TW506229B - Electronic device comprising organic compound having p-type semiconducting characteristics - Google Patents

Electronic device comprising organic compound having p-type semiconducting characteristics Download PDF

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TW506229B
TW506229B TW90111193A TW90111193A TW506229B TW 506229 B TW506229 B TW 506229B TW 90111193 A TW90111193 A TW 90111193A TW 90111193 A TW90111193 A TW 90111193A TW 506229 B TW506229 B TW 506229B
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chemical formula
layer
emitting device
organic light
compound
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Se-Hwan Son
Ok-Hee Kim
Seok-Hee Yoon
Kong-Kyeom Kim
Youn-Gu Lee
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Lg Chemical Ltd
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    • HELECTRICITY
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    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
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    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D487/00Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
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    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40Organic transistors
    • H10K10/46Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462Insulated gate field-effect transistors [IGFETs]
    • H10K10/484Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • H10K10/486Insulated gate field-effect transistors [IGFETs] characterised by the channel regions the channel region comprising two or more active layers, e.g. forming pn heterojunctions
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    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/657Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40Organic transistors
    • H10K10/46Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462Insulated gate field-effect transistors [IGFETs]
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    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10Transparent electrodes, e.g. using graphene
    • H10K2102/101Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
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    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30Coordination compounds
    • H10K85/321Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
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    • H10K85/615Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/917Electroluminescent
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]

Description

鳥229 發明說明( 釐Jg背景— 相關申請的交又參考 (請先閱讀背面之注意事項再填寫本頁) 本申請案係基於1999年12月31日和2000年12月 26日刀別向韓國工業產權局所申請之第 號及第義〇侧5號申請案,並在下面引用了其内容。 (a) 發明領域 本發明係有關一種電子裝置,特別是關於一種含有具 p型半導體特性並實現空穴注人或輸運功制有機化合物 的電子裝置。 (b) 相關技術的描述 經濟部智慧財產局員工消費合作社印制衣 具有P型半導體特性、電導介於絕緣和導電材料之間 的有機化合物已被廣泛用於〇PC (有機光導體)磁鼓,與 及用於複製印刷或雷射印表機等❶具體地說,芳香胺類材 料以與聚合物例如聚碳酸酯形成的混合物在雷射印表機的 鼓上形成一層薄膜,以便形成一層空穴輸運層。為了這種 應用,具有P型半導體特性的有機化合物必須有適當的空 六遷移率並對空穴有電、熱和形態的穩定性。 採用P型有機半導體的裝置大體上分為以下兩組。 第一組應用於OPC鼓或太陽能電池或光生伏特電地。 具體地說,把外光源引入裝置中以便產生激子,激子又被 分離為電子和空穴。這時P型有機半導體在裝置中起輸運 被分離空穴的作用。 第二組是把電壓加到兩個或兩個以上電極上,以便把 本紙張尺度適用中國國家標準(CNS)A4規袼(210 x 297公釐) 6 五、發明說明(2 ) $飢子直m到與€極構成介面的有機半導體巾。可以 T例說明’如分別同時從兩個電極注入電子 ::機"(電致發幻裝置’又如通過給栅極加電塵:; 机子從源極輸運到漏極以便實現開關功能 時在P型有機半導體物質和電極之間形成穩是= 要的。-般來說,由於電極是由金屬或金屬氧化物構成的, 裝置的性能因加在裝置上的電場或因外加的或内部產生的 熱而明顯變壞’除非無機物和有機物之間的介面是稃定的。 上述芳香胺類化合物被廣泛用作含有具p型特性的有 機物的半導體材料,人們也知道,當在實驗上用於製作薄 膜電晶體時,低噻吩或聚噻吩也表現出高的載流子遷移率。 這些化合物的這種特性使其能有各種各樣的應用。且 體地說,用於OPC鼓的芳香胺類p型有機半導體也被應用 於有機發光二極體,用於薄膜電晶體的低噻吩也被用於有 機發光二極體的空穴注入或空穴輸運材料。此外,採用固 恶空穴輸運材料的有機太陽能電池也使用用作有機發光二 極體空穴輸運材料的芳香胺衍生物(Adv. Mater. 12, 447 2000)。考慮到能級、空穴輸運能力、環境等因素,這種 相容性說明具有P型半導體特性的有機物能被廣泛地用於 裝置的製備。 ' 用於有機發光二極體的P型有機半導體促進從陽極注 入空穴,同時把注入的空穴輸運到發光層。這時發光層被 分為空穴注入層和空穴輸運層兩層。為了保證裝置的穩定 性,這種有機物應該從能夠與由金屬或金屬氡化物構成的 506229 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(3 ) 陽極形成穩定介面的那些物質中選擇。此外,為了使空穴 容易注入因而能使裝置低電壓工作,該物質應該有適當的 氧化勢和注入空穴的高輸運能力。 為了滿足运些要求,暮顾奎 ^果國專利第4, 356, 429號公開了 駄青銅,美國專利第5,540,999號公開了低嚷吩。此外還 知道美國專利第5,616,427號公開的五〇丫㈣類材料對裝 置的穩定性也有貢獻。 近來通過在金屬氣化物嫌# ’礼化物構成的陽極和發光材料之間
