TWI322157B - Electroluminescent polymer, and light-emitting element and light-emitting device using the same - Google Patents

Description

[Technical Field] The present invention relates to a polymer electroluminescent material, n n , and a light-emitting element and a light-emitting device using the same. [Prior Art] Since the angle of view of the conventional liquid crystal display is wide and the anti-coin is fast, the development of the light-emitting element using the organic light-emitting material has been quite active recently. In the case of using an organic compound as a light-emitting material, it is expected to realize a self-luminous source and a flat display having a high reaction speed regardless of the viewing angle. When these light-emitting elements are incorporated in consumer electronic devices such as digital cameras, personal digital assistants (PDAs), and video telephones, they provide advantages such as low power consumption, high brightness, and slim design. Representative examples of the light-emitting element are a light-emitting diode device such as an Organic Light-Emitting Diode (OLED) and a high molecular light-emitting diode (PLED). In general, an organic light-emitting diode device has a film disposed between a transparent anode and a metal cathode, the film comprising a luminescent material that emits light via an applied current. In order to manufacture a full-color light-emitting diode display panel, it is necessary to have high-efficiency red, green, and blue electroluminescent materials having sufficient luminous efficiency and appropriate chromaticity. A red light material 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostryl)-4 //-pyran (DCM) and its derivatives have been proposed by Kodak Company in U.S. Patent 4,769,292, but the luminous efficiency of the material And the wavelength of the light is still to be improved.丄J厶厶上J/ Therefore, it is necessary to mention the 屮 丄 ', and the red light material with longer luminous efficiency and longer illuminating wavelength, which is applied to the red-haired first-pole device with long wall length , so that organic light has a more display quality. Fang Feifa has no device [invention] to provide a light-emitting layer that can be used as a light-emitting element

The main purpose of the present invention is an electroluminescent material. Another main effect of the present invention is to provide an electroluminescent material which can serve as a red light-emitting element light-emitting layer. In order to achieve the above and other objects, the present invention provides a polymer electroluminescent material having the structure represented by the following formula: "10" Adn where 11 is a positive integer, preferably a positive integer greater than 1, preferably For a positive integer between 20 and 90, χ is the molar fraction, between 〇99, Α represents a substituted or unsubstituted oxime group, and β represents a formula (II), formula (III). Or a group represented by formula (IV): (II)

(III) 1322157

To achieve the above and other objects, the present invention further provides an electroluminescent material having a structure represented by the following formula (V), formula (VI) or formula (VII). (V)

(VI)

To achieve the above and other objects, the present invention further provides a light-emitting element or a light-emitting device manufactured using the aforementioned electroluminescent material. [Embodiment] The present invention relates to an electroluminescent material which can be used to manufacture a light-emitting element. The light-emitting element can be applied to a light-emitting device such as a display (television or screen), a backlight, a light source, and the like. The present invention provides a polymer electroluminescent material having a structure represented by the following formula (I): a positive integer of 10, preferably 'between 0.005 and 0.99, where η is a positive integer, preferably greater than 1 A positive integer between 20 and 90, which is between the molar fractions. 'Substituted or unsubstituted In the structural formula (I), fluorene represents a fluorene group, and its structure is as follows:

It is to be understood that the argon atom in the above structure may be optionally substituted by halogen, alkyl, sulfalkyl, alkoxy, alkenyl, alkynyl, alkenyloxy, methoxy or aryl. Wherein the alkyl group, the alkoxy group, the alkenyl group, the late group, the alkenyl group, the alkynyl group preferably have 1 to 12 carbon atoms, and may be a direct bond or a bond. B of the formula (I) represents a group as shown in formula (II), formula (III) or formula (IV):

(II)

(III) 1322157

The present invention further provides an electroluminescent material having a structure as shown in the following formula (V), formula (VI) or formula (VII): (V)

(VI)

