TWI293234B - White organic light-emitting diode and fabrication method - Google Patents

Description

1293234 IX. Description of the invention: [Technical field to which the invention pertains] • This case relates to a white organic electroluminescent diode and a manufacturing method thereof. More specifically, it relates to a white light which can improve performance and simplify the process. Electroluminescent diodes and methods of manufacture. [Prior Art] An Organic Light-Emitting Diode (OLED) display is a flat-panel display using an organic compound as a light-emitting material, and its structure is composed of a yin-yang electrode package. Composition, since the light must be led out, a transparent material such as indium timoxide (indium timoxide) is used as the conductive electrode, and another metal is selected as the other conductive electrode; The voltage is applied, the hole is injected by the anode and the electron is injected by the cathode, and the potential difference caused by the applied electric field causes the charge carrier to move in the film, thereby generating a cladding in the light-emitting layer (rec〇mbinati〇r〇 The electronic electricity, combined with the released energy, excites the molecules of the luminescent layer to form an excited state. When the luminescent molecules change from the excited state to the ground state, a certain proportion of the energy is released in the form of photons, and the emitted light is Electroluminescence. The luminescent color of 0LED depends on the organic material with luminescent properties in the component, or the organic luminescent dye mixed with the desired light color in one body. / 0LH) According to the type of organic light-emitting materials, it can be divided into two categories: small molecule materials and polymer materials: ^ Small molecule 0LED is Kodak, which was first used by Deng Qingyun and others in 1987. This 〇 LED device has been described in the US Pat. No. 4,356,429, the entire disclosure of which is incorporated herein by reference. ‘Eight 0LED, first published in 1990 by the research team of the University of Cambridge, UK, and later transferred to

Technology (CDT), the basic patent US-A5, 247, 190 of the polymer 〇 LE: D is owned by CDT. The ancient eight-handed 0LED is made by a solution process. Its advantage is that it can be manufactured by coating or ink-jet. It does not need to use large-scale equipment, so the process can be greatly simplified and the investment is small. In addition, when using screen printing or inkjet printing, the substrate has a small tolerance and is highly attractive for developing large-sized displays or lighting elements. In recent years, due to the application of white light 0LE:D in lighting 'flat displays, and other optoelectronic products, it has received extensive attention. White light is a combination of series-wavelength visible light, unlike monochromatic light--single-side; white light can be composed of red, green and blue light colors, white light can also be combined by yellow and blue light colors, and various light-color combinations; Color, can be dispersed in the multi-type light-emitting structure, each emitting light, ^ light-emitting layer structure in a layer structure - Fuzhong in early and white light 0LH), can be divided into multi-layer and single-layer; multi-layer light-emitting structure White light, 1293234

^ 267 4, f 1332 ^0995)^ APLVol. 64. ρ. 815 (1994) ΪΓ ΐ 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗 斗And with ^ ί ίί 1 a ^ ^ ^ ^: Hatwary 627, 333 ^ US-A20040058193 · Sat is by - blue light emitting layer and an electron or hole with yellow dye mixed ΐ ΐ ^ 169 〇 LED f. £ ^ 1 The hole transport layer of the light dye together constitutes white light. However, the (4) sub- and the electric if and change with the voltage change, so that the cladding of the carrier to be combined with the application of the voltage t of the white system ed, its color will produce color shift; in addition, the 听, molecular listening to use vacuum It is limited to small-sized panel applications. a ΐ layer structure 5 white 5 * _, such as J · Shi in its US-A a 5 683 823 patent and D, she * 瘘 tt ^ % 624 Ι (2004 ^ * ^ ring H will be a knife orange, Work light and blue light miscellaneous materials, or red, green and blue light dyes, which are simultaneously incorporated into the small molecule host material, the proportion of dyes doped by the optical device, relative to the host material, the difficulty of the phase, Zhu The composition of the material is easy to change, the color reproduction is poor, and the yield is low. In the production of if-color white light, three or more dye molecules are simultaneously regulated, and the host material is added, and the difficulty is more souther and the reproducibility is lower. The yield is even worse, and a practical obstacle is formed.

