(171) Onto the above-obtained hole transport layer over the substrate over which the hole transport layer was formed, Light Emitting Layer Forming Composition A was applied by the spin coating method, thus obtaining a coating film having a thickness of 80 nm. After the substrate having the coating film was heated for 10 minutes at 130 C. under an inert atmosphere (a nitrogen atmosphere) to evaporate the solvent, the substrate was naturally cooled to room temperature, thus obtaining the substrate over which a light emitting layer was formed.

(172) Methanol and Composition 1 were mixed, thus obtaining a solution including 0.2% by weight of Composition 1. Onto the light emitting layer of the above-obtained substrate over which the light emitting layer was formed, the solution was applied by the spin coating method, thus obtaining a coating film having a thickness of 10 nm. After the substrate having the coating film was heated for 10 minutes at 130 C. under an inert atmosphere (a nitrogen atmosphere) to evaporate the solvent, the substrate was naturally cooled to room temperature, thus obtaining the substrate over which a layer including Composition 1 was formed.

(173) The above-obtained substrate over which a layer including Composition 1 was formed was inserted into vacuum apparatus. An Al film having a thickness of 80 nm was formed on the layer by a vacuum deposition method to form a cathode, and thereby Layered Structure 1 was prepared.

(174) The above-obtained Layered Structure 1 was taken out from the vacuum apparatus and was sealed with sealing glasses and a two-component epoxy resin under an inert atmosphere (a nitrogen atmosphere), thus obtaining Electroluminescent Device 1.

Example 27

Preparation of Electroluminescent Device 2

(175) Electroluminescent Device 2 was obtained in a similar manner to Example 26 except that Composition 2 was used instead of Composition 1 in Example 26.

Example 28

Preparation of Electroluminescent Device 3

(176) Electroluminescent Device 3 was obtained in a similar manner to Example 26 except that Composition 3 was used instead of Composition 1 in Example 26.

Example 29

Preparation of Electroluminescent Device 4

(177) Electroluminescent Device 4 was obtained in a similar manner to Example 26 except that Composition 4 was used instead of Composition 1 in Example 26.

Example 30

Preparation of Electroluminescent Device 5

(178) Electroluminescent Device 5 was obtained in a similar manner to Example 26 except that Composition 5 was used instead of Composition 1 in Example 26.

Example 31

Preparation of Electroluminescent Device 6

(179) Electroluminescent Device 6 was obtained in a similar manner to Example 26 except that Composition 6 was used instead of Composition 1 in Example 26.

Example 32

Preparation of Electroluminescent Device 7

(180) Electroluminescent Device 7 was obtained in a similar manner to Example 26 except that Composition 7 was used instead of Composition 1 in Example 26.

Example 33

Preparation of Electroluminescent Device 8

(181) Electroluminescent Device 8 was obtained in a similar manner to Example 26 except that Composition 8 was used instead of Composition 1 in Example 26.

Example 34

Preparation of Electroluminescent Device 9

(182) Electroluminescent Device 9 was obtained in a similar manner to Example 26 except that Composition 9 was used instead of Composition 1 in Example 26.

Example 35

Preparation of Electroluminescent Device 10

(183) Electroluminescent Device 10 was obtained in a similar manner to Example 26 except that Composition 10 was used instead of Composition 1 in Example 26.

Example 36

Preparation of Electroluminescent Device 11

(184) Electroluminescent Device 11 was obtained in a similar manner to Example 26 except that Composition 11 was used instead of Composition 1 in Example 26.

Example 37

Preparation of Electroluminescent Device 12

(185) Electroluminescent Device 12 was obtained in a similar manner to Example 26 except that Composition 12 was used instead of Composition 1 in Example 26.

Example 38

Preparation of Electroluminescent Device 13

(186) Electroluminescent Device 13 was obtained in a similar manner to Example 26 except that Composition 13 was used instead of Composition 1 in Example 26.