12 (VII) 15221^1

In the structural formula (II) to the sister ceremony f νττ, and the mouth configuration (νπ), R, and Rz may be the same or different and each represents a hydrogen atom, a _ atom or an aryl group. The structural formula (Π) to Ari, Ar2 and Ar3 in the formula (VII) may be the same or different from each other and each represents a substituted or unsubstituted c6 to c3. An aryl group or a substituted or unsubstituted c"c3 he heteroaryl group. The aromatic group of the month 1J contains phenyl, naphthyl, and stupid. Diphenyl, anthry, pyrenyl, phenanthryl and nu〇rene or other forms of polyphenyl ring substituents. ^香香团 can be benzofuran, thiophene, pyridine, quinoUne, isoquinoline, pyrimidine, pyrrole, ° Pyrazole, imidazole, indole, thiazole, isothiazole, benzothiazole or other forms of heteronuclear aromatic rings. , Ar, Ar2 and Ar3 may be a group represented by the following structural formula Ar-1, Ar_2 'Ar-3 or Ar-4: 13 (Ar-1) (Ar-2)

(A"3) (AM)

And each represents a hydrogen atom or wherein I and R4 may be the same or different and are a substituent. The nickname I u) to the structural formula (v dan, vii) ζ ι 〇丨丨 02 are the same or different, and each represents a ring used for the gentleman z „ 乂 乂 乂 一 一 一a film of a cycloalkyl ring. ... an atomic group. The structure which can be used in the present invention is of the formula (V), the formula (VI) or the formula (VI1) = the electroluminescent material will be listed below. However, the invention is inadvertently inferred to be limited to these compounds.

14 1322157

B-4

B-6

15 1322157

B-8

The polymer electroluminescent materials used in the examples of the present invention will be listed below, but the present invention should not be construed as being limited to these polymers. (1)

16 (2) 1322157

17 (5) 1322157

The compound represented by the formula (i) according to the present invention can be copolymerized with a compound represented by the following structural formula Al, A-2 or A-3 with a compound represented by the following structural formula II-l, III-1 or IV-1. Made by:

A-l A-2 A-3 Factory 〇, 〇-\

Br-A-Br < B-A-B^ ) A represents a substituted or unsubstituted fluorene group. (Π-1)

(m-ι) 18 1322157

(IV-l)

The Br sense system is the same as the above structural formula (II) to the structural formula (VII). The synthesis example of the compound of the present invention will be described in the following Example 1 Synthesis of (4-bromophenyl)diphenylamine.

The synthetic reaction formula is as shown in the following formula 1. Take 2.66 g (ι〇〇8 • 宅耳) Diphenylamine (Triphenylamine) dissolved in 20 ml of N,N-Dimethylformamide (DMF), stir under nitrogen, take 2 12 g (11.91 millimoles of millimolar) N-Bromosuccinimide (NBS) was dissolved in 20 ml of DMF, slowly dropped into the reactor, and heated to 100 ° C for 3 hours. . After purification, the product was obtained in a yield of 86.2%. Melting point: 107~108 °C. W-NMR (Acetone-d6, ppm): δ 7.44~7.24 (m, 6Η, Ar-ϋ), 7.1 3~6.9 1 (m, 8Η, Ar-H).Anal. Calcd. for C)8HMBrN: C , 66.68 %; H, 4.35 19 1322157 %; N, 4.32 %. Found: C, 66.00 %; H, 4.28 %; N, 4.25 %. Formula 1

Example 2 Synthesis of 4-(4-bromo)aniline phenylfurfural The synthesis reaction scheme is as shown in the following formula 2. Take 8 ml of 1,2-dichloroethane and add 0.65 g (2.00 mmol) of (4-bromophenyl)diphenylamine to the ice bath. Lamine) ' 0.92 g (5.96 mmol) of Phosphorus oxychloride (POC13), 0.447 g (6.11 mmol) of dimethylformamide (DMF), mixed under aeration , slowly warm to 90 ° C for 24 hours. After purification, the product was obtained in a yield of 92.12%. 111*^]\411(八.61〇1^-(16,??111):(5 9.86~9.81(1 lH,-Cii〇), 7.79~7.70(m,2H,Ar-ii),7_56 ~7.52(m,2H, Ar-ii), 7.44-7.39 (t,2 Η, Ar-ϋ), 7.25~6.94 (m,7 H, A r - Η). Anal. Calcd. for Ci9Hi4BrNO: C, 64.79 %; H, 4.01 %; N, 3.96 %. Found: C, 65.52 %; H, 4.16 %; N, 3.96 %. Equation 2 20 1322157