Kawamura et al., in Journal of Applied Physics, Vol. 92, p. 87 (2002), in which the white LED light-emitting layer* is applied in a solution process*, and the red, green and blue dyes are simultaneously pushed together. The structure of the molecular host material, however, its molecular size is still poor in brightness, luminous efficiency, and lifetime, and there should still be problems; in addition, the stability and purity of its light color are not good, and these problems are all The difficulty of causing white light 〇 LED g. SUMMARY OF THE INVENTION The purpose of the present invention is to provide a single light-emitting layer white organic electro-luminescence method which can improve the performance and simplify the process. Wherein, the white electroluminescent layer utilizes an electroluminescent dye and a molecular host material for the above purpose, and can be achieved in an organic light-emitting device, the device sequentially comprising the following constituent items: a) a white photo-emitting layer, wherein The white light emitting layer is composed of one or more kinds of luminescent or non-emitting light 5 1293234

丨 替换 替换 替换 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光b) - a first electrode adjoining the first surface of the white electroluminescent layer; and a second electrode adjacent to the second filament of the electroluminescent layer. The white light OLED of the present invention has the following advantages: 1·=sub-material replaces the polymer material as the light-emitting turn and the main county material, effectively improving the light of the white light. • The early-light-emitting layer white light QLED' effectively improves the voltage applied by the fruit. The white silk color shift is now 3' empty ίίίϋΐ, the liquid process makes small molecular type leakage, the process is relatively simple, and the production is low and can be applied on a large area; in particular, the regulation of pure white light color makes its advantages even more obvious. . 4. Preparation of molecular type white OLED by the Lok process, which can be used with the dark - -20, dyes and suitable host materials, the difficulty of controlling the concentration of the shirt at the same time, so that the white one is good = good = 5. This case can easily and accurately control each light color dye to any desired concentration, and the reproducibility is excellent. [Embodiment] Doping >, 曰2^^^光$: Depends on the organic material with luminescent properties in the device, Yu-main county material, fj" map, first machine luminescent dye; in the previous art organic In the structure of the light-emitting diode, such as ^150 · 17011, it must be made of light, so the substrate and anode electrode should be transparent; the substrate can be glass substrate or plastic? The _ made of the substrate has flexible properties. The well-known anode * can be transparent and has a conductive 匕 孟 匕 匕 ΙΤΟ ΙΤΟ ΙΤΟ 铟 铟 铟 铟 铟 铟 铟 铟 铟 铟 铟 铟 铟 铟 铟 in in in in in in in in in in in in in in in in , , , , , , , , , Materials, but other materials can be used, such as: λ Ming or Zhen ί1, and Oxidation. The hole injection layer can help the hole to inject and improve the subsequent organic Τ曰ΓΓΛ. The materials suitable for the hole injection layer include Not limited to PEDOT, PED〇T: PSS, CuPc, electron transfer μΓΜΤΜΤΑ, and TlQPG and derivatives of the above materials. The use of this material to help electron transport is limited to, TAZ, BCP, AlQ3 and PBD and the derivative of the above materials. The material used for the present invention may be a low work function metal or a gold compound, but may be, but not limited to, two CDs, Li2 and MgF2. The cathode electrode used in this case may in principle be For any metal material, the cathode material used must be a metal with a low work function (<4 〇eV) for electronic metal materials, but for 6

The cathode material must be a metal having a low work function (M.OeV) for electron formation and implantation, including but not limited to Ca, Ag, Li, Mg, A1 or a combination of the above metals. 1293234 The white light emitting layer of the production case consists of one or more molecular host materials with or without luminescence and red, green and blue electroluminescent dyes, yellow and blue electroluminescent dyes, or any other substance that can be associated with this molecule. The materials are combined with the light electroluminescent dye, which is prepared by a solution process and prepared by a solution process; applicable red, green, and blue light-emitting dyes include, but are not limited to, red dyes such as DCM and DCM2. DCJT, DCJTB, PtOEP,

Eu(DBM)3(Phen), Rubrene, and Btp2lr(acac), Ir(MDQ)2(acac), Ir(DBQ)2(acac), PQIr, derivatives of the above materials; green dyes are c〇 Umarin6, C545T, DMQA, Ir(mppy)3, Ir(ppy)3盥,#, derivatives, ·blue dyes are BCzVBi, BCzVB, TBPe, Perylene, DpAVB, DpAVBi II, jl, FIttr=c, Flr6 And the derivative of the above materials; and the host material may be an electron transport material, a hole transport material, and a hole blocking material or other suitable energy gap, and the electron-electric coating ^ ^ BCP PF0, DPVB j, BNA, TBAB, AND, and TPB1 are derivatives of the above materials. FIG. 2 is a structural diagram of a white light 〇 LED device 2〇〇 proposed in the present application. This 詈LED nightmare, when the 程 程 匕 匕 而 组成 组成 组成 组成 组成 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材 基材I ^ .1 marriage replacement page £ 600 light 0 (10) device 7 ^, device, white light assembly Γ〇 Γ〇 material _ and electron transport material 670 blended in white photoluminescent layer 65 ;; this white electrode 690 'From bottom to top, the substrate _, the first electrode 620, the white photo luminescent layer 650, and the second illuminating OLED device 700 are structurally arranged. Compared to the device, white light_装 7 7^ Λ, The transmission material and the electron transporting material 770 are blended in the white electroluminescent layer 75〇; the white electrode 79f is disposed, and the substrate 710, the first electrode 720, the white photoluminescent layer 750, and the two