Example 39

Preparation of Electroluminescent Device 14

(187) Electroluminescent Device 14 was obtained in a similar manner to Example 26 except that Composition 14 was used instead of Composition 1 in Example 26.

Example 40

Preparation of Electroluminescent Device 15

(188) Electroluminescent Device 15 was obtained in a similar manner to Example 26 except that Composition 15 was used instead of Composition 1 in Example 26.

Example 41

Preparation of Electroluminescent Device 16

(189) Electroluminescent Device 16 was obtained in a similar manner to Example 26 except that Composition 16 was used instead of Composition 1 in Example 26.

Example 42

Preparation of Electroluminescent Device 17

(190) Electroluminescent Device 17 was obtained in a similar manner to Example 26 except that Composition 17 was used instead of Composition 1 in Example 26.

Example 43

Preparation of Electroluminescent Device 18

(191) Electroluminescent Device 18 was obtained in a similar manner to Example 26 except that Composition 18 was used instead of Composition 1 in Example 26.

Example 44

Preparation of Electroluminescent Device 19

(192) Electroluminescent Device 19 was obtained in a similar manner to Example 26 except that Composition 19 was used instead of Composition 1 in Example 26.

Example 45

Preparation of Electroluminescent Device 20

(193) Electroluminescent Device 20 was obtained in a similar manner to Example 26 except that Composition 20 was used instead of Composition 1 in Example 26.

Example 46

Preparation of Electroluminescent Device 21

(194) Electroluminescent Device 21 was obtained in a similar manner to Example 26 except that Composition 21 was used instead of Composition 1 in Example 26.

Example 47

Preparation of Electroluminescent Device 22

(195) Electroluminescent Device 22 was obtained in a similar manner to Example 26 except that Composition 22 was used instead of Composition 1 in Example 26.

Example 48

Preparation of Electroluminescent Device 23

(196) Electroluminescent Device 23 was obtained in a similar manner to Example 26 except that Composition 23 was used instead of Composition 1 in Example 26.

Example 49

Preparation of Electroluminescent Device 24

(197) Electroluminescent Device 24 was obtained in a similar manner to Example 26 except that Composition 24 was used instead of Composition 1 in Example 26.

Example 50

Preparation of Electroluminescent Device 25

(198) Electroluminescent Device 25 was obtained in a similar manner to Example 26 except that Composition 25 was used instead of Composition 1 in Example 26.

Example 51

Preparation of Electroluminescent Device 26

(199) Electroluminescent Device 26 was obtained in a similar manner to Example 26 except that Ag was used instead of Al in Example 26.

Example 52

Preparation of Electroluminescent Device 27

(200) Electroluminescent Device 26 was obtained in a similar manner to Example 26 except that Au was used instead of Al in Example 26.

Comparative Example 1

Preparation of Electroluminescent Device A1

(201) Electroluminescent Device A1 was obtained in a similar manner to Example 26 except that the layer including Composition 1 was not formed and the cathode was directly formed on the light emitting layer in Example 26.

Comparative Example 2

Preparation of Electroluminescent Device A2

(202) Electroluminescent Device A2 was obtained in a similar manner to Example 51 except that the layer including Composition 1 was not formed and the cathode was directly formed on the light emitting layer in Example 51.

Comparative Example 3

Preparation of Electroluminescent Device A3

(203) Electroluminescent Device A3 was obtained in a similar manner to Example 52 except that the layer including Composition 1 was not formed and the cathode was directly formed on the light emitting layer in Example 52.

(204) [Evaluation of Electroluminescent Device]

(205) To Electroluminescent Devices 1 to 27 and Electroluminescent Devices A1 to A3, 10 V of forward direction voltage was applied and light emitting brightness and light emitting efficiency were measured. The results are listed in Table 1.

