469 75 1 Α7 __ Β7 五、發明說明（f ) 本發明關於電致發光材料及倂有此之裝置。 當電流通過時會放出光線的材料係爲眾所周知的，且 用於廣範圍的顯示應用。液晶裝置及以無機半導體系統爲 基礎的裝置係被廣泛使用著，但是其缺點爲高的能量消耗 、高的製造成本、低的量子效率及不能用於製造平面顯示 器、反射問題(即在光亮條件下之低的可見度以及窄的視角 ，例如+/-45°)。 已有人提議有機聚合物可用於電致發光裝置，但是不 可能獲得純色，它們在製造上係昂貴的，且具有比較低的 效率。 另一種已經提議的化合物係醌醇鋁，但是其需要使用 摻雜劑以便獲得一系列的顏色，而具有比較低的效率。469 75 1 Α7 __ B7 V. Description of the invention (f) The present invention relates to electroluminescent materials and devices incorporating the same. Materials that emit light when current passes are well known and are used in a wide range of display applications. Liquid crystal devices and devices based on inorganic semiconductor systems are widely used, but their disadvantages are high energy consumption, high manufacturing costs, low quantum efficiency, and inability to use in the manufacture of flat displays, reflection problems (that is, in bright conditions) Lower visibility and narrow viewing angle, such as +/- 45 °). Organic polymers have been proposed for use in electroluminescent devices, but it is not possible to obtain pure colors. They are expensive to manufacture and have relatively low efficiency. Another compound that has been proposed is aluminum quinolate, but it requires a dopant in order to obtain a series of colors, and has relatively low efficiency.
Kido等人在化學通訊第657-660頁（1990)的文章中揭示 一種乙醯丙酮酸铽（ΠΙ)錯合物爲綠色電致發光的，且Kido 等人在1994年十月的應用物理通訊65 (17) 24之文章中揭 示一種三伸苯二胺銪（m)錯合物爲紅色電致發光的，但是 它們在大氣條件下係不穩定的且難以製成薄膜。 這些文章中所揭示的錯合物具有比較低的光致發光效 率’且僅能用於產生綠或紅光，而不能產生其他顏色。 電致發光係難以產生白色光線，且必需使用數種不同 的電致發光材料成混合的或連續層。另一種改變發光顏色 的方法係使用螢光染料或混有電致發光材料的染料，或爲 連續層。Kido et al.'S article on pages 657-660 (1990) of the Chemical Bulletin revealed that a fluorene (II) acetamidine pyruvate complex is green electroluminescence, and Kido et al.'S Applied Physics Bulletin, October 1994 Article 65 (17) 24 reveals that a triphenylene diamine hydrazone (m) complex is red electroluminescence, but they are unstable under atmospheric conditions and difficult to make into thin films. The complexes disclosed in these articles have relatively low photoluminescence efficiency 'and can only be used to produce green or red light, but not other colors. Electroluminescence is difficult to produce white light, and several different electroluminescent materials must be used in mixed or continuous layers. Another method to change the color of light emission is to use a fluorescent dye or a dye mixed with an electroluminescent material, or a continuous layer.
Takeo Wakimoto等人在應用表面科學113/114(1997)第 3 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公楚> ' · . <請先Mtt背面之注意事項再填寫本頁) Γ 經濟部智慧財產局員工消费合作杜印製 4 69 75 1 B7 五、發明說明（> ) 698-704頁的文章中揭示電致發光元件，其中使用酲醇鋁當 作發射體且其摻有喹吖啶衍生物，它係螢光染料，以便改 變發光顏色。 我們現在已經發現一些電致發光化合物，其中藉改變 外加電壓可改變所發出的光線，且其可發出白色光線。 本發明提供一種電致發光裝置，其中電致發光化合物 係 Tb(TMHD)3〇PNP。 其中TMHD係2,2,6,6-四甲基-3,5-庚烷二酯酮，而 OPNO係二苯基膦醯亞胺三苯基正磷。 光線的顏色係主觀的，而可用二維圖上的座標來定義 顏色’其中顏色係圖上的面積。在本發明中可看到白色， 而白光可定義爲色圖CIE 1931中的面積。 電:致發光化合物可混合能改變發光顏色的其他過渡金 屬、鑭系或锕系有機錯合物。 電致發光裝置包括一充當陽極的導電基材、一層電致 發光材料及一連接於電致發光層而充當陰極的金屬接觸。 當電流通經電致發光層時，該層發出光線。 本發明的電致發光裝置最好包括一透明基材，其爲導 電玻璃或塑膠料而充當陽極，較佳的基材係導電玻璃，如 姻錫氧化物披覆玻璃，但是可用任何導電的或具有導電層 的玻璃。亦可使用導電聚合物及經導電聚合物披覆的玻璃 或塑膠材料當作基材。可藉由溶於有機溶劑的溶液蒸發而 直接在基材上沉積Tb(TMHD)3〇PNP。可用的溶劑例如醇類（ 如乙醇）、酮類(如丙酮及乙醯丙酮酸甲酯)及氯化烴(如二氯 本紙張尺度巾 -------------% i. • · - (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 (210 X 297 公釐） 469751 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（i ) 甲烷）。 另外’可藉旋塗或真空沉積而由固態來沉積材料，例 如可用濺鍍或任何其他習知的方法。 較佳爲藉由混合Tb(TMHD)3和OPNP，於真空下加熱 所形成的混合物，使混合物氣化，及將蒸氣凝聚在基材上 ，以在基材上形成有機金屬錯合物的膜或層，而製得 Tb(TMHD)3〇PNP膜。另外，可依序地將Tb(TMHD)3和 OPNP沉積在基材上。 在本發明一實施例中，一電洞輸送層沉積在透明基材 上，且Tb(TMHD)3〇PNP沉積在電洞輸送層上。電洞輸送層 係用於輸送電洞及阻擋電子，因而防止電子移動進入電極 而沒有與電洞再次結合。載體的再次結合因而主要發生在 發射層中。 