TWI583746B - Polythiophene-containing ink compositions for inkjet printing - Google Patents

Description

用於噴墨印刷的含聚噻吩墨水組成物 Polythiophene-containing ink composition for inkjet printing 【相關申請案之交叉參考】[Cross-Reference to Related Applications]

本申請案主張於2013年10月31日申請之題為用於噴墨印刷的含聚噻吩墨水組成物之美國臨時專利申請案第61/898343號之優先權，該專利申請案之全部內容以引用之方式併入本文中。本申請案為題為用於基板印刷的成膜調配物之美國專利申請案第13/618,157號之部分接續申請案，該專利申請案係於2012年9月14日申請，且其主張2011年9月16日申請之美國臨時專利申請案第61/535,413號之優先權，該等專利申請案之全部內容以引用之方式併入本文中。 The present application claims priority to U.S. Provisional Patent Application No. 61/89,834, filed on Oct. 31, 2013, which is incorporated herein by reference in its entirety in its entirety in The manner of reference is incorporated herein. This application is a continuation-in-part application of U.S. Patent Application Serial No. 13/618,157, the disclosure of which is incorporated herein in its entirety in The priority of U.S. Provisional Patent Application Serial No. 61/535,413, filed on Sep. 6, the entire disclosure of which is hereby incorporated by reference.

本發明係關於用於噴墨印刷的含聚噻吩墨水組成物。 This invention relates to polythiophene-containing ink compositions for ink jet printing.

已提出用於有機發光二極體(organic light emitting diode；OLED)中之噴墨印刷層的墨水組成物。然而，與墨水組成物之不充分潤濕特性相關之問題已抑制可印刷墨水之發展，因為不當潤濕導致形成非均一膜且因此導致併有經印刷之膜的有機發光二極體像素之非均一發光。已阻礙用於OLED應用之可噴墨印刷組成物之發展的另一挑戰為不能將高濃度之活性聚合物併入墨水中，同時保持可噴墨調配物。 An ink composition for an inkjet printed layer in an organic light emitting diode (OLED) has been proposed. However, problems associated with inadequate wetting characteristics of ink compositions have inhibited the development of printable inks because improper wetting results in the formation of non-uniform films and thus the resulting organic light-emitting diode pixels with printed films. Uniform illumination. Another challenge that has hindered the development of ink jet printable compositions for OLED applications is the inability to incorporate high concentrations of active polymer into the ink while maintaining ink jettable formulations.

提供包含聚噻吩之墨水組成物，其經調配用於噴墨印刷OLED之電洞注入層(hole injecting layer；HIL)。墨水組成物之一些具體實例的特徵為包括甲基聚矽氧烷(methicone)作為釘紮劑(pinning agent)。其他具體實例的特徵為包括使得能夠於墨水中併入高濃度之聚噻吩的非質子性溶劑。亦提供使用墨水組成物噴墨印刷HIL之方法。 An ink composition comprising polythiophene is provided which is formulated for ink jet printing of a hole injecting layer (HIL) of an OLED. Some specific examples of the ink composition are characterized by including a methyl methicone as a pinning agent. Other specific examples are characterized by including an aprotic solvent that enables the incorporation of a high concentration of polythiophene into the ink. A method of inkjet printing HIL using an ink composition is also provided.

形成有機發光二極體之HIL的方法的一個具體實例包含以下步驟：在有機發光二極體之像素單元中的電極層上噴墨印刷墨水組成物之液滴(亦即至少一個液滴)，像素單元由像素堤(bank)界定；及使墨水組成物之揮發性組分蒸發，藉此形成電洞注入層。可用於該方法中之墨水組成物之具體實例包含：導電聚噻吩；水；至少一種有機溶劑；及甲基聚矽氧烷，其中甲基聚矽氧烷以提供像素單元中液滴之接觸線釘紮之量存在。 A specific example of the method of forming the HIL of the organic light-emitting diode includes the steps of: ink-jet printing a droplet of the ink composition (ie, at least one droplet) on the electrode layer in the pixel unit of the organic light-emitting diode, The pixel unit is defined by a pixel bank; and the volatile component of the ink composition is evaporated, thereby forming a hole injection layer. Specific examples of the ink composition usable in the method include: conductive polythiophene; water; at least one organic solvent; and methyl polyoxyalkylene, wherein the methyl polyoxyalkylene provides a contact line of the droplets in the pixel unit The amount of pinning exists.

墨水組成物之一些具體實例包含：聚(3,4-伸乙二氧基噻吩)；水；至少一種有機溶劑，其於25℃下之表面張力不大於55達因/公分、於25℃下之黏度不大於15厘泊且沸點為至少200℃；及甲基聚矽氧烷。該至少一種有機溶劑可例如為環丁碸。 Some specific examples of the ink composition include: poly(3,4-ethylenedioxythiophene); water; at least one organic solvent having a surface tension of not more than 55 dynes/cm at 25 ° C at 25 ° C The viscosity is not more than 15 centipoise and the boiling point is at least 200 ° C; and methyl polyoxyalkylene. The at least one organic solvent may be, for example, cyclobutyl hydrazine.

當審閱以下圖式、實施方式及所附申請專利範圍時，本發明之其他主要特徵及優勢對熟習此項技術者來說將變得顯而易見。 Other essential features and advantages of the present invention will become apparent to those skilled in the art from this disclosure.

100‧‧‧OLED噴墨印刷系統 100‧‧‧OLED inkjet printing system

110‧‧‧基板輸送系統 110‧‧‧Substrate delivery system

120‧‧‧基板支撐設備 120‧‧‧Substrate support equipment

130‧‧‧運動系統 130‧‧‧ sports system

140‧‧‧印刷頭總成 140‧‧‧Print head assembly

150‧‧‧印墨傳遞系統 150‧‧‧Ink delivery system

160‧‧‧控制系統 160‧‧‧Control system

200‧‧‧氣體封閉系統/氣體封閉總成 200‧‧‧Gas closure system / gas enclosure assembly

230‧‧‧氣體純化迴路 230‧‧‧ gas purification circuit

231‧‧‧出口管線 231‧‧‧Export pipeline

232‧‧‧溶劑移除組件/溶劑移除系統 232‧‧‧Solvent removal component / solvent removal system

233‧‧‧入口管線 233‧‧‧Inlet pipeline

234‧‧‧氣體純化系統 234‧‧‧Gas purification system

240‧‧‧熱調節系統 240‧‧‧thermal regulation system

241‧‧‧冷卻器 241‧‧‧cooler

243‧‧‧流體出口管線 243‧‧‧ Fluid outlet pipeline

245‧‧‧流體入口管線 245‧‧‧ fluid inlet line

250‧‧‧氣體封閉總成 250‧‧‧ gas sealing assembly

260‧‧‧惰性氣體再循環系統 260‧‧‧Inert gas recirculation system

300‧‧‧面板 300‧‧‧ panel

320‧‧‧展開視圖 320‧‧‧Expanded view

330‧‧‧具有複數個像素單元之配置 330‧‧‧With multiple pixel units

332‧‧‧發紅光像素單元 332‧‧‧Red light pixel unit

334‧‧‧發綠光像素單元 334‧‧‧Green light pixel unit

336‧‧‧發藍光像素單元 336‧‧‧Blue light pixel unit

338‧‧‧積體電路 338‧‧‧Integrated circuit

500‧‧‧溢出像素單元之側面 500‧‧‧Side of the overflow pixel unit

600‧‧‧像素單元溢出 600‧‧‧Pixel unit overflow

602‧‧‧抗濕潤區域 602‧‧‧Anti-wet area

下文將參考隨附圖式描述本發明之說明性具體實例，其中相同數字表示相同元件。 The illustrative embodiments of the present invention are described below with reference to the accompanying drawings, wherein

圖1為說明OLED噴墨印刷系統之方塊圖。 1 is a block diagram illustrating an OLED inkjet printing system.

圖2為可容納圖1中所示之印刷系統之氣體封閉系統的示意性圖示。 2 is a schematic illustration of a gas enclosure system that can accommodate the printing system shown in FIG.

圖3為包含複數個配置於像素單元之矩陣中之OLED的平板顯示器之示意性圖解，各像素單元由像素堤界定。 3 is a schematic illustration of a flat panel display comprising a plurality of OLEDs arranged in a matrix of pixel cells, each pixel cell being defined by a pixel bank.

圖4A為釘紮於OLED像素單元中之含有0.08wt.%甲基聚矽氧烷之墨水組成物之顯微照片影像。 4A is a photomicrograph of an ink composition containing 0.08 wt.% methyl polyoxyalkylene pinned in an OLED pixel unit.

圖4B為圖4A中之顯微照片之黑白線圖。 Figure 4B is a black and white line drawing of the photomicrograph of Figure 4A.

圖5A為不含甲基聚矽氧烷之墨水組成物溢出OLED像素單元之顯微照片影像。 Figure 5A is a photomicrograph of an ink composition containing no methyl polyoxyalkylene spilled over the OLED pixel unit.

圖5B為圖5A中之顯微照片之黑白線圖。 Figure 5B is a black and white line drawing of the photomicrograph in Figure 5A.

圖6A為不含甲基聚矽氧烷之墨水組成物使OLED像素單元抗濕潤之顯微照片影像。 Figure 6A is a photomicrograph of an OLED pixel unit that is resistant to wetting by an ink composition that does not contain methyl polyoxyalkylene.

圖6B為圖6A中之顯微照片之黑白線圖。 Figure 6B is a black and white line drawing of the photomicrograph in Figure 6A.

圖7A為自具有用包含甲基聚矽氧烷作為釘紮劑之墨水組成物印刷之HIL的OLED像素發光的顯微照片。 Figure 7A is a photomicrograph of OLED pixel illumination from a HIL having an ink composition printed with an ink composition comprising methyl polyoxyalkylene as a pinning agent.

圖7B為圖7A中之顯微照片之黑白線圖。 Figure 7B is a black and white line drawing of the photomicrograph in Figure 7A.

圖8A為自用包含甲基聚矽氧烷作為釘紮劑及環丁碸作為有機溶劑之墨水組成物印刷HIL之OLED像素發光之顯微照片。 Fig. 8A is a photomicrograph of OLED pixel luminescence from a printed HIL using an ink composition comprising methyl polyoxyalkylene as a pinning agent and cyclobutyl hydrazine as an organic solvent.

圖8B為圖8A中之顯微照片之黑白線圖。 Figure 8B is a black and white line drawing of the photomicrograph in Figure 8A.

圖9A為自用包含甲基聚矽氧烷作為釘紮劑及1,3-丙二醇作為有機溶劑之墨水組成物印刷HIL之OLED像素發光之顯微照片。 Figure 9A is a photomicrograph of OLED pixel illumination from a printed HIL using an ink composition comprising methyl polyoxyalkylene as a pinning agent and 1,3-propanediol as an organic solvent.

圖9B為圖9A中之顯微照片之黑白線圖。 Figure 9B is a black and white line drawing of the photomicrograph in Figure 9A.

