TWI220640B - Polymer organic light emitting device with cross-linked emitting layer and manufacturing method thereof - Google Patents
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1220640 遠篮 921136681220640 Far basket 92113668
五、發明說明(1) 【發明所屬之技術領域】 tj本發明係一種交聯發光層之高分子有機發光元件及其 製作f法,尤指一種藉由對高分子發光層作熱交聯之製程 使咼分子有機發光元件上亦可設置一電子傳輸層,藉由 該電子傳輸層來增加電子注入與傳輸效率。 【先前技術】 由於有機發光二極體(〇rganic Hght emitting diode ’ 0LED)具備自發光、厚度薄、反應速度快、視角 廣、,析度佳、高亮度、可用於撓曲性面板及使用溫度範 圍廣等多項優點’被認為係繼薄膜型液晶顯示器(Th i η film transistor liquid crystal display ; TFT-LCD) 為新一代之平面顯示器技術,而該有機發光二極體(〇LED )的發光原理是利用材料的特性,將電子電洞在發光層上 結合,而將電子由激發態的形式降回基態,而將多餘的能 量以光波的形式釋出,因而達到有不同光波長的發光元件 的產生。 其中,陽極(Anode)係為氧化銦錫(indium tin oxide,I TO )之透明導電膜,以濺鍍或蒸鍍方式,附著於 玻璃或透明塑膠基板上,陰極則含有鎂(M g )、鋁(A i ) 、經(L i )等金屬’在二個電極間則是多個有機薄膜形成 的發光£域’包含電,同,主入區(H〇ie injecti〇n iayer ; HIL·)電洞傳遞區(Hole Transport Layer ;HTL)有機發 光層(Emitting layer)及電子傳遞層(Eiectr〇nV. Description of the invention (1) [Technical field to which the invention belongs] tj The present invention is a polymer organic light-emitting element with a cross-linked light-emitting layer and a method for manufacturing the same, especially a method for thermally cross-linking a polymer light-emitting layer. The manufacturing process allows an electron transport layer to be provided on the fluorene molecular organic light-emitting element, and the electron transport layer is used to increase the efficiency of electron injection and transmission. [Previous technology] Because organic light emitting diode (0rganic Hght emitting diode '0LED) has self-luminous, thin thickness, fast response speed, wide viewing angle, good resolution, high brightness, can be used for flexible panels and operating temperature Many advantages such as a wide range are considered to be thin film liquid crystal display (TFT-LCD) is a new generation of flat display technology, and the light-emitting principle of the organic light-emitting diode (〇LED) It uses the characteristics of the material to combine the electron holes on the light-emitting layer, and reduces the electrons from the excited state back to the ground state, and releases the excess energy in the form of light waves, thus achieving light-emitting elements with different light wavelengths. produce. The anode (Anode) is a transparent conductive film of indium tin oxide (I TO). It is attached to a glass or transparent plastic substrate by sputtering or evaporation. The cathode contains magnesium (M g), Metals such as aluminum (A i) and warp (L i) are 'luminous regions' formed by multiple organic thin films between the two electrodes, including electricity. In the same way, the main entrance region (H0ie injection iayer; HIL · ) Hole Transport Layer (HTL) organic light emitting layer (Emitting layer) and electron transfer layer (Eiectr〇n
Transport Layer ; ETL),在實際應用量產時,基於不同Transport Layer; ETL), in actual application mass production, based on different
第5頁 ^20640Page 5 ^ 20640