Dream Office: 8 different 5; white light 0 (10) device _ structure. Compared with the 200~700 device, a white light OLED 'an' is added between the electrode 820 and the white photoluminescent layer 850, and a hole injection layer 830 is added; white Ϊμ m 820 ' 830 '

@w 2 is a structural diagram of another white light OED device 900. Compared with the 800 device, the white light OLED iln adds an electron transport layer 970 between the 6L photoluminescence layer 950 and the second electrode 990; and the white substrate is sequentially implanted into the substrate 910, the first electrode 920, and the hole. The layer 93, the white electroluminescent layer 950, the electron transport layer 970, and the second electrode 990.

Ϋ〇 ί Another physical white OLED device 1000 structure diagram proposed by the gas. Compared with the 90-inch device, an electron injecting layer 1080 is added between the white light OLED LED transport layer 1070 and the second electrode 1090; the white is sequentially from the bottom to the substrate 10101, the first electrode 1020, and the hole 3 main entry layer 1030, white photo-induced light layer 1050, electron transport layer 1〇7〇, electron injection layer 〇8〇, and second electrode 1〇9〇. Zhuangban H is another structural diagram of the white light OLED device 1100 proposed in this case. Compared with the 1000 device, the white light 0LED $^, 1100' is between the white photoluminescent layer 1150 and the electron transport layer 117, and a hole blocking layer llbj + the white light 1100 device is added, which is based on the bottom-up sequence. The material mo, the first electrode I120, the hole injection layer H30, the chalk light-emitting layer 1150, the hole barrier layer 1160, the electron transport layer 1170, the electron injection layer nso, and the second electrode 1190. FIG. 12 is a structural diagram of another white light 〇 led device 1200 proposed in the present application. Compared with the 11 〇〇 device, the white light 〇 LED device 1200 ′ between the hole injection 膺 1230 and the white photo luminescent layer 1250, a hole transport layer 1240, the white light 1200 device is added, from bottom to top. a substrate 121 〇, a first electrode 122 〇, a hole injection layer ι 23 〇, a hole transport layer 1240, a white photo luminescent layer 1250, a hole blocking layer 1260, an electron transport layer 1270, an electron injection layer 1280, and Second electrode 1290. 8 1293234 n:—1~— --n year month turn. (more) positive replacement page j [Comparative example 1] Ageing L1 is produced according to the prior art to produce a white* 〇led device, which is based on a polymer The main body 1 knife 120 is constructed according to the figure of Figure A, in the order of: substrate 1110; the formation of the anode is the electrode Π 50 1120 ± • forming an electron 偻;; 17ί11 hole resist layer 1160 in the above white photoelectric The luminescent layer is on the surface of the electron-injecting layer 1160; the electron-injecting layer is formed on the hole-blocking layer 1170, and a cathode electrode 119 is formed on the electron-injecting layer 118. The spine will be placed on the production process. The hole is injected into the material PED0T: PSS, and the 1τ is washed first by the spin. On the