圖10為如實施例2中所述在噴墨印刷噴嘴閒置30分鐘前後，墨水組成物之液滴體積隨時間推移之圖。 Figure 10 is a graph showing the droplet volume of the ink composition as a function of time before and after the ink jet printing nozzle was left idle for 30 minutes as described in Example 2.

圖11為如實施例2中所述在噴墨印刷噴嘴閒置30分鐘前後，墨水組成物之液滴速度隨時間推移之圖。 Figure 11 is a graph showing the droplet velocity of the ink composition as a function of time before and after the ink jet printing nozzle was left idle for 30 minutes as described in Example 2.

圖12為如實施例2中所述在噴墨印刷噴嘴閒置30分鐘閒置前後，墨水組成物之液滴角度隨時間推移之圖。 Figure 12 is a graph showing the droplet angle of the ink composition as a function of time before and after the ink jet printing nozzle is idle for 30 minutes as described in Example 2.

提供經調配用於噴墨印刷OLED之HIL之包含聚噻吩的墨水組成物。亦提供使用墨水組成物噴墨印刷HIL之方法。 An ink composition comprising polythiophene formulated to ink-print OLED HIL is provided. A method of inkjet printing HIL using an ink composition is also provided.

墨水組成物之特徵為高濃度之導電聚噻吩，諸如聚(3,4-伸乙二氧基噻吩)(poly(3,4-ethylenedioxythiophene)；PEDOT)，但提供使其良好地適合於噴墨印刷至像素化基板(諸如OLED像素單元)上之潤濕、噴射及潛伏特性。此外，墨水組成物提供具有高度均一厚度及均質組成之經印刷之HIL。因此，經印刷之HIL促成併有該等HIL之OLEQ的高度均一光發射特徵。由墨水組成物提供之增強之可印刷性可至少部分歸因於甲基聚矽氧烷於適當濃度下可充當像素單元中墨水組成物之液滴的接觸線釘紮劑的實現。藉由提供接觸線釘紮，甲基聚矽氧烷確保沈積至像素單元中之墨水組成物之液滴的足跡在乾燥製程期間相對於其初始形式保持不變。 The ink composition is characterized by a high concentration of conductive polythiophene, such as poly(3,4-ethylenedioxythiophene) (PEDOT), but provides a good fit for inkjet Wetting, jetting, and latent properties printed onto a pixelated substrate, such as an OLED pixel cell. In addition, the ink composition provides a printed HIL having a highly uniform thickness and a homogeneous composition. Thus, the printed HIL contributes to the highly uniform light emission characteristics of the OLEQ of such HILs. The enhanced printability provided by the ink composition can be attributed, at least in part, to the achievement of a contact line pinning agent that can act as a droplet of the ink composition in the pixel unit at the appropriate concentration of methyl polyoxyalkylene. By providing contact line pinning, the methyl polyoxyalkylene ensures that the footprint of the droplets of the ink composition deposited into the pixel unit remains unchanged relative to its original form during the drying process.

墨水組成物之基本具體實例為包含導電聚噻吩、甲基聚矽氧烷、至少一種有機溶劑及水之水溶液。使用一種墨水組成物形成OLED之HIL的方法的基本具體實例包含以下步驟：在有機發光二極體陣列之像素單元中之導電材料層(亦即陽極)上沈積墨水組成物之液滴；及使墨水 組成物之揮發性組分蒸發，從而留下固體HIL。可藉由使經印刷之墨水組成物經受減壓(亦即使其暴露於真空)、藉由使經印刷之墨水組成物暴露於高溫或二者之組合來促進使揮發性組分(例如水及有機溶劑)蒸發之步驟。 A basic specific example of the ink composition is an aqueous solution containing conductive polythiophene, methyl polyoxyalkylene, at least one organic solvent, and water. A basic specific example of a method of forming an HIL of an OLED using an ink composition includes the steps of: depositing a droplet of the ink composition on a layer of a conductive material (ie, an anode) in a pixel unit of the organic light-emitting diode array; ink The volatile components of the composition evaporate leaving a solid HIL. Volatile components (eg, water and water) can be promoted by subjecting the printed ink composition to reduced pressure (and even if exposed to a vacuum), by exposing the printed ink composition to elevated temperatures, or a combination of the two. Organic solvent) the step of evaporation.

甲基聚矽氧烷為自矽氧烷聚合之聚矽氧油。其亦稱為甲基氫矽氧烷或甲基矽氧烷。甲基聚矽氧烷可在市面上購得且由Botanigenics(Northridge,CA)以商標名Botanisil®作為界面活性劑出售。此等產品包括Botanisil® AD-13、AM-14、ATC-21、BPD-100、CD-80、CD-90、CE-35、CM-12、CM-13、CM-70、CP-33、CPM-10、CS-50、CTS-45、DM-60M、DM-85、DM-90、DM-91、DM-92、DM-93、DM-94、DM-95、DM-96、DM-97、DTS-13、DTS-35、GB-19、GB-20、GB-23、GB-25、GB-35、L-23、ME-10、ME-12、PSS-150、PT-100、S-18、S-19、S-20、TSA-16及TSS-1。甲基聚矽氧烷亦可以商標名SilSense®購自Lubrizol公司(Wickliffe,Ohio)。此等產品包括SilSense®共聚醇-1聚矽氧(PEG-33(及)PEG-8二甲基聚矽氧烷(及)PEG 14)、SilSense® DW-18聚矽氧(二甲基聚矽氧烷PEG-7異硬脂酸酯)、SilSense® SW-12聚矽氧(二甲基聚矽氧烷PEG-7椰油酸酯)、SilSense® IWS(二甲基聚矽氧烷醇酯醚二甲基聚矽氧烷醇硬脂酸酯)、SilSense® A-21聚矽氧(PEG-7胺基封端二甲基聚矽氧烷)、SilSense® PE-100聚矽氧(二甲基聚矽氧烷PEG-8磷酸酯)及Ultrabee^TM WD聚矽氧(二甲基聚矽氧烷PEG-8蜂蠟)。 The methyl polyoxyalkylene is a polyoxyxane polymer polymerized from decane. It is also known as methylhydroquinone or methyl decane. Methyl polyoxyalkylene is commercially available and sold by Botanigenics (Northridge, CA) under the trade name Botanisil® as a surfactant. These products include Botanisil® AD-13, AM-14, ATC-21, BPD-100, CD-80, CD-90, CE-35, CM-12, CM-13, CM-70, CP-33, CPM-10, CS-50, CTS-45, DM-60M, DM-85, DM-90, DM-91, DM-92, DM-93, DM-94, DM-95, DM-96, DM- 97, DTS-13, DTS-35, GB-19, GB-20, GB-23, GB-25, GB-35, L-23, ME-10, ME-12, PSS-150, PT-100, S-18, S-19, S-20, TSA-16 and TSS-1. Methyl polyoxyalkylene is also available from Lubrizol (Wickliffe, Ohio) under the trade name SilSense®. These products include SilSense® copolyol-1 polyoxyl (PEG-33 (and) PEG-8 dimethyl polyoxyalkylene (and) PEG 14), SilSense® DW-18 polyoxyl (dimethylation) Alkane PEG-7 isostearate), SilSense® SW-12 polyoxyl (dimethyl polyoxane PEG-7 cocoate), SilSense® IWS (dimethyl polyoxyl alkanol) Ester ether dimethyl polyoxyl alkanol stearate), SilSense® A-21 polyoxyl (PEG-7 amine-terminated dimethyl polyoxane), SilSense® PE-100 polyoxyl ( dimethylpolysiloxane silicon oxide alkyl phosphate PEG-8) and Ultrabee ^TM WD poly silicon oxide (silicon oxide dimethylpolysiloxane alkoxy PEG-8 beeswax).

在本發明墨水組成物中，謹慎地控制甲基聚矽氧烷之量以使得甲基聚矽氧烷充當接觸線釘紮劑。此為重要的，因為其防止經釘紮之墨水組成物液滴自像素單元之堤的部分脫離(抗濕潤)，該脫離有時伴隨有在像素單元之其他部分的溢出。其亦防止如在更完全潤濕之情況下將發生 的墨水組成物於像素單元之側面堆積或擴散超出像素單元。 In the ink composition of the present invention, the amount of methyl polyoxyalkylene is carefully controlled so that methyl polyoxyalkylene acts as a contact pinning agent. This is important because it prevents the pinned ink composition droplets from escaping (moisture resistant) from the portion of the bank of the pixel unit, which is sometimes accompanied by spillage in other portions of the pixel unit. It also prevents it from happening if it is more completely wetted The ink composition is deposited or diffused beyond the pixel unit on the side of the pixel unit.

墨水組成物可用於在多種OLED電極材料上形成HIL。最通常地，電極基板將包含透明導電材料，諸如透明導電氧化物(TCO)或矽。墨水組成物中之甲基聚矽氧烷的適當濃度範圍將取決於下層基板之性質。然而，對於給定基板，可藉由觀測具有不同甲基聚矽氧烷濃度之墨水液滴的潤濕特性來測定甲基聚矽氧烷提供接觸線釘紮之濃度範圍，該等墨水液滴已經由滴落塗佈法塗覆至表面。舉例說明，本發明墨水組成物之一些具體實例包含以墨水組成物之總重量計不大於0.15重量百分比(wt.%)、不大於0.12wt.%或不大於0.1wt.%之量的甲基聚矽氧烷。此包括以墨水組成物之總重量計，甲基聚矽氧烷以0.02至0.15wt.%範圍內之量存在之墨水組成物的具體實例，進一步包括甲基聚矽氧烷以0.03至0.12wt.%範圍內之量存在的具體實例，且進一步包括甲基聚矽氧烷以0.05至0.1wt.%範圍內之量存在的具體實例。當HIL墨水組成物印刷至已知用於OLED裝置中之陽極材料上時，該等範圍為合適的。舉例而言，在經由陽極發光(稱為底部發光)之OLED裝置的情況下，使用透明或半透明陽極材料。透明或半透明陽極材料可包括氧化銦、氧化鋅、氧化銦錫(indium tin oxide；ITO)及氧化銦鋅(indium zinc oxide；IZO)或其類似物。在經由陰極發光(稱為頂部發光)之OLED裝置的情況下，在透明陽極下方形成反射層。反射層材料包括銀(Ag)、銀-鈀-銅(silver-palladium-copper；APC)、銀-銣-金(silver-rubidium-gold；ARA)、鉬-鉻(molybdenum-chromium；MoCr)或其類似物。 The ink composition can be used to form an HIL on a variety of OLED electrode materials. Most commonly, the electrode substrate will comprise a transparent conductive material such as a transparent conductive oxide (TCO) or tantalum. The appropriate concentration range of methyl polyoxyalkylene in the ink composition will depend on the nature of the underlying substrate. However, for a given substrate, the concentration range of the contact line pinning can be determined by observing the wetting characteristics of ink droplets having different concentrations of methyl polyoxyalkylene, such ink droplets. It has been applied to the surface by drop coating. By way of example, some specific examples of the ink composition of the present invention include methyl groups in an amount of not more than 0.15 weight percent (wt.%), not more than 0.12 wt.%, or not more than 0.1 wt.%, based on the total weight of the ink composition. Polyoxane. This includes a specific example of the ink composition in which the methyl polyoxyalkylene is present in an amount ranging from 0.02 to 0.15 wt.%, based on the total weight of the ink composition, further including methyl polyoxyalkylene at 0.03 to 0.12 wt. Specific examples of amounts present in the range of .%, and further include specific examples in which the methyl polyoxyalkylene is present in an amount ranging from 0.05 to 0.1 wt.%. Such ranges are suitable when the HIL ink composition is printed onto an anode material known for use in OLED devices. For example, in the case of an OLED device that emits light through an anode (referred to as bottom emission), a transparent or translucent anode material is used. The transparent or translucent anode material may include indium oxide, zinc oxide, indium tin oxide (ITO), and indium zinc oxide (IZO) or the like. In the case of an OLED device that emits light through a cathode (referred to as top emission), a reflective layer is formed under the transparent anode. The reflective layer material comprises silver (Ag), silver-palladium-copper (APC), silver-rubidium-gold (ARA), molybdenum-chromium (MoCr) or Its analogues.