Example 3 Synthesis of (2,6-dimethyl-4-hydro-furan-4-yl) malononitrile The synthetic reaction scheme is shown in the following formula 3. Take 1.25 g (10.06 mmol) of 2,6-dimethyl-γ-. More than 1 (2,6-dimethyl-y-pyrone), 0.783 g (11.85 mmol) of malononitrile dissolved in 5 ml of Acetic anhydride, mixed with nitrogen, heated React to 140 ° C for 1 hour. After purification, the product was obtained in a yield of 65.8 %. Melting point: 192~195. 'H-NMR (Acetone-d6, PPm) · δ 6.60 (s, 1Η, Ar-H), 2.74 (s, 3H, -CH3). Anal. Calcd. for C10H8N2O: C, 69.76 %; H, 4.68 % N, 16.27 %. Found: C, 69.43 %; H, 4.76 %; N, 16.12 %.

NC^ XN

Example 4 Synthesis of Compound Bl-Br The synthetic reaction scheme is shown in the following formula 4. Take 0.634 g (1.80 mmol) of 4-(4-indiylphenyl)benzine (4-((4-bromophenyl)phenylamino)benzaldehyde) and 0.148 g (0.86 mmol) 2,6-dimethyl 2,6-dimethyl-4H-pyran-4-ylidine propanedintrile dissolved 21 1322157

In 10 ml of acetonitrile (Acetonitrile), the mixture was stirred under nitrogen, and after all the solids were dissolved, 5 drops of pentylamine (Piperidine) was added and reacted at 8 ° C for 1 day. After purification, the product 4-dinitrite-Methyl-2,6-bis((4- phenyl)aniline)-phenethyl-4-nitro-anthracene (4-dicyanomethylene-2,6-bis(4- Bromophenyl) phenylamino)-styry l-4/f-pyran » D ADP-Br, compound Bl-Br), yield: 75.1%. iH_NMR (Acet〇ne-d6, ppm): $ 7.80-7.66 (m, 6H, Ar-H), 7.51-7.35 (m, 8H, Ar-H), 7.21-6.74 (m, 16H, Ar-H) , 6.39 (s, 2H, Ar-H). Anal.

Calcd. for C48H32Br2N40: C, 68.58 %; H, 3.84 %; n, 6.67 %. Found: C,67.34 %; H,4.07 %; N,6.35 % 〇, using gasoform (Chloroform, CHCI3) as solvent The B1_Br was dissolved by ultrasonic vibration at room temperature 25 ° C, and then spin-coated on a quartz glass by a spin coater at a rotation speed of 1 rpm for 1 minute to place the coated quartz glass. Vacuum was applied for 30 minutes in a vacuum oven. The spectrum of the ph〇t〇iuminescence (PL) was measured by a Hitachi F-4500 fluorescence spectrometer. See Figure 1. Equation 4

