201033301 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種含電洞傳輸材料、電洞注入材料、發 光聚合物材料、電子傳輸材料或電子注入層材料之組合 物，該組合物適於在有機發光裝置製造中，藉由噴墨印 刷、噴嘴塗覆、喷塗、輥印、浸塗、狹縫塗佈、或膠版印 刷沉積。 【先前技術】 典型的有機發光裝置（0LED)包括一基板，於其上支撐 一陽極、一陰極及一位於陰極與陽極之間並包括至少一種 聚合物電致發光材料的發光層。在操作中，電洞係通過該 陽極注入該裝置中及電子係通過該陰極注入該裝置中。該 等電洞及電子在發光層中組合，以形成一隨後經歷放射性 衰變而發光之激子。 在該OLED内可存在其他層，例如，可在該陽極與該發 光層之間設置一電洞注入材料（如，聚（乙n塞吩）/聚 苯乙稀讀❹旨（PED〇T/PSS))層，以協助電洞自該陽極注入 該發光層。此外，可在該陽極與該發光層之間設置一由電 洞傳輸材料製得之電洞傳輸層，以協助電洞傳輸至該發光 層。 發光共軛聚合物係一類重要材料，其將被用於下一代以 資訊技術為主之消費產品的有機發光裝置中。相對於無機 半導體及有機染料材料，使用聚合物的主要好處在於利用 成臈材料之溶液處理生產低成本裝置的範疇。在過去十年 I45811.doc 201033301 内，已付出諸多努力以藉由開發高效率材料或有效的裝置 結構來提高有機發光二極體（OLED)的發射效率。 共輕聚合物之另-優點係其可容易地藉由铃木咖別叫 • 或山本（Yamamoto)聚合形成。此能高度控制所得聚合物之 區域規則度。 因為存在適當的增溶基團，故餘聚合物可係溶液可處 理。適用於聚伸芳基，尤其係聚第類之溶劑包括單·或多 &基苯類’如甲苯及二甲苯。特別佳的溶液沉積技術係旋 • 塗及噴墨印刷。 旋塗尤其適用於其_不需要電致發光材料之圖案化的裝 置，例如用於照明應用或簡單的單色分段顯示器。 喷墨印刷尤其適用於高資訊含量顯示器，尤其係全彩顯 . 示器。 其他溶液沉積技術包括浸塗、輥印及絲網印刷。 OLED之發光層之喷墨印刷描述於（例如）Ep 中。 籲 I稱該發光層係由一有機化合物製得。據教示，適用於喷 墨P刷的有機發光材料之組合物需要滿足對接觸角、黏度 、 張力之至少一者所給定之數值範圍的條件。接觸角 •的、°定範圍為30至170度。黏度的給定範圍為1至20 cp。 •表面張力的給定範圍為20至70達因/cm。據稱一較佳實施 例係其中該有機發光化合物為電洞注入及傳輸類型材料。 亦揭示一思人 r 增。至該發光層之分開的電洞注入及傳輸層。對 匕 'p-.、 /5注入及傳輸層之形成方法並無特定限制，但據稱 吏^ 用 jra γ 墨方法（舉例而言）形成該層。其給出構成該電洞 I45811.doc 201033301 注入及傳輸層之材料之實例係：基於芳族二胺之化合物 (如 TPD)、MTDATA、喹 ％ 啶酮、（bisstil)蒽衍生物、 P VK基於酞·菁之錯合物（如銅敝菁）、基於。卜吩之化合 物、NPD、TAD、聚苯胺及其類似物。 在EP 0880303之實例2中，藉由喷墨印刷將一 ρνκ電洞 注入層沉積於紅色及綠色發光層上。並未提供該ρνκ之物 理特性（黏度 '表面張力、接觸角）。在Ερ 〇88〇3〇3之實例3 中，利用一喷墨裝置將一電洞注入層材料與紅色' 綠色及 藍色發光材料混合以形成紅色、綠色及藍色發光層。 WO 2006/123 167係關於用於噴墨印刷用來製造光電裝置 之導電或半導電有機材料之組合物。w〇 2〇〇6/123167中稱 電荷注入層可以一包括在高沸點溶劑中之導電有機材料之 組合物沉積。PEDOT:PSS經舉例為導電有機材料。其揭示 種藉由噴墨印刷包括PEDOT(或其他可能的電洞注入材 料）及高沸點溶劑之調配物而形成一裝置之方法。 WO 2006/123167亦揭示-種組合物，其包括有機電致發 光材料及沸點高於水之高沸點溶劑。在w〇 2〇〇6/123167中 並未揭示或建議藉由噴墨印刷沉積半導體電洞傳輸材料以 形成分開的電洞傳輸層。 對喷墨印刷感興趣的關鍵原因係其之可放大性及可適應 性。前者允許將任意大尺寸的基板圖案化，及後者係指與 從一個產品轉變至另一個產品相關的工具成本微不足道， 因為印刷於基板上之點之圖像係由軟體界定。初看，此將 類似於印刷圖像-可取得可於廣告牌大小的基板上印刷任 145811.doc 201033301 意圖像之商業印刷設備。然而，圖形印刷機與顯示面板間 的顯著差異在於：前者使用多孔基板或使用υν可固化的 油墨’以致乾燥環境對膜形成之影響極小。相比而言，用 於製造OLED顯示器之油墨係噴墨印刷於無孔表面，且從 濕油墨轉變至乾膜的過程係受像素中該油墨之乾燥環境主 宰。因為該印刷製程涉及印刷油墨之條紋（或長條）（對應於 該喷墨頭寬度），所以乾燥環境存在内在不對稱性。此 外〇LED裝置需求該等膜係奈米容限均勻。因此獲得可 ^ 放大性及可適應性需要控制油墨的成膜特性及此製程對像 素尺寸及覆蓋時間變化的穩定性。 然而，喷墨印刷之一關鍵問題係平面膜中的層間邊緣增 厚。此清晰地顯示於圖3中。此邊緣增厚導致該電致發光 層之邊緣變薄。貫穿-個像素的電致發光膜厚度的變化導 致不均勻的發射且降低裝置效率及壽命。 因此有需要提供用於喷墨印刷之調配物，其可為平面膜 φ 裝置產生平坦邊緣或甚至更薄的邊緣層間。 據此’本發明者已確^需要提供適於藉由嘴墨印刷沉積 以獲得平面膜，且可克服上述問題之另外的組合物。 【發明内容】 本發明之第-態樣提供一種適於一光電裝置之嗜墨印 刷、喷嘴塗覆、喷塗、輕印、浸塗、狹縫塗佈或膠版印刷 之組合物，該組合物包括半導體電洞傳輸材料、電洞注入 材料、發光聚合物材料、電子傳輸材料或電子注入層、第 -溶劑及第二溶劑，其中該等溶劑可彼此混溶，該第一溶 145811.doc 201033301 比該第二㈣更低’及該電洞傳輸材料在該第一 溶劑中的溶解度比在該第二溶劑中更高。 使用該層間聚合物較不可於其中溶解的高彿點溶劑可解 決上述問題，因為該聚合物在乾燥時析出更快速且 向像素邊緣遷移。 該第二溶劑之介電常數範圍較佳為。該 第-溶劑之介電常數範圍通常為高於22且低於2〇。 μ 在沒有特定限制下’該第一溶劑可係以下任一者：環己 基苯、甲基苯甲醚、苯甲酸甲醋、苯甲酸丁醋、苯甲酸乙 酯、苯曱酸丙酯、乙基苯甲醚、二甲基苯甲醚、苯甲醚、Θ 己苯、庚苯、辛笨。 該第一心劑可例如為二環己基、單己基環己烷、單辛基 環己烷。 第一溶劑的量占該組合物之！至99體積％。較佳地第 一洛劑的量係占該組合物之20至80體積％，及甚至更佳 地，第二溶劑的量係占該組合物之30至70體積〇/〇。 在，又有特定限制下’該第一溶劑的沸點為1〇〇至2〇〇t»c之 ❹ 間。该第二溶劑的沸點通常為210至350°C之間。 在本發明第一態樣之一較佳實施例中，該組合物包括第 二溶劑，其與該第一及第二溶劑可混溶，及其沸點比該第 ‘ 一溶劑更高。 該第二溶劑可作為膜平滑劑以進一步降低任何粗糙度。 在沒有特定限制下’該第三溶劑可係苯氧基甲苯、二苄 醚、苯氧基笨。 145811.doc • 8 - 201033301 s亥第二》谷劑較佳占該組合物之〇·〇][至ι〇體積％。甚至更 佳地，該第三溶劑占該組合物之〇.5至2體積〇/0。 通常情況下’包括發光材料及溶劍之組合物具有約1 w/ν%之固體含量。採用此範圍係由於發射體之分子量及 該組合物之黏度限制，其需在喷墨印刷頭之黏度臨限值 内。在喷墨組合物中，發光材料之濃度通常經最大化，以 致於每一滴組合物中沉積儘可能多的發光材料。即使如 此，為沈積足量的發光材料，一般需要使喷墨頭通過兩或 二次，以產生厚度約60 nm之發光層，該厚度係最佳裝置 性能所需之厚度。然而，本發明者已發現一電洞傳輸層可 在低許多的厚度下（約10 nm)提供最佳性能。因此，電洞 傳輸組合物可以低許多的濃度提供。 在該半導體電洞傳輸材料係一聚合物的情況下發現使用 此低湲度之-特別效益，其中可使用甚高分子量的半導體 電洞傳輸聚合物而非相應分子量的發光聚合物。該半導體 電洞傳輸聚合物之分子量範圍可為4G，_至彻，_道爾頓 (Dalton)。此半導體電洞傳輸聚合物之分子量較佳為至少 35〇，_道爾頓(除非另外說明，否則本文提供之聚合物分 子量係藉由凝谬滲透層㈣得之相料聚苯乙稀之以道爾 頓計的分子量）。如果該組合物之聚合物包括可交聯基團 尤其有利’因為在較高分子量的聚合物中每個聚合物鍵有 較高數量的可交聯基團。 匕括刀子里低於250,〇〇〇道爾頓之發光聚合物之裝置的 裝置性能較差，所以不會利用此等低分子量聚合物調配適 145811.doc 201033301 已發現未對電 於喷墨印刷之發光組合物。然:而，本發明者 洞傳輸聚合物發現如此差的裝置性能。 組合物之噴射性能很大程度取決於固體含量（組合物之 =體含置可簡單地藉由蒸發溶劑並稱重剩餘固體而 定）。 通常而言，用於喷墨印刷之含發光材料之組合物將具有 /v /。之較同固體含量。在該組合物中該半導體電洞 傳輸材料之遭度較佳係0.8 w/v°/((或更低。 ° 在本文描述之任何組合物中，該半導體電洞傳輸材料可 由於存在可父聯基團而係可交聯的。 在本文描述之任何組合物中，該半導體電洞傳輪材料較 佳包括聚合物。較佳的半導體電洞傳輸聚合物包括三芳胺 重複單元。 較佳的三芳胺重複單元符合通式1:201033301 VI. Description of the Invention: [Technical Field] The present invention relates to a composition comprising a hole transporting material, a hole injecting material, a light emitting polymer material, an electron transporting material or an electron injecting layer material, the composition being suitable for In the manufacture of organic light-emitting devices, by inkjet printing, nozzle coating, spray coating, roll printing, dip coating, slit coating, or offset printing. [Prior Art] A typical organic light-emitting device (OLED) includes a substrate on which an anode, a cathode, and a light-emitting layer between the cathode and the anode and including at least one polymer electroluminescent material are supported. In operation, a hole is injected into the device through the anode and electrons are injected into the device through the cathode. The holes and electrons are combined in the luminescent layer to form an exciton that subsequently undergoes radioactive decay to emit light. Other layers may be present in the OLED. For example, a hole injecting material may be disposed between the anode and the light emitting layer (eg, poly(ethylene nsec)/polystyrene read) (PED〇T/ a layer of PSS) to assist the hole in injecting the luminescent layer from the anode. In addition, a hole transport layer made of a hole transporting material may be disposed between the anode and the light-emitting layer to assist in the transmission of holes to the light-emitting layer. Luminescent conjugated polymers are an important class of materials that will be used in the next generation of organic light-emitting devices based on information technology-based consumer products. The main benefit of using polymers over inorganic semiconductor and organic dye materials is the use of solution treatment of tantalum materials to produce low cost devices. In the past decade, I45811.doc 201033301, many efforts have been made to improve the emission efficiency of organic light-emitting diodes (OLEDs) by developing highly efficient materials or effective device structures. Another advantage of co-light polymers is that they can be easily formed by Suzuki coffee or Yamamoto polymerization. This highly controls the degree of regularity of the resulting polymer. Because of the presence of suitable solubilizing groups, the residual polymer can be treated as a solution. Suitable solvents for the poly(arylene) group, especially