水性墨水組成物進一步包括一或多種導電聚噻吩。舉例而言，PEDOT及PEDOT與聚(苯乙烯磺酸酯)之混合物(PEDOT：PSS)可包括 於墨水組成物中。值得注意的是，如下文更詳細地論述與適當溶劑組合，聚噻吩可以極高濃度包括於墨水組成物中。舉例而言，墨水組成物之一些具體實例包含以墨水組成物之總重量計至少30wt.%聚噻吩、至少40wt.%聚噻吩、至少50wt.%聚噻吩、至少55wt.%聚噻吩或至少60wt.%聚噻吩。在該等具體實例中，聚噻吩可為PEDOT。 The aqueous ink composition further includes one or more conductive polythiophenes. For example, PEDOT and a mixture of PEDOT and poly(styrene sulfonate) (PEDOT:PSS) may include In the ink composition. It is worth noting that, as discussed in more detail below, in combination with a suitable solvent, the polythiophene can be included in the ink composition at very high concentrations. For example, some specific examples of the ink composition include at least 30 wt.% polythiophene, at least 40 wt.% polythiophene, at least 50 wt.% polythiophene, at least 55 wt.% polythiophene, or at least 60 wt%, based on the total weight of the ink composition. .% polythiophene. In these specific examples, the polythiophene can be PEDOT.

水性墨水組成物包含至少一種有機溶劑。舉例而言，組成物可包含降低組成物之表面張力及/或黏度的溶劑、增加經印刷之墨水組成物之潛伏期的溶劑或此等類型溶劑之組合。至少一種有機溶劑可為具有相對高沸點的溶劑，其增加經印刷之墨水組成物的潛伏期。此為有利的，因為其有助於防止墨水組成物在印刷期間於印刷噴嘴上乾燥且將其堵塞。該等溶劑之沸點宜為至少200℃。其沸點更宜為至少230℃、至少250℃或甚至至少280℃。諸如丙二醇、戊二醇、二乙二醇及三乙二醇之二醇(diol/glycol)為可用於增加潛伏期之有機溶劑的實例。然而，令人遺憾的是，二醇傾向於具有相對高之黏度及表面張力，其可降低包括該等二醇之墨水組成物之可噴射性。因此，本發明墨水組成物之一些具體實例不含二醇溶劑。在此等具體實例中，可使用沸點為至少240℃、黏度不大於15厘泊且表面張力不大於55達因/公分之非質子性溶劑替代二醇。此包括黏度不大於12厘泊之非質子性溶劑，且進一步包括黏度不大於10厘泊之非質子性溶劑。出於本發明之目的，所述沸點係指在大氣壓下之沸點。所述黏度及表面張力係指在印刷溫度下之黏度及表面張力。舉例來說，若在室溫下進行印刷，則黏度及表面張力將為在約25℃下之黏度及表面張力。 The aqueous ink composition contains at least one organic solvent. For example, the composition can include a solvent that reduces the surface tension and/or viscosity of the composition, a solvent that increases the latency of the printed ink composition, or a combination of such types of solvents. The at least one organic solvent can be a solvent having a relatively high boiling point which increases the latency of the printed ink composition. This is advantageous because it helps to prevent the ink composition from drying on the printing nozzle during printing and clogging it. The solvents preferably have a boiling point of at least 200 °C. The boiling point is more preferably at least 230 ° C, at least 250 ° C or even at least 280 ° C. Examples of diols such as propylene glycol, pentylene glycol, diethylene glycol, and triethylene glycol (diol/glycol) are organic solvents that can be used to increase the incubation period. However, unfortunately, diols tend to have relatively high viscosity and surface tension which can reduce the ejectability of ink compositions comprising such diols. Thus, some specific examples of the ink compositions of the present invention are free of glycol solvents. In such specific examples, an aprotic solvent having a boiling point of at least 240 ° C, a viscosity of not more than 15 centipoise, and a surface tension of not more than 55 dynes/cm can be used in place of the diol. This includes aprotic solvents having a viscosity of no greater than 12 centipoise and further comprising an aprotic solvent having a viscosity of no greater than 10 centipoise. For the purposes of the present invention, the boiling point refers to the boiling point at atmospheric pressure. The viscosity and surface tension refer to the viscosity and surface tension at the printing temperature. For example, if printing is performed at room temperature, the viscosity and surface tension will be the viscosity and surface tension at about 25 °C.

環丁碸(2,3,4,5-四氫噻吩-1,1-二氧化物，亦稱為四亞甲碸) 為提供良好潛伏期而不犧牲可噴射性之相對高沸點、相對低黏度之非質子性溶劑的實例。此外，包括環丁碸作為有機溶劑之墨水組成物可併入高濃度之溶劑與聚噻吩，同時保持良好可噴射性。舉例而言，墨水組成物可包含至少5wt.%、至少10wt.%或至少12wt.%之量的環丁碸。墨水組成物中環丁碸的合適之濃度範圍包括約3wt.%至約15wt.%之範圍。在此等環丁碸濃度下，墨水組成物可併入高濃度之PEDOT(例如35至76wt.%)。在一些墨水組成物中，環丁碸為大多數的溶劑，亦即其佔墨水組成物之總有機溶劑含量的大於50wt.%。其他合適之溶劑包括碳酸伸丙酯及1,3-二甲基-3,4,5,6-四氫-2(1H)-嘧啶酮，亦稱為二甲基伸丙基脲。 Cyclobutane (2,3,4,5-tetrahydrothiophene-1,1-dioxide, also known as tetramethylene) An example of an aprotic solvent that provides a good incubation period without sacrificing relatively high boiling, relatively low viscosity sprayability. Further, an ink composition including cyclobutyl hydrazine as an organic solvent can incorporate a high concentration of solvent and polythiophene while maintaining good ejectability. For example, the ink composition can comprise cyclobutene in an amount of at least 5 wt.%, at least 10 wt.%, or at least 12 wt.%. Suitable concentrations of cyclobutadiene in the ink composition range from about 3 wt.% to about 15 wt.%. At such concentrations of cyclobutane, the ink composition can incorporate a high concentration of PEDOT (e.g., 35 to 76 wt.%). In some ink compositions, cyclobutane is the most solvent, i.e., it accounts for greater than 50 wt.% of the total organic solvent content of the ink composition. Other suitable solvents include propyl carbonate and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone, also known as dimethyl-propyl propyl urea.

墨水組成物可進一步包括充當表面張力降低劑之共溶劑以增強組成物之可噴射性。舉例而言，包含二醇(diol/glycol)、環丁碸或其他高沸點溶劑之墨水組成物可包括另一溶劑，該溶劑相比於彼等溶劑具有較低表面張力且典型地具有較低沸點。丙二醇甲醚或其他類似醚可用於此目的。 The ink composition may further include a co-solvent serving as a surface tension reducing agent to enhance the sprayability of the composition. For example, an ink composition comprising a diol (diol/glycol), cyclobutanil or other high boiling solvent may include another solvent that has a lower surface tension than the solvents and typically has a lower Boiling point. Propylene glycol methyl ether or other similar ethers can be used for this purpose.

一般而言，對於適用於噴墨印刷應用之墨水組成物而言，墨水組成物之表面張力、黏度、潛伏期及潤濕特性應經定製以使得組成物在用於印刷之溫度(例如室溫；約25℃)下經由噴墨印刷噴嘴分配而不於噴嘴上乾燥或將其堵塞。因此，最佳特性將視諸如噴嘴尺寸、印刷速度及印刷溫度之因素而變化。一般而言，可接受之黏度將包括在約1至約20厘泊範圍內之黏度且可接受之表面張力將包括低於約50達因/公分之表面張力。為消除噴嘴堵塞或使其降至最低，20分鐘或更長(例如30分鐘或更長)之潛伏期(在室溫下且不在真空情況下)為合乎需要的，其中潛伏期係指 在效能顯著降低(例如液滴速度降低，其將顯著影響影像品質)之前噴嘴可保持未經覆蓋且閒置的時間。 In general, for ink compositions suitable for ink jet printing applications, the surface tension, viscosity, latency, and wetting characteristics of the ink composition should be tailored to allow the composition to be at the temperature used for printing (eg, room temperature) ; about 25 ° C) dispensed via an inkjet printing nozzle without drying on the nozzle or clogging it. Therefore, the optimum characteristics will vary depending on factors such as nozzle size, printing speed, and printing temperature. Generally, an acceptable viscosity will include a viscosity in the range of from about 1 to about 20 centipoise and an acceptable surface tension will include a surface tension of less than about 50 dynes/cm. To eliminate or minimize nozzle clogging, a latency of 20 minutes or longer (eg, 30 minutes or longer) (at room temperature and not under vacuum) is desirable, where latency refers to The nozzle can remain uncovered and idle for a significant reduction in performance (eg, reduced droplet velocity, which will significantly affect image quality).

適合於印刷墨水組成物之噴墨印刷機可在市面上購得且包括按需滴墨印刷頭，其可購自例如Fujifilm Dimatix(Lebanon,N.H.)、Trident International(Brookfield,Conn.)、Epson(Torrance,Calif.)、Hitachi Data systems公司(Santa Clara,Calif.)、Xaar PLC(Cambridge,United Kingdom)及Idanit Technologies,Limited(Rishon Le Zion,Isreal)及Rieoh Printing Systems America公司(Simi Valley,CA)。舉例而言，可使用Dimatix Materials印刷機DMP-3000。 Ink jet printers suitable for printing ink compositions are commercially available and include drop-on-demand printheads available from, for example, Fujifilm Dimatix (Lebanon, NH), Trident International (Brookfield, Conn.), Epson ( Torrance, Calif.), Hitachi Data Systems (Santa Clara, Calif.), Xaar PLC (Cambridge, United Kingdom) and Idanit Technologies, Limited (Rishon Le Zion, Isreal) and Rieoh Printing Systems America (Simi Valley, CA) . For example, the Dimatix Materials printer DMP-3000 can be used.