另外引入一層空穴輪運a p妳I 勒建層已、也大大地改善了聚合物發光二 極體的穩定性。特別是在熱穩定的聚合物發光二極體中, 插在陽極和發光聚合物之間的物質儘管高的玻璃化轉變溫 度,是為了穩定介面和方便空穴的注入,其能夠大大改善 裝置的性能’特別是裝置的壽命和工作電壓(】.Appi.如 84, 6859, 1998) 〇 當用作空穴注入材料_,p財機半導體顯示出防止 發光二極體短路和延長裝置壽命的作用,在製造裝置的工 藝過程中可能會發生短路的情況。一般地說,有機物的厚 度為100 —200mn㈣機發光二極體由於在有機物澱積的 過程中或在陽極和有機物之間的不穩定介面處可能產生的 針孔而使裝置短路。這時穩定的空穴注入層的插入能夠降 低裝置短路的可能性,特別是厚空穴注入層的插入能大大 降低這種可能性。 但是,在空穴注入材料具有半導體特性而不是導體特 性的一般情況下,根據空穴注入材料的厚度可表現出工个 參紙張尺度適用中國國家標準(CNS)A4規袼(2_1〇 X 297公爱)一 ft -I--— !Γ -裝1 — ! I 丨訂-----I I J 線 (請先閱讀背面之注意事項再填寫本頁) 506229
五、發明說明(4 ) 電壓增加的反作用。 發明概卷 本發明係考慮到現有技術的問題而促成的,因而本發 明的目的係提供一種含有一層能輸運或注入空穴、降低工 作電壓和增加裝置壽命的有機化合物的電子裝置。 本發明的另一個目的係提供一種含有一層能與電極 形成穩定介面的有機化合物的電子裝置σ 圖式之簡單描述 通過參考下面結合附圖的詳細敘述對本發明較完整 瞭解和許多優點將顯而易見並能較好地理解,其中附圖有: 第一圖··係按照本發明一實施例的有機發光二極體的 簡化橫截面圖。 第二圖:係按照本發明另一實施例有不同結構的有機 發光二極體的簡化橫截面圖。 第二圖:係表示本發明的有機發光二極體的亮度和電 壓之間的關係曲線。 第四圖:係表示為了檢驗本發明中所使用物質的ρ型 半導體特性而製作的裝置的電流密度和電壓之間的關係曲 參考號碼(11)和(21)表示透明襯底,(丨2)和(22) 表不陽極,(13)表示空穴注入層,(14)表示空穴輸運 層’ (15)和(25)表示發光層,(16)和(26)表示電 «^1 II 1 n n n ϋ n n n ϋ I · n n n n ϋ n n B n ·1 ϋ I n I— n I <請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適財@國家標準(CNS)A4規格(21 万 297公釐) 9 506229 A7
--------------t--------^----------------LI _________ —————III— (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 A7 ___B7 五、發明說明(6 ) 穴注入層,一層空穴輸運層或一層空穴的注入和輸運層。 本發明也提供一種含有薄膜層的電子裝置,所述裝置 匕括由化子式1表示的有機化合物的空穴注入層、空穴輸 運層及空穴的注入和輸運層中的至少一層。 現在對本發明進行更詳細的說明。 首先對本發明電子裝置中由化學式1表示的化合物進 4亍說明。 在美國專利第4,780,536號中公開了化學式!的化合 物月b被用作熱阻聚合物的交聯劑,並且已經預示,這種化 合物由於它的還原勢低’能被用作在基於這種有機物的電 子裝置中輸運電子的n型有機半導體(p〇lyaier preprint 40’ 404,1 999 )。特別是已經知道,當每個R為氰基時, 化學式1的化合物的還原勢僅為〇 〇lv,因此狼清楚,它 有η型有機半導體的特性。 本發明人已經發現,與現有技術中它可能是η型有機 半導體的預示相反’化學式1的有機化合物是Ρ型有機半 導體,在諸如有機發先二極體的電子裝置中用它作為空穴 注入、空穴輸運或空穴的注入和輸運材料,因而降低了電 子裝置的工作電壓並延長了裝置的壽命。此外,由於這種 化合物有與金屬氧化物形成穩定介面的能力,它可被用於 各種電子裝置。 本發明化學式1的化合物中有代表性的例子包括由下 列化學式1 a、1 b、1C.和1 d表示的化合物: [化學式la] Γ» -------I ^---------^ (請先閱讀背面之注意事項再填寫本頁)