the polycondensation type, include mono- or poly- <-phenylbenzenes such as toluene and xylene. Particularly good solution deposition techniques are spin coating and ink jet printing. Spin coating is particularly suitable for devices that do not require patterning of electroluminescent materials, such as for lighting applications or simple monochrome segmented displays. Inkjet printing is especially suitable for high-information displays, especially full-color displays. Other solution deposition techniques include dip coating, roll printing, and screen printing. Ink jet printing of the luminescent layer of an OLED is described, for example, in Ep. I claim that the luminescent layer is made of an organic compound. It is taught that the composition of the organic luminescent material suitable for the ink jet P brush needs to satisfy the conditions of the numerical range given by at least one of the contact angle, the viscosity and the tension. Contact angle • The range of ° is 30 to 170 degrees. The viscosity is given in the range of 1 to 20 cp. • The given range of surface tension is 20 to 70 dynes/cm. A preferred embodiment is said to be wherein the organic luminescent compound is a hole injecting and transporting type of material. It also reveals that a person is increasing. Separate hole injection and transport layers to the luminescent layer. There is no particular limitation on the method of forming the 匕 'p-., /5 implant and transport layer, but it is said that the layer is formed by, for example, the jra gamma ink method. An example of a material constituting the injection and transport layer of the hole I45811.doc 201033301 is given: an aromatic diamine-based compound (such as TPD), MTDATA, quinacridone, (bisstil) anthracene derivative, P VK based on酞·Cyanine complex (such as copper phthalocyanine), based. Compounds, NPD, TAD, polyaniline and the like. In Example 2 of EP 0880303, a ρνκ hole injection layer was deposited on the red and green light-emitting layers by inkjet printing. The physical properties of the ρνκ (viscosity 'surface tension, contact angle') are not provided. In Example 3 of Ερ 〇88〇3〇3, a hole injecting layer material was mixed with red 'green and blue luminescent materials' to form red, green and blue luminescent layers using an ink jet device. WO 2006/123 167 relates to compositions for ink jet printing of electrically conductive or semiconductive organic materials used to make photovoltaic devices. The charge injection layer may be deposited as a composition comprising a conductive organic material in a high boiling solvent, as described in w〇 2〇〇6/123167. PEDOT: PSS is exemplified by a conductive organic material. It discloses a method of forming a device by ink jet printing a formulation comprising PEDOT (or other possible hole injecting material) and a high boiling solvent. WO 2006/123167 also discloses a composition comprising an organic electroluminescent material and a high boiling point solvent having a boiling point higher than that of water. The deposition of a semiconductor hole transport material by ink jet printing to form a separate hole transport layer is not disclosed or suggested in WO 〇 6/123167. The key reason for interest in inkjet printing is its scalability and adaptability. The former allows for the patterning of any large-sized substrate, and the latter refers to the negligible cost of the tool associated with transitioning from one product to another because the image of the dots printed on the substrate is defined by the software. At first glance, this would be similar to a printed image - a commercial printing device that can print a 145811.doc 201033301 image on a billboard-sized substrate. However, a significant difference between the graphic printer and the display panel is that the former uses a porous substrate or uses a υν curable ink so that the influence of the dry environment on film formation is extremely small. In contrast, inks used in the manufacture of OLED displays are inkjet printed on non-porous surfaces, and the process of transitioning from wet ink to dry film is dominated by the dry environment of the ink in the pixels. Because the printing process involves strips (or strips) of printing ink (corresponding to the width of the head), there is inherent asymmetry in the dry environment. This external LED device requires uniform uniformity of these membranes. Therefore, it is necessary to control the film formation characteristics of the ink and the stability of the process to changes in pixel size and coverage time. However, one of the key issues in inkjet printing is the thickening of the interlaminar edges in the planar film. This is clearly shown in Figure 3. This edge thickening causes the edges of the electroluminescent layer to become thin. Variations in the thickness of the electroluminescent film throughout the pixels result in uneven emission and reduce device efficiency and lifetime. There is therefore a need to provide formulations for ink jet printing that can produce a flat edge or even a thinner edge layer for a planar film φ device. Accordingly, the inventors have made it necessary to provide an additional composition suitable for depositing by nozzle ink printing to obtain a planar film and which overcomes the above problems. SUMMARY OF THE INVENTION A first aspect of the present invention provides a composition suitable for ink-jet printing, nozzle coating, spray coating, light printing, dip coating, slit coating or offset printing of an optoelectronic device, the composition The invention comprises a semiconductor hole transporting material, a hole injecting material, a light emitting polymer material, an electron transporting material or an electron injecting layer, a first solvent and a second solvent, wherein the solvents are miscible with each other, the first solvent is 145811.doc 201033301 Lower than the second (four)' and the hole transport material has a higher solubility in the first solvent than in the second solvent. The use of the high point solvent in which the interlayer polymer is less soluble therein solves the above problem because the polymer precipitates more rapidly upon drying and migrates toward the edge of the pixel. The dielectric constant of the second solvent is preferably in the range of. The dielectric constant of the first solvent is usually in the