如圖1之方塊圖中所描繪，OLED噴墨印刷系統100之各種具體實例可包含若干裝置、設備及系統及其類似物，其使墨滴可靠地置放至基板上之特定位置上。根據系統及方法之各種具體實例，印刷系統可包括例如(但不限於)基板輸送系統110、基板支撐設備120、運動系統130、印刷頭總成140、墨水傳遞系統150及控制系統160。 As depicted in the block diagram of FIG. 1, various specific examples of OLED inkjet printing system 100 can include a number of devices, devices, and systems and the like that enable ink droplets to be reliably placed at specific locations on a substrate. Printing systems may include, for example, but are not limited to, substrate transport system 110, substrate support apparatus 120, motion system 130, printhead assembly 140, ink delivery system 150, and control system 160, depending on various embodiments of the system and method.

OLED基板可使用基板輸送系統110***印刷系統100及自其移除。視印刷系統100之各種具體實例而定，基板輸送系統110可為機械輸送機、具有夾持器總成之基板浮動台、具有末端執行器之機器手及其組合。另外，在印刷製程期間，基板可由支撐設備120支撐，該支撐設備可為例如(但不限於)夾盤或浮動台。由於印刷需要印刷頭與基板之間相對運動，印刷系統100之各種具體實例可具有運動系統130，其可為例如(但不限於)台架或分離軸XYZ系統。 The OLED substrate can be inserted into and removed from the printing system 100 using the substrate transport system 110. Depending on various embodiments of printing system 100, substrate transport system 110 can be a mechanical conveyor, a substrate floating table with a holder assembly, a robotic hand with an end effector, and combinations thereof. Additionally, during the printing process, the substrate may be supported by a support device 120, which may be, for example, but not limited to, a chuck or a floating table. Since printing requires relative movement between the printhead and the substrate, various embodiments of the printing system 100 can have a motion system 130, which can be, for example, but not limited to, a gantry or a split-axis XYZ system.

印刷頭總成140可包括至少一個可安裝至運動系統130上之 印刷頭裝置。包括於印刷頭總成140中之至少一個印刷頭裝置可具有至少一個噴墨印刷頭，該印刷頭能夠經由至少一個孔以受控速率、速度及規模噴射墨水組成物之液滴。根據本發明教示之印刷系統100的各種具體實例可具有約1個至約60個之間的印刷頭裝置。另外，印刷頭裝置之各種具體實例可於各印刷頭裝置中具有約1個至約30個之間的噴墨印刷頭，其中各噴墨印刷頭可具有約16個至約2048個之間的噴嘴。根據印刷頭總成140之各種具體實例，各噴墨印刷頭之各噴嘴可射出約0.1pL至約200pL之間的液滴體積。具有至少一個噴墨印刷頭之印刷頭總成140可與墨水組成物傳遞系統150流體連通，該傳遞系統可為印刷頭總成140之一或多個噴墨印刷頭供應墨水組成物。 The printhead assembly 140 can include at least one mountable to the motion system 130 Print head device. At least one of the printhead devices included in the printhead assembly 140 can have at least one inkjet printhead that is capable of ejecting droplets of the ink composition at a controlled rate, speed, and scale via at least one aperture. Various embodiments of printing system 100 in accordance with the teachings of the present invention can have between about 1 and about 60 printhead devices. Additionally, various embodiments of the printhead device can have from about 1 to about 30 inkjet printheads in each printhead device, wherein each inkjet printhead can have between about 16 and about 2048 nozzle. Depending on various embodiments of the printhead assembly 140, each nozzle of each inkjet printhead can eject a droplet volume of between about 0.1 pL and about 200 pL. A printhead assembly 140 having at least one inkjet printhead can be in fluid communication with an ink composition delivery system 150 that can supply ink composition to one or more of the printhead assemblies 140.

關於運動系統130之各種具體實例，在印刷製程期間，印刷頭總成140可在固定基板上移動(台架型)，或在分離軸組態之情況下，印刷頭總成140與基板均可移動。對於分離軸組態之各種具體實例，可藉由使印刷頭總成140相對於基板移動來提供Z軸控制。在運動系統之另一具體實例中，印刷頭總成140可經固定，且基板可相對於印刷頭總成140沿X軸及Y軸移動，且藉由印刷頭總成140之Z軸移動或藉由基板之Z軸移動來提供Z軸運動。在印刷製程期間，當印刷頭總成140相對於基板移動時，墨水組成物之液滴在適當時間噴出以沈積於基板上之所需位置中。 With regard to various specific examples of the motion system 130, the print head assembly 140 can be moved on a fixed substrate (rack type) during the printing process, or in the case of a split shaft configuration, both the print head assembly 140 and the substrate mobile. For various specific examples of split shaft configurations, Z-axis control can be provided by moving printhead assembly 140 relative to the substrate. In another embodiment of the motion system, the printhead assembly 140 can be secured and the substrate can be moved along the X and Y axes relative to the printhead assembly 140 and moved by the Z axis of the printhead assembly 140 or Z-axis motion is provided by Z-axis movement of the substrate. During the printing process, as the printhead assembly 140 moves relative to the substrate, droplets of the ink composition are ejected at the appropriate time for deposition in the desired location on the substrate.

對於印刷系統100之各種具體實例，控制系統160可用於控制印刷製程之功能。經由用戶介面，終端用戶可獲得控制系統160之各種具體實例。控制系統180可用於控制基板輸送系統110、基板支撐設備120、運動系統130、印刷頭總成140及墨水組成物傳遞系統150；向其發送及自 其接收資料。控制系統160可為電腦系統、微控制器、特殊應用積體電路(application specific integrated circuit；ASIC)、現場可程式閘陣列(field programmable gate array；FPGA)、能夠發送及接收控制及資料資訊及能夠執行指令之電子電路及其組合。舉例而言，出於在組件之間提供連通之目的，控制系統160可包括分佈於基板輸送系統110、基板支撐設備120、運動系統130、印刷頭總成140及墨水組成物傳遞系統150中之一個電子電路或多個電子電路。 For various specific examples of printing system 100, control system 160 can be used to control the functionality of the printing process. Through the user interface, end users can obtain various specific examples of the control system 160. Control system 180 can be used to control substrate delivery system 110, substrate support apparatus 120, motion system 130, printhead assembly 140, and ink composition delivery system 150; It receives the data. The control system 160 can be a computer system, a microcontroller, an application specific integrated circuit (ASIC), a field programmable gate array (FPGA), capable of transmitting and receiving control and data information, and capable of An electronic circuit that executes instructions and combinations thereof. For example, control system 160 may be distributed among substrate transport system 110, substrate support apparatus 120, motion system 130, printhead assembly 140, and ink composition delivery system 150 for purposes of providing communication between components. An electronic circuit or multiple electronic circuits.

另外，印刷系統100之控制系統160之各種具體實例可提供資料處理、顯示及報告準備功能。所有該等儀器控制功能均可局部地專屬於印刷系統100，或控制系統160可對控制、分析及報導功能提供部分或全部的遙控。最後，印刷設備100之各種具體實例可容納於圖2之封閉系統200中。 Additionally, various specific examples of control system 160 of printing system 100 may provide data processing, display, and report preparation functions. All of these instrument control functions may be localized exclusively to the printing system 100, or the control system 160 may provide some or all of the remote control of the control, analysis, and reporting functions. Finally, various specific examples of printing apparatus 100 can be accommodated in the enclosed system 200 of FIG.

圖2為根據各種具體實例，可容納圖1之印刷系統100之氣體封閉系統200的示意性圖示。氣體封閉系統200之各種具體實例可包含根據本發明教示之氣體封閉總成250、與氣體封閉總成250流體連通之氣體純化迴路230及至少一個熱調節系統240。另外，氣體封閉系統之各種具體實例可具有加壓惰性氣體再循環系統260，其可供應惰性氣體用於操作各種裝置，諸如OLED印刷系統之基板浮動台。加壓惰性氣體再循環系統260之各種具體實例可利用壓縮機、吹風機及二者之組合作為惰性氣體再循環系統260之各種具體實例的來源。另外，氣體封閉系統200可具有在氣體封閉系統200內部之過濾及循環系統(圖中未示)，其連同其他組件(諸如浮動台)一起可提供實質上低粒子之印刷環境。 2 is a schematic illustration of a gas enclosure system 200 that can accommodate the printing system 100 of FIG. 1 in accordance with various embodiments. Various embodiments of the gas enclosure system 200 can include a gas enclosure assembly 250 in accordance with the teachings of the present invention, a gas purification circuit 230 in fluid communication with the gas enclosure assembly 250, and at least one thermal conditioning system 240. Additionally, various embodiments of the gas enclosure system can have a pressurized inert gas recirculation system 260 that can supply an inert gas for operating various devices, such as a substrate floating table of an OLED printing system. Various specific examples of pressurized inert gas recirculation system 260 may utilize a compressor, a blower, and combinations of the two as a source of various specific examples of inert gas recirculation system 260. Additionally, the gas enclosure system 200 can have a filtration and circulation system (not shown) within the gas enclosure system 200 that, along with other components, such as a floating table, can provide a substantially low particle printing environment.

如圖2中所描繪，對於根據本發明教示之氣體封閉總成200之各種具體實例，氣體純化迴路230可包括自氣體封閉總成250至溶劑移除組件232、且接著達至氣體純化系統234之出口管線231。脫掉溶劑及其他反應氣體種類(諸如氧及水蒸氣)而純化之惰性氣體隨後經由入口管線233返回至氣體封閉總成250中。氣體純化迴路230亦可包括適當之管道及接線，及感測器，例如氧氣、水蒸氣及溶劑蒸氣感測器。諸如風扇、吹風機或馬達及其類似物之氣體循環單元可分別地提供或整合於例如氣體純化系統234中，以使氣體循環穿過氣體純化迴路230。根據氣體封閉總成之各種具體實例，儘管在圖2中所示之示意圖中溶劑移除系統232及氣體純化系統234顯示為分開的單元，但溶劑移除系統232及氣體純化系統234可一起容納作為單一純化單元。熱調節系統240可包括例如(但不限於)至少一個冷卻器241，其可具有用於使冷卻劑循環至氣體封閉總成中之流體出口管線243，及用於使冷卻劑返回至冷卻器中之流體入口管線245。 As depicted in FIG. 2, for various specific examples of gas enclosure assembly 200 in accordance with the teachings of the present invention, gas purification loop 230 can include gas purge assembly 250 to solvent removal assembly 232, and then to gas purification system 234. The exit line 231. The inert gas purified from the solvent and other reactive gas species, such as oxygen and water vapor, is then returned to the gas enclosure assembly 250 via inlet line 233. Gas purification circuit 230 may also include suitable piping and wiring, as well as sensors such as oxygen, water vapor, and solvent vapor sensors. Gas circulation units such as fans, blowers or motors and the like may be separately provided or integrated, for example, in gas purification system 234 to circulate gas through gas purification circuit 230. Depending on various embodiments of the gas enclosure assembly, although the solvent removal system 232 and the gas purification system 234 are shown as separate units in the schematic shown in FIG. 2, the solvent removal system 232 and the gas purification system 234 can be housed together. As a single purification unit. The thermal conditioning system 240 can include, for example, but is not limited to, at least one cooler 241 that can have a fluid outlet line 243 for circulating coolant into the gas enclosure assembly, and for returning coolant to the cooler Fluid inlet line 245.