/考量’有時還會包含其他不同薄膜。 分為有機發光二極體依其使用之有機發光層材料不同,可 :以染料或顏料為主的小分子有機發光二極體(Organic 高八T tmiUing Di〇de ;〇LED)及以共軛性高分子為主的 门刀子有機發光二極體(Ploymer Light Emitti Di〇de ,PLED)。 高分子有機發光二極體(PLED)因其輕薄短小與廣視 專優點而漸受到重視,且因為其製程不須高價的真空裝 加上70件構造較為簡單,以及有機薄膜製程速度快等 丨生所以其將有不同於小分子有機發光二極體(〇 L E D)之 應用’但是由於高分子有機發光二極體(PLED)之高分子 有機發光層材料性質之限制,所以高分子有機發光二極體 (PLEDj元件需使用溶液塗佈或喷墨印刷製程,但在塗佈另 一層馬分子時其溶液於既有之高分子膜上時,原有之高分 子膜會受到溶劑的破壞,因此習知之PLED製作方法無法如 同小分子有機發光二極體(0LED)元件,在發光層與陰極之 間製作電子傳輸層,可藉由電子傳輸層來增加電子注入效 率,以改善發光效率。 ^ 因此’習知PLED構造較缺乏水溶性之電子傳輸層材料 可形成於高分子有機發光層與陰極之間,使得目前高分子 材料多屬於電洞傳輸性質,也因此目前高分子有機發光二 極體(PLED)元件皆於高分子有機發光層上即形成一陰極 層,所以高分子有機發光二極體(PLED)元件之電洞與電 子之注入平衡較不容易藉由製作多層元件結構調整,導致/ Consideration 'sometimes includes other different films. Divided into organic light-emitting diodes depending on the material used in the organic light-emitting layer, can be: small molecules of organic light-emitting diodes (Organic high eight T tmiUing Di〇de; oLED) based on dyes or pigments and conjugated Polymer-based door knife organic light emitting diode (Ploymer Light Emitti Diode, PLED). High-molecular organic light-emitting diodes (PLEDs) have received increasing attention due to their thinness, shortness, and wide-viewing advantages, and because their manufacturing process does not require expensive vacuum packaging, with a simple structure of 70 pieces, and fast organic film processing speeds, etc. 丨Therefore, it will have different applications from small molecule organic light emitting diodes (OLEDs). However, due to the limitations of the material properties of polymer organic light emitting layers of polymer organic light emitting diodes (PLEDs), polymer organic light emitting diodes Polar bodies (PLEDj elements need to use solution coating or inkjet printing processes, but when the solution of another layer of horse molecules is coated on an existing polymer film, the original polymer film will be damaged by the solvent, so The conventional PLED manufacturing method cannot be like a small molecule organic light emitting diode (0LED) element. An electron transport layer is formed between the light emitting layer and the cathode. The electron transport layer can be used to increase the electron injection efficiency to improve the luminous efficiency. ^ Therefore 'The conventional PLED structure, which lacks water-soluble electron transport layer materials, can be formed between the polymer organic light-emitting layer and the cathode, making current polymer materials mostly belong to The hole transmission properties, and therefore the current polymer organic light-emitting diode (PLED) elements all form a cathode layer on the polymer organic light-emitting layer, so the polymer organic light-emitting diode (PLED) elements of the holes and electrons The injection balance is less easily adjusted by making a multilayer component structure, resulting in
第6頁 l22〇64〇 修正 案號92113668_年 月 日 五、發明說明(3) 高分子有機發光二極體(PLED)元件之發光效率不佳。 【發明内容】 爰是,本發明之主要Θ的,在於解決上述之缺失, 免缺失的存在,本發明利用經過熱交聯之製程將高分子 光層製作於元件上,由於經過熱交聯製程後的高分子 層材料不受溶劑之破壞,可再塗佈電子傳輸材料於發光 ^,藉由此電子傳輸層來增加電子注入與傳輸效率, 回分子有機發光二極體(PLED)元件之電子與電洞注入 2 i使高分子有機發光二極體(PLED)元件之發光效率增 已圖利用一透明導電基板,料電基板上係 導,製作一水溶性之電洞傳輸層於上述 ,二上述發光層上,製作金屬陰極層於上述電子傳輸】: 主上經過熱交聯製程將高分子發 < 製程後的高分子發光層破:於 於上K㊁於發光層^最後蒸錢金屬陰極層 於上述之電子傳輸層上,再經過封裝 含電洞傳輪層、發光層盘電子傳輸 4,可付一匕 件。 