電洞輸送層係用於聚合物電致發光裝置中，且可用薄 膜形式的任何已知之電洞輸送材料。 可由芳族胺錯合物，如聚（乙烯咔唑）、N，N’-二苯基_ N，N’-雙(3-甲基苯基)-Ι，Γ-聯苯基_4,4’_二胺〇'?0)、聚苯胺等 ，來製造電洞輸送層。 視情況地，可包含像是螢光雷射染料、發光雷射染料 等染料，來改變發光的色譜，以及增加光致發光和電致發 光的效率。 在一實施例中，Tb(TMHD)3〇PNP混合一種聚合材料， 如聚烯烴，例如聚乙烯、聚丙烯等，且較佳爲聚苯乙烯。 混合物中的活性材料的量較佳爲95至5重量％的混合物， 5 本紙張尺度適用令國國家標準（CNS)A4規格（210 X 297公釐） !|1 — · — — — — ···隻 i I 11 I I 訂- — — „ - (請先閱讀背面之注意事項再填窝本頁) A7 B7 4 6 9 75 1 五、發明說明（P) 更佳爲25至20重量％>。 電洞輸送材料視需要可混合Tb(TMHD)3〇PNP,比率爲 5-95%的Tb(TMHDh〇PNP對95-5%的電洞輸送化合物。 在本發明另一實施例中，有一層電子輸送材料介於陰 極與Tb(TMHDh〇PNP間，此電子輸送層較佳係一種金屬錯 合物，如錕醇金屬，例如醌醇鋁，其在電流通過時將輸送 電子。另外，電子輸送材料也可混合Tb(TMHD)3〇PNP及與 它共同沉積。 在一較佳結構中，有一由透明導電材料所形成的基材 ’其爲陽極’此陽極上依序沉積有一電洞輸送層、一Takeo Wakimoto et al. Applied Surface Science 113/114 (1997) 3rd paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 cm) > '·. ≪ Please note before Mtt (This page) Γ Consumption cooperation by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 69 75 1 B7 V. Description of the invention The article on pages 698-704 reveals electroluminescence elements in which aluminum alkoxide is used as the emitter And it is doped with a quinacridine derivative, which is a fluorescent dye in order to change the luminous color. We have now discovered some electroluminescent compounds in which the light emitted can be changed by changing the applied voltage, and it can emit white light. The present invention provides an electroluminescent device in which the electroluminescent compound is Tb (TMHD) 30PNP. Among them, TMHD is 2,2,6,6-tetramethyl-3,5-heptane diester ketone, and OPNO is diphenylphosphine imine triphenyl orthophosphate. The color of the light is subjective, and the coordinates on the two-dimensional graph can be used to define the color ', where the area of the color is on the graph. White can be seen in the present invention, and white light can be defined as the area in the color map CIE 1931. Electroluminescence compounds can be mixed with other transition metal, lanthanide or actinide organic complexes that can change the color of light. The electroluminescent device includes a conductive substrate serving as an anode, a layer of electroluminescent material, and a metal contact connected to the electroluminescent layer and serving as a cathode. When an electric current is passed through the electroluminescent layer, the layer emits light. The electroluminescent device of the present invention preferably includes a transparent substrate, which is a conductive glass or plastic material and serves as an anode. The preferred substrate is a conductive glass, such as a tin oxide-coated glass, but any conductive or Glass with a conductive layer. It is also possible to use conductive polymers and glass or plastic materials coated with conductive polymers as the substrate. Tb (TMHD) 30PNP can be deposited directly on the substrate by evaporation of a solution dissolved in an organic solvent. Available solvents such as alcohols (such as ethanol), ketones (such as acetone and methyl ethyl pyruvate), and chlorinated hydrocarbons (such as dichloro paper scale towels) i. • ·-(Please read the notes on the back before filling out this page) Order printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (210 X 297 mm) 469751 A7 B7 Printed by the Employee Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Description of the invention (i) Methane). Alternatively, the material may be deposited from a solid state by spin coating or vacuum deposition, such as by sputtering or any other conventional method. Preferably, by mixing Tb (TMHD) 3 and OPNP, heating the resulting mixture under vacuum to vaporize the mixture, and condensing the vapor on the