506229 A7 B7 五、發明說明(
NC CN
N N
CN
[化學式lb] RO2C C02Rl
[化學式lc] R^NOC CONR1; <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制衣
N N
[化學式1 d ] 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 12 506229 五、發明說明(8
O.N NO. N N
經濟部智慧財產咼員1消費^阼:±1中^1 其中,化學式lb和1C的化合物 胺的每個取代基,它單獨或同時從氫、' 其他芳香基等中選擇的,並舍 烴、本土、 時優選且有季性古 θ用决逮旋轉塗層形成薄臈 f 异有系性雨的C3-15以上的烴。 置。有機發光二極體是—種具有;·層薄膜結構的電子裳 本發明:有機發光二極體包括至少—層插在陽極和 陰極之間的潯膜式的有機物層,它構成一層空穴注入層, 從陽極接收空穴或者起把空穴輸運到發先層的作用,^者 在注入空穴的同時輸運空穴。 多層結構的有機發光二極體的一般結構如第一圖所 示,其中,例如在透明襯底(u)上塗敷一層氧化銦錫薄膜, 以便形成一個透明電極,即陽極(1 2 ),在陽極層(i 2 ) 上依次覆蓋一層空穴注入層(13),一層空穴輸運層(14), 一層發光層(15),一層電子輸運層(16)和一層陰極層 (1 7 )。另外,如第二圖所示,它可以有一種結構,該結 構包括一個透明襯底(21)、一個透明電極(22)、一層 R 表示的I旨和 --• -----1 — t --------^---I---- ·線 (請先閱讀背面之注意事項再填寫本頁) 私紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 506229 A7 B7
五、發明說明(9 ) 同時進行空穴注入和輸運的層(24)、一層發光層(U) 經濟部智慧財產局員工消費合作社印製 一層電子輸運層(26)和一層陰極層(27)。 如果需要的話,裝置可有數目可多可少的多層結構, 且可有多層發光層。含有化學式i的化合物的空穴、、 層,空穴輸運層或空穴的注入和輸運層可以根據裝置的= 構形成多層並能用不同方式添加這些層。 Ό 可優選使用非晶性質的玻璃或塑膠作為透明概底 (11,21),並可根據其用途使用具有適當機械強度和表 面平整度的襯底,如金屬片。 ^ 此外,可以採用金屬氧化物或混合金屬氧化物如氧化 錫、氧化銦錫、氧化鋅、氧化銦鋅等作為透明電極,可以 使用具有高功函的金屬如金或導電聚合物,在該導電聚人 物中可以加一些適當的摻雜物,如pED〇R聚[3,4〜’(乙 撐-1 , 2 -二氧)噻吩]、聚苯胺、聚吡咯、聚噻吩等等。 用化學式1表示的化合物可以單獨或與其他種類的空 穴注入材料給合用作第一圖中的形成空穴注入層(U)的 材料。P型有機半導體,如酞青銅或低噻吩等可作為與化 學式1的化合物一起使用的其他空穴注入材料的例子。當 與其他材料一起使用時,化學式丨的化合物的使用量$ lwttlOO%wt。此外,層的厚度優選為〇1〜1〇,〇〇〇咖,更優 選 10〜300nm。 當其他種類的空穴注入材料,即p型有機半導體與化 學式1的化合物-起使用時’注入空穴的量可按照混合物 的比例來控制。具體地說,當材料有不同的空穴能級和遷 I---l· I Γ -----------I I (請先閱讀背面之注意事項再填寫本頁) 14 五、發明說明(*10 ) 3率時’能夠試驗得錢空穴的濃度控㈣㈣合裝置結 構的混合物種類和混合比例。 、、研究結果表明,當用化學式1的有機化合物作為空穴 庄入層時’紐青銅相反,即使空穴輸運層的厚度由⑽ 變到2〇〇_時工作電屋也沒有很大的增加。因此,通過採 用層二八注入層作為空穴輸運層的隔離臈(back f Uflj) 可以減少產生裝置短路的可能性並能降低工作電壓。 當化學式1的有機化合物形成空穴注入層(13)而不 穴輸運層(14) _,可用常規的芳香胺類化合物或 夕環芳香族化合物獨立形成空穴輸運層。4, 4,—雙(卜 萘基)-N-苯基-氨基]聯苯(NPB)可作為空穴輸運材料的例 子,而且為了優化注入電子和空穴的比例可以使用其他類 型的空穴輸運材料。此外,如第二圖所示,當化學式^的 有機化合物形成空穴注入和輸運層(24)時,它起從陽極 平穩地注入空穴和直接把空穴輪運到發光層的作用。 