transparent conductive glass, a hole injection layer with a thickness of 4G nanometers is formed. The preparation of the white light layer is to first uniformly blend the red light dye Btp2Ir (acac) and green H material to be blended. In the polymer PVK host material, the blending method is: , Rongzi Ϊ ϋϊ ϋϊ, house liter 15 mg (15 mg / mL) and 1 mg per ml (1 / mL) 5 丄 丄 forming a uniform mixture of the liquid; Then, the mixed solution is spin-coated: a dichroic white 5 luminescent layer is described on the transparent conductive glass of the PED0T: PSS which has been prepared for the hole; in the glove box of the gas, the aforementioned mixture is dropped into the Prepare the hole into the transparent transparent conductive glass of the second hole, and transfer the coating machine to the rotation speed of 2, 5GGrPm, spin-coat 20 U, and J light in the hole transmission layer i. Finally, the component which has been spin-coated with the white light-emitting layer is placed in a vacuum for 1 hour and 12 hours (the solvent-heat treatment process of rc is formed, that is, white light is generated, ^ 15 Balq3 > 20 Alqa ^ 0. 5 ^ ^ The electric=injection layer LiF and the 120 nm negative electrode aluminum were vacuum-deposited on the white electroluminescent layer under a vacuum pressure of 1〇-5T〇rr, that is, the white light OLED device of the comparative example 1 was completed. The electroluminescence characteristics of the device were measured by PR650spcctrometer. 'Drive voltage (defined as brightness > 1 candle / square 5 (volts), 2.6 (candle / amp), and 3, 060 (candle as shown in Table 1) , compare the voltage of the white light OLED device of the first example, the maximum efficiency, and the maximum brightness, in order of 6. light / square meter. 1293234 (Table 1) Organic electroluminescent diode dye concentration (blue) (green) (red) Example: FIrpic JrCppy^ : BtpJr (acac) Drive voltage (V) Maximum performance (cd/A) (lm/W) Maximum brightness (cd/m2) CIE color coordinates (7 volt hours) Remark 1 12 ΟΛ 0.35 6.5 2.6/1.3 3060 (0. “3, 〇.3s) Reference 2 12 ΟΛ 0.35 U 3.5/1.7 “00 (0.38, 0.36) Pre-invention 3 12 ΟΛ 0.35 4 3.9/1.8 5070 Ι°·37 (0.38) Current invention 12 ΟΛ 0.3S 4.25 7.9/3.7 6870 (0.35, 0.38) Current invention 5 12 ΟΛ 0.35 U 11.3/5.6~ 15200 (0.34, 0.39 Present invention 6 12 0.2 0.2 4 9.3/4.2~ 12600 (0 30,0.38) Current invention 7 12 0.2 0.35 4 8.8/4.2 12500 (0.35.0.37) Current invention 8 12 0.2 0.5 4.25 8.4/3.8 8700 (0.39, 〇 .36 Factory present invention 9 12 0.0 0.35 4.75 6.6/2.9 9600 , 0 ^, 0.35) Current invention 10 12 0.3 0.35 U 11/17 13100 丨〇. '0.38) Current invention 11 12 0Λ 0.35 4.25 11.8/5.7 13840 (0 3. 〇乂0) Current invention 12 12 0.5 0.35 4.25 13.7/6Λ 15250 丨0.35,0") Current invention 13 12 0.6 0.35 U 13.9/6.3 15410 1〇35, 〇乂3 丨 Current invention 14 12 0.7 0.35 4.25 K .7/7.1 16220 (0-35,0Λ5) Current invention 15 10 0Λ 0.35 U5 11.5/4.5 13U0 (0.33,040} Current invention 16 12 0Λ 0.35 US 11.8/B.1 13820 1°-^, 0.39) 17 K 0Λ 0.35 4.75 12.7/5.3 12970 10 ^,0.38) Current invention 18 16 0Λ 0.35 5 13.1/5.5 13"0 (〇· 乂, (K〇) Present invention 19 12 0.2 0.35 4.5 2.8/1.1 5250 (0.艽,〇乂1丨 Current invention +: Compare OLED performance with the same red, green, and blue dye concentrations, but offset manufacturing.