對於氣體封閉總成200之各種具體實例，氣體源可為惰性氣體(諸如氮氣)、任何稀有氣體及其任何組合。對於氣體封閉總成200之各種具體實例，氣體源可為諸如清潔乾空氣(clean dry air；CDA)之氣體源。對於氣體封閉總成200之各種具體實例，氣體源可為供應惰性氣體及諸如CDA之氣體的組合之來源。 For various embodiments of the gas enclosure assembly 200, the gas source can be an inert gas such as nitrogen, any noble gas, and any combination thereof. For various embodiments of the gas enclosure assembly 200, the gas source can be a gas source such as a clean dry air (CDA). For various embodiments of the gas enclosure assembly 200, the gas source can be a source of a combination of an inert gas and a gas such as CDA.

氣體封閉系統200可維持各種不同反應性氣體種類之含量，包括維持各種反應大氣氣體(諸如水蒸氣及氧氣)以及有機溶劑蒸氣在100ppm或100ppm以下，例如在10ppm或10ppm以下、在1.0ppm或1.0ppm以下或在0.1ppm或0.1ppm以下。此外，氣體封閉總成之各種具體 實例可提供低粒子環境，該環境符合根據ISO 14644第1級至第5級清潔室標準的空中顆粒物規格的範圍。 The gas enclosure system 200 can maintain a variety of different reactive gas species, including maintaining various reactive atmospheric gases (such as water vapor and oxygen) and organic solvent vapors below 100 ppm or less, such as below 10 ppm or less, at 1.0 ppm or 1.0. Below ppm or below 0.1 ppm or below 0.1 ppm. In addition, various specifics of the gas enclosure assembly The example provides a low particle environment that meets the range of airborne particulate specifications according to ISO 14644 Class 1 to Class 5 clean room standards.

雖然上文中所給出者為例示性OLED噴墨印刷系統及氣體封閉系統，但熟習此項技術者可理解該等系統可用圖1及圖2之裝置及設備中之一或多者之任何組合以及其他裝置及設備來構建。 Although those given above are exemplary OLED inkjet printing systems and gas enclosure systems, those skilled in the art will appreciate that any combination of one or more of the devices and devices of FIGS. 1 and 2 can be utilized by those skilled in the art. And other devices and equipment to build.

最終噴墨印刷產物為具有高度均一厚度及組成之HIL。舉例而言，整個層寬度上之厚度變化不大於10%的層為可能的。可使用計量工具(諸如觸針式輪廓儀或干涉計顯微鏡)量測整個層之厚度。用於光學干涉量測之合適干涉計可購自Zygo儀器公司。 The final inkjet printed product is a HIL having a highly uniform thickness and composition. For example, a layer having a thickness variation of no more than 10% over the entire layer width is possible. The thickness of the entire layer can be measured using a metrology tool such as a stylus profilometer or an interferometer microscope. Suitable interferometers for optical interference measurements are available from Zygo Instruments.

墨水組成物可用於在多層OLED架構中直接印刷HIL。典型OLED包含支撐基板、陽極、陰極、安置於陽極上之HIL及安置於HIL與陰極之間的發光層(light-emitting layer；EML)。可存在於裝置中之其他層包括提供於HIL與發光層之間的電洞傳輸層，以輔助傳輸電洞至發光層；及安置於EML與陰極之間的電子傳輸層(electron transporting layer；ETL)。基板一般為透明玻璃或塑膠基板。 The ink composition can be used to directly print the HIL in a multi-layer OLED architecture. A typical OLED comprises a support substrate, an anode, a cathode, an HIL disposed on the anode, and a light-emitting layer (EML) disposed between the HIL and the cathode. Other layers that may be present in the device include a hole transport layer provided between the HIL and the light-emitting layer to assist in transporting the holes to the light-emitting layer; and an electron transport layer (ETL) disposed between the EML and the cathode ). The substrate is generally a transparent glass or plastic substrate.

在此等多層架構中，可經由噴墨印刷形成除HIL以外之一或多個層，同時可使用其他成膜技術沈積其他層。典型地，各種層將形成於一或多個像素單元內。各像素單元包含底部且藉由界定單元之周邊的堤界定。單元內之表面視情況可塗佈有表面改質塗層，諸如界面活性劑。然而，在一些具體實例中，由於該等界面活性劑可使發光層之發光淬滅，因此不存在界面活性劑。 In such multi-layer architectures, one or more layers other than the HIL can be formed via inkjet printing while other layers can be deposited using other film forming techniques. Typically, various layers will be formed within one or more pixel cells. Each pixel unit includes a bottom and is defined by a bank defining the perimeter of the unit. The surface within the unit may optionally be coated with a surface modifying coating such as a surfactant. However, in some embodiments, no surfactant is present because the surfactants can quench the luminescence of the luminescent layer.

圖3為包含複數個配置於像素單元之矩陣中之OLED的平 板顯示器的示意性圖解。圖3描繪面板300之一區域的展開視圖320，其顯示具有複數個像素單元之配置330，該複數個像素單元包括發紅光像素單元332、發綠光像素單元334及發藍光像素單元336。另外，可在平板顯示器基板上形成積體電路338，以出於在使用期間以可控方式施加電壓至各像素之目的使得電路鄰接於各像素單元。像素單元尺寸、形狀及縱橫比可視例如(但不限於)所需解析度而變化。舉例而言，100ppi之像素單元密度對於用於電腦顯示器之面板而言可為足夠的，在例如約300ppi至約450ppi之間的高解析度情況下，可產生能夠在基板表面上有效填充較高像素密度的各種像素單元設計。 3 is a flat diagram of an OLED including a plurality of matrices arranged in a pixel unit. Schematic illustration of a board display. 3 depicts an expanded view 320 of a region of panel 300 showing a configuration 330 having a plurality of pixel units including red-emitting pixel unit 332, green-emitting pixel unit 334, and blue-emitting pixel unit 336. Additionally, integrated circuitry 338 can be formed on the flat panel display substrate such that the circuitry is adjacent to each pixel cell for the purpose of applying a voltage to each pixel in a controlled manner during use. The pixel cell size, shape, and aspect ratio may vary, for example, but not limited to, the desired resolution. For example, a pixel cell density of 100 ppi may be sufficient for a panel for a computer display to produce an effective fill on the surface of the substrate at high resolutions, for example between about 300 ppi and about 450 ppi. Various pixel unit designs for pixel density.

雖然本發明上文已集中於經調配用於噴墨印刷基於聚噻吩之HIL的水性墨水組成物，但本發明技術之另一態樣提供經調配用於噴墨印刷OLED之HIL或HTL的基於非水性有機溶劑之墨水組成物。有機HIL/HTL墨水組成物包含習知地被視為潤濕劑之組分，但其係以謹慎控制之量併入HTL墨水中，以使得其實際上阻止可由於潤濕而產生之不受控制的擴散及像素單元溢出。在一些具體實例中，有機墨水包含：(1)電洞注入材料或電洞傳輸材料；(2)一或多種溶解電洞注入或電洞傳輸材料之有機溶劑；及(3)氟界面活性劑。電洞注入或電洞傳輸材料典型地以墨水組成物之總重量計以不大於約5wt.%、更典型地不大於2wt.%且更典型地不大於約1wt.%(例如約0.1至約1wt.%)之量存在。有機溶劑典型地佔墨水組成物之約95至約99.8wt.%。氟化界面活性劑典型地以不大於約0.15wt.%之量存在。舉例而言，在基於有機溶劑之墨水組成物的一些具體實例中，氟化界面活性劑以約0.03wt.%至約0.1wt.%範圍內之量存在。 While the present invention has been focused above on aqueous ink compositions formulated for ink jet printing of polythiophene-based HILs, another aspect of the present technology provides a basis for formulating HIL or HTL for ink jet printing OLEDs. An ink composition of a non-aqueous organic solvent. The organic HIL/HTL ink composition comprises a component that is conventionally considered a wetting agent, but is incorporated into the HTL ink in a carefully controlled amount such that it actually prevents it from being wetted Controlled diffusion and pixel cell overflow. In some embodiments, the organic ink comprises: (1) a hole injection material or a hole transport material; (2) one or more organic solvents that dissolve the hole injection or hole transport material; and (3) a fluorine surfactant. . The hole injection or hole transport material is typically no more than about 5 wt.%, more typically no more than 2 wt.%, and more typically no more than about 1 wt.% (e.g., about 0.1 to about), based on the total weight of the ink composition. The amount of 1 wt.%) is present. The organic solvent typically comprises from about 95 to about 99.8 wt.% of the ink composition. The fluorinated surfactant is typically present in an amount of no greater than about 0.15 wt.%. For example, in some embodiments of the organic solvent-based ink composition, the fluorinated surfactant is present in an amount ranging from about 0.03 wt.% to about 0.1 wt.%.

適合用於基於有機溶劑之墨水組成物之電洞注入材料包括如上文所述之聚噻吩。合適之電洞傳輸材料包括聚乙烯咔唑或其衍生物、聚矽烷或其衍生物、在側鏈或主鏈具有芳族胺之聚矽氧烷衍生物、吡唑啉衍生物、芳基胺衍生物、二苯乙烯衍生物、三苯基二胺衍生物、聚苯胺或其衍生物、聚噻吩或其衍生物、聚芳基胺或其衍生物、聚吡咯或其衍生物、聚(對伸苯基伸乙烯基)或其衍生物或聚(2,5伸噻吩基伸乙烯基)或其衍生物。 A hole injecting material suitable for use in an organic solvent-based ink composition includes polythiophene as described above. Suitable hole transport materials include polyvinylcarbazole or a derivative thereof, polydecane or a derivative thereof, a polyoxyalkylene derivative having an aromatic amine in a side chain or a main chain, a pyrazoline derivative, an arylamine a derivative, a stilbene derivative, a triphenyldiamine derivative, a polyaniline or a derivative thereof, a polythiophene or a derivative thereof, a polyarylamine or a derivative thereof, a polypyrrole or a derivative thereof, a poly(pair) A phenyl extended vinyl group or a derivative thereof or a poly(2,5-threquivalent vinyl group) or a derivative thereof.