CHO

Synthesis of polymer (1) 22 1322157 Take 0.256 g (0.5 mmol) 9,9-dihexyl-2,7-di (trim shed) (9,9-dihexylfluorene-2,7-bis ( Trimethyleneborate), HFB), 0.241 g (0.49 mmol) 9,9-dihexyl-2,7-dibromofluorene (HBrF) and 4 mg (〇. 〇1 mM) Compound Bl-Br was placed in the reactor, and 6 ml of toluene (Toluene), 4 ml of 2 M cesium carbonate (K2C03) and 2 ml of ethanol were added, and the mixture was stirred under nitrogen to dissolve. .〇i gram catalyst Pd(PPh3)4, heated to 80 °C for 48 hours, can obtain 1% copolymerized polymer (polymer (1)) 0.296 g. The product can be used as an organic electroluminescent material by reprecipitation and Soxhlet extraction. Element Anal. Found: C,88.97 %; N, 0.14%; H, 9.57 %. The synthesis of the polymer (2) of Example 6 was carried out by taking 0.128 g (0.25 mmol) of 9,9-dihexyl-2,7-di(trimyl boron) (9,9-dihexylfluorene-2,7-bis). (trimethyleneborate), HFB), 0.114 g (0.225 mmol) 9,9-dihexyl-2,7-dibromofluorene (HBrF) and 21 mg (0.025) Millol) compound b 1 -Br was placed in the reactor, add 3 ml of Toluene, 2 ml of 2M carbonate (POA3) and 1 ml of ethanol, stir to dissolve under nitrogen, add 5 The milligram of catalyst Pd(PPh3)4 was heated to 8〇. (: After reacting for 48 hours, 5% of the copolymer molecules (to the molecule (2)) 0.119 g can be obtained. The product can be used as an organic electroluminescent material by re-sinking and Soxhlet extraction. Element Anal. Found: C , 85.62 %; N, 0.705 %; H, 8.90 %. 23 1322157 Example 7 Synthesis of polymer (3) Take 0.128 g (0.25 mmol) of 9,9-dihexyl-2,7-di ( (9,9-dihexylfluorene-2,7-bis(trimethyleneborate), HFB), 0.101 g (〇·20 mmol) 9,9-dihexyl-2,7-dibromoindole (9 , 9-dihexyl-2,7-dibromofluorene, HBrF) and 42 mg (0.05 mmol) of compound Bl-Br were placed in the reaction unit, and 3 ml of Toluene and 2 ml of 2 M potassium carbonate (Potassium carbonate, K2C03) and 1 ml of ethanol, stir to dissolve under nitrogen, add 5 mg of catalyst Pd(PPh3)4, and heat up to 80 °C for 48 hours to obtain 1〇〇/0 copolymerized polymer (polymer (3) )) 0.18 g. The product can be used as an organic electroluminescent material after reprecipitation and Soxhlet extraction. Element Anal. Found: C, 83.1 %; N, 1.18 %; Η, 8.37%. molecule( The synthesis of 4) is 0.128 g (0.25 mmol) of 9,9-dihexylfluorene-2,7-bis(trimethyleneborate, HFB) 61.5 mg (0.125 mmol) 9,9-dihexyl-2,7-dibromofluorene (HBrF) and 1〇5 mg (0.125 mmol) The compound Bl-Br was placed in a reactor, and 3 ml of toluene (Toluene), 2 ml of 2 M potassium carbonate (Potassium carbonate ΚΑ〇3) and 1 ml of ethanol were added to stir under nitrogen to dissolve, and 5 mg of catalyst Pd was added ( PPh3)4, heating to 80 °C for 48 hours, can obtain 25% copolymerization molecule (polymer (4)) 0.223 g. The product can be used as organic electroluminescence after re-sinking and Soxhlet 24 1322157 extraction and purification. Material: Element Anal·Found: C, 84.25 %; N, 3.04%; H, 7.51 %. Example 9 Synthesis of polymer (5) 77 mg (0.15 mmol) 9,9-dihexyl- 2,7-di(three-forked shed) (9,9-dihexylfluorene-2,7-bis (trimethyleneborate), HFB) and 126 mg (0.15 mmol) of compound Bl-Br were placed in the reactor, added 3 ML Toluene, 2 ml 2 M carbonated clock (Potassium carbonate, K2C03) and 1 ml of ethanol were stirred until dissolved by nitrogen, 3 mg of catalyst Pd(PPh3)4 was added, and the temperature was raised to 80 °C for 48 hours to obtain 50% copolymerized polymer. Polymer (5)) 0.118 g. The product can be used as an organic electroluminescent material by reprecipitation and Soxhlet extraction. Element Anal· Found: C, 82.2 0/〇; N, 5.13 0/〇; H, 6.20 %. Fabrication of Light Emitting Element The electroluminescent material of the present invention can be used as an electroluminescent medium for a light emitting element. The light-emitting element of the present invention may comprise a light-emitting layer disposed between an anode and a cathode or a plurality of organic compound layers containing the light-emitting layer. Further, an element comprising an electron transporting layer and an electromotive transfer layer may be further formed, wherein the electroluminescent material of the present invention acts as an electroluminescent layer which is disposed between the electron conducting layer and the hole conducting layer. The light-emitting element of the present invention is not limited to the system, the driving method, and the use form as long as it contains the polymer electroluminescent material of the present invention. A representative example of a light-emitting element is a light-emitting diode device such as an Organic Light-Emitting Diode (OLED) and a high score.