[Example 2~5] Small molecular material, the white form of the sample 2~5 is selected, firstly, the main molecular material and each of the photo-dye dyes are respectively 15 g/ml (gmg (lmg/❹ in the terpene solvent). And use the stirring spoon to pass 2 liters & the required color of each of the dissolved words ^ 士士祖饮皮盏 I du, sentence uniform '谷液. The invention is selected in the examples 2 to 5 molecule

IrCDDV^t^ R? \TCTi' TAZ ' ^ CBP ; Flrpic(M) ^ ppy 3U0 Btp2Ir(acac)(red), > Chen is 12wt%, 〇·4 wt%, and 〇. 35 wt %. 10 1293234

The invention adopts IN0 (indium-tin oxide) transparent conductive glass as an anode substrate, and the steps of re-cleaning are as follows: First, the IT0 immersion is immersed in an appropriate proportion of water and detergent, and then superimposed to deionized water. , _, and isopropyl alcohol, respectively, vibrate by ultrasonic 20"

The white gas OLED device is prepared by injecting a hole into the material pED〇T: pss, and spin-coating the above-mentioned pre-washed in a nitrogen-filled glove box at a spin speed of 4,000 rpm using a spin coater. On the net buckle transparent conductive glass, a hole injection layer with a thickness of 40 nm was formed; then the white light solution which had been uniformly mixed was rotated at 2,500 rpm, and spin-coated for 20 seconds to prepare a white light emitting light. The layer is on the above-mentioned hole transport layer; finally, the component which has been spin-coated with the white light-emitting layer is placed in a vacuum oven, and under a vacuum of l〇-3t〇rr, a desolvation heat treatment process of j〇艽2j, ie, Forming a white photoluminescence layer; thereafter, sequentially, 15 nm of the hole blocking layer BA1 20 nm electron transport layer Αίφ, 0.5 nm electron injection layer LiF, and 12 〇 nanometer cathode electrode aluminum The white light OLED device of Comparative Example 1 was completed by vacuum evaporation at 10 Torr under vacuum pressure on the white electroluminescent layer. The electroluminescence properties of the device were measured with a PR650 spectrometer. ^ Figure 13 is a graph showing the luminance-voltage characteristics of the white light-emitting LED device of Comparative Example 1 and Examples 2 to 5. Compare the main molecular materials selected in Example 1 and Examples 2 to 5, followed by the polymer ρνκ and the small molecule 〇1 (^, 1^1^, 1[8, CBP; organic luminescent dye Flirpic, Ir(ppy) 3. The concentration of Btp2Ir(acac) is fixed to uwto/o, 〇·4 wt%, and 0·35 wt°/. Compared with the comparative example of polymer PVK, examples 2~5 are small. The white light device with the molecule as the main material f can obtain better light-emitting brightness; wherein, when CBP is used as the host material, the light-emitting brightness is optimal. As shown in Fig. 1, examples 2 to 5 are small molecules mCP, TCTA, TAZ. And CBP as the main material, the maximum brightness of the white light device is 3, 060 (candle / square meter) of the polymer PVK of Comparative Example 1, and the maximum current efficiency is 2.6 (candle / ampere). Increased to 3.5, 3.9, 7.9, and 11.3 (candle/ampere): The driving voltage of the device is reduced from 6.5 to 4 (volts) of polymer PVK. The above results show that the case The white light 0LED device uses small molecules instead of polymer as the main material, which can effectively improve the luminous efficacy of the white light 〇1^]) device.

[Examples 6 to 18] Compared with the example 5, the white light OLED device of the example 6 to 18, except for the mixed red, green and blue dye concentrations, the white light device structure and preparation method of the examples 6 to 18 are Same as described in Example 5. As shown in Examples 6 to 8 of Table 1, when the concentrations of Flirpic and Ir(ppy)3 in CBP were fixed at 12 wt% and 0.35 wt%, the concentration of BtpdKacac was changed, with the concentration of Btp2Ir(acac) from 〇. When the 2wt% is increased to 0.5% by weight, the maximum current efficiency and energy efficiency of the device will be reduced from 8.3 (candle/amperes) and 4.2 (lumens/watt) to 8.4 (clouding/amperes) and 3.8, respectively. (Lumens/Watt); for maximum brightness, it is raised from 12,600 (candles per square meter) to 8,700 (candles per square meter). This phenomenon is attributed to the fact that Btp2Ir(acac) has poor luminescence efficiency relative to FIrpic and Ir(ppy)3, and as the concentration of red dye Btp2Ir(acac) increases, more BtpdKacac molecules participate in electrolysis. Luminescence, which reduces the probability of energy transfer to FIrpic and 11 1293234 S8 with higher luminous efficacy, and the probability of being more than 1 Ir(ppy)3, thus guiding the hair filling and widening of the right-filled farm Ding ^ 卞 - drop case ttri; 祀 Example 7, 9~14, when the concentration of fixed FI卬ic*BtP2lr(acac) in CBP is 12 Ιί and ^, when changing the concentration of Ir(PPy)3, When the Ir(ppy)3 concentration increases from 〇·5 to 〇· 7 Wt%, the electrical efficiency, rate and energy efficiency are increased from 8.8 (candle/amperes) and 4.2 (lumens/watt) to Bucket J 1 (lumen/watt, etc.); in terms of maximum brightness, it is also i6 two square meters from 12,500 (candles per square meter). This is attributed to an increase in the concentration of Ir(ppy)3, which can improve the luminous efficacy of the white light device. It. As shown in Examples 15 to 18, when the concentrations of Ir(ppy)3 and Btp2lr(acac) in CBP were fixed, 〇·4 and 0:35 wt/. 'When the FIrpic concentration is changed, the device will increase from 11.5 to 13·1 (candle/amperes) as the FIrpic concentration increases from 1〇 to 16 wt%; in terms of maximum brightness, it is 134, 〇〇〇=4 〇〇 (candle / square meter). = The driving voltage of the white light device in this case is about 4~5 volts; among them, the white light 〇 LED shovel of Example 14 can obtain a maximum current efficiency and energy efficiency of 14·7 (candle/amper) and 7.1, respectively. (Lumens/Watt) 最大 and the maximum brightness is 16,200 (cloudy / square meter); and Comparative Example 5 can get a CIE color coordinates (〇34, 〇35) white light color. ,·