適合用於HIL/HTL墨水組成物之有機溶劑包括烷氧基醇、烷基醇、烷基苯、苯甲酸烷基酯、烷基萘、辛酸戊酯、苯甲醚、芳基醇、苯甲醇、丁基苯、苯丁酮、順-十氫萘、二丙二醇甲醚、十二烷基苯、均三甲苯、甲氧基丙醇、甲基苯甲酸酯、甲基萘、甲基吡咯啶酮、苯氧基乙醇、1,3-丙二醇、吡咯啶酮、反-十氫萘、苯戊酮及其混合物。 Organic solvents suitable for use in HIL/HTL ink compositions include alkoxy alcohols, alkyl alcohols, alkyl benzenes, alkyl benzoates, alkyl naphthalenes, amyl octanoate, anisole, aryl alcohols, benzyl alcohol Butylbenzene, phenylbutanone, cis-decalin, dipropylene glycol methyl ether, dodecylbenzene, mesitylene, methoxypropanol, methyl benzoate, methylnaphthalene, methylpyrrole Pyridone, phenoxyethanol, 1,3-propanediol, pyrrolidone, trans-decahydronaphthalene, phenylpentanone, and mixtures thereof.

氟界面活性劑為包含氟化烷基鏈之界面活性劑。杜邦公司(E.I.du Pont de Nemours and Company)(Wilmington,Delaware)以商標名Capstone及Zonyl出售氟化界面活性劑。氟界面活性劑可為例如氟調聚物(fluorotelomer)(例如具有聚乙二醇或2-全氟烷基)乙醇之調聚物B單醚)。市售氟界面活性劑包括Zonyl® FS 1033D、Zonyl® FS 1176、Zonyl® FSG、Zonyl® FS-300、Zonyl® FSN、Zonyl® FSH、Zonyl® FSN、Zonyl® FSO、Zonyl® FSN-100、Zonyl® FSO-100、Zonyl® FSH、Zonyl® FSN、Zonyl® FSO、Zonyl® FSH、Zonyl® FSN、Zonyl® FSO、Zonyl® FS 500、Zonyl® FS 510、Zonyl® FSJ、Zonyl® FS-610、Zonyl® 9361、Zonyl® FSA、FSP、FSE、FSJ、Zonyl® FSP、Zonyl® 9361、Zonyl® FSE、Zonyl® FSA、Zonyl® UR、Zonyl® 8867L、Zonyl® FSG、Zonyl® 8857A、Foraperle® 225、Forafac® 1268、Forafac® 1157、Forafac® 1183、Zonyl® 8929B、Zonyl® 9155、Zonyl® 9815、Zonyl® 9933LX、Zonyl® 9938、Zonyl® PFBI、Zonyl® PFBEI、Zonyl® PFBE、Zonyl® PFHI、Zonyl® BA、-8-Zonyl® PFHEI、Zonyl® TM、Zonyl® 8932、Zonyl® 7910、Zonyl® 7040、Foraperle® 321/325、Zonyl® 9464、Zonyl® NF、Zonyl® RP、Zonyl® 321、Zonyl® 8740、Zonyl® 225、Zonyl® 227、Zonyl® 9977、Zonyl® 9027、Zonyl® 9671、Zonyl® 9338及Zonyl® 9582；Capstone® ST-500、Capstone® ST-300、Capstone® ST-200、Capstone® ST-110、Capstone® P-640、Capstone® P-623、Capstone® P-620、Capstone® P-600、Capstone® FS-10、Capstone® FS-17、Capstone® FS-22、Capstone® FS-30、Capstone® FS-31、Capstone® FS-3100、Capstone® FS-34、Capstone® FS-35、Capstone® FS-50、Capstone® FS-51、Capstone® FS-60、Capstone® FS-61、Capstone® FS-63、Capstone® FS-64、Capstone® FS-64、Capstone® FS-65、Capstone® FS-66、Capstone® FS-81、Capstone® FS-83、Capstone® LPA、Capstone® 1460、Capstone® 1157、Capstone® 1157D、Capstone® 1183、Capstone® CPS、Capstone® E、Capstone® LMC、Capstone® CP、Capstone® PSB、Capstone® 4-I、Capstone® 42-I、Capstone® 42-U、Capstone® 6-I、Capstone® 62-AL、Capstone® 62-I、Capstone® 62-MA、Capstone® TC、Capstone® TR及Capstone® TS。 The fluorosurfactant is a surfactant comprising a fluorinated alkyl chain. Fluorinated surfactants are sold by E. I. du Pont de Nemours and Company (Wilmington, Delaware) under the tradenames Capstone and Zonyl. The fluorosurfactant can be, for example, a fluorotelomer (e.g., a telomer B monoether having polyethylene glycol or 2-perfluoroalkyl) ethanol). Commercially available fluorosurfactants include Zonyl® FS 1033D, Zonyl® FS 1176, Zonyl® FSG, Zonyl® FS-300, Zonyl® FSN, Zonyl® FSH, Zonyl® FSN, Zonyl® FSO, Zonyl® FSN-100, Zonyl ® FSO-100, Zonyl® FSH, Zonyl® FSN, Zonyl® FSO, Zonyl® FSH, Zonyl® FSN, Zonyl® FSO, Zonyl® FS 500, Zonyl® FS 510, Zonyl® FSJ, Zonyl® FS-610, Zonyl ® 9361, Zonyl® FSA, FSP, FSE, FSJ, Zonyl® FSP, Zonyl® 9361, Zonyl® FSE, Zonyl® FSA, Zonyl® UR, Zonyl® 8867L, Zonyl® FSG, Zonyl® 8857A, Foraperle® 225, Forafac ® 1268, Forafac® 1157, Forafac® 1183, Zonyl® 8929B, Zonyl® 9155, Zonyl® 9815, Zonyl® 9933LX, Zonyl® 9938, Zonyl® PFBI, Zonyl® PFBEI, Zonyl® PFBE, Zonyl® PFHI, Zonyl® BA, -8-Zonyl® PFHEI, Zonyl ® TM, Zonyl® 8932, Zonyl® 7910, Zonyl® 7040, Foraperle® 321/325, Zonyl® 9464, Zonyl® NF, Zonyl® RP, Zonyl® 321, Zonyl® 8740, Zonyl® 225, Zonyl® 227, Zonyl ® 9977, Zonyl® 9027, Zonyl® 9671, Zonyl® 9338 and Zonyl® 9582; Capstone® ST-500, Capstone® ST-300, Capstone® ST-200, Capstone® ST-110, Capstone® P-640, Capstone ® P-623, Capstone® P-620, Capstone® P-600, Capstone® FS-10, Capstone® FS-17, Capstone® FS-22, Capstone® FS-30, Capstone® FS-31, Capstone® FS -3100, Capstone® FS-34, Capstone® FS-35, Capstone® FS-50, Capstone® FS-51, Capstone® FS-60, Capstone® FS-61, Capstone® FS-63, Capstone® FS-64 , Capstone® FS-64, Capstone® FS-65, Capstone® FS-66, Capstone® FS-81, Capstone® FS-83, Capstone® LPA, Capstone® 1460, Capstone® 1157 , Capstone® 1157D, Capstone® 1183, Capstone® CPS, Capstone® E, Capstone® LMC, Capstone® CP, Capstone® PSB, Capstone® 4-I, Capstone® 42-I, Capstone® 42-U, Capstone® 6 -I, Capstone® 62-AL, Capstone® 62-I, Capstone® 62-MA, Capstone® TC, Capstone® TR and Capstone® TS.

實施例 Example 實施例1：甲基聚矽氧烷對像素內均一性之影響 Example 1: Effect of methyl polyoxyalkylene on the homogeneity in pixels

以下實施例說明由HIL噴墨墨水組成物中之甲基聚矽氧烷提供之接觸線釘紮效應；及於發光均一性中之所得改良。 The following examples illustrate the contact line pinning effect provided by methyl polyoxyalkylene in the HIL inkjet ink composition; and the resulting improvement in luminescence uniformity.

材料及方法Materials and methods

HIL墨水組成物之製備：Preparation of HIL ink composition:

用表1中所示之組分及濃度製備HIL墨水組成物A及B。組成物A與B包括呈所指示濃度之甲基聚矽氧烷。作為比較實施例，製備包括表2中所列之成分、但缺乏甲基聚矽氧烷之墨水組成物(比較組成物)。 HIL ink compositions A and B were prepared using the components and concentrations shown in Table 1. Compositions A and B include methyl polyoxane at the indicated concentrations. As a comparative example, an ink composition (comparative composition) including the components listed in Table 2 but lacking methyl polyoxyalkylene was prepared.

藉由將清潔小瓶置放於天平上且使用Pasteur吸管將所需量之Botanisil S-18轉移至小瓶中來調配墨水組成物。用天平稱瓶重且將1,3-丙二醇、水及DPGME依序吸取至小瓶中。隨後將小瓶自天平上移去，封蓋並旋轉以混合所得水溶液。隨後將小瓶放回天平且將所需量之PEDOT分散 液(Haraeus Clevios TM PVP A1 4083)吸取至小瓶中。隨後將小瓶自天平上移去、封蓋並旋轉以將PEDOT與混合物之其他組分混合。隨後用聚四氟乙烯(PTFE)濾膜(2.0μm)過濾所得PEDOT墨水組成物且將經過濾之組成物收集於琥珀色瓶中。最後，在使用前將該瓶音波處理15分鐘。 The ink composition was formulated by placing a cleaning vial on a balance and transferring the desired amount of Botanisil S-18 to a vial using a Pasteur pipette. The bottle was weighed with a balance and the 1,3-propanediol, water and DPGME were sequentially aspirated into the vial. The vial was then removed from the balance, capped and spun to mix the resulting aqueous solution. The vial is then returned to the balance and the required amount of PEDOT is dispersed. The liquid (Haraeus CleviosTM PVP A1 4083) was pipetted into the vial. The vial is then removed from the balance, capped and rotated to mix the PEDOT with the other components of the mixture. The resulting PEDOT ink composition was then filtered through a polytetrafluoroethylene (PTFE) filter (2.0 μm) and the filtered composition was collected in an amber bottle. Finally, the bottle was sonicated for 15 minutes before use.

在無Botanisil S-18之情況下使用相同程序製得比較墨水組成物。 Comparative ink compositions were prepared using the same procedure without Botanisil S-18.

黏度及表面張力量測：Viscosity and surface tension measurement:

使用DV-I Prime Brookfield流變儀進行黏度量測。用SITA鼓泡壓力張力計量測表面張力。含甲基聚矽氧烷之墨水組成物A及B及比較墨水組成物(比較組成物)之量測值提供於表1及2中。 Viscosity measurements were made using a DV-I Prime Brookfield rheometer. The surface tension was measured using SITA bubbling pressure tension. The measured values of the ink compositions A and B containing methylpolysiloxane and the comparative ink composition (comparative composition) are shown in Tables 1 and 2.