25 1322157 Sub-Light Emitting Diode (PLED). The structure of the light-emitting diode device is generally classified into (1) an anode light transmission type (Bottom Emission type) and (2) a cathode light transmission type (T〇p Emission • type). The anode of the Bottom Emission type device is a transparent electrode 'for example, an indium tin oxide-oxide (ιτο) electrode on a substrate (such as a glass or plastic substrate); the cathode is an opaque or reflective low work function metal Such as the Ming or calcium aluminum alloy; the electroluminescent layer is placed between the anode and the cathode, and the Luguang is emitted from the transparent anode surface. The anode of the cathode Emission type device is opaque or reflective metal such as aluminum/nickel or aluminum/titanium oxide; the cathode is a transparent low work function metal obtained by adjusting the thickness such as office, Ming, Zhenming alloy, IT The electroluminescent layer is disposed between the anode and the cathode, and the light is emitted from the transparent cathode surface. The Bottom Emission type device can be fabricated in the following manner. The device is formed by using a glass substrate, and a transparent anode, a hole injection modification layer (omitted), a hole transmission layer, a light emitting layer, and the like are sequentially formed on the substrate. Holes • Barrier layer, electron transport layer and electron injection layer (KF, potassium fluoride) (optional) and cathode. The electroluminescent medium of the present invention is formed by dissolving the above-mentioned polymer electroluminescent material into a solution by using a solvent, and coating the solution into a crucible by spin coating, inkjet or screen printing. Further, the electroluminescent medium of the present invention may be formed by vapor deposition of an electroluminescent material represented by the formula (V), the formula (VI) or the formula (VII). The following is a fabrication example of an anode light transmissive element. First, a glass substrate is provided, which is plated with IT 作为 as a first electrode, and then formed into a conductive pattern by a yellow etching process to clean 26 1322157 isopropyl alcohol to clean the IT0 in ultrasonic oscillation

After the agent, deionized water, acetone, and isopropyl substrate, the hole was transported • ethylendioxythi〇phene-p〇1ystyrenesulfonate) (speed: 3000 • rpm), and the substrate was baked at 15 〇t. Using toluene as a solvent, a solution of polymer (1) to polymer (1), a J rotation = • (1 000 rpm) to form an organic electroluminescent layer on the substrate, and then placing the substrate in a vacuum to pump the solution Dry, finally put the second electrode aluminum (A1) on the 10-5 Pa, and complete the fabrication of the light-emitting element. The results of all the components (Examples 10 to 14) are listed in Table 1, and the structure of the components is as follows: Example 10: Substrate/ITO/PEDOT: PSS/Light Emitting Layer (Polymer • (1) /A1 - Example 11: Substrate/ITO/PEDOT: PSS/Light Emitting Layer (Polymer (2)) / A1 Example 12: Substrate HTO/PEdotiPSS/Light Emitting Layer (High Score • Sub (3)) / A1 Example 13: Substrate/ITO/PEDOT: PSS/Light Emitting Layer (High Score. Sub (4)) / A1 Example 14: Substrate/IT0/PED0T: PSS/Light Emitting Layer (Polymer (5)) / A1 27 The present invention has been disclosed in the above-described preferred embodiments of the present invention, and is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS In order to make the above and other objects, features and advantages of the present invention more comprehensible, Chua's County Xiaobo·&quot; m' exemplifies a preferred embodiment and cooperates with the drawings. The details are as follows:

EXAMPLES Maximum Light-Emitting Wavelength (nm) Electrical Excitation (EL) Spectrum ^ Ten 572 See Figure 2 ~ Η 593 See Figure 3, Figure 12, 626 See Figure 4 - 13 628 See Figure 5 _ 14635 See Fig. 6 Fig. 1 1 : Photoexcitation (PL) spectrum of the compound Bl-Br. Fig. 2 is a diagram showing the photoexcitation (PL) spectrum of the light-emitting element of Example 10. 3 is a diagram showing the photoexcitation (PL) spectrum of the light-emitting element of Example 11. Flute 4: Photoexcitation (PL) spectrum of the light-emitting element of Example 12. Figure 5: Photoexcitation (PL) spectrum of the light-emitting element of Example 13. Fig. 6 is a diagram showing the photoexcitation (PL) spectrum of the light-emitting element of Example 14. 】 Main component symbol description 28

