527432 A7 B7 五、發明說明（ 本發明係有關一種用於發光裝置（LED)中沈積共軛聚 合物層之配方。 使用作為發光層之半導體共軛聚合物之發光裝置係已 知。第1圖顯示簡單發光裝置之構造。玻璃或塑膠基材2以 陽極層4(例如，銦錫氧化物之形式）塗覆。陽極可以延長 條狀之形式形成圖案。陽極層可以電洞轉移層塗覆。然後 ，發光聚合物層6被沈積，其後，沈積電子轉移層。然後 ，此裝置結構藉由沈積陰極層8而完成。舉例而言，陰極 層可為鈣或鋁。陰極層8可以交叉條狀形成圖案，以界 像素P’其間陽極及陰極係重疊。另外，藉由不具圖案 陰極，發光條可被界定。另外，像素可於活性基質後表回 上界疋，而陰極可被形成圖案或未被形成圖案。當電場於 陽極與陰極間施加時，電洞及電子被射入發光聚合物層、 内。電洞及電子係於聚合物層内重新結合，且一比例輻 衰變而產生光。 電洞轉移層一般可由能維持電洞轉移之任何化合物所 組成。適當㈣之财係有機導體，諸如下料電性聚合 物：聚苯胺、聚伸乙基二氧嗔吩及其它聚嗔吩、聚扯㈣ ’其等係以其摻雜形式。其它另外材料係共輛聚胺，及低 分子量胺（諸如，丁PD)。 - 發光層可包含於裝置趨動條件下能維持電荷載體轉 及亦能發光之任何分子或聚合化合物。例子包含榮光有 化合物及共«合物，諸如，Alq3、聚笨揮及衍生物、 苟及衍生物、㈣吩及衍生物、聚苯撐乙烯撐及衍生物 定 之 面 6 射 移 機 聚527432 A7 B7 V. Description of the invention (The present invention relates to a formulation for depositing a conjugated polymer layer in a light emitting device (LED). A light emitting device using a semiconductor conjugated polymer as a light emitting layer is known. Figure 1 Shows the structure of a simple light-emitting device. The glass or plastic substrate 2 is coated with an anode layer 4 (for example, in the form of indium tin oxide). The anode can be patterned in the form of an elongated strip. The anode layer can be coated with a hole transfer layer. Then, the light-emitting polymer layer 6 is deposited, and thereafter, an electron transfer layer is deposited. Then, the device structure is completed by depositing a cathode layer 8. For example, the cathode layer may be calcium or aluminum. The cathode layer 8 may be intersected. A pattern is formed in the shape of a boundary pixel P ′, and the anode and the cathode are overlapped. In addition, with no patterned cathode, the light-emitting strip can be defined. In addition, the pixel can be returned to the upper boundary after the active substrate, and the cathode can be patterned Or no pattern is formed. When an electric field is applied between the anode and the cathode, holes and electrons are injected into the light-emitting polymer layer. The holes and electrons are recombined in the polymer layer, and Proportional radiation decays to produce light. The hole transfer layer can generally be composed of any compound that can maintain hole transfer. Appropriate organic conductors such as blanking electrical polymers: polyaniline, polyethylenoxide And other polyfluorenes, polyisocyanates, etc. are in their doped form. Other additional materials are polyamines, and low molecular weight amines (such as butyl PD).-The light-emitting layer may be included in the device actuation conditions Any molecule or polymeric compound that can maintain charge carrier transfer and also emit light. Examples include glorious compounds and co-compositions, such as Alq3, polybenzyl derivatives, pyrene and derivatives, phenphenes and derivatives, Polyphenylene vinylene and derivatives fixed surface 6
· :線· -n n n n ί請先閱讀背面之注意事項再填寫本頁) 丨-」攻 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）·: Line · -n n n n ί Please read the precautions on the back before filling in this page) 丨-"attack This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)
I 4 527432I 4 527432