按照本發明的有機發光二極體的發光層(15,25)採 用了具有高螢先效率的材料,從兩個相反電極注入的電子 和空穴在發光層中複合並發光。作為具有代表性的例子, 這些材料可以是8—羥基啉鋁鹽(Alq3)、美國專利第 5, 366, 811號敘述的二聚苯乙烯基化合物、苯並噁唑衍生 物及其金屬絡合物、苯並咪唑衍生物及其金屬絡合物,以 及如聚對亞乙烯基苯(p〇ly (p-phenyl ene vinylene))及 其衍生物或共聚物衍生物、聚苟(p〇lyflu〇rene)&其衍生 物等聚合物。 A7 五、發明說明(ΊΊ 签一®丢極(17,2?)接收電子並把電子輸運到發光層的 I及第二圖的電子輸運層(16, 26)採用這樣的材料, 二料從陰極平穩地注入電子,同時與陰極形成一個穩定 二面。發先層(15 ’ 25)可用作這樣—個層,在沒有分 汗,、電子輸運層㈣況下該層發力同時也輸運電子。作為 代表隱的電子輸運材料的例子,Alq3是使用最普遍的材 料,也能用駄青銅。此外,為了實現染料中的光發射,第 :圖:的發光材料必須是類似或小於形成發光層的主材 料,它摻雜能輸運空穴並能在染料中引起發光的材料,例 如帶螢光染料的芳香胺化合物。紅㈣等列為有代表性的 營光染料的例子。具有低功函的材料可用作形成陰極的材 料’使得容易柄電子注入到電子輸運層。例如,可使用合 金’如經銘合金、錢銀合金等,以及鎮和約等。此外,可 用有例如UF/Ai和u2〇/A1兩層結構的電極。此外,通過 混合澱積電子輸運層和電極使電子的注入更容易,且能使 電極和電子輸運層之間的介面更穩定。 化學式1的化合物可被應用於採用p型有機半導體的 有機薄膜電晶體,光生伏特電池,雷射印表機的0PC或複 製印刷等’以及應用于有機發光二極體。特別是,由於有 機薄膜電晶體必須與柵極絕緣體形成一個穩定的介面,'並 且迅速地把空穴從源極輸運到漏極,所以化學式i的化合 物適合於P型有機薄膜電晶體。 通過下面的實施例和對比實施例來詳細敘述本發 明。但疋,這些實轭例是為了說明本發明而不是限制本發 本i張尺度適用中國國家標準(CNS)A4規格(210 X 297公f ) 16 I l··!-------訂---------線_ _____.___Γ — , III — — — n ! I I I f (請先閱讀背面之注意事項再填寫本頁) 506229 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(1?·) 明。 [實施例] 實施例1 為了證實滿足化學式i的化合物可以降低有機發光裝 置的激勵電麼,用滿足化學式i的化學式la的化合物作為 空六注入材料,製作了下面有機發光裝置。 在含有清洗劑的溶液中超聲清洗覆蓋有15峨厚度的 ΙΤ0 (氧化姻錫)薄膜的玻璃襯底,然後進行乾燥,之後把 它傳入轉子料洗裝置巾料體清洗該槪底5 分鐘,再把它傳送到真空汽相澱積裝置中。 •通過在導電的襯底上真空熱澱積滿足化學式丨的化學 式la的化合物形成厚度為2〇〇人的空穴注入層。依次在 該襯底上澱積作為空穴輸運材料的NpB(6〇〇A)&具有電 子輸運和發光兩種性質的Alq3(6〇〇A)。然後在電子輸運層 上通過澱積5A氟化鋰和25〇〇A鋁形成電極。在該工藝中, 澱積速率保持在:對於有機材料為lA/sec,對於氟化鋰為 0· 2A/sec,對於鋁為3〜7A/sec。第三圖表示所製作的有 機發光裝置的電壓—亮度關係曲線。 實施例2 一種有機發光裝置是用與實施例1相同的工藝製作 的/、中作為玉八注入層的化學式1 a化合物的厚度增加 到1000A而不疋2〇〇A。第三圖表示所製作的有機發光裝 置的電壓一亮度關係曲線。 ^--------1----—---線 (請先閲讀背面之注意事項再填寫本頁) 實施例3
506229 經濟部智慧財產局員工消費合作社印製 A7 --- B7__ 五、發明說明(13 ) 為了證明當用滿足化學式i的化學式la的化合物與 其他對空穴穩定的材料的混合物形成空穴注入層時表現出 低激勵電壓的特性,製作了下面的裝置並測量了它的特性。 有機發光裝置是用與實施例1相同的工藝製作的,其 中,採用共蒸發方法,用由90wt%的化學式u的化合物和 l〇wt%的酞青銅絡合物組成的厚度為5〇〇 A的混合物代替 厚度為200A的化學式1 a的化合物作為空穴注入層。第 三圖表示所製作的有機發光裝置的電壓—亮度關係曲線。 實施例4 為了證明當用滿足化學式i的化學式la的化合物和 其他對空穴穩定的材料的混合物形成空穴注入層時,它有 激勵電壓低的特性並能延長發光壽命而製作了以下裝置並 測量了它的特性。 