Claims (1)

1322157 X. Patent Application 1. An electroluminescent material comprising a compound represented by the following formula (I): wherein: η is a positive integer greater than 1; X is a molar fraction, and X is between 0.005 and Between 0.99; Α represents a substituted or unsubstituted oxime group; B represents a group of formula (II), formula (III) or formula (IV): (II) NCy /CN (III) NC~CN 29 1322157 (ιν) Wherein 'R! and R2 may be the same or different' and each represents a hydrogen atom, a halogen atom or a cyano group; ΑΓι, An and Ah may be the same or different, and each represents a substituted or unsubstituted C6~ a Cso aromatic group or a substituted or unsubstituted C6-C3 heteroaryl group; and Z101 and Z102 may be the same or different, and each represents a substitution or An atomic group of an unsubstituted cycloalkane ring. 2. The electroluminescent material of claim 1, wherein B represents the following structural formula B-1, ' Β·3 ' Β'4 ' Β·5, B-6 Β-7, Β-8 or Β-9 groups: Bl 3〇1322157 31 1322157 32 X) 1322157 3. The electroluminescent material according to claim i, wherein Ari, Ar2 and Ar3 each represent a group represented by the following structural formula: Αγ-1, αΓ-2, ΑΓ-3 or Αγ-4: (Ατ-1) (Αγ-2) (Αγ-3) (Αγ-4) Wherein R·3 and Han 4 may be the same or different and each represents a hydrogen atom or a substituent. 4. The electroluminescent material of claim 1, wherein n is between 2 Å and 9 Å. 5. The electroluminescent material according to claim 1, wherein the luminescent material comprises a compound represented by the following structural formula (1), (2), (3), (4) or (5): 33 (i) 1322157 (2) (3) 34 (4) (4) 1322157 (5) 6. A light-emitting element comprising: a substrate; a first electrode disposed on the substrate; a second electrode; and an electroluminescent medium sandwiched between the first electrode and the second electrode Medium), wherein the electroluminescent medium comprises a compound represented by the following formula (I): 35 1322157 wherein: η is a positive integer greater than 1; X is a molar fraction, and X is between 0.005 and 0.99; Α represents a substituted or unsubstituted anthracene group; B represents a group as shown in formula (II), formula (III) or formula (IV): (Π) (III) (IV) 36 1322157 wherein: R! and R2 may be the same or different and each represents a hydrogen atom, a halogen atom or a cyano group; An, Ah and A1·3 may be the same or different and each represents a substituted or unsubstituted C6~ C3. An aromatic group (aryl gr〇up) or a substituted or unsubstituted CrCw heteronuclear aromatic group (heter〇aryi; z, a gate or a different, and each representing a ring that is substituted or unsubstituted in the form of a moon Pm , an atomic group of a cycloalkyl ring, a light-emitting element according to item 6, wherein B, B-3, B-4, B-5, B-6, B-7, 7. If the scope of the patent application represents a group as shown in the following structural formula B-1, B-8 or b_9: B-1 37 1322157 38 1322157 B-7 8. The light-emitting element according to claim 6, wherein Ar!, Ar2 and Ar3 each represent a group represented by the following structural formula: Ar-1, Ar-2, Ar-3 or Ar-4: Ar-1) (Ar-2) (Ar-3) (Ar-4) 39 1322157 wherein r3 and r4 may be the same or different and each represents a hydrogen atom or a substituent. 9. The illuminating element of claim 6, wherein η is between 20 and 90. 10. The light-emitting element of claim 6, wherein the electroluminescent medium comprises a compound represented by the following structural formula (1), (2), (3), (4) or (5): 1) (2) 40 (3) 1322157 (5) 11. The light-emitting element of claim 6, wherein when the voltage is applied to the first electrode and the second electrode, the light-emitting element generates red light. 41