έ有雜芳香族環之聚合物等。 (請先閱讀背面之注意事項再填寫本頁) 電子轉移層一般可包含能維持電子轉移之任何物料 例子包含m、Alq3、聚苟或聚苟共聚物、含^ 族環之聚合物等。 〃方1 此裝置可含有上述層之任何組合，但其係包 發光層。 夕一 ^ OLED係描述於美國專利第5,247,丨％號案或美國專^ 第4,539,507唬案，其等案之内容在此被併入以供參考。 於美國專利第5,247，190號案中，活性有機層係發光半導 體共軛聚合物，且於美國專利第4,539,507號案中，活也 有機層係發光昇華分子膜。 ;绢· 舜傳，上’聚合物層典型上係藉由使聚合物溶液旋轉塗 後或计里刀塗覆於陽極上，及其後使溶劑於時蒸發， 或使用熱處理及/或減壓使溶液趨除而被沈積。聚合物待 直接自溶液鑄塑之發光聚合物本身，或聚合物之先質（其 ^於熱處理步㈣隨轉化成發絲合物。聚合物層可包 含二或更多種物料之摻合物’諸如，二或多種聚合物之擔 合物。 經濟部智慧財產局員工消費合作社印製 聚合物層亦可藉由經數個延長孔洞且經由重力作用或 於加壓下或利用表面張力之作用供應包含聚合物之可溶液 加工處理之物料而被沈積。在匕係促進所需之聚合物膜之直 接沈積或形成圖案。 藉由噴墨方法沈積聚合物層係一種特別佳之技術。喷 墨方法係描述於，例如，Ep〇88〇3〇3A1，其内容在此被併 本紙張尺度適用中國國家標準(CNS)A4規·^⑽x 297公是·^ 5 經濟部智慧財產局員工消費合作社印製 527432 A7 --------- B7 五、發明說明（3 ) 入以供參考。 期望使用藉此可產生展現優異發射均勻性之薄聚合物 膜之物料配方。 本案申請人擁有之先前申請案PCT/GB00/03349號案 係揭示用於沈積以聚烷基化苯（諸如，對甲基異丙基苯及 異均四甲苯）為主之共軛聚合物之配方之例子。 提供促進具圖案之聚合物膜之直接沈積之配方亦係本 發明之目標。特別地，本發明之目標係提供一種藉此展現 改良之發射均勻性之共輛聚合物膜可被沈積之配方。 依據本發明之第一方面，其係提供一種於生產發光裝 置中沈積聚合物層之配方，此配方包含溶於溶劑内之共軛 聚合物，該溶劑包含二烷基_或三烷基_取代之芳香族烴， 至少二烷基取代基係彼此呈鄰位。 溶劑較佳係包含^-二甲基苯、三烷基苯及 1，2,4-三烷基苯之一或多者。丨，、二甲基笨及込乙夂三烷基 苯係特別佳。 、 依據本务明之第二方面，其係提供一種於生產發光裝 置中沈積聚合物層之配方，此配方包含溶於溶劑内之共軛 聚合物，該溶劑包含三烷基苯。 依據本龟明之第二方面，其係提供一種藉由經數個延 長孔洞使依據本發明之第一或第二方面之可溶液加工處理 之配方供應至基材上而沈積聚合物層之方法。 依據本發明之第四方面，其係提供一種於基材上形成 聚合物層之方法，其係包含藉由噴墨方法使依據本發明之 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------訂---------線赢 (請先閱讀背面之注意事項再填寫本頁) 6 527432 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（4 第一或第二方面之配方沈積於基材上之步驟。 為了此申請案之目的，“聚合物，，一辭係包含均聚物或 共聚物，且亦包含聚合物摻合物之層狀物及單一聚合物之 層狀物·，且‘‘聚合物層，，-辭係包含—相對較小尺寸之層狀 物，諸如，具相對應於像素顯示器内之單一像素之尺寸之 層狀物，及更大尺寸之層狀物。 為了本申請案之目的，‘‘烷基，，一辭係指具最高達6個 石反原子之線性或分支之烧基取代基。 形成之配方較佳係具有25至4〇11^/111(2〇。〇範圍内之 表面張力，2至8厘泊（20C)之黏度，及〇25至15%(較佳係 〇·^至1%)之w/v聚合物濃度。具此等性質之配方係特別適 於猎由喷墨印刷沈積。此配方亦需具有對基材適當而能於 其上成沈積之接觸角。例如，於聚醯亞胺之情況中，接 觸角應為30至60度之範圍。 只要形成之配方具有特殊沈積技術所需之流體性質， 配方可包含一或多種另外型式之溶劑。配方中即使小對較 J比例之’例如’一或多種三烷基苯之存在可作為改良配 方之安定性及/或配方之流體性f。於某些例子中，較佳 係使用另外包含作為相對較佳溶劑之一或多種不同化合物 之溶劑摻合物’以改良藉由沈積及乾燥配方而產生之聚合 物膜之均勻性。 為了此申請案之目的，共輛聚合物一辭係指完全共親 (即，沿著整個聚合物鏈長度共軛）或部份共軛（即，除共 軛區ί又外亦包含非共軛區段)之聚合物(包含寡聚物，諸如 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂---------線—▲ (請先閱讀背面之注意事項再填寫本頁) n n n - 527432 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（ ，二聚物、三聚物等）。 聚合物可具有10,000至500,000範圍内之平均分子量 ，且更佳係10,〇〇〇至3〇〇〇〇〇範圍内。 聚合物可為適用於有機發光裝置中之發光層、電洞轉 移層或電子轉移層之聚合物。· 於較it範例中’共耗聚合物可為發光聚合物、電洞轉 移聚合物或電子轉移聚合物本身，或為發光聚合物、電洞 轉移聚合物或電子轉移聚合物之先質。共軛聚合物或其先 質可為任何適當之聚合物，且特別係能為下述之任一者·· 幼導電性聚合物，諸如，聚苯胺（PANI)及衍生物、聚 基刀及衍生物、聚σ比洛及衍生物、聚伸乙基二氧嘆吩；所 有此等之払雜开》式，且特別是聚苯乙烯續酸-摻雜之聚伸 本基一氧σ塞吩（PEDT/PSS); b)可溶液加工處理之電荷轉移及/或發光/電子-發光之 聚合物，較佳係共轭聚合物，冑如：$苯撐&衍生物、聚 苯撐乙烯撐及彳m聚苟及衍生物、含三芳基之聚合物 及何生物、各種不同‘形式之先質聚合物、共聚物（包含上 述聚合物種類）（一般係無規及嵌段之共聚物）、具有附接 至主鍵作為μ基之活性（電㈣矛多及/或發光）物種之聚合 物、噻吩及衍生物等。 亦被直覺者係本發明亦可應用至包含其它化合物（諸 如，可洛液加工處理之分子化合物，包含螺旋化合物，諸 如，EP-A-067646H#b案中所述者；及其它無機化合物， 例如，可溶液加工處理之有機金屬&質化合物）之配方， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------------------^-------1^ (請先閱讀背面之注意事項再填寫本頁} ⑷2Polymers with heteroaromatic rings. (Please read the notes on the back before filling this page.) The electron transfer layer can generally contain any material that can maintain electron transfer. Examples include m, Alq3, poly or poly copolymers, polymers containing ^ ring, etc. Formula 1 This device may contain any combination of the above layers, but it includes a light emitting layer. Xi Yi ^ OLED is described in US Patent No. 5,247,% or US Patent No. 4,539,507, the contents of which are incorporated herein by reference. In