substrate to form an organometallic complex film on the substrate Or layer, and Tb (TMHD) 30PNP film was prepared. In addition, Tb (TMHD) 3 and OPNP can be sequentially deposited on the substrate. In one embodiment of the present invention, a hole transporting layer is deposited on a transparent substrate, and Tb (TMHD) 30PNP is deposited on the hole transporting layer. The hole transport layer is used to transport holes and block electrons, thus preventing electrons from moving into the electrode without recombining with holes. The recombination of the carriers therefore mainly takes place in the emission layer. The hole-transporting layer is used in a polymer electroluminescent device, and any known hole-transporting material can be used in the form of a thin film. Aromatic amine complexes, such as poly (ethylene carbazole), N, N'-diphenyl_N, N'-bis (3-methylphenyl) -1, Γ-biphenyl_4, 4'_diamine 0 '? 0), polyaniline, etc., to produce a hole transport layer. Optionally, dyes such as fluorescent laser dyes and luminescent laser dyes can be included to change the color spectrum of light emission and increase the efficiency of photoluminescence and electroluminescence. In one embodiment, Tb (TMHD) 30PNP is mixed with a polymer material, such as polyolefin, such as polyethylene, polypropylene, etc., and is preferably polystyrene. The amount of active material in the mixture is preferably 95 to 5% by weight of the mixture. 5 This paper size applies the national standard (CNS) A4 specification (210 X 297 mm)! | 1 — · — — — — ·· · Only I I 11 II order---"-(Please read the notes on the back before filling in this page) A7 B7 4 6 9 75 1 V. Description of the invention (P) 25-25% by weight > The hole-transporting material can be mixed with Tb (TMHD) 30PNP as required, with a ratio of 5-95% of Tb (TMHDh0PNP to 95-5% hole-transporting compound. In another embodiment of the present invention, there is A layer of electron-transporting material is between the cathode and Tb (TMHDh0PNP). This electron-transporting layer is preferably a metal complex, such as a metal alcohol, such as aluminum quinolate, which will transport electrons when a current passes. In addition, electron The transport material can also be mixed with Tb (TMHD) 30PNP and co-deposited with it. In a preferred structure, there is a substrate formed of a transparent conductive material, which is an anode, and a hole is sequentially deposited on the anode to transport Layer, one
Tb(TMHD)3〇PNP層及一連接至陰極的電子輸送層^陰極可 爲任何低工作函數的金屬，例如鋁、鈣、鋰、銀/鎂合金等 〇 在較低的電壓，例如低於10伏特時，所發出的光主要 爲淡黃綠色’且對應於铽m錯合物之典型發光顏色，而當 電壓增加時，所發出的光變成較接近白色，且在電壓超過 12伏特時眼睛看起來爲白色。 可能由於輻射強度的增加（因爲增加電壓使得配位體發 出較短波長的光線），而改變發光的波長，因此總效果係錯 合物內的各種成分之貢獻及其與電洞輸送層交互作用之組 合。 非常令人驚異地，此效果可以產生白光。 實例中說明本發明。 實例1 本紙張尺度適用+國國家標準（CNS)A4規格（210 X 297公爱） JIIIIII1IIII1- I--I 11 — « — — — — III — - . (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 4 69 75 1 A7 ______B7_______ 五、發明說明（f ) (i) Tb(TMHD)3〇PNP 薄膊 (請先閱讀背面之ii意事項再填寫本頁) 用硏缽及杵棒將50毫克Tb(TMHD)3(7xlO_5莫耳）與 33·68毫克ΟΡΝΡ(7·05χ10·5莫耳)一起硏磨，及將3毫克部份 置於Edwards (Ε306)真空披覆器內的鉬船上。將光譜純石英 (spectrosil)玻璃片（UV級）固定於樣品夾具上。將真空披覆 器抽真空到1(Τ7托，及用在10至90A和10V的電熱器來加 熱樣品，最長二十秒鐘，而產生Tb(TMHD)3〇PNP膜。 (ii) 製浩基於Tb(TMHDLOPNP的雷致發光裝置 將3毫克如⑴中所製備的Tb(TMHD)3〇PNP混合物蒸發 到一圖案化的IT0電極上，而產生50nm厚的膜。該圖案 化的IT0已經事先披覆有20nm由TPD所形成的電洞輸送 層。然後將醌醇鋁(Alq3)蒸發在該層的頂上而產生20nm厚 的膜，其充當電子輸送層。製作一鋁頂接觸(900nm)，以形 成第1圖之結構，其中⑵爲IT0層，⑷爲電洞輸送層，（1) 爲發射層，⑸爲電子輸送層而⑶爲陰極。 -線 使一測量電壓通過裝置及測量所發出的光線波長。結 果示於第2圖中。如所見的，隨著電壓的增加，Tb峰以外 的波長光線強度亦增加，此導致所發出的光線變成白色。 第2c圖中所發出的光線之CIE色座標係x:0.22、y:0.25， 其爲白色光。 圖式簡單說明 第1圖顯示一種基於Tb(TMHD>OPNP的電致發光裝置 〇 第2圖顯示測量電壓通過裝置及測量所發出的光線波 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 469 75 1 A7 _ B7____ 五、發明說明（心） 長之結果。 (第2a圖係於10-v的條件下；第2b爲12v而第2c爲13v) 元件符號說明 1.發射層 2.IT0陽極 3. 陰極 4. 電洞輸送層 5. 電子輸送層 1 -----裝--------訂----^---11 線 (請先Μ讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Tb (TMHD) 30PNP layer and an electron transport layer connected to the cathode ^ The cathode can be any metal with a low work function, such as aluminum, calcium, lithium, silver / magnesium alloy, etc. at lower voltages, such as lower than At 10 volts, the light emitted is mainly yellowish green and corresponds to the typical luminous color of the 铽 m complex. When the voltage is increased, the emitted light becomes closer to white, and when the voltage exceeds 12 volts, the eyes It looks white. The wavelength of luminescence may be changed due to the increase in radiation intensity (because the increased voltage causes the ligand to emit shorter wavelengths of light), so the total effect is the contribution of various components in the complex and its interaction with the hole transport layer Of combination. Very surprisingly, this effect produces white light. The examples illustrate the invention. Example 1 This paper size applies + National Standard (CNS) A4 specification (210 X 297 public love) JIIIIII1IIII1- I--I 11 — «— — — — III —-. (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 69 75 1 A7 ______B7_______ V. Description of Invention (f) (i) Tb (TMHD) 3〇PNP (Please read the notice on the back before filling in this page ) 50 milligrams of Tb (TMHD) 3 (7xlO_5 moles) with 33.68 milligrams of PP (7.05 × 10 · 5 moles) with a mortar and pestle and place 3 milligrams in Edwards (E306 ) On the molybdenum boat inside the vacuum coater. Spectral pure quartz (UV-grade) glass plates are fixed to the sample holder. The vacuum coater was evacuated to 1 (T7 Torr, and the heater was used at 10 to 90A and 10V to heat the sample for a maximum of twenty seconds to produce a Tb (TMHD) 30PNP film. (Ii) Zhihao A Tb (TMHDLOPNP-based electroluminescent device evaporates 3 mg of the Tb (TMHD) 30PNP mixture prepared in Rhenium onto a patterned IT0 electrode to produce a 50 nm thick film. The patterned ITO has been previously prepared. Covered with a 20nm hole transporting layer formed by TPD. Then aluminum quinolate (Alq3) is evaporated on top of this layer to produce a 20nm thick film that acts as an electron transporting layer. An aluminum top contact (900nm) is made, The structure shown in Figure 1 is formed, where ⑵ is the IT0 layer, 电 is the hole transport layer, (1) is the emission layer, ⑸ is the electron transport layer and ⑶ is the cathode.-The line causes a measurement voltage to pass through the device and the measurement The wavelength of the light. The results are shown in Figure 2. As you can see, as the voltage increases, the intensity of light at wavelengths other than the Tb peak also increases, which causes the emitted light to become white. The CIE color coordinate system is x: 0.22, y: 0.25, which is white light. An electroluminescent device based on Tb (TMHD > OPNP) is shown. Figure 2 shows the measurement voltage passing device and the light wave emitted from the measurement. 7 This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) 469 75 1 A7 _ B7____ V. The result of the invention description (heart) (Figure 2a is under the condition of 10-v; 2b is 12v and 2c is 13v) Element symbol description 1. Emission layer 2. IT0 anode 3. Cathode 4. Hole-transporting layer 5. Electron-transporting layer 1 ----- Installation -------- Order ---- ^ --- 11 line (Please read the precautions on the back first (Fill in this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)