有機發光裝置是用與實施例丨相同的工藝製作的,其 中,採用共蒸發方法,用由70wt%化學式la的化合物和 3〇w伐的酞青銅絡合物組成的厚度為5〇〇A的混合物代替 20 0A厚度的化學式la的化合物作為空穴注入層。第三圖 j示所製作的有機發光裝置的電壓—亮度關係曲線。在直 流電流密度為l〇〇mA/Cffl2的條件下測量該裝置的亮度的丰 寿命,所測得的亮度的半壽命為i8〇小時。 對比實施例1 為了證明滿足化學式!的化學式la的化合物比常規 的空穴注入層有激勵電壓更低的特性,下面使用最廣為人 知的酞青銅絡合物並使用最廣泛使用的厚度。 本紙張尺度適用中闕家標準(CNS)A4規χ挪公 --- -------I ^ Γ------^----I--- (請先閱讀背面之注意事項再填寫本頁) 18 506229 經濟部智慧財產局員工消費合作钍印製 A7 五、發明說明(u) 用與實施例1相同的工藝製作的有機發光裝置,其中 用殿積厚度15GA的駄青鋼絡合物來代替化學式的化合 物。第三圖表示所製作的有嬙恭 < F幻有機發先裝置的電壓—亮度關係 曲線。在直流電流密度為i⑽mA/em2的條件下測量了該裝 置的亮度的半壽命,所測得的亮度的半壽命為93小時。 實施例5 為了測量滿足化學式i的化學式la的化合物有注入 和輸運空穴的能力’當給通過殿積化學式ia的材料製作的 薄膜加正偏壓時得到了電壓—電流關係曲線。這時ιτ〇用 作陽極,具有高功函的則作陰極。該裝置用下述方法製 作。 在含有清洗劑的溶液中超聲清洗覆蓋有15〇〇 Α厚度 的ΙΤ0 (氧化銦錫)薄膜的玻璃襯底,然後進行乾燥,之 後傳入等離子體清洗裝置中。襯底用氧等離子體清洗5 = 鐘,然後傳送到真空汽相澱積裝置中。通過在襯底上真空 熱澱積滿足化學式1的化學式1 a的化合物,形成厚度為 2000A的空穴注入層。通過澱積厚度為25〇〇A的鋁在該層 上形成陰極。在該工藝中,澱積速率保持在:對於有機材 料為1A/Sec,對於链為3〜7Asec。在第四圖表示的所製作 的有機發光裝置的電壓一電流關係曲線中,用化學式i a 的化合物的裝置剛過〇伏就注入空穴了,空穴的濃度總是 高於對比實施例1所示採用NPB的裝置的空穴濃度,正如 以上所公開的,它證明了化學式la材料的空穴注入比廣為 人知的P型有機半導體材料更容易,而且它的空穴輸運能 參紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 19 - I ^ - -------I--------線 (請先閱讀背面之注意事項再填寫本頁) 506229 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(15 力也更強。 選Lfe實施 為了與化學4 1 a化合物的空穴注入和空穴輸運能力 作對比,用與實施例1相同的方法把基於NPB的芳香胺應 ;衣置獲得了外加電壓—注入電流關係曲線,腿B曾經 是廣泛用於有機發先裝置和〇^磁鼓的空穴輸運材料的p 型有機半導體。 在含有清洗劑的溶液中超聲清洗覆蓋厚度為15〇〇a 〇(氧化銦錫)薄膜的玻璃襯底,然後進行乾燥,之後傳 入等離子體清洗裝置中。用氧等離子體清洗該襯底5分 鐘η後傳送到真空汽相澱積裝置中。通過在該襯底上真 空熱澱積形成厚度為1 600人的空穴注入層。通過在該層上 澱積厚度為2500Α的鋁形成陰極。在該工藝中,澱積速率 保持在:對於有機材料為lA/sec,對於鋁為3〜7A/sec。 第圖表示所製作裝置的電壓—電流關係曲線。 在第四圖表示的所製作的有機發光裝置的電壓—電流 關係曲線中’採用NPB的裝置在約1伏時注入空穴,空穴 濃度低於用化學式la化合物的裝置的空穴濃度。 正如在上述實施例子和對比實施例中所表示的那 才心滿足化學式1的化學式1 a的化合物有p型有機半導體 的特性’當它用於獲得P型半導體特性的空穴注入層時, 月b夠在有機發光裝置中使用低的激勵電壓,並且當它與其 他適合的材料混合時能保持低的激勵電壓,此電壓大小依 相對混合比而定。 « t Sii?7FNS)A4 ^ (210 x 297 ) 20 -------l· I --------β-------- (請先閱讀背面之注意事項再填寫本頁) 五、發明說明(16) 而且,已經發現,裝置的半毒 青銅絡合物更穩定。這種現象表 保持穩定的酞 <强巩象表明,本發明 化合物有更優良的空穴注入能力, 匕:式1的 力’並且能與電極形成穩定的介面。 I八輪運能 因此它表明’該化合物在其他.欲獲得空穴注入或空穴 輪運特性的裝置中有用途。 二 本發明的裝置能大大增加發光壽命,並且由於包含了 具有p型半導體特性的有機化合物而能有低的激勵電壓。 雖然已經參考優選實施例對本發明作了詳細敘述,但 本專業的技術人員會理解,在不離開本發明的精神和後附 權利要求書的範圍的情況下可對本發明做各種修改和替 代0 . 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 21