Figure 14 shows the white light 0LE1D device of Example 5~1〇. The electroluminescence spectrum of the electroluminescent white light device at 7 volts has two peaks at 476 and 616 nm, respectively, the characteristics of FI ic g BtpdKacac). The peak, the other peak is at 496 nm, and the electroluminescence wavelength ranges from 38 domes to nanometers. With the increase of Ir(ppy)3 concentration, the luminescence intensity of FIrpic is higher than that of Btp2Ir (ff, f peak, and shifts to nanometer; this phenomenon is 11^7)3, / Chen The increase, there are more 11 « (1)] ^) 3 molecules involved in electroluminescence. In addition, the radiation intensity of 'FIrpic and Ir(ppy)3 also increases when the concentration of the needle %) decreases, which is due to an increase in energy transfer from the host materials 钊FT· and Ir(ppy)3. ^Φ+ijMrpic Figure 15 shows the white light 0LEI device of Example 7. The electroluminescence spectrum increases with the applied voltage, and the Btp2Ir(acac) luminescence intensity shows a decreasing trend compared to Finnic and Ir(ppy)3. Heat 7, 'J: The luminescence spectrum exhibits a slight blue shift. As shown in Figure 16, for the white light 〇LE:D device of Example 7, the CIF is applied with a voltage change. When the applied voltage is changed from 5 volts to 9 volts, i is only moved from (0·36, 0.37) to (〇·34, 0. 38), exhibiting a rather ambiguous light color stability. Eight color seat shows [Example 19] 12 1293234 Year 1 change Μ Compared with the above example, the white light 〇 LED device of Example 19 has a hole in the white photoelectroluminescent layer and the electronic value in the booth. Layer ΒΑ1Φ, the 结构 structure is shown in Figure 5, in order: substrate 1〇1〇 · electrode 1020 on the substrate 1〇1〇; forming a hole injection layer 1〇30 on the anode electrode 1〇2 a light-emitting layer 1〇5〇 is formed on the hole injection layer 1〇3〇; an electron transport layer m is formed on the white “=1050; an electron injection layer 1080 is formed on the electron transport layer 1〇70 And forming a layer on the electron injection layer 1080. Figure 17 shows the white light 〇LE:D brightness-voltage-efficiency characteristic diagram of the example 19. As shown in Table 1, the dream point M〇 White light 0LE1D device, drive voltage, maximum current efficiency, and maximum brightness, in order of 4 ^ ft, ff 9 light / ampere, and 5,250 (candle / square meter)., Qiu Te) 2.8 (candle shown in Figure 18 The white light OLED device of Example 19 is an electrogram at a voltage of 7 volts. The resulting electroluminescent wavelength ranges from 380 to 776 nm. In the middle, the two peaks of the luminescence spectrum at the wave county & two nanometers are the characteristic peaks of FIrpic and BtpdKacac, respectively, and the other peak is 'jf〇: 35^^ C〇mffllSSi〇n ^ Eclalrag^ 19 shows a device with or without a hole barrier layer φ1φ for the white light 〇LED electrocavitation barrier layer of the case (Example 19), the three main peaks of the electroluminescence spectrum fall at 476 θ and ^ 0 too "half" The device for obstruction of the hole (example 7) can be observed - additional "two nanometers"; the contribution of electroluminescence spectrum is due to the charge carrier moving to the electron transport layer Α1φ, resulting in 曰A each radiant emission 528 奈The green light of the meter wavelength is also caused by the fact that these partial charge cuts have a device with a hole-resisting layer, thus affecting the light of the white organic electroluminescent device. In the case of the 0LED device, the hole is incident on the Leifu Helmet, but the sub-proportion makes it impossible for the _ hole carrier to be valid _ come! The number of t is equal to the weight of g, and the excess hole can be added. The carrier can be effectively limited to the probability of white light 3, thus improving the luminous efficacy of the device. Shown in the second, its ^ electricity, 5 hole light / square meter)], with a 15 nm hole barrier BAlq3 wearing 々丨, and 5,250 (candle), and 12, _ (cloudy / square meter )], the light color stability of the white light device of the 曰BAlq3 is also better than that of the non-electric hole resist layer ^ 丄: When the hole barrier layer is changed to 9 volts, the holeless resistance layer device (example f9f) In combination, add (〇·34, 0·45), and wear through the hole barrier layer (7, color seat “a from (〇·%, 〇·40) moved to (〇. 34, 0· 38) ), this phenomenon shows that using the appropriate ^ hole resistance material ^, ^H36, 〇 · 37) moved into the electroluminescent layer 'In addition to improving the luminous efficacy of the device, the state excitons at 13:1293234 ice · 6 -f Ί Ί 日 修 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The process of preparing white light 〇LED has excellent performance reproducibility; wherein the device driving voltage, maximum brightness, and light efficiency are sequentially 4.25 Ϊ0. 25 (volts), 142601530 (candles/square meters) And 11 · 6ΐ0.2 (cd / ampere); and a white light is almost no color change, is maintained at (34,0 · 39 · 0), exhibit excellent light show color reproducibility. In the above example, the liquid crystal OLED device having a light-emitting layer was prepared by successfully using a solution process and using a molecular host material. The white light 〇LED device of the structural arrangement and the manufacturing method has the advantages of simple, simple process, easy to adjust white light color, and high reproducibility; the white light 〇 LED device produced in this case has the highest strict light shell degree. 16,200 (cloudiness / square meter); maximum current efficiency and energy efficiency are 1 ^.7 (candle / amp) and 7.1 (lumens / watt); and a CIE color coordinates (〇 · 34, 0.35 ) white light color. When the voltage applied by the animal changes, the light color of the white light device in this case changes only slightly, showing excellent light color stability.