range of more than 22 and less than 2 Å. μ Without any particular limitation, the first solvent may be any of the following: cyclohexylbenzene, methylanisole, methyl benzoate, butyl benzoate, ethyl benzoate, propyl benzoate, B. Alkylaniline, dimethylanisole, anisole, hexylbenzene, heptane, and stupid. The first cardiac agent may, for example, be dicyclohexyl, monohexylcyclohexane or monooctylcyclohexane. The amount of the first solvent is in the composition! Up to 99% by volume. Preferably, the amount of the first agent is from 20 to 80% by volume of the composition, and even more preferably, the amount of the second solvent is from 30 to 70% by volume of the composition. The first solvent has a boiling point of from 1 Torr to 2 〇〇 t»c. The second solvent typically has a boiling point between 210 and 350 °C. In a preferred embodiment of the first aspect of the invention, the composition comprises a second solvent which is miscible with the first and second solvents and which has a higher boiling point than the first solvent. This second solvent can act as a film smoothing agent to further reduce any roughness. The third solvent may be phenoxytoluene, dibenzyl ether or phenoxy stray without any particular limitation. 145811.doc • 8 - 201033301 s Hai 2nd gluten preferably accounts for 组合·〇] of the composition [to ι〇 volume%. Even more preferably, the third solvent comprises from 55 to 2 volumes 〇/0 of the composition. Typically, a composition comprising a luminescent material and a spirulina has a solids content of about 1 w/v%. The use of this range is due to the molecular weight of the emitter and the viscosity of the composition, which is within the viscosity threshold of the ink jet printhead. In ink jet compositions, the concentration of the luminescent material is typically maximized such that as much luminescent material as possible is deposited in each drop of composition. Even so, in order to deposit a sufficient amount of luminescent material, it is generally desirable to pass the ink jet head two or two times to produce an illuminating layer having a thickness of about 60 nm, which is the thickness required for optimum device performance. However, the inventors have discovered that a hole transport layer can provide optimum performance at much lower thicknesses (about 10 nm). Thus, the hole transport composition can be provided in much lower concentrations. In the case where the semiconductor hole transporting material is a polymer, it has been found to use this low degree of special benefit in which a very high molecular weight semiconductor hole transport polymer can be used instead of a corresponding molecular weight luminescent polymer. The semiconductor hole transport polymer may have a molecular weight ranging from 4G to _Dalton. The molecular weight of the semiconductor hole transport polymer is preferably at least 35 Å, _ Dalton (unless otherwise stated, the molecular weight of the polymer provided herein is obtained by condensing the permeable layer (4) to obtain the phase polystyrene. Dalton's molecular weight). It is especially advantageous if the polymer of the composition comprises a crosslinkable group' because in the higher molecular weight polymer there is a higher number of crosslinkable groups per polymer bond. Included in the knife is less than 250, the device of the luminescent polymer device of Dalton has poor performance, so it will not be used to blend with these low molecular weight polymers. 145811.doc 201033301 A luminescent composition. However, the inventors of the present invention have discovered such poor device performance. The spray performance of the composition is highly dependent on the solids content (the composition = composition can be simply determined by evaporating the solvent and weighing the remaining solids). In general, compositions containing luminescent materials for ink jet printing will have /v /. The same solid content. The semiconductor hole transport material in the composition is preferably 0.8 w/v° / (or lower. ° In any of the compositions described herein, the semiconductor hole transport material may be present due to presence The semiconductor group is preferably crosslinkable. In any of the compositions described herein, the semiconductor hole transport material preferably comprises a polymer. Preferred semiconductor hole transport polymers include triarylamine repeat units. The triarylamine repeat unit conforms to Formula 1:
〃中Ar及Ar2係視情況經取代的芳基或雜芳基，n為大於 或等於1，較佳為1或2，及R為H或取代基，較佳為取代 基R較佳為烷基或芳基或雜芳基，最佳為芳基或雜芳 基。在式1單元中之任何芳基或雜芳基可經取代。較佳的 取代基包括烷基及烧氧基。在式1重複單元中之任何芳基 或雜芳基可藉由直接鍵或二價連接原子或基團相連接。較 145811.doc •10· 201033301 佳的二價連接原子及基團包括〇小經取代的N、及經取 代的c。 符合式1之特佳單元包括式2至4之單元：Ar and Ar2 in the oxime are optionally substituted aryl or heteroaryl, n is greater than or equal to 1, preferably 1 or 2, and R is H or a substituent, preferably the substituent R is preferably an alkane Or an aryl or heteroaryl group, most preferably an aryl or heteroaryl group. Any aryl or heteroaryl group in the unit of formula 1 may be substituted. Preferred substituents include alkyl groups and alkoxy groups. Any aryl or heteroaryl group in the repeating unit of Formula 1 may be bonded by a direct bond or a divalent linking atom or group. 145811.doc •10· 201033301 The preferred divalent linking atom and group includes a small substituted N and a substituted c. The special unit that conforms to Equation 1 includes the units of Equations 2 through 4:
Ar3 Ar3Ar3 Ar3
其：Ar及Ar係如上定義，及Αγ3係視情況經取代的芳基或 雜方基。當存在時，Ar3之較佳取代基包括烷基及烷氧 基0 此類型之尤其佳的電洞傳輸聚合物係三芳胺重複單元與 第重複單元之共聚物（特別是ΑΒ共聚物）。該第二重複單 元較佳為第重複單元，更佳為式5之重複單元：It is: Ar and Ar are as defined above, and Αγ3 is an optionally substituted aryl or heteroaryl group. When present, preferred substituents for Ar3 include alkyl and alkoxy groups. A particularly preferred hole transporting polymer is a copolymer of a triarylamine repeating unit and a repeating unit (particularly a ruthenium copolymer). The second repeating unit is preferably a repeating unit, more preferably a repeating unit of formula 5:
/、中R及R係獨立選自氫或視情況經取代之烧基、统氧 土 2芳基、芳基烷基、雜芳基及雜芳基烷基。更佳地，Ri —者包括視情況經取代之(：4至(：2。烧基或芳 本毛明之第=態樣係關力一種形成有機#光裝置之方 法，其包括以下步驟： 145811.doc 201033301 a.提供一陽極層； b·視情況在該陽極層上提供一導電電洞注入層； c·藉由噴墨印刷在該陽㈣電洞注人層上沉積—如技術 方案!至15中任一項所定義之組合物，以形成一半導體電 洞傳輸層，限制條件為：當藉由噴墨印刷沉積該半導體電 洞傳輸材料時，則該半導體電洞傳輸材㈣在—電洞注入 層上沉積。 本發明之第二態樣係、—種形成有機發光裝置之方法 包括以下步驟： 、 1.藉由噴墨印刷沉積一如技術方案丨至15項中任一項所 疋義之組合物以形成一半導體電洞傳輸層。 根據本發明之第二或第三態樣之方法較佳包括藉由加熱 太共烤6亥半導體電洞傳輸層之另一步驟。 應選擇供烤條件以使該半導體電洞傳輸層之至少一部分 變得不可溶，以致可沉積發光層而不會溶解該半導體電二 傳輸層。技術界已知此供烤半導體電洞傳輸層之技術。用 ❹ 於烘烤之適宜溫度範圍係⑽至22代，較佳為⑽ 20〇〇C。 關於本發明之第二及第三態樣’應瞭解該定義組合物之 沉積通常將係在一陽極或一導電電洞注入層上。 在根據本發明之第二及第三態樣之方法中1半導㈣ 洞傳輸層之厚度範圍較佳為5至40 nm，更佳為5至3〇 再更佳為8至20 nm ’及最佳為約1〇 nm。該溶劑可在數秒 至數分鐘内乾燥並形成與最初的「油墨」體積㈣相對薄 145831.doc •12. 201033301 的膜。通常沉積許多液滴（較佳於乾燥開始前），以提供足 夠的乾燥材料厚度。 & 在所有根據本發明之第二及第三態樣之方法中，該等方 法通常將包括以下步驟：在該半導體電洞傳輸層上沉積— 發先層，視情況在該發光層上沉積—電子傳輸層，及在該 發先層或電子傳輸層（當存在時）上沉積一陰極。 應瞭解，在本發明之第二及第三態樣中，該等方法較佳 包括以下步驟··在該半導體電洞傳輸層形成後，自其 =:，了 (等)溶劑之較佳方法包括於高溫下(通常最高 』、取決於真空屋力）真空乾燥。提供高海點溶劑 會增加該組合物之乾燥時間。 在根據本發明之第二及第三態樣之方法中，應明白印刷 一般將係進入由堤岸結構界定之像素令。在此方面，該组 / 合物之所需黏度將在某種程度上取決於像素大小、液滴直 在、液滴體積、液滴頻率、及將沉積該組合物之表面的可 濕杜對於小像素’一般使用較高的固體含量。對於較大 ^素會使用較低的固體含量。對於較大像素，降低該組合 物之;農度以獲得良好的成膜特性。 =合物較佳應與該堤岸具有一接觸角，使得其潤濕該 开之基。P，但不會溢出該井。 —發月之第四態樣提供一種藉由根據本發明之第二或第 三態樣之方法製得的有機發光裝置。 根據本發明第四態樣之裝置之較佳特性提供如下： 參考圖1，根據本發明第四態樣之電致發光裝置之結構 145811.doc -13· 201033301 較佳包括一（通常係透明玻璃或塑料）基板卜-陽極2及一 陰極4。在陽極2與陰極4之間設置一發光層3。 在一實際裝置中，至少一個電極係半透明以使光可發 射。當該陽極係透明時’其通常包括氧化銦錫。 該半導體電洞傳輸層係存在於陽極2與發光層3之間。於 陽極2與陰極3之間可設置其他層，如電荷傳輸、電荷注人 或電荷阻擋層。 特定言之，需要提供—導電電洞注人層，其可自位在該 陽極2與該半導體電洞傳輸層之間的導電有機或無機材料 形成，以協助電洞自該陽極注入該半導體電洞傳輸層。經 摻雜有機電洞注入材料之實例包括經摻雜的聚（乙烯二氧 噻吩）(PEDT)，尤其係摻雜有電荷平衡多元酸之pEDT，該 多元酸例如EP 〇901176&ep 〇947123所揭示之聚苯乙烯磺 酸醋（PSS)、聚丙烯酸或氟化磺酸（例如Nafi〇n⑧）；us 5723873及US 5798170所揭示之聚苯胺；及聚（噻吩并噻 吩）。導電無機材料之實例包括過渡金屬氧化物，如揭示 於 Journal of Physics D: Applied Physics (1996), 29(11)， 2750至 2753 中之 VOx MoOx及 RuOx。 位於陽極2與發光層3間之該電洞傳輸層之homo值較佳 低於或等於5.5 eV ’更佳為約4.8至5.5 eV。HOMO值可藉 由循環伏安法（舉例而言）測量。 若存在之位於電致發光層3與陰極4之間之電子傳輸層較 佳具有約3至3.5 eV之LUMO值。 本發明之第五態樣提供一種全彩顯示器，其包括根據本 145811.doc -14· 201033301 發明第四態樣之有機發光裝置。 「較{的全I顯不器包括「紅色」像素、「綠色」像素 及藍色」像素，每一像素包括一如關於第四態樣定義之 紅色」像素將具有—包括紅色電致發光材料 之發光層 綠色」像素將具有-包括綠色電致發光材 ;斗之發光># Μ色」像素將具有—包括藍色電致發光 材料，發光層。該電洞傳輸層較佳係通用於所有顏色。/, R and R are independently selected from hydrogen or optionally substituted alkyl, oxo 2 aryl, arylalkyl, heteroaryl and heteroarylalkyl. More preferably, Ri-includes a method of forming an organic #光装置, which includes the following steps: 145811. The method includes the following: (4: (2). Doc 201033301 a. Providing an anode layer; b· providing a conductive hole injection layer on the anode layer as appropriate; c· depositing on the anode layer of the anode by inkjet printing - as in the technical solution! The composition defined in any one of 15 to form a semiconductor hole transport layer, wherein the semiconductor hole transport material (four) is in-situ when the semiconductor hole transport material is deposited by inkjet printing Depositing on the hole injection layer. The second aspect of the present invention, the method for forming an organic light-emitting device comprises the following steps: 1. Depositing by inkjet printing as one of the technical solutions to 15 The composition of the invention forms a semiconductor hole transport layer. The method according to the second or third aspect of the invention preferably comprises the further step of heating the conductive layer of the semiconductor via 6 gallon. The semiconductor hole transport layer At least a portion becomes insoluble so that the light-emitting layer can be deposited without dissolving the semiconductor electrical two-transport layer. The technique for baking a semiconductor hole transport layer is known in the art. The suitable temperature range for baking is (10) to 22 generations, preferably (10) 20 〇〇 C. Regarding the second and third aspects of the invention 'should be understood that the deposition of the defined composition will typically be on an anode or a conductive hole injection layer. In the second and third aspects of the invention, the thickness of the one-half (four) hole transport layer is preferably from 5 to 40 nm, more preferably from 5 to 3, still more preferably from 8 to 20 nm. About 1 〇 nm. The solvent can be dried in a few seconds to several minutes to form a film that is relatively thin compared to the original "ink" volume (four) 145831.doc • 12. 201033301. Usually many droplets are deposited (preferably before the start of drying) To provide sufficient dry material thickness. & In all methods according to the second and third aspects of the invention, the methods generally comprise the steps of: depositing on the semiconductor hole transport layer - the first layer Depositing on the luminescent layer as appropriate - a sub-transport layer, and a cathode deposited on the precursor layer or electron transport layer (when present). It will be appreciated that in the second and third aspects of the invention, the methods preferably include the following steps: After the formation of the semiconductor hole transport layer, the preferred method from which the solvent is included includes vacuum drying at a high temperature (usually the highest, depending on the vacuum house force). Providing a high sea point solvent increases the Drying time of the composition. In the method according to the second and third aspects of the invention, it will be understood that the printing will generally enter a pixel order defined by the bank structure. In this respect, the desired viscosity of the composition The higher solids content will generally be used for small pixels' to some extent depending on pixel size, droplet straightness, droplet volume, droplet frequency, and wettable surface on which the composition will be deposited. A lower solids content will be used for larger ones. For larger pixels, the composition is reduced; the degree of agronomy is obtained to obtain good film forming properties. Preferably, the compound should have a contact angle with the bank such that it wets the open matrix. P, but will not overflow the well. The fourth aspect of the moon provides an organic light-emitting device produced by the method according to the second or third aspect of the invention. The preferred characteristics of the apparatus according to the fourth aspect of the present invention are as follows: Referring to Figure 1, the structure of the electroluminescent device according to the fourth aspect of the present invention is preferably 145811.doc -13· 201033301, which preferably includes a (usually transparent glass) Or plastic) substrate - anode 2 and a cathode 4. A light-emitting layer 3 is disposed between the anode 2 and the cathode 4. In an actual device, at least one of the electrodes is translucent to allow