增〃冤千傳輸層之尚分子有機發光元 【實施方式】 明如$關本發明之詳細說明及技術内&,現就配合圖式說 第7頁 1220640 η 曰 修正 i號92m咖 五、發明說明(4) 、裝閱:第卜_2圖所示』,係本發明之製造流程 分;有機‘朵-:圖所7^ :本發明係一種交聯發光層之高 分子發光層30製作於;::方:係;過熱交聯製程將高 ^丨pw - μ 件 習知因為高分子有機發光二 你另一展^ ^ 需使用溶液塗佈或噴墨印刷製程,在塗 溶液於既有之高分子膜上時,原有之高分 二:::: 因此目前高分子有機發光二極體( =:Λ 傳輸層40,本發明係利用經過熱交聯製 程後的兩分子發光層30材料不受溶劑之破壞,可再塗佈電 子傳輸材料於發光層30上,最後蒸鑛金屬陰極層5〇於上述 之電子傳輸層40上,再經過封裝製程之後,可得一包含電 洞傳輸層20、發光層30與電子傳輸層4〇之高分子有機發光 元件’該高分子有機發光元件製作步驟包括有: a) 取一導電基板10,該導電基板1〇上係為一基板上配 置有圖案化陽極透明導電層,其中該透明導電層 銦錫—氧今有機官能基之鍵結者。导電層係具有 b) 製作水溶性之電洞傳輸層20於上述導電基板丨〇上。 c) 製作油溶性之發光層3 0材料於上述電洞傳輸層2 〇上 ’其中该發光層3 0係為一含側鏈取代基團之聚芴高分子(Page 6 l22〇64〇 Amendment No. 92113668_Year Month Day 5. Description of the invention (3) The luminous efficiency of polymer organic light emitting diode (PLED) elements is not good. [Summary of the Invention] 爰 Yes, the main Θ of the present invention is to solve the above-mentioned deficiencies, so as to avoid the existence of the deficiencies. In the present invention, the polymer optical layer is made on the element by a thermal cross-linking process. The subsequent polymer layer material is not damaged by the solvent, and the electron transport material can be coated on the light emitting ^. The electron transport layer can increase the electron injection and transmission efficiency, and return the electrons of the molecular organic light emitting diode (PLED) element. Injecting 2 i with holes to increase the luminous efficiency of high-molecular organic light-emitting diode (PLED) elements. A transparent conductive substrate is used to guide the substrate to create a water-soluble hole-transport layer. On the above light-emitting layer, a metal cathode layer is fabricated for the above-mentioned electron transmission.]: The polymer light-emitting layer is broken by a thermal cross-linking process on the main surface: on the light-emitting layer on the top, and finally the metal cathode is steamed. Layer on the above-mentioned electron transport layer, and then encapsulated with the hole transfer wheel layer and the light-emitting layer disk for electronic transmission4, a dagger can be paid. [Embodiment] As detailed in the detailed description and technical aspects of the invention &, we will now cooperate with the illustration on page 7 1220640 Description of the invention (4), binding: shown in Figure _2 ", is the manufacturing process of the present invention; organic 'Duo-: Figure 7 ^: The present invention is a polymer light-emitting layer 30 of a cross-linked light-emitting layer Produced by ::: 方: 系; Overheated cross-linking process will be high ^ 丨 pw-μ pieces are known because of polymer organic light-emitting diodes. You need to use a solution coating or inkjet printing process. When the existing polymer film is on, the original high score is 2 :::: So the current polymer organic light-emitting diode (=: Λ transmission layer 40, the present invention uses two molecules to emit light after undergoing a thermal crosslinking process The material of the layer 30 is not damaged by the solvent. The electron transporting material can be coated on the light-emitting layer 30. Finally, the metal cathode layer 50 is evaporated on the above-mentioned electron transporting layer 40. After the encapsulation process, a layer containing electricity can be obtained. High-molecular organic light emitting of the hole transport layer 20, the light emitting layer 30 and the electron transport layer 40 