Although the preferred example of the case has been disclosed above, it is not intended to limit the case. Anyone who is familiar with the art can make some changes and refinements in the spirit and scope of the case. Therefore, the scope of protection of this case is This is subject to the definition of the scope of the patent application. [Simple description of the drawing] Fig. 1 illustrates a prior art organic light-emitting diode device. Fig. 2 illustrates a white light emitting organic light emitting diode device 2 according to the present invention. Fig. 3 is a view showing another white light-emitting organic light-emitting diode device manufactured in accordance with the present invention. Fig. 4 is a view showing another white light-emitting organic light-emitting diode device 4 manufactured in accordance with the present invention. Fig. 5 illustrates another white light-emitting organic light-emitting diode device 5〇Q fabricated in accordance with the present invention.

Fig. 6 illustrates another white light-emitting organic light-emitting diode device 6〇Q fabricated in accordance with the present invention. Figure 7 illustrates another apparatus for producing a white organic light emitting diode fabricated in accordance with the present invention. Fig. 8 illustrates another white light-emitting organic light-emitting diode device 8 manufactured in accordance with the present invention. Fig. 9 illustrates another white light-emitting organic light-emitting diode device g (9) fabricated in accordance with the present invention. Fig. 10 illustrates another apparatus for producing a white organic light-emitting diode according to the present invention. Fig. 11 illustrates another white light-emitting organic light-emitting diode device 11 manufactured in accordance with the present invention. Fig. 12 illustrates another π(9) device for producing a white organic light-emitting diode according to the present invention. Figure 13 is a comparison example 丨 and the white light 〇LE of the example 2~5; D device, brightness-voltage characteristic diagram. Figure 14 is an electroluminescence spectrum of a white light 0LE:D device of Examples 5 to 10 at an applied voltage of 7 volts. 14 -1293234 卩 6: Fei Yi ^ _ ^ Year and month repair (more) positive lean; ^j ^ is the white light 〇 LED device of Example 7, the electroluminescence spectrum-free change situation.

Chu 1 C The picture shows the white light OLED device of Example 7, and the CIE color coordinates change with the applied voltage. Figure 17 is a graph showing the brightness-voltage-efficiency characteristics of the white light OLED of Example 5. Figure 18 is an electroluminescence spectrum of a white light 〇LK device of Example 5 at an applied voltage of 7 volts. Figure 19 shows the effect of the presence or absence of a hole-resisting layer BAlq3 on the luminescence spectrum of a white OLED device. Figure 20 is a graph showing the effect of the hole barrier BAlq3 on the brightness and efficiency of a white OLED device. The mi map, because the thickness of each layer in the device is too different, can not be scaled according to the scale, only the structure of the device is not outlined. [Description of main component symbols] 110, 210, 310, 41G, 510, 610, 71G, 810, 910, 1G1G, 111G, 1210 to substrate 120, 220, 320, 420, 520, 620, 720, 820, 920, 1020, 1120, 1220 ~ first electrodes 830, 930, 1030, 1130, 1230 ~ hole injection layers 140, 440, 640, 740, 840, 940, 1040, 1140, 1240 ~ hole transport layer 14: 1 ~ electricity hole