light to be emitted. When the anode is transparent, it typically comprises indium tin oxide. The semiconductor hole transport layer is present between the anode 2 and the light-emitting layer 3. Other layers, such as charge transport, charge injection or charge blocking layers, may be disposed between the anode 2 and the cathode 3. In particular, it is desirable to provide a conductive hole injection layer that can be formed from a conductive organic or inorganic material between the anode 2 and the semiconductor hole transport layer to assist the hole in injecting the semiconductor from the anode. Hole transport layer. Examples of the doped organic hole injecting material include doped poly(ethylene dioxythiophene) (PEDT), especially pEDT doped with a charge-balanced polybasic acid such as EP 〇 901176 & ep 〇 947123 Polystyrene disclosed in polystyrene sulfonate (PSS), polyacrylic acid or fluorinated sulfonic acid (for example, Nafi〇n8); us 5723873 and US 5798170; and poly(thienothiophene). Examples of the conductive inorganic material include transition metal oxides such as VOx MoOx and RuOx disclosed in Journal of Physics D: Applied Physics (1996), 29(11), 2750 to 2753. The hole transport layer between the anode 2 and the light-emitting layer 3 preferably has a homo value of less than or equal to 5.5 eV', more preferably about 4.8 to 5.5 eV. The HOMO value can be measured by cyclic voltammetry (for example). The electron transport layer between the electroluminescent layer 3 and the cathode 4 preferably has a LUMO value of about 3 to 3.5 eV. A fifth aspect of the present invention provides a full color display comprising the organic light-emitting device according to the fourth aspect of the invention of the invention of 145811.doc -14 201033301. "Compared with the "red" pixel, the "green" pixel and the blue "pixel", each pixel includes a red color as defined in the fourth aspect. "The pixel will have - including the red electroluminescent material. The illuminating layer green" pixel will have - including a green electroluminescent material; the bucket illuminating ># Μ color" pixel will have - including a blue electroluminescent material, a luminescent layer. The hole transport layer is preferably used in all colors.
=明、红色電致發光材料」係指—藉由電致發光發射波 長範圍為600至750 nm之輕射，較佳為6。。至糊nm，更佳 為61〇至650 nm及最佳為具有約㈣至66〇⑽之發射峰的有 機材料。 所謂「綠色電致發光材料」係指—藉由電致發光發射波 長範圍為510至580 nm之輻射，較佳為51〇至57〇 nm的有機 材料。 所胡「藍色電致發光材料」係指一藉由電致發光發射波 長範圍為400至500 nm之輻射，較佳為43〇至5〇〇 nm的有機 材料。 紅色、綠色及藍色電致發光材料係技術界已知。 【實施方式】 現將參考附圖更詳細地描述本發明。 參考根據第四態樣之裝置，發光層3可僅由發光材料組 成或可包括該發光材料與一或更多種其他材料的組合。特 疋§之’該電致發光材料可與如揭示於（例如）W〇 99/48 160中之電洞及/或電子傳輸材料摻合，或可包括存於 145811.doc -15- 201033301 主體基μ之—發光摻_。或者，該發光#料 可/、價鍵結至電荷傳輸材料及/或主體材料。 發光層3可經圖案化或未經圖案化。包括一未圖案化層 '置可使用作為照明光源（舉例而言）^白光發射裝置係 尤其適用於此目的。一種包括一圖案化層之裝置可為（例 ^ )主動矩陣顯示器或被動矩陣顯示器。在主動矩陣顯示 器之情況中，一圖案化電致發光層通常係與一圖案化陽極 層及-未圖案化陰極組合使用。在被動矩陣顯示器之情況 中，該陽極層係由陽極材料之平行條紋形成，且電致發光 材料及陰極材料之平行條紋係垂直於該陽極材料設置，其 中電致發光材料及陰極材料之條紋通常係經藉由光微影形 成之絕緣材料之條紋（「陰極分離器」）分隔。 適用於發光層3之材料包括小分子、聚合物及樹狀高分 子材料及其組合物。適用於層3之電致發光聚合物包括聚 (伸芳基伸乙烯基）(如，聚（對伸苯基伸乙烯基）)及聚伸芳基 (如聚第類，尤其係2,7-連接的9,9二烷基聚第類或2,7-連接 的9,9二芳基聚蕹類）；聚螺第類’尤其係2,7_連接的聚_ 9,9-螺第類；聚茚并苐類，尤其係2,7-連接的聚茚并苐 類；聚伸苯基’尤其係經烷基或烷氧基取代的聚·154_伸苯 基。此等聚合物揭示於（例如）Adv. Mater. 2000 12(23) P37至1750及其中之參考文獻中。適用於層3之電致發光 樹狀高分子類包括帶有樹狀高分子基團之電致發光金屬錯 合物，如揭示於（例如）WO 02/066552中者。 陰極4係選自具有允許電子注入該發光層之功函數之材 145811.doc • 16 - 201033301 料。其他因素會影響該陰極之選擇，如該陰極與該電致發 光材料間之不良相互作用可能性。該陰極可由單一材料， 如鋁層組成。或者，其可包括多種金屬（例如）低功函數材 料及高功函數材料（如揭示於wo 98/1〇621中之鈣及鋁）之 雙層、元素鋇（如揭示於曹〇 98/57381、八？？1.?1^3.1^«· 2002, 81(4)，634、及WO 02/84759中）、或金屬化合物之薄 層（尤其係鹼金屬或鹼土金屬之氧化物或氟化物）以協助電 子注入（例如，揭示於w〇 〇〇/48258中之氟化鋰、揭示於= bright, red electroluminescent material means a light-emitting emission having a wavelength range of from 600 to 750 nm by electroluminescence, preferably 6. . To paste nm, more preferably 61 〇 to 650 nm and most preferably an organic material having an emission peak of about (four) to 66 〇 (10). The term "green electroluminescent material" means an organic material having an emission wavelength ranging from 510 to 580 nm, preferably from 51 Å to 57 Å, by electroluminescence. The "blue electroluminescent material" refers to an organic material which emits light having a wavelength in the range of 400 to 500 nm by electroluminescence, preferably 43 to 5 Å. Red, green and blue electroluminescent materials are known in the art. [Embodiment] The present invention will now be described in more detail with reference to the accompanying drawings. Referring to the apparatus according to the fourth aspect, the light-emitting layer 3 may be composed only of a light-emitting material or may include a combination of the light-emitting material and one or more other materials. The electroluminescent material may be blended with a hole and/or electron transport material as disclosed, for example, in W〇99/48 160, or may be included in the body of 145811.doc -15- 201033301 The base μ-light-doped _. Alternatively, the luminescent material may be valence-bonded to the charge transport material and/or the host material. The luminescent layer 3 can be patterned or unpatterned. The inclusion of an unpatterned layer 'can be used as an illumination source (for example) is a white light emitting device that is particularly suitable for this purpose. A device comprising a patterned layer can be an active matrix display or a passive matrix display. In the case of an active matrix display, a patterned electroluminescent layer is typically used in combination with a patterned anode layer and an unpatterned cathode. In the case of a passive matrix display, the anode layer is formed by parallel strips of anode material, and the parallel strips of electroluminescent material and cathode material are disposed perpendicular to the anode material, wherein the stripes of the electroluminescent material and the cathode material are generally It is separated by stripes of insulating material ("cathode separator") formed by photolithography. Suitable materials for the luminescent layer 3 include small molecules, polymers and dendritic polymeric materials and combinations thereof. Electroluminescent polymers suitable for layer 3 include poly(exoaryl extended vinyl) (eg, poly(p-phenylene vinyl)) and poly-aryl (eg, poly, especially 2,7-linked) 9,9 dialkyl polyclass or 2,7-linked 9,9 diaryl polyfluorene); polyspiro class 'especially 2,7_linked poly-9,9-spiral class Poly-indenes, especially 2,7-linked polyfluorenes; poly-phenylenes are especially poly-154-phenyl groups substituted by alkyl or alkoxy groups. Such polymers are disclosed, for example, in Adv. Mater. 