(206) TABLE-US-00001 TABLE 1 LUMINOUS BRIGHTNESS EFFICIENCY COMPOSITION CATHODE (cd/m.sup.2) (cd/A) EXAMPLE 26 COMPOSITION 1 Al 5855.3 3.56 (ELECTROLUMINESCENT DEVICE 1) EXAMPLE 27 COMPOSITION 2 Al 5618.6 3.31 (ELECTROLUMINESCENT DEVICE 2) EXAMPLE 28 COMPOSITION 3 Al 4490.0 3.69 (ELECTROLUMINESCENT DEVICE 3) EXAMPLE 29 COMPOSITION 4 Al 1535.0 3.23 (ELECTROLUMINESCENT DEVICE 4) EXAMPLE 30 COMPOSITION 5 Al 2976.7 2.85 (ELECTROLUMINESCENT DEVICE 5) EXAMPLE 31 COMPOSITION 6 Al 8762.7 3.08 (ELECTROLUMINESCENT DEVICE 6) EXAMPLE 32 COMPOSITION 7 Al 2748.7 2.89 (ELECTROLUMINESCENT DEVICE 7) EXAMPLE 33 COMPOSITION 8 Al 502.1 2.41 (ELECTROLUMINESCENT DEVICE 8) EXAMPLE 34 COMPOSITION 9 Al 2677.0 3.40 (ELECTROLUMINESCENT DEVICE 9) EXAMPLE 35 COMPOSITION 10 Al 4713.3 3.14 (ELECTROLUMINESCENT DEVICE 10) EXAMPLE 36 COMPOSITION 11 Al 4452.9 1.02 (ELECTROLUMINESCENT DEVICE 11) EXAMPLE 37 COMPOSITION 12 Al 9356.0 3.11 (ELECTROLUMINESCENT DEVICE 12) EXAMPLE 38 COMPOSITION 13 Al 4385.1 3.73 (ELECTROLUMINESCENT DEVICE 13) EXAMPLE 39 COMPOSITION 14 Al 6532.6 3.27 (ELECTROLUMINESCENT DEVICE 14) EXAMPLE 40 COMPOSITION 15 Al 374.8 1.80 (ELECTROLUMINESCENT DEVICE 15) EXAMPLE 41 COMPOSITION 16 Al 3476.0 2.88 (ELECTROLUMINESCENT DEVICE 16) EXAMPLE 42 COMPOSITION 17 Al 5148.0 3.69 (ELECTROLUMINESCENT DEVICE 17) EXAMPLE 43 COMPOSITION 18 Al 6102.4 3.44 (ELECTROLUMINESCENT DEVICE 18) EXAMPLE 44 COMPOSITION 19 Al 6662.9 4.47 (ELECTROLUMINESCENT DEVICE 19) EXAMPLE 45 COMPOSITION 20 Al 4664.2 4.71 (ELECTROLUMINESCENT DEVICE 20) EXAMPLE 46 COMPOSITION 21 Al 8534.1 5.07 (ELECTROLUMINESCENT DEVICE 21) EXAMPLE 47 COMPOSITION 22 Al 5161.1 4.93 (ELECTROLUMINESCENT DEVICE 22) EXAMPLE 48 COMPOSITION 23 Al 19554.8 3.80 (ELECTROLUMINESCENT DEVICE 23) EXAMPLE 49 COMPOSITION 24 Al 6549.0 4.30 (ELECTROLUMINESCENT DEVICE 24) EXAMPLE 50 COMPOSITION 25 Al 6410.8 5.14 (ELECTROLUMINESCENT DEVICE 25) EXAMPLE 51 COMPOSITION 1 Ag 96.1 1.10 (ELECTROLUMINESCENT DEVICE 26) EXAMPLE 52 COMPOSITION 1 Au 19.1 0.22 (ELECTROLUMINESCENT DEVICE 27) COMPARATIVE EXAMPLE 1 NOT INCLUDED Al 1.50 0.01 (ELECTROLUMINESCENT DEVICE A1) COMPARATIVE EXAMPLE 2 NOT INCLUDED Ag 12.8 0.5 (ELECTROLUMINESCENT DEVICE A2) COMPARATIVE EXAMPLE 3 NOT INCLUDED Au NOT EMIT NOT EMIT (ELECTROLUMINESCENT DEVICE A3)