Element 'The manufacturing process of the polymer organic light emitting element includes: a) taking a conductive substrate 10 on which a patterned anode transparent conductive layer is arranged on a substrate, wherein the transparent conductive layer is indium tin-oxygen Those who bond organic functional groups today. The conductive layer has b) a water-soluble hole transport layer 20 is formed on the conductive substrate. c) Fabricate an oil-soluble light-emitting layer 30 material on the hole transport layer 20 above, where the light-emitting layer 30 is a polyfluorene polymer containing a side chain substitution group (
Poly_Fluorene )的7Γ共軛高分子材料,該側鏈取代基團 選自環氧乙烷、環氧丙烷及甲基壓克力基團。 d )加熱交聯發光層3 0材料,其中該熱交聯製程溫度係 為1 0 0 °C至1 5 0 °C,係依發光層3 0材料進行調整,由於此方 法可以突破習知高分子有機發光二極體(PLED)元件結構 第8頁 1220640Poly_Fluorene) 7Γ conjugated polymer material, the side chain substitution group is selected from ethylene oxide, propylene oxide and methyl acrylic group. d) heating the cross-linked light-emitting layer 30 material, wherein the temperature of the thermal cross-linking process is 100 ° C to 150 ° C, which is adjusted according to the light-emitting layer 30 material, because this method can break through the conventional high Molecular organic light emitting diode (PLED) element structure Page 8 1220640
可在發光層30之上製作高分子電子傳輸層4〇,可以幫助 。元件之電子注入性質,對元件的電子輸效能有相當 程度的改善。 e)製作電子傳輸層4〇於上述發光層3〇上。 ^ f)製作金屬陰極層5〇於上述電子傳輸層40上,其中該 陰極層50係包含一鈣(Ca)層,及於鈣(Ca)層上之鋁金屬層 〇 一叫參閱『第2圖所示』,係本發明之高分子有機發光 几件結構示意圖,如圖所示··本發明係先製成一導電基板 、〇 4導電基板10上係為一基板上配置有圖案化陽極透明 導電層’一位於上述導電基板丨〇上之電洞傳輸層2 〇,一位 於上述電洞傳輸層2 〇上之發光層3 〇材料,然後將該發光層 3 〇材料經過熱交聯製程,該熱交聯製程溫度係為1 0 0 °C至 1 5 0 C,係依發光層3 〇材料進行調整,由於經過熱交聯製 程後的南刀子發光層3 〇材料不受溶劑之破壞,可再塗佈電 子傳輸材料於發光層30上,所以再設置電子傳輸層4〇於上 述之發光層30上,最後設置一陰極層50於上述之電子傳輸 層40上’再經過封裝製程之後,可得一包含電洞傳輸層 20、發光層30與電子傳輸層4〇之高分子有機發光二極體 (PLED) το件’亦因為發光層3〇與陰極層5〇之間設置有一電 子傳輸層40,係突破習知高分子有機發光二極體(pLED) 兀件結構’可在發光層3〇之上製作高分子電子傳輸層4〇, y以幫助改善το件之電子注入性質,對元件的電子傳輸效 能有相當程度的改善,藉此電子傳輸層4〇來增加電A polymer electron transport layer 40 can be fabricated on the light emitting layer 30, which can help. The electron injection properties of the device have improved the electronic transmission efficiency of the device to a certain extent. e) An electron-transporting layer 40 is formed on the light-emitting layer 30. ^ f) Fabricating a metal cathode layer 50 on the above-mentioned electron transport layer 40, wherein the cathode layer 50 comprises a calcium (Ca) layer and an aluminum metal layer on the calcium (Ca) layer. The figure below is a schematic diagram of the structure of the polymer organic light emitting device of the present invention, as shown in the figure. The present invention firstly makes a conductive substrate, and the 04 conductive substrate 10 is a substrate with a patterned anode. The transparent conductive layer is a hole-transporting layer 20 on the above-mentioned conductive substrate and a light-emitting layer 30 on the hole-transporting layer 20. The material of the light-emitting layer 30 is then subjected to a thermal crosslinking process. The temperature of the thermal cross-linking process is 100 ° C to 150 ° C, which is adjusted according to the material of the light-emitting layer 30. Since the material of the light-emitting