Claims (1)

  1. 知降:Μ杯 祀裝置’該有機發光裝置係名甘抓 和陰極間插入至少一 在其陽極 六、申請專利範圍 ΐ· 一種有機發杂 、 層或一層以上含有化學式1砉-機化合物: 人表不的有 [化學式1] R R Ν Μ
    R 片式中:個R單獨或同時從氩原子、CH2烴、卣素、 烧,基彡香胺、醋、酰胺、芳香烴、雜環化合物、硝基 和氰基(-CN )中選擇。 2.如申請專利範圍帛1項所述的有機發光裝置,其 中’含有由化學式1表示的有機化合物層是空穴注入層、 空穴輸運層或空穴的注入和輸運層。 3·如申凊專利範圍第i項所述的有機發光裝置,其 中,該發光裝置依次包括: a) 一個透明襯底; b) —個陽極; c) 一層空穴注入層; d) 一層空穴輸運層; e) 一層發光層; 本紙張尺度適用中國國家標準(CNS)A4攀格(210 X 297公釐) 22 ------------—裂i-------訂---------線 (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 506229 經濟部智慧財產局員工消費合作社印製 A8 B8 C8 D8 六、申請專利範圍 f ) 一層電子輸運層;及 g ) 一個陰極。 4.如申請專利範圍第1項所述的有機發光裝置,其 中,該發光裝置依次包括: a) 一個透明襯底; b) 一個陽極; c) 一層空穴的注入和輸運層; d) —層發光層,·. e) —層電子輸運層;及 f ) 一個陰極。 5 ·如申請專利範圍第1項所述的有機發光裝置’其 化學式1的化合物用化學式1 a表示: [化學式la] NC CN )={
    CN 6·如申請專利範圍第1頊所述的有機發光裝置,其 中,化學式1的化合物用化學式1 b表示: [化學式lb] 本紙張尺度適用中國國豕標準(CNS)A4規格(2^Q x 297公麓) 23 (請先閱讀背面之注意事項再填寫本頁) 中 訂·· -線· Jr . 506229 A8 B8 C8 D8
    •CO,R, 六、申請專利範圍 RO2C Μ Μ
    式中每個R,單獨戒同時為有1 一15個碳原子的烴、苯 基或芳香基。 7·如申請專利範園第1項所述的有機發光裝置,其 中’化學式1的化合物由化學式lc表示’ [化學式lc] R^NOC CONR (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 式中R’單獨或同時為有1-15個碳原子的烴、笨基或 芳香基。 8·如申請專利範圍第丨項所述的有機發光裝置,复 中’化學式1的化合物由化學式1 d表示: [化學式Id] 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 24 六、申請專利範圍 〇2N、 N A8 B8 C8 D8
    n〇2 ki
    經濟部智慧財產局員工消費合作社印製 9 ·如申請專利||園笛1 s, 人^ 辄1^第1項所述的有機發光裝置,其中含有由也學式1 ,Λ ^ 1表不的有機化合物的層厚為 10〜10, OOOnm 〇 • 1/0 ·如申明專利範圍第丨項所述的有機發光裝置,其 中’ 3、有由化學式1表示的有機化合物的層還含有-種從 酞青銅絡合物、低噻吩、基於芳香胺的化合物和多環芳香 族化合物中選擇的空穴注入材料。 11·如申請專利範圍第1項所述的有機發光裝置,其 中’陽極含有一種導電聚合物或導電的金屬氧化物。 12· —種電子裝置,其含有至少一層或一層以上由空 穴注入層、空穴輸運層、空穴的注入和輸運層中選擇的層, 這些層含有一種由化學式1表示的有機化合物: [化學式1 ] R · R
    R 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 25 -------------^ I ^----- t---------線 (請先閱讀背面之注意事項再填寫本頁)
    本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) 26
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