2000 12(23) P37 to 1750 and references therein. Electroluminescence suitable for layer 3 dendrimers include electroluminescent metal complexes with dendritic polymeric groups as disclosed, for example, in WO 02/066552. The cathode 4 is selected from materials having a work function that allows electrons to be injected into the light-emitting layer 145811.doc • 16 - 201033301. Other factors can influence the choice of the cathode, such as the potential for adverse interaction between the cathode and the electroluminescent material. The cathode can be composed of a single material, such as an aluminum layer. Alternatively, it may comprise a plurality of metals, such as a low work function material and a high work function material (such as calcium and aluminum disclosed in WO 98/1〇621), a double layer, element 钡 (as disclosed in Cao Yu 98/57381 , eight??1.1^3.1^«· 2002, 81(4),634, and WO 02/84759), or a thin layer of a metal compound (especially an oxide or fluoride of an alkali or alkaline earth metal) ) to assist in electron injection (for example, lithium fluoride disclosed in w〇〇〇/48258, disclosed in
Appl. Phys. Lett. 2001，79(5)，2001 中之氟化鋇、及氧化 鋇）。為提供有效的電子注入至該裝置，該陰極較佳具有 低於3.5 eV之功函數，更佳低於3 2 eV，最佳低於3 eV。 金屬之功函數可見於（例如）Michaels〇n，j Appl. phys 48(11)，4729，1977。 忒陰極可係不透明或透明的。透明陰極尤其有利於主動 矩陣裝置，因為通過此等裝置中之透明陽極之發射會至少 部分地被位於該發射像素下方之驅動電路所阻斷。透明陰 極將包括一層足夠薄而呈透明之電子注入材料。由於其薄 又此層之橫向電導率通常將較低。在此情況下，該電子 注入材料層係與透明導電材料（如氧化銦錫）之較厚層組合 使用。 應瞭解，透明陰極裝置不需具有透明陽極（當然，除非 ，，完全透明的裝置），且因此用於底部發光裝置之該透 明陽極可用一反射性材料層（如銘層）取《或補充。透明陰 極裝置之實例揭示於（例如）GB 2348316中。 145811.doc 17· 201033301 光學裝置往往對水分及氧氣敏感。據此，該基板較佳具 有避免水分及氧氣滲入該裝置之良好阻隔特性。該基板一 般係玻璃，然而亦可使用替代基板，尤其係當該裝置需要 可撓性時。例如，該基板可包括如us 6268695(其揭示一 交替的塑料及阻隔層之基板）中之塑料或揭示於Ep 〇94985〇 中之薄玻璃及塑料之層壓板。 »亥裝置較佳用一密封材料密封（沒有顯示於圖丨）以防止 水分及氧氣之滲入。適宜的密封材料包括玻璃板材、具有 適宜阻隔特性的膜（如交替堆疊之聚合物及介電質，如揭 不於（例如）WO 01/81649中）或一氣密容器（如揭示於（例 如）WO 01/19142中）。可將用於吸收任何可能滲透通過該 基板或密封材料之環境中之水分及/或氧氣之吸收劑材料 設置於該基板與該密封材料之間。 聚合方法 用於製備半導體聚合物之較佳方法係鈴木聚合反應（如 描述於（例如）WO 00/53656中）及山本聚合反應（如描述於 (例如）T. Yamamoto, "Electrically Conducting And Thermally Stable π - Conjugated Poly(arylene)s Prepared by Organometallic Processes", Progress in Polymer Science 1993，17，1153-1205中）。此等聚合技術皆係通過「金屬插 入」而操作，其中使一金屬錯合物觸媒之金屬原子插入於 一芳基與一單體之一離去基之間。在山本聚合之情況下， 使用錄錯合物觸媒；在龄木聚合之情況下，使用把錯合物 觸媒。 145811.doc •18- 201033301 例如，在藉由山本聚合合成線性聚合物時，使用具有兩 個活性鹵素基之單體^類似地，根據鈐木聚合方法，至少 一個活性基係领衍生物基（如晒酸或目朋酸酯）及另一個活性 基係鹵素。較佳的鹵素係氣、溴及碘，以溴為最佳。 因此應明白’如在整篇專利說明書中說明之包括芳基之 重複單元及端基可衍生自一帶有適宜離去基之單體。 可使用鈴木聚合以製備區域規則性、嵌段及無規共聚 物。特定言之，當一個活性基係鹵素及另一個活性基係硼 • 衍生物基時，可製備得均聚物或無規共聚物。或者，當第 一單體之兩個活性基係硼且第二單體之兩個活性基係鹵素 時，可製備得嵌段或區域規則性（尤其係八8型）共聚物。 作為齒化物之替代，能參與金屬插入之其他離去基包括 含甲苯磺酸鹽（酯）、曱磺酸鹽（酯）及三氟甲磺酸鹽（酯）之基 溶液處理 可自溶液沉積單一聚合物或多種聚合物以形成層3。適 用於聚伸芳基（尤其係聚第類）之溶劑包括單_或多_烷基苯 類，如甲苯及一甲苯。尤其佳的溶液沉積技術係旋塗及噴 墨印刷。 旋塗特別適用於其中不需要電致發光材料之圖案化之裝 置，例如，用於照明應用或簡單的單色分段顯示器。 喷墨印刷特別適用於高資訊含量顯示器，尤其係全彩顯 示器OLED之嘴墨印刷描述於（例如）ep 0880303中。 其他溶液沉積技術包括浸塗、輥印及絲網印刷。 145811.doc -19- 201033301 如果該裝置之多個層係藉由溶液處理形成，則熟悉技藝 人士當知曉防止相鄰層混雜之技術，例如，藉由先交聯一 層隨後再沉積另一層，或選擇相鄰層之材料使得首先形成 層之材料不會溶於用於沉積第二層之溶劑中。 可將有機LED沉積於一基板上之一像素矩陣中以形成單 色或多色像素化顯示器。一多色顯示器可使用紅色、綠 色、及藍色發光像素之群組組建。所謂的主動矩陣顯示器 具有一與各像素相關聯之記憶元件（通常係一儲存電容器 及一電晶體）’而被動矩陣顯示器則不具有此記憶元件且 取而代之為重複地掃描以提供一穩定圖像之印象。 圖2顯示通過一 OLED裝置1〇〇之一實例之垂直截面。在 主動矩陣顯示器中，部分的像素面積被相關的驅動電路佔 據（未顯示於圖2中）。該裝置之結構為說明之目的而梢有簡 化。 該OLED 100包括一基板102，通常係〇 7爪瓜或〗」爪爪之 玻璃’但視情況係透明塑料，已於其上沉積一陽極層1〇6。 該陽極層通常包括約150 nm厚之ITO(氧化銦錫），於其上 提供一金屬接觸層（通常係約5〇〇 nm之鋁，有時稱為陽極 金屬）。經塗布ITO及接觸金屬之玻璃基板可購自c〇rning, USA。該接觸金屬（及視情況該IT〇)視需要藉由光微影接 著蝕刻之習知方法圖案化，以致其不會遮掩該顯示器。 於該陽極金屬上提供一實質上透明的導電電洞注入層 l〇8a，接著該半導體電洞傳輸層⑺訃及一電致發光層1〇以。 可在忒基板上形成堤岸112(例如由正或負光阻材料形成）， 145811.doc -20· 201033301 、（可於#中選擇性地沉積此等活性有機層&井Η#。 該等井SUb界定該顯示器之發光區域或像素。 隨後藉由（如）物理氣相沉積施用一陰極層"ο。該陰極層 $常包括經較厚的銘封蓋層覆蓋之低功函數金屬如約或 2 Hit況包括-與該電致發光層直接相鄰之用於改善 ②子此)％匹g&之額外層’如氟化㈣。可通過使用陰極分 離器達成陰極線之相互電隔離。通常在單一基板上製造多 個.4不盗，且在製程結束時，將該基板劃線並分離該等顯 φ π益。利用密封材料，如玻璃板或金屬罐，以抑制氧化及 水分滲入。 如圖所示，該等堤岸之邊緣或面it常係以10至40度之間 的角度傾斜於該基板之表面上。該等堤岸呈現一疏水性表 面，使其不會被沉積有機材料之溶液满濕，從而有助於將 該’儿積材料局限在一井内。此係藉由利用〇2/CF4電漿處理 是岸材料（諸如聚醯亞胺）而達成，如揭示於Ep 0989778 或者可藉由使用氟化材料（如氟化聚酿亞胺）而避免 該電漿處理步驟’如揭示於w〇 〇3/〇8396〇。熟習此項技 術者已知多種其他堤岸結構。例如，該堤岸可包括多個相 Θ或不同材料|，例如經疏水層封蓋之親水層。該堤岸亦 可包括下切口，即，由該堤岸所界定之孔係小於該井之基 部表面積，如揭示於（例如）WO 2005/076386中者。 該堤岸及分離器結構可自抗蝕劑材料形成，例如使用一 正（負）抗蝕劑作為該等堤岸及一負（或正）抗蝕劑作為該等 刀離器此兩種抗蚀劑可係基於聚醯亞胺並旋塗於該基板 145811.doc -21- 201033301 上，或可應用一氟化或類氟化光阻。 實例 用於一層間材料（電洞傳輸材料 何料）之層間調配物（稱為層間 υ為於苯甲醚/苯氧基甲苯W)中包括Q28%固體之固體材 料溶液。當用此調配物印刷時，產生具有邊緣增厚（最高 達40 nm)之膜斷面（15 nm)。邊緣增厚不利於裝置性能， 因為： i)印刷該EL油墨會導致裝置壽命減少， u)隨後印刷的EL層之膜斷面係取決於該比斷面。因此如 果該IL膜邊緣增厚，則該EL層將顯示邊緣變薄。貫穿 個像素之EL膜厚度的變化導致非均勻發射並降低裝 置效率及壽命。 本發明者之此研究已證實用於層間油墨之新穎溶劑組合 可消除層間邊緣增厚。 表1顯示用於根據本發明之新賴組合物中之該等溶劑之 物理特性。所有此等調配物皆成功地消除邊緣增厚。 圖4至6顯示當在PEDOT(PD239)上印刷時衍生的層間膜 斷面。目前使用的A/P1調配物顯示邊緣增厚，而該等新賴 調配物使邊緣稍變薄。 145811.doc -22- 201033301 溶劑 溶劑 沸點 °C 溶劑表面 張力 mN/m 溶劑 黏度 mPa.s 作用 二環己基50% 227 32 3.4 DC :較不佳 /苯曱醚50% (A/DC1) 154 34 1 苯氧基曱苯 271 38.7 5.0 已添加P至上述調配物 /二環己基49.5% 227 32 3.4 以降低粗縫度 /苯曱醚50% (P/DC/A80) 154 34 1 1-四氫萘酮80% 255 43 8.6 TET :高黏度-高表面 /對稱三曱苯20% (TET/MES9) 165 29 0.6 張力 對稱三甲苯60% 165 29 0.6 BZB :高黏度-高表面 /苯曱酸苄酯40% (MES/BZB2) 323 43 10 張力 1-曱氧基萘50% 270 43 7.2 MON .南黏度-南表面 /對稱三曱苯50% (MON/MES1) 165 29 0.6 張力 表1 圖4顯示當在PEDOT(PD239)上印刷時衍生的層間膜斷 面。目前使用的A/P1調配物顯示邊緣增厚，而兩種新調配 物（A/DC1及TET/MES9)使邊緣稍變薄。該A/DC1調配物亦 產生粗糙膜，可能係由於該聚合物在此特定溶劑中之不溶 性所導致。 φ A/P1 =苯曱醚-3-苯氧基曱苯（1-1) A/DC1 =苯甲醚-二環己基（1-1) TET/MES9 = 1-四氫萘酮-對稱三曱苯（8-2)(新穎調配物2) 圖5顯示添加不同量之苯氧基甲苯至該A/DC 1以降低 '粗糙度之結果。從下方的圖可看到，僅0.5%之苯氧基曱苯 (P/DC/A 81(新穎調配物1))添加量可充分降低粗糙度並保 持梢呈圓頂形之斷面。 圖6顯示由另兩種調配物證實之1-四氫萘酮（具有高黏度 145811.doc -23- 201033301 及高表面張力之高沸點溶劑）之影響之結果。 MON/MES1 : 1-甲氧基萘（50%):對稱三甲苯（50%)(新穎 調配物3) MES/BZB2 :對稱三甲苯（60%):苯甲酸苄酯（40%)(新穎 調配物4) 【圖式簡單說明】 圖1顯示一典型OLED之結構； 圖2顯示一通過一 〇LED實例之垂直截面； 圖3顯示在一薄膜之層間之邊緣增厚；及 圖4至6顯示由不同溶劑調配物所得之層間膜斷面。 