layer 30 of the south knife after the thermal cross-linking process is not damaged by the solvent, An electron-transporting material can be coated on the light-emitting layer 30, so an electron-transporting layer 40 is disposed on the above-mentioned light-emitting layer 30, and a cathode layer 50 is finally disposed on the above-mentioned electron-transporting layer 40. After the packaging process is performed, To obtain a hole-transporting layer 20 Polymer organic light-emitting diode (PLED) of 30 and electron-transporting layer 40 also has an electron-transporting layer 40 between light-emitting layer 30 and cathode layer 50, which is a breakthrough of the conventional polymer organic light-emitting diodes. The polar body (pLED) element structure can be used to fabricate a high-molecular electron transport layer 40 on top of the light-emitting layer 40, y to help improve the electron injection properties of the το element, and to substantially improve the electron transmission efficiency of the device. This electron transport layer 40 is used to increase electricity
第9頁 1220640 _案號92113668_年月日__ 五、發明說明(6) 子注入率與傳輸效率,可使高分子有機發光二極體 (PLED)元件之驅動電壓降低,元件使用壽命增加。 惟以上所述者,僅為本發明之較佳實施例而已,當不 能以之限定本發明實施之範圍,即大凡依本發明申請專利 範圍所作之均等變化與修飾,皆應仍屬本發明專利涵蓋之 範圍内。Page 9 1220640 _Case No. 92113668_ Year Month Day__ V. Description of the invention (6) The sub-injection rate and transmission efficiency can reduce the driving voltage of polymer organic light emitting diode (PLED) devices and increase the service life of the devices . However, the above are only the preferred embodiments of the present invention. When the scope of implementation of the present invention cannot be limited, that is, all equal changes and modifications made in accordance with the scope of the patent application of the present invention shall still belong to the patent of the present invention. Covered.
第10頁 1220640 _案號92113668_年月曰 修正_ 圖式簡單說明 【圖式簡單說明】 第1圖,係本發明之製造流程示意圖 第2圖,係本發明之高分子有機發光元件結構示意圖 【圖式之符號說明】 已圖案化之導電基板............a 設置電洞傳輸層於導電基板上........b 設置發光層材料於電洞傳輸層上.......c 熱交聯發光層材料.............d 設置電子傳輸層於發光層上.........e 製作金屬陰極層於電子傳輸層上.......f 導電基板.................10 電洞傳輸層......... 20 發光層............. 30 電子傳輸層................40 陰極層..................50Page 10 1220640 _Case No. 92113668_ Year Month Amendment _ Brief Description [Schematic Illustration] Figure 1 is a schematic diagram of the manufacturing process of the present invention. Figure 2 is a schematic diagram of the polymer organic light-emitting device of the present invention. [Illustration of symbols in the figure] Patterned conductive substrate ............ a A hole transmission layer is provided on the conductive substrate ........ b A light-emitting layer material is provided on the substrate. On the hole transport layer ... c Thermally cross-linked light-emitting layer material ......... d Setting an electron transport layer on the light-emitting layer ... e Fabricate a metal cathode layer on the electron transport layer ... f conductive substrate ... 10 hole transport layer ... 20 Light-emitting layer ......... 30 Electron-transport layer ... 40 Cathode layer ... ....... 50
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