Preparation Example 50

Synthesis of Silver Nanostructure A

(207) A flask having a capacity of 50 mL in which 5 ml of ethylene glycol was placed was immersed in an oil bath of 150 C., and pre-heating was carried out with ethylene glycol being bubbled with air for 60 minutes. After the pre-heating, the atmosphere in the flask was replaced with nitrogen gas by switching air to nitrogen gas and the bubbling was stopped. Subsequently, 1.5 mL of 0.1 M silver nitrate-ethylene glycol solution, 1.5 mL of 0.15 mol/L polyvinylpyrrolidone-ethylene glycol solution (polyvinylpyrrolidone may be abbreviated to PVP, manufactured by Sigma-Aldrich Corp., weight average molecular weight listed in the catalog: 5.510.sup.4), and 40 L of 4 mmol/L copper chloride dihydrate-ethylene glycol solution were poured and stirred for 120 minutes, thus obtaining a dispersion of silver nanostructure. After the obtained dispersion was cooled to 40 C., the dispersion was centrifuged to obtain a precipitate. The obtained precipitate was dried, thus obtaining a silver nanostructure (hereinafter referred to as Silver Nanostructure A).

(208) When the obtained Silver Nanostructure A was visually inspected using a photograph taken by a scanning electron microscope (manufactured by JEOL Ltd., trade name: JSM-5500) (hereinafter referred to as SEM), Silver Nanostructures A had a shape of a wire, an average value of the shortest diameter of about 30 nm, and an average value of the longest diameter of 15 m. An average value of the aspect ratio of at least ten Silver Nanostructures A observed by the method described above was about 500.

Preparation Example 51

Synthesis of Composition 26

(209) Conjugated Polymer Compound 1 (2 mg) and cesium hydroxide monohydrate (0.7 mg) were mixed, thus obtaining Composition 26 made of Conjugated Polymer Compound 1 and cesium hydroxide.

Preparation Example 52

Synthesis of Composition for Cathode A

(210) Silver Nanostructure A (10.0 mg) was mixed with 1.3 mL of water and the mixture was stirred for 1 hour to prepare Composition for Cathode A.

Example 53

Preparation of Electroluminescent Device 28

(211) A hole injection material solution was applied onto an ITO anode (thickness: 45 nm) that is formed and patterned on a surface of a glass substrate by a spin coating method to form a film of a hole injection layer having a thickness of 70 nm. The glass substrate on which the film of the hole injection layer was formed was heated for 10 minutes at 200 C. under an inert atmosphere (under a nitrogen atmosphere) to insolubilize the hole injection layer. The substrate was naturally cooled to room temperature, thus obtaining a substrate on which the hole injection layer was formed.

(212) Here, as the hole injection material solution, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (manufactured by H. C. Starck GmbH, PEDOT: PSS solution, product name: CLEVIOS (registered trademark) P VP AI 4083) was used.

(213) Subsequently, Hole Transport Polymer Material A and xylene were mixed, thus obtaining Hole Transport Layer Forming Composition B including 0.6% by weight of Hole Transport Polymer Material A.

(214) Onto the above-obtained hole injection layer on the substrate on which the hole injection layer was formed, Hole Transport Layer Forming Composition B was applied by the spin coating method, thus obtaining a coating film having a thickness of 33 nm. After the substrate having the coating film was heated for 20 minutes at 200 C. under an inert atmosphere (a nitrogen atmosphere) to insolubilize the coating film, the substrate was naturally cooled to room temperature, thus obtaining the substrate over which a hole transport layer was formed.