U.S. Patent No. 5,247,190, the active organic layer is a light-emitting semiconductor conjugated polymer, and in U.S. Patent No. 4,539,507, the organic layer is a light-emitting sublimation molecular film. Shun Shun Chuan, the upper polymer layer is typically applied to the anode by spin coating the polymer solution or a scribe knife, and then evaporating the solvent at that time, or using heat treatment and / or decompression. The solution was allowed to dislodge and was deposited. The light-emitting polymer itself, or the precursor of the polymer, which is to be directly cast from solution, is converted into a hairline compound in a heat treatment step. The polymer layer may include a blend of two or more materials 'Such as, a complex of two or more polymers. The polymer layer printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs can also be used through several elongated holes and through the action of gravity or under pressure or using surface tension. Supply solution-processable materials containing polymers to be deposited. Promote the direct deposition or patterning of the required polymer film in the system. Deposition of polymer layers by inkjet is a particularly good technique. Inkjet Department is described in, for example, Ep〇88〇3〇3A1, the content of which is incorporated herein. This paper standard applies Chinese National Standard (CNS) A4 regulations. ^ ⑽ x 297 is ^ 5 Printed by the Intellectual Property Bureau employee consumer cooperatives 527432 A7 --------- B7 V. Description of the invention (3) is for reference. It is expected to use a material formula that can produce a thin polymer film that exhibits excellent emission uniformity. first The previous application, PCT / GB00 / 03349, discloses examples of formulations for depositing conjugated polymers based on polyalkylated benzenes such as p-toluene and iso-m-toluene. Provided Formulas that promote the direct deposition of patterned polymer films are also an object of the present invention. In particular, the object of the present invention is to provide a formula whereby a total polymer film that can exhibit improved emission uniformity can be deposited. According to a first aspect of the present invention, a formulation for depositing a polymer layer in the production of a light-emitting device is provided. The formulation includes a conjugated polymer dissolved in a solvent containing a dialkyl- or trialkyl-substituted Aromatic hydrocarbons, at least the dialkyl substituents are ortho to each other. The solvent preferably contains one or more of ^ -dimethylbenzene, trialkylbenzene, and 1,2,4-trialkylbenzene. 丨, Dimethylbenzyl and acetofluorene trialkylbenzene are particularly good. According to the second aspect of the present invention, it provides a formula for depositing a polymer layer in the production of a light-emitting device, the formula comprising a solvent dissolved in a solvent Conjugated polymer, the solvent contains trialkylbenzene According to a second aspect of the present invention, a method for depositing a polymer layer by supplying a solution-processable formulation according to the first or second aspect of the present