HIL噴墨印刷及OLED製造：HIL inkjet printing and OLED manufacturing:

將HIL墨水組成物印刷至OLED架構中之ITO陽極上。OLED之基板為厚度為0.5mm之玻璃，在該基板上具有60nm氧化銦錫(indium tin oxide；ITO)之陽極經圖案化。堤材料(亦稱為像素界定層)隨後於ITO上經圖案化，形成沈積噴墨印刷層之單元。堤材料為經設計用於噴墨印刷之負型光阻劑。所得單元具有高度在約0.5至2μm範圍內且相對於單元之底部成45°角之堤，以使得各單元之開口寬於其基底。45°角代表典型堤角度，該等角度在約5°至約70°範圍內。單元之寬度及長度尺寸為約60×175μm。隨後使用表1及2之墨水組成物將HIL層噴墨印刷至單元中，真空乾燥且於高溫下烘烤以自該層移除水及溶劑。 The HIL ink composition was printed onto an ITO anode in an OLED architecture. The substrate of the OLED is glass having a thickness of 0.5 mm, and an anode having 60 nm of indium tin oxide (ITO) on the substrate is patterned. The bank material (also known as the pixel defining layer) is then patterned on the ITO to form a unit for depositing an inkjet printed layer. The bank material is a negative photoresist designed for ink jet printing. The resulting unit has a bank having a height in the range of about 0.5 to 2 μm and a 45° angle with respect to the bottom of the unit such that the opening of each unit is wider than its base. The 45° angle represents a typical bank angle ranging from about 5° to about 70°. The width and length dimensions of the unit are about 60 x 175 μm. The HIL layer was then inkjet printed into the unit using the ink compositions of Tables 1 and 2, vacuum dried and baked at elevated temperature to remove water and solvent from the layer.

在室溫下，使用描述於PCT申請公開案第WO 2013/158310號中之噴墨印刷系統印刷HIL墨水組成物，該申請公開案之全部揭示內容 以引用之方式併入本文中。藉由用HIL墨水組成物填充大容量墨水儲集器來進行噴墨印刷至像素單元中。大容量墨水儲集器與初級分配儲集器流體連通且在印刷期間為初級分配儲集器提供持續供應之HIL墨水組成物。隨後將HIL墨水組成物饋入包含複數個噴嘴之印刷頭中，HIL墨水組成物經由該複數個噴嘴噴射至像素單元中。印刷期間之典型液滴體積為約10pl且將約3至10滴印刷至各單元中以在單元中形成墨水組成物的液滴。 The HIL ink composition is printed at room temperature using an inkjet printing system as described in PCT Application Publication No. WO 2013/158310, the entire disclosure of which is incorporated herein by reference. This is incorporated herein by reference. Inkjet printing into the pixel unit is performed by filling the bulk ink reservoir with the HIL ink composition. The bulk ink reservoir is in fluid communication with the primary distribution reservoir and provides a continuous supply of HIL ink composition to the primary distribution reservoir during printing. The HIL ink composition is then fed into a printhead comprising a plurality of nozzles through which the HIL ink composition is ejected into the pixel unit. A typical drop volume during printing is about 10 pl and about 3 to 10 drops are printed into each cell to form droplets of the ink composition in the cell.

如下製造併有由墨水組成物A印刷之HIL的OLED。將HTL層噴墨印刷至HIL層上，接著真空乾燥且於高溫下烘烤以移除溶劑且誘導可交聯聚合物之交聯。隨後將EML層噴墨印刷至HTL層上，接著真空乾燥且於高溫下烘烤以移除溶劑。使用上文所述之印刷機噴墨印刷HTL及EML層。HTL墨水組成物包含基於酯之溶劑系統中之電洞傳輸聚合物材料，該溶劑系統由重量比為1：1之經蒸餾及脫氣之辛酸二乙酯及辛酸辛酯的混合物組成。EML墨水組成物包含癸二酸二乙酯中之有機電致發光材料。 An OLED having an HIL printed by the ink composition A was produced as follows. The HTL layer was inkjet printed onto the HIL layer, followed by vacuum drying and baking at elevated temperature to remove solvent and induce cross-linking of the crosslinkable polymer. The EML layer is then inkjet printed onto the HTL layer, followed by vacuum drying and baking at elevated temperature to remove solvent. The HTL and EML layers were inkjet printed using the printer described above. The HTL ink composition comprises a hole transporting polymeric material in an ester based solvent system consisting of a mixture of distilled and degassed diethyl octoate and octyl octanoate in a weight ratio of 1:1. The EML ink composition comprises an organic electroluminescent material in diethyl sebacate.

隨後藉由真空熱蒸發塗覆ETL層，接著塗覆陰極層。ETL材料包含喹啉鋰(lithium quinolate；LiQ)作為發光材料且陰極層由100nm之鋁組成。 The ETL layer was then coated by vacuum thermal evaporation followed by coating of the cathode layer. The ETL material contains lithium quinolate (LiQ) as a luminescent material and the cathode layer is composed of 100 nm of aluminum.

結果result

印刷至像素單元中之組成物A及B之液滴釘紮至像素堤且既不經歷溢出亦不經歷拉回。使用印刷於像素單元中且釘紮至像素單元之組成物A(0.1wt.%甲基聚矽氧烷)製得之HIL層的影像顯示於圖4A中。相比之下，印刷至像素單元中之比較組成物的影像(圖5及6)顯示在不存在甲基聚矽氧烷之情況下，墨水組成物不可控制地擴散且溢出像素單元之 側面500(圖5A)或自像素單元之堤拉回(抗濕潤)，從而在結合有一些像素單元溢出600之單元底部形成抗濕潤區域602(圖6A)。 The droplets of the compositions A and B printed into the pixel unit are pinned to the pixel bank and neither experience spillage nor undergo pullback. An image of the HIL layer prepared using the composition A (0.1 wt.% methyl polyoxyalkylene) printed in the pixel unit and pinned to the pixel unit is shown in Fig. 4A. In contrast, the image of the comparative composition printed into the pixel unit (Figures 5 and 6) shows that in the absence of methyl polyoxyalkylene, the ink composition spreads uncontrollably and overflows the pixel unit. Side 500 (Fig. 5A) or pull back (wet resistant) from the bank of the pixel unit to form a wetted region 602 (Fig. 6A) at the bottom of the cell incorporating some of the pixel cell overflows 600.

對於上文所述之圖4A-6A中所示及下文所述之圖7A-9A中所示之各顯微照片，提供黑白線圖且將其標記為相應『B』圖。 For each photomicrograph shown in Figures 4A-6A and described below in Figures 7A-9A, a black and white line drawing is provided and labeled as a corresponding "B" diagram.

亦研究包括用組成物A製得之噴墨印刷之HIL的OLED像素的電致發光特性。一旦製得OLED，即藉由在二極體兩端施加電流且對光發射進行成像來研究其電致發光之均一性。所得發光顯示於圖7A之顯微照片中。如該圖中可見，用墨水組成物A印刷之HIL層有助於併有其之OLED像素之均一發光。 The electroluminescent properties of the OLED pixels comprising the inkjet printed HIL made with Composition A were also investigated. Once the OLED is made, the homogeneity of its electroluminescence is investigated by applying a current across the diode and imaging the light emission. The resulting luminescence is shown in the photomicrograph of Figure 7A. As can be seen in this figure, the HIL layer printed with ink composition A contributes to uniform illumination of the OLED pixels.

實施例2：環丁碸對印刷特性之影響 Example 2: Effect of cyclobutyl hydrazine on printing characteristics

以下實施例說明藉由環丁碸賦予HIL墨水組成物的經改良之印刷特性。 The following examples illustrate the improved printing characteristics imparted to the HIL ink composition by cyclobutene.

材料及方法Materials and methods

HIL墨水組成物之製備：Preparation of HIL ink composition:

製備包括甲基聚矽氧烷、環丁碸及表3中所列之其他成分的HIL墨水組成物。 HIL ink compositions including methyl polyoxyalkylene, cyclobutyl hydrazine, and other ingredients listed in Table 3 were prepared.

如實施例1中所述調配墨水組成物，除了使用環丁碸替代1,3-丙二醇。 The ink composition was formulated as described in Example 1, except that cyclobutane was used instead of 1,3-propanediol.

黏度及表面張力量測：Viscosity and surface tension measurement:

如實施例1中進行黏度及表面張力量測。 Viscosity and surface tension measurements were performed as in Example 1.

HIL噴墨印刷及OLED製造：HIL inkjet printing and OLED manufacturing:

如實施例1中所述印刷HIL墨水組成物且形成OLED像素用於電致發光測試。 The HIL ink composition was printed as described in Example 1 and OLED pixels were formed for electroluminescence testing.

潛伏期量測：Latency measurement:

使用描述於PCT申請公開案第WO 2013/158310號中之噴墨印刷系統進行墨水之潛伏期量測。藉由起動一個噴嘴且量測體積、速度及方向性之300個數據點來進行量測。隨後使噴嘴閒置30分鐘。在30分鐘之後，重新起動噴嘴且再記錄300個數據點。 The latency measurement of the ink was performed using an inkjet printing system as described in PCT Application Publication No. WO 2013/158310. The measurement was performed by starting a nozzle and measuring 300 data points of volume, velocity and directivity. The nozzle was then left idle for 30 minutes. After 30 minutes, the nozzle was restarted and 300 more data points were recorded.

標繪數據組且進行比較以查看相比於穩態噴射(第一數據組結束，30分鐘閒置前)，在第二組組開始時(30分鐘閒置後)之任何起動效果(通常為速度下降及體積改變)。 Plot the data sets and compare them to see any start-up effect (usually a drop in speed) at the beginning of the second set (after 30 minutes of inactivity) compared to steady-state injection (before the end of the first data set, 30 minutes before idle) And volume change).

亦使用Dimatix Fujifilm DMP-2831印刷機進行墨水之潛伏期量測。在液滴觀看裝置中，開啟所有16個噴嘴且確認所有噴嘴為起動的。隨後停止噴射5分鐘。恢復噴射且檢驗確認所有噴嘴仍在工作。隨後，進行持續噴射15及30分鐘之時間。以噴射結束與未封蓋噴嘴中之墨水開始乾燥之間的時間量測潛伏時間，該乾燥產生不當液滴起動。為確定墨水組成物何時乾燥，將其在顯微鏡下以白光及螢光模式進行檢驗。 The incubation period of the ink was also measured using a Dimatix Fujifilm DMP-2831 printer. In the drop viewing device, all 16 nozzles are turned on and all nozzles are confirmed to be activated. The spraying was then stopped for 5 minutes. The injection is resumed and the test confirms that all nozzles are still working. Subsequently, continuous spraying was carried out for 15 and 30 minutes. The latency is measured at the time between the end of the jet and the start of drying of the ink in the uncapped nozzle, which produces improper droplet initiation. To determine when the ink composition is dry, it is examined under a microscope in white and fluorescent mode.