(215) Subsequently, Light Emitting Polymer Material A and xylene were mixed, thus obtaining Light Emitting Layer Forming Composition B including 1.3% by weight of Light Emitting Polymer Material A.

(216) Onto the above-obtained hole transport layer over the substrate over which the hole transport layer was formed, Light Emitting Layer Forming Composition B was applied by the spin coating method, thus obtaining a coating film having a thickness of 99 nm. After the substrate having the coating film was heated for 15 minutes at 130 C. under an inert atmosphere (a nitrogen atmosphere) to evaporate the solvent, the substrate was naturally cooled to room temperature, thus obtaining the substrate over which a light emitting layer was formed.

(217) Methanol and Composition 26 were mixed, thus obtaining a solution including 0.2% by weight of Composition 26. Onto the above-obtained light emitting layer over the substrate over which the light emitting layer was formed, the solution was applied by the spin coating method, thus obtaining a coating film having a thickness of 10 nm. After the substrate having the coating film was heated for 10 minutes at 130 C. under an inert atmosphere (a nitrogen atmosphere) to evaporate the solvent, the substrate was naturally cooled to room temperature, thus obtaining the substrate over which a layer including Composition 26 was formed.

(218) Composition for Cathode A was applied to the above-obtained substrate over which the layer including Compound 26 was formed to form a coating film having a thickness of about 200 nm. After the substrate over which the coating film was formed was heated for 10 minutes at 130 C. under a nitrogen atmosphere to evaporate the solvent, the substrate was naturally cooled to room temperature, thus obtaining Layered Structure 2 in which a cathode was formed.

(219) The above-obtained Layered Structure 2 was sealed with sealing glasses and a two-component epoxy resin under an inert atmosphere (a nitrogen atmosphere), thus obtaining Electroluminescent Device 28.

Example 54

Preparation of Electroluminescent Device 29

(220) Electroluminescent Device 29 was obtained in a similar manner to Example 53 except that, instead of Cathode Composition A, a cathode was formed in a manner that Cathode Composition B that is a dispersion of silver nanoparticles having a number average Feret diameter of 7 nm (NPS-JL, manufactured by Harima Chemicals, Ltd., aspect ratio of silver particles: 1.0) was applied by the casting method to form a coating film having a thickness of 200 nm, the substrate over which the coating film was formed being heated for 10 minutes at 130 C. under a nitrogen atmosphere to evaporate the solvent, and the sample being naturally cooled to room temperature to form a cathode.

Comparative Example 4

Preparation of Electroluminescent Device A4

(221) Electroluminescent Device A4 was obtained in a similar manner to Example 53 except that the layer including Composition 26 was not formed in Example 53.

Comparative Example 5

Preparation of Electroluminescent Device A5

(222) Electroluminescent Device A5 was obtained in a similar manner to Example 54 except that the layer including Composition 26 was not formed in Example 54.

(223) [Evaluation of Electroluminescent Device]

(224) To Electroluminescent Devices 28 and 29 and Electroluminescent Devices A4 and A5, 14 V of forward direction voltage was applied and light emitting brightness and light emitting efficiency were measured. The results are listed in Table 2.

(225) TABLE-US-00002 TABLE 2 Light Light emission emission brightness efficiency Composition Cathode (cd/m.sup.2) (cd/A) Example 53 Composition Silver Nano- 21.0 0.41 (Electroluminescent 26 structure A Device 28) Example 54 Composition Silver 409.7 1.82 (Electroluminescent 26 nanoparticle Device 29) Comparative None Silver Nano- Not Not Example 4 structure A emitted emitted (Electroluminescent Device A4) Comparative None Silver Not Not Example 5 nanoparticle emitted emitted (Electroluminescent Device A5)

(226) As is clear from Table 1 and Table 2, the electroluminescent devices including the composition of the present invention emits light in high brightness compared with the electroluminescent devices not including the composition. In addition, the electroluminescent device including the composition of the present invention has high light emitting efficiency compared with the electroluminescent device not including the composition.