invention to a substrate through a plurality of extended holes is provided. According to a fourth aspect of the present invention, a method for forming a polymer layer on a substrate is provided, which includes adapting the paper size according to the present invention to the Chinese National Standard (CNS) A4 specification (210) by an inkjet method. X 297 mm) -------- Order --------- Line Win (Please read the notes on the back before filling out this page) 6 527432 A7 B7 Employee Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printing 5. Description of the Invention (4 The first or second aspect of the step of depositing the formulation on the substrate. For the purposes of this application, "polymer" means the term homopolymer or copolymer, and also includes layers of polymer blends and layers of single polymers. Layers, "-" include-relatively small-sized layers, such as layers with a size corresponding to a single pixel in a pixel display, and larger-sized layers. The term "alkyl" refers to a linear or branched alkynyl substituent having up to 6 stone counteratoms. The formula formed preferably has 25 to 4011 ^ / 111 (20.0. Surface tension in the range, viscosity of 2 to 8 centipoise (20C), and w / v polymer concentration of 0.25 to 15% (preferably 0 to 1%). Formulas with these properties are special Suitable for depositing by inkjet printing. This formulation also needs to have a contact angle suitable for the substrate to be deposited thereon. For example, in the case of polyimide, the contact angle should be in the range of 30 to 60 degrees As long as the resulting formula has the fluid properties required for a particular deposition technique, the formula may include one or more additional types of solvents The presence of 'for example' one or more trialkylbenzenes even in small to J ratios in the formulation can be used to improve the stability of the formulation and / or the fluidity of the formulation f. In some examples, it is preferred to use additional inclusions As a relatively preferred solvent, one or more solvent blends of different compounds are used to improve the uniformity of the polymer film produced by the deposition and drying of the formulation. For the purposes of this application, the term “polymer” refers to Fully conjugated (ie, conjugated along the entire polymer chain length) or partially conjugated (i.e., contains non-conjugated segments in addition to the conjugated region), including oligomers such as Paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -------------------- Order --------- Line— ▲ (Please read the precautions on the back before filling this page) nnn-527432 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of invention (, dimer, trimer, etc.) Polymer can have 10,000 The average molecular weight is in the range of 500,000 to 500,000, and more preferably in the range of 10,000 to 30,000. Polymer It may be a polymer suitable for a light emitting layer, a hole transfer layer or an electron transfer layer in an organic light emitting device. In the more it example, the 'co-consumptive polymer may be a light emitting polymer, a hole transfer polymer or an electron transfer