【主要元件符號說明】 1 基板 2 陽極 3 發光層 4 陰極 100 有機發光裝置（OLED) 102 基板 106 陽極 l〇8a 導電電洞注入層 108b 半導體電洞傳輸層 108c 電致發光層 110 陰極層 112 堤岸 114 井 145811.docAppl. Phys. Lett. 2001, 79(5), cesium fluoride and yttrium oxide in 2001). To provide efficient electron injection into the device, the cathode preferably has a work function of less than 3.5 eV, more preferably less than 3 2 eV, and most preferably less than 3 eV. The work function of metals can be found, for example, in Michaels〇n, j Appl. phys 48(11), 4729, 1977. The tantalum cathode can be opaque or transparent. Transparent cathodes are particularly advantageous for active matrix devices because the emission through the transparent anodes in such devices is at least partially blocked by the drive circuitry located beneath the emitter pixels. The transparent cathode will include a thin, transparent, electron injecting material. The lateral conductivity of this layer will generally be lower due to its thinness. In this case, the electron injecting material layer is used in combination with a thicker layer of a transparent conductive material such as indium tin oxide. It will be appreciated that the transparent cathode device need not have a transparent anode (unless, of course, a completely transparent device), and thus the transparent anode for the bottom illuminator can be "or supplemented" with a layer of reflective material (e.g., a layer of inscription). Examples of transparent cathode devices are disclosed, for example, in GB 2348316. 145811.doc 17· 201033301 Optical devices are often sensitive to moisture and oxygen. Accordingly, the substrate preferably has good barrier properties that prevent moisture and oxygen from penetrating into the device. The substrate is typically glass, although alternative substrates may be used, especially when the device requires flexibility. For example, the substrate may comprise a plastic such as us 6268695 (which discloses an alternating substrate of plastic and barrier layers) or a thin glass and plastic laminate disclosed in Ep 〇94985. The Hai device is preferably sealed with a sealing material (not shown) to prevent infiltration of moisture and oxygen. Suitable sealing materials include glass sheets, films having suitable barrier properties (e.g., alternately stacked polymers and dielectrics, such as those disclosed in, for example, WO 01/81649) or an airtight container (as disclosed, for example). WO 01/19142). An absorbent material for absorbing any moisture and/or oxygen in the environment that may penetrate the substrate or sealing material may be disposed between the substrate and the sealing material. Polymerization Processes The preferred method for preparing semiconducting polymers is Suzuki Polymerization (as described, for example, in WO 00/53656) and Yamamoto Polymerization (as described, for example, in T. Yamamoto, "Electrically Conducting And Thermally Stable π - Conjugated Poly (arylene)s Prepared by Organometallic Processes", Progress in Polymer Science 1993, 17, 1153-1205). These polymerization techniques operate by "metal insertion" in which a metal atom of a metal complex catalyst is interposed between an aryl group and a leaving group of a monomer. In the case of Yamamoto polymerization, a recording compound catalyst is used; in the case of ageing wood polymerization, a complex catalyst is used. 145811.doc • 18- 201033301 For example, when synthesizing a linear polymer by Yamamoto polymerization, a monomer having two active halogen groups is used. Similarly, according to the eucalyptus polymerization method, at least one reactive group is a derivative group ( Such as sun acid or guanoate) and another active halogen. Preferred halogen gas, bromine and iodine are preferred. Thus, it should be understood that the repeating units and terminal groups including the aryl group as described throughout the patent specification can be derived from a monomer having a suitable leaving group. Suzuki polymerization can be used to prepare regional regular, block and random copolymers. Specifically, a homopolymer or a random copolymer can be prepared when one reactive group is halogen and the other reactive group is boron. Alternatively, when the two reactive groups of the first monomer are boron and the two reactive groups of the second monomer are halogen, a block or regioregular (especially octa 8) copolymer can be prepared. As an alternative to the dentate, other leaving groups that can participate in metal insertion include a solution containing tosylate, an oxime sulfonate, and a triflate solution. A single polymer or a plurality of polymers to form layer 3. Suitable solvents for the polycondensation aryl group (especially the condensed type) include mono- or poly-alkyl benzenes such as toluene and mono-toluene. Particularly preferred solution deposition techniques are spin coating and ink jet printing. Spin coating is particularly suitable for devices in which no patterning of electroluminescent material is required, for example, for lighting applications or simple monochrome segmented displays. Ink jet printing is particularly suitable for high information content displays, especially for full color display OLED ink jet printing, as described, for example, in ep 0880303. Other solution deposition techniques include dip coating, roll printing, and screen printing. 145811.doc -19- 201033301 If multiple layers of the device are formed by solution processing, those skilled in the art will be aware of techniques for preventing mixing of adjacent layers, for example, by first crosslinking one layer and then depositing another layer, or The material of the adjacent layer is selected such that the material from which the layer is first formed is not soluble in the solvent used to deposit the second layer. The organic LEDs can be deposited in a matrix of pixels on a substrate to form a single or multi-color pixelated display. A multi-color display can be organized using groups of red, green, and blue illuminating pixels. A so-called active matrix display has a memory element (usually a storage capacitor and a transistor) associated with each pixel' and a passive matrix display does not have this memory element and instead is repeatedly scanned to provide a stable image. impression. Figure 2 shows a vertical section through an example of an OLED device. In active matrix displays, part of the pixel area is occupied by the associated drive circuitry (not shown in Figure 2). The structure of the device is simplified for illustrative purposes. The OLED 100 includes a substrate 102, typically a 7-clawed or "glass" of claws, but is optionally a transparent plastic to which an anode layer 1 〇 6 has been deposited. The anode layer typically comprises about 150 nm thick ITO (indium tin oxide) on which a metal contact layer (typically about 5 Å nm aluminum, sometimes referred to as an anode metal) is provided. Glass substrates coated with ITO and contact metals are commercially available from c〇rning, USA. The contact metal (and optionally IT) is patterned as desired by