結果result

一旦製得OLED，即藉由在各二極體兩端施加電流且對光發射進行成像來研究其電致發光的均一性。量測具有由表3之墨水組成物印刷之HIL的OLED及具有由表1之墨水組成物印刷之HIL的OLED的電致發光。圖8及9之顯微照片的比較顯示HIL墨水組成物中之環丁碸相比於丙二醇(圖9A)提供更均一之像素發光(圖8A)。 Once the OLED is produced, the homogeneity of its electroluminescence is investigated by applying a current across the diodes and imaging the light emission. Electroluminescence of an OLED having an HIL printed by the ink composition of Table 3 and an OLED having an HIL printed by the ink composition of Table 1 was measured. A comparison of the photomicrographs of Figures 8 and 9 shows that cyclobutene in the HIL ink composition provides more uniform pixel illumination compared to propylene glycol (Figure 9A) (Figure 8A).

此外，含環丁碸之墨水組成物的最大穩定噴射頻率(1000Hz)比含二醇之墨水組成物高。最後，相比於含二醇之墨水組成物的僅15分鐘，含環丁碸之墨水組成物的潛伏時間為超過30分鐘。使用描述於PCT申請公開案第WO 2013/158310號中之噴墨印刷系統量測之潛伏期測試的結果顯示於圖10至12中。在此等圖中，含環丁碸之墨水指定為P113。圖10為墨水組成物在閒置之前及在30分鐘閒置之後於14分鐘內之液滴體積之圖。圖11為墨水組成物在閒置之前及在30分鐘閒置之後於14分鐘內之液滴速度之圖。如在此圖中可見，重新起動時之液滴速度僅比閒置前之液滴速度低4%。圖12為墨水組成物在閒置之前及在30分鐘閒置之後於14分鐘內之液滴角度之圖。在閒置前後未觀測到液滴角度之顯著差異。 Further, the maximum stable ejection frequency (1000 Hz) of the ink composition containing cyclohexane is higher than that of the diol-containing ink composition. Finally, the incubation time of the cyclobutene-containing ink composition was more than 30 minutes compared to only 15 minutes of the diol-containing ink composition. The results of the latency test using the inkjet printing system measurement described in PCT Application Publication No. WO 2013/158310 are shown in Figures 10 to 12. In these figures, the ink containing cyclopentane is designated as P113. Figure 10 is a graph of droplet volume for 14 minutes before the ink composition is idle and after 30 minutes of inactivity. Figure 11 is a graph of droplet velocity for 14 minutes before the ink composition is idle and after 30 minutes of inactivity. As can be seen in this figure, the droplet velocity at restart is only 4% lower than the droplet velocity before idle. Figure 12 is a graph of the droplet angle of the ink composition in 14 minutes before being idle and after being idle for 30 minutes. No significant difference in droplet angle was observed before and after idle.

字語「說明性(illustrative)」在本文中用於意謂充當實例、例子或說明。本文中描述為「說明性」之任何態樣或設計未必理解為較佳或優於其他態樣或設計。此外，除非另外明確指明，否則出於本發明之目的，「及(and)」或「或(or)」之使用意欲包括「及/或(and/or)」。 The word "illustrative" is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as "illustrative" is not necessarily to be construed as preferred or advantageous. In addition, the use of "and" or "or" is intended to include "and/or (or/or)", unless otherwise specified.

出於說明及描述之目的，已呈現對本發明之說明性具體實例之前述描述。其並不意欲為詳盡的或限制本發明於所揭示之確切形式， 且根據以上教示，修改及變化為可能的或可自本發明之實踐獲得。選擇且描述該等具體實例以解釋本發明之原則且作為本發明之實際應用，以使得熟習此項技術者能夠在各種具體實例中且在適合於涵蓋之特定用途的各種修改的情況下利用本發明。預期本發明之範疇由在此隨附之申請專利範圍及其等效物界定。 The foregoing description of the illustrative embodiments of the invention has the It is not intended to be exhaustive or to limit the invention. And modifications and variations are possible in light of the above teachings. The specific examples were chosen and described in order to explain the principles of the embodiments of the invention of the invention invention. The scope of the invention is intended to be defined by the scope of the appended claims and their equivalents.

100‧‧‧OLED噴墨印刷系統 100‧‧‧OLED inkjet printing system

110‧‧‧基板輸送系統 110‧‧‧Substrate delivery system

120‧‧‧基板支撐設備 120‧‧‧Substrate support equipment

130‧‧‧運動系統 130‧‧‧ sports system

140‧‧‧印刷頭總成 140‧‧‧Print head assembly

150‧‧‧墨水傳遞系統 150‧‧‧Ink delivery system

160‧‧‧控制系統 160‧‧‧Control system

Claims (21)

一種形成有機發光二極體之電洞注入層之方法，該方法包含：於有機發光二極體之像素單元中之電極層上噴墨印刷墨水組成物之液滴，該像素單元由像素堤(bank)界定，該墨水組成物包含：導電聚噻吩；水；至少一種有機溶劑；及甲基聚矽氧烷(methicone)，其中該甲基聚矽氧烷以提供該像素單元中之該液滴之接觸線釘紮的量存在；且使該墨水組成物之揮發性組分蒸發，藉此形成該電洞注入層。 A method for forming a hole injection layer of an organic light-emitting diode, the method comprising: ink-jet printing a droplet of an ink composition on an electrode layer in a pixel unit of an organic light-emitting diode, the pixel unit being a pixel bank Defining that the ink composition comprises: a conductive polythiophene; water; at least one organic solvent; and a methyl polymethoxane, wherein the methyl polysiloxane is used to provide the droplet in the pixel unit The amount of contact line pinning exists; and the volatile component of the ink composition is evaporated, thereby forming the hole injection layer. 如申請專利範圍第1項之方法，其中該導電聚噻吩為PEDOT。 The method of claim 1, wherein the conductive polythiophene is PEDOT. 如申請專利範圍第2項之方法，其中該PEDOT以至少50wt.%之量存在。 The method of claim 2, wherein the PEDOT is present in an amount of at least 50 wt.%. 如申請專利範圍第2項之方法，其中該電極層包含透明導電材料。 The method of claim 2, wherein the electrode layer comprises a transparent conductive material. 如申請專利範圍第4項之方法，其中該透明導電材料為氧化銦錫且該甲基聚矽氧烷以約0.03wt.%至約0.12wt.%之量存在。 The method of claim 4, wherein the transparent conductive material is indium tin oxide and the methyl polyoxyalkylene is present in an amount of from about 0.03 wt.% to about 0.12 wt.%. 如申請專利範圍第1項之方法，其中該至少一種有機溶劑為在25°下表面張力不大於55達因/公分且黏度不大於15厘泊之非質子性溶劑。 The method of claim 1, wherein the at least one organic solvent is an aprotic solvent having a surface tension of not more than 55 dynes/cm at 25° and a viscosity of not more than 15 centipoise. 如申請專利範圍第6項之方法，其中該至少一種有機溶劑之沸點在大氣壓下為240℃或高於240℃。 The method of claim 6, wherein the at least one organic solvent has a boiling point of 240 ° C or higher than 240 ° C at atmospheric pressure. 如申請專利範圍第1項之方法，其中該至少一種有機溶劑為環丁碸。 The method of claim 1, wherein the at least one organic solvent is cyclobutyl hydrazine. 如申請專利範圍第8項之方法，其中環丁碸佔該墨水組成物中之總有機溶劑含量的大於50wt.%。 The method of claim 8, wherein the cyclobutyl hydrazine accounts for more than 50 wt.% of the total organic solvent content of the ink composition. 如申請專利範圍第8項之方法，其中該環丁碸以至少5wt.%之量存在。 The method of claim 8, wherein the cyclopentanthene is present in an amount of at least 5 wt.%. 如申請專利範圍第3項之方法，其中該電極層包含氧化銦錫，該甲基聚矽氧烷以約0.05wt.%至約0.1wt.%之量存在，且該至少一種有機溶劑為環丁碸，其以約5至約12wt.%範圍內之量存在。 The method of claim 3, wherein the electrode layer comprises indium tin oxide, the methyl polyoxyalkylene is present in an amount of from about 0.05 wt.% to about 0.1 wt.%, and the at least one organic solvent is a ring Ding, which is present in an amount ranging from about 5 to about 12 wt.%. 如申請專利範圍第8項之方法，其中該墨水組成物進一步包含相比於環丁碸具有較低表面張力及較低沸點之第二有機溶劑。 The method of claim 8, wherein the ink composition further comprises a second organic solvent having a lower surface tension and a lower boiling point than the cyclobutanil. 如申請專利範圍第12項之方法，其中該第二有機溶劑為丙二醇甲醚。 The method of claim 12, wherein the second organic solvent is propylene glycol methyl ether. 如申請專利範圍第1項之方法，其中該墨水調配物之表面張力在25℃下不大於47達因/公分、黏度在25℃下不大於15厘泊且潛伏時間在25℃下為至少20分鐘。 The method of claim 1, wherein the ink formulation has a surface tension of not more than 47 dynes/cm at 25 ° C, a viscosity of not more than 15 centipoise at 25 ° C, and a latent time of at least 20 at 25 ° C. minute. 如申請專利範圍第1項之方法，其中該導電聚噻吩佔該墨水組成物至少30wt.%。 The method of claim 1, wherein the conductive polythiophene comprises at least 30 wt.% of the ink composition. 一種墨水組成物，其包含：PEDOT，其中該PEDOT以至少30wt.%之量存在；水；至少一種有機溶劑，其表面張力在25℃下不大於55達因/公分、黏度在25℃下不大於15厘泊且沸點為至少200℃；及甲基聚矽氧烷。 An ink composition comprising: PEDOT, wherein the PEDOT is present in an amount of at least 30 wt.%; water; at least one organic solvent having a surface tension of not more than 55 dynes/cm at 25 ° C and a viscosity at 25 ° C More than 15 centipoise and a boiling point of at least 200 ° C; and methyl polyoxyalkylene. 如申請專利範圍第16項之墨水組成物，其中該至少一種有機溶劑為環丁碸。 The ink composition of claim 16, wherein the at least one organic solvent is cyclobutyl hydrazine. 如申請專利範圍第17項之墨水組成物，其進一步包含相比於環丁碸具有較低表面張力及較低沸點之第二有機溶劑。 The ink composition of claim 17, which further comprises a second organic solvent having a lower surface tension and a lower boiling point than the cyclobutanil. 如申請專利範圍第18項之墨水組成物，其中該第二有機溶劑為丙二醇甲醚。 The ink composition of claim 18, wherein the second organic solvent is propylene glycol methyl ether. 如申請專利範圍第18項之墨水組成物，其包含：約50至約70wt.% PEDOT；約3wt.%至約10wt.%環丁碸；及約0.03wt.%至0.12wt.%甲基聚矽氧烷。 An ink composition according to claim 18, which comprises: from about 50 to about 70 wt.% PEDOT; from about 3 wt.% to about 10 wt.% of cyclobutanthene; and from about 0.03 wt.% to 0.12 wt.% of methyl Polyoxane. 如申請專利範圍第16項之墨水組成物，，其中該PEDOT以至少50wt.%之量存在。 The ink composition of claim 16, wherein the PEDOT is present in an amount of at least 50 wt.%.