polymer Material itself, or a precursor of a luminescent polymer, hole transfer polymer or electron transfer polymer. The conjugated polymer or its precursor may be any suitable polymer, and in particular can be any of the following ·· Young conductive polymers, such as polyaniline (PANI) and derivatives, polykids and derivatives, polyσbilo and derivatives, poly (ethylene dioxanthine); all of these are mixed 》 Type, and especially polystyrene continuous acid-doped polyextendyl-oxygen stilbene (PEDT / PSS); b) charge transfer and / or luminescent / electron-luminescent polymer that can be processed by solution , Preferably conjugated polymers, such as: $ phenylene & derivatives, polyphenylene vinylene and 彳 m polymer and derivatives, polymers containing triaryl groups and any organisms, various different forms of Polymers and copolymers (including the above polymer types) (generally random and block Copolymer), having attached to the primary key of an active group as μ (iv spear multiple electrical and / or luminescent) species of polymer, and thiophene derivatives. Also the intuition is that the present invention can also be applied to compounds containing other compounds such as molecular compounds processed by colo fluid, including spiral compounds such as those described in the case of EP-A-067646H # b; and other inorganic compounds, For example, the formula of solution-processable organometallic & quality compounds), this paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -------------- ------- ^ ------- 1 ^ (Please read the notes on the back before filling out this page} ⑷2
發明說明（6 經¾部智慧財產局員工消費合作社印製 以製造絕緣體或導體。 共軛聚合物可，例如， ^ ^ u ^ %為主之聚合物，或含 有％早兀及其它皁兀（諸如，二 — 一方暴胺早凡或苯甲基噻 噁唑（ΒΤ)單元）之共聚物， „ $ 一或夕種此等聚合物之摻合 物。 . 為了更仏瞭解本發明及顯示相同者可被作用，本發明 具體例將於其後藉由範例及參考附圖而描述之，其中： 第1圖係發光裝置之作圖； 第2圖係例示沈積各種不同聚合物層之作圖；且 第3圖係顯示用於範例中之重複單元及聚合物之結構 Ο 第2圖例示使聚合物層6沈積於具圖案之陽極4上之沈 積技術。數個延長孔洞1()被例示，每—者係與個別之槽排 列。延長孔洞ίο係經由導管12連接至儲存器14，其係容納 名人被沈積之/谷液。溶液係於加壓下或藉由重力經延長孔洞 10供應，以沈積發光聚合物層6。 依據本發明之特殊配方係如下所探討。 範例1 第一例示配方係1% w/v之三摻合物，其係含有於l52,4_ 三甲基苯中之約14重量％之三元聚合物（含有芴（F8)單元（ 第3a圖所示者）、苯甲基噻二噁唑（BT)單元（第扑圖所示者） 及三伸芳基單元（第3c圖所示者））、56重量％2F8BT(第3d 圖所示者）及30重量％2TFB(第3e圖所示者）。形成之配方 具有3.8厘泊（2〇。〇之黏度及28mN/m(20°C)之表面張力。 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） 9 C請先閱讀背面之注音？事項再填寫本頁：> 餐 訂---------線· 527432 A7 B7 五、發明說明（7 範例2 依據第二範例，配方係包含於含有20體積％之1，2,4-三甲基苯及80體積％之二甲苯之溶液混合物中之i〇/〇 w/v之 範例1中所指之三摻合物。配方具有2.9厘泊（20。〇之溶液 黏度及28mN/m(20°C)之表面張力。 配方樣品被沈積於基材上，並真空乾燥。因而製得之 聚合物層之PL效率被發現係43%。於80°C時乾燥相同配方 之層狀物13.5小時造成具39%之PL效率之聚合物層。 範例3 依據第三範例，配方係包含於含有5〇體積％之丨，2,4_ 二甲基本及50體積％之二甲苯之溶液混合物中之1〇/〇 w/V2 範例1中所指之三摻合物。配方具有2·82厘泊（20°C)之溶 液黏度及28mN/m(20°C )之表面張力。 二甲基本之添加發現能顯著地增加配方之安定性。 1，2-二甲基苯、1，2,3-三甲基苯及丨，2,4-三甲基苯亦被 發現係具約266,000平均分子量之芴-噻吩聚合物之良好溶 劑0 . ------- — 訂---------線 1«-- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 元件符號對照 2…基材 4…陽極層 6…發光聚合物層 8…陰極層 10…延長孔洞 12…導管 14…儲存器 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） 10Description of the Invention (6 Printed by ¾ of Intellectual Property Bureau staff consumer cooperatives to manufacture insulators or conductors. Conjugated polymers can be, for example, ^ ^ u ^% based polymers, or contain% Zao Wu and other soaps ( For example, a copolymer of