150~ electroluminescent layer 250, 350, 450, 550, 650, 750, 850, 950, 1050, 1150, 1250~ white photoelectric luminescent layer 560, 760, 860, 960, 1060, 1160, 1260~ hole blocking Layers 170, 370, 670, 770, 870, 970, 1070, 1170, 1270 to electron transport layer Π1 to 880, 980, 1080, 1180, 1280 to electron injection layer 190, 290, 390, 490, 590, 690, 790, 890, 990, 1090, 1190, 1290 ~ second electrode ten, the scope of patent application: 15

Claims (1)

293234 荦· % Vf (more) is replacing the page white; 4 inclusions, mixed into layers and electro-optic, machine-made system has a material process photoelectric system white light main liquid species white matter one to include inclusions Extreme material ^ dye light light hairless or electric machine light hair has a variety of seeds and more or a group of color light first layer light hair call light white before the neighbor 1 first surface table two first layer •, the optical layer is transmitted and transmitted, and the photoelectric white or junction, the adjacent layer is filled with the same electricity or the X-pole. The first surface of the surface is the red layer, which can be dyed with the resistance material. Electric dimming or encircling the illusion,!? To its layer of electricity or transport special planes 传 有 有 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申 申Huang Chengji or Group II, while the light material is dyed and dyed, and the light-emitting material is made of blue body, the main light green white, the light distribution network, the brush printing machine ink V light, the white method of coating In the case of 艮 Ρ 1 no. The first is to enclose the package of the package. The material is specially prepared for dyeing. The other is 'painted body polar or 11 light ο ο 第 ο ο 围 围 范 范 范 范 范 范 范 范 范 范 范 ο ο ο ο ο ο ο 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请 请There are materials for light-staining white light, such as the machine, thick material ο body body -3 Q-dyed as ο 4 light can be U red material 3⁄43⁄4 the thick material electricity, the main material dyeing is light green, The thick t% of the material W is dyed by the material 10, the base can be supported by the body, or the two pieces of the light can be connected to the hair, and the electric power can be used to make the machine, and the light and the light are based on the white light. Not the extreme or the item of electricity, the second is the first, and the JI is a Lidi. The specific supporter please apply for the basis of the material, and ϋ 中 中 曰 曰 7t organic electroluminescence,, a..., /Μ 7 Which · at the end of the material PED〇T: PSS spin coating has been pre-washed On the net transparent conductive glass, a red dye Btp2Ir (acac), a green dye (lr(ppy)3, and a blue light oblique FT · c) are formed to be uniformly mixed. In the polymer PVK host material, a uniformly mixed solution is formed; a pico coating method is used to prepare a white light emitting layer in the above-mentioned prepared hole injecting material d, and the component of the white light emitting layer is placed in a vacuum oven. In the desolvation heat treatment process of 1〇_3t〇rr vacuum 纟120 C, the white photoelectroluminescent layer is formed; 、、、二小寺,, the 15 nm hole blocking layer Baiq3, 20 nm electrons The transport layer Α1φ, the ytterbium implant layer LiF, and the 120 nm cathode electrode aluminum, under ι〇-5τ〇ΙΤ vacuum pressure·μ 1 method, plating (4) on the white photoluminescent layer, that is, complete Ϋϋϋ真U clock, according to the method of the white light organic electroluminescence method described in Item 6 of the patent application scope of J Kang, The concentration of the red light dye may be the 主体 of the host material. The concentration of the green light dye may be 主体. 〇丨 i i , , , , , , , , , , , , , , , , , , , , , , , , , 。 。 。 。 。 。 。 。 Now the 16-1293234 of the wood section, according to Shen Qing patent van..t, The t-electrode method of electroluminescent diodes can be: firstly, the main molecule and each photochromic dye are respectively 15 mg (15 mg/mL) per ml and 1 g per ml (img/). mL) is dissolved in toluene solvent, and then the blue, green and red dyes are blended in the main molecule solution according to the ratio of 12wt%, 0.4% wt% and 〇·35 rt%. The method for manufacturing a white organic electroluminescent diode according to the invention, wherein the spin coating method is to fill the mixture into a well prepared hole in a glove box filled with nitrogen. A white light-emitting layer was formed on the hole transport layer by injecting it onto the indium tin oxide transparent conductive glass by spin coating at a spin coating speed of 2,500 rpm for 20 seconds.