photolithography followed by etching so that it does not obscure the display. A substantially transparent conductive hole injecting layer 8a is provided on the anode metal, followed by the semiconductor hole transporting layer (7) and an electroluminescent layer. A bank 112 may be formed on the crucible substrate (for example, formed of a positive or negative photoresist material), 145811.doc -20· 201033301, (the active organic layer & well # may be selectively deposited in #. The well SUb defines a light emitting region or pixel of the display. A cathode layer is then applied by, for example, physical vapor deposition. The cathode layer $ often includes a low work function metal covered by a thicker capping layer. About or 2 Hit conditions include - an additional layer that is directly adjacent to the electroluminescent layer for improving 2%), such as fluorination (4). The mutual electrical isolation of the cathode lines can be achieved by using a cathode separator. Typically, a plurality of .4 are not stolen on a single substrate, and at the end of the process, the substrate is scribed and separated. Sealing materials such as glass plates or metal cans are used to inhibit oxidation and moisture infiltration. As shown, the edges or faces of the banks are often inclined at an angle of between 10 and 40 degrees to the surface of the substrate. The banks exhibit a hydrophobic surface that is not wetted by the solution of deposited organic material, thereby helping to confine the material to a well. This is achieved by treating the ruthenium 2/CF4 plasma with a bank material such as polyimine, as disclosed in Ep 0989778 or by using a fluorinated material such as fluorinated polyimide. The plasma treatment step 'is disclosed in w〇〇3/〇8396〇. A variety of other bank structures are known to those skilled in the art. For example, the bank may comprise a plurality of layers or different materials, such as a hydrophilic layer that is capped with a hydrophobic layer. The bank may also include a lower cut, i.e., the aperture defined by the bank is less than the base surface area of the well, as disclosed, for example, in WO 2005/076386. The bank and separator structure can be formed from a resist material, for example using a positive (negative) resist as the banks and a negative (or positive) resist as the knife removers. It may be based on polyimine and spin coated on the substrate 145811.doc -21-201033301, or a fluorinated or fluorinated photoresist may be applied. EXAMPLE A layered formulation of inter-layer material (hole transport material) (called inter-layer υ in anisole/phenoxytoluene W) included a Q28% solids solids solution. When printed with this formulation, a cross-section of the film (15 nm) with edge thickening (up to 40 nm) is produced. Edge thickening is detrimental to device performance because: i) printing of the EL ink results in reduced device life, u) the film cross-section of the subsequently printed EL layer depends on the specific cross-section. Therefore, if the edge of the IL film is thickened, the EL layer will thin the display edge. Variations in the thickness of the EL film throughout the pixels result in non-uniform emission and reduce device efficiency and lifetime. This study by the inventors has confirmed that a novel solvent combination for interlayer inks can eliminate interlayer edge thickening. Table 1 shows the physical properties of the solvents used in the novel compositions according to the present invention. All of these formulations successfully eliminated edge thickening. Figures 4 through 6 show cross-sectional film sections derived when printed on PEDOT (PD239). The currently used A/P1 formulations show edge thickening, and these new formulations make the edges slightly thinner. 145811.doc -22- 201033301 Solvent solvent boiling point °C Solvent surface tension mN/m Solvent viscosity mPa.s Action Dicyclohexyl 50% 227 32 3.4 DC: Poor / phenyl ether 50% (A/DC1) 154 34 1 phenoxy benzene 271 38.7 5.0 P has been added to the above formulation / dicyclohexyl 49.5% 227 32 3.4 to reduce the coarseness / phenyl ether 50% (P / DC / A80) 154 34 1 1-tetrahydrogen Naphthone 80% 255 43 8.6 TET : High viscosity - high surface / symmetric triterpenal 20% (TET / MES9) 165 29 0.6 Tension symmetry trimethylbenzene 60% 165 29 0.6 BZB : High viscosity - high surface / benzyl benzoate Ester 40% (MES/BZB2) 323 43 10 Tension 1-methoxynaphthalene 50% 270 43 7.2 MON. South Viscosity - South Surface / Symmetric Triterpenoid 50% (MON/MES1) 165 29 0.6 Tension Table 1 Figure 4 The interlayer film section derived when printed on PEDOT (PD239) is shown. The currently used A/P1 formulations show edge thickening, while the two new formulations (A/DC1 and TET/MES9) make the edges slightly thinner. The A/DC1 formulation also produces a rough film, possibly due to the insolubility of the polymer in this particular solvent. φ A/P1 = benzoquinone-3-phenoxypurine benzene (1-1) A/DC1 = anisole-dicyclohexyl (1-1) TET/MES9 = 1-tetralone-symmetric three Toluene (8-2) (novative formulation 2) Figure 5 shows the results of adding different amounts of phenoxytoluene to the A/DC 1 to reduce 'roughness. As can be seen from the graph below, only 0.5% of phenoxybenzene (P/DC/A 81 (new formulation 1)) is added in an amount sufficient to reduce the roughness and maintain a dome-shaped cross section. Figure 6 shows the results of the effects of 1-tetralone (high viscosity 145811.doc -23- 201033301 and high boiling point solvent with high surface tension) confirmed by the other two formulations. MON/MES1 : 1-methoxynaphthalene (50%): Symmetrical trimethylbenzene (50%) (novel formulation 3) MES/BZB2: symmetrical trimethylbenzene (60%): benzyl benzoate (40%) (new Formulation 4) [Simple Description of the Drawings] Figure 1 shows the structure of a typical OLED; Figure 2 shows a vertical section through an example of LED; Figure 3 shows the edge thickening between layers of a film; and Figures 4 to 6 The interlayer film cross sections obtained from different solvent formulations are shown. [Main component symbol description] 1 substrate 2 anode 3 light-emitting layer 4 cathode 100 organic light-emitting device (OLED) 102 substrate 106 anode 10 8a conductive hole injection layer 108b semiconductor hole transport layer 108c electroluminescent layer 110 cathode layer 112 bank 114 well 145811.doc