two-party amine amines or benzyl thiaxazole (BT) units, a blend of these polymers. For a better understanding of the present invention and showing the same The present invention will be described later by examples and with reference to the drawings, wherein: FIG. 1 is a drawing of a light-emitting device; FIG. 2 is a drawing illustrating the deposition of various polymer layers Figure 3 shows the structure of the repeating unit and polymer used in the example. Figure 2 illustrates the deposition technique for depositing a polymer layer 6 on a patterned anode 4. Several extension holes 1 () are exemplified. Each one is arranged with an individual slot. The extension hole is connected to the storage 14 via a conduit 12, which houses the celebrity / cereal solution. The solution is supplied under pressure or by gravity through the extension hole 10. To deposit a luminescent polymer layer 6. According to this The special formula of the invention is discussed as follows. Example 1 The first example formula is a 1% w / v tri-blend, which is a terpolymer containing about 14% by weight of 152,4-trimethylbenzene ( Contains a fluorene (F8) unit (shown in Figure 3a), a benzyl thiadioxazole (BT) unit (shown in Figure 3), and a triaryl unit (shown in Figure 3c)), 56% by weight 2F8BT (shown in Figure 3d) and 30% by weight 2TFB (shown in Figure 3e). The resulting formulation has a viscosity of 3.8 centipoise (20.0% and a viscosity of 28mN / m (20 ° C) Surface tension. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 x 297 mm) 9 C Please read the phonetic on the back? Matters before filling out this page: > Order --------- Line · 527432 A7 B7 V. Description of the invention (7 Example 2 According to the second example, the formula is contained in a solution mixture containing 20% by volume of 1,2,4-trimethylbenzene and 80% by volume of xylene. 〇 / 〇w / v The three blends referred to in Example 1. The formula has a solution viscosity of 2.9 centipoise (20.0 and a surface tension of 28 mN / m (20 ° C). The formula sample is deposited on the substrate Up and Vacuum drying. The PL efficiency of the polymer layer thus obtained was found to be 43%. Drying a layer of the same formula at 80 ° C for 13.5 hours resulted in a polymer layer with a PL efficiency of 39%. Example 3 According to the third For example, the formula is a tri-blend referred to in Example 1 in a solution mixture containing 50% by volume of 2,2,4-dimethylbenzyl and 50% by volume of xylene. The formula has a solution viscosity of 2.82 centipoise (20 ° C) and a surface tension of 28mN / m (20 ° C). The addition of dimethyl is found to significantly increase the stability of the formula. 1,2-Dimethylbenzene, 1,2,3-trimethylbenzene and 1,2,4-trimethylbenzene have also been found to be good solvents for fluorene-thiophene polymers with an average molecular weight of about 266,000. ------- — Order --------- Line 1 «-(Please read the precautions on the back before filling out this page) Symbol Component 2 … Substrate 4… anode layer 6… light-emitting polymer layer 8… cathode layer 10… extension hole 12… conduit 14… reservoir This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 10