TWI287532B - The use of an organic matrix material for producing an organic semiconductor material, and also to an organic semiconductor material comprising an organic matrix material and an organic dopant, and also to an electronic component - Google Patents
The use of an organic matrix material for producing an organic semiconductor material, and also to an organic semiconductor material comprising an organic matrix material and an organic dopant, and also to an electronic component Download PDFInfo
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1287532 九、發明說明: 發明所屬技術領域 * 本發明係關於使用有機基質材料製造有機半導體 材料,及亦關於包含有機基質材料及有機掺雜劑的有 機半導體材料,及亦關於電子組件。 先月彳技術 • 已知掺雜可改變有機半導體的電子性質,特別是 *· 它們的電傳導性,對無機半導體如矽半導體亦為此情 況。 在此情況下,電荷載體於基質材料的產生增加起 初相當低的電傳導性,及依據所使用掺雜劑的形式達 到半導體費米能位的變化,掺雜造成電荷傳輸層導電 率的增加,此減少電限損失,及產生接觸點及有機層 之間的改良電荷載體傳輸。 對此種有機半導體的掺雜,強的電子接受體如四 氰基醌二甲烷(TCNQ)或2,3,5,6·四氟四氰基苯醌-一甲烧(F4-TCNQ)為已知;參考 M.Pfeiffer,A· Beyer,T· Fritz, Κ· Leo,應用物理信件,73 (22) 3202-3204 (1998) 及 J. Blochwitz,M.Pfeiffer,T· Fritz,K· Leo,應用物理 信件,73 (6) 729-732 (1998)。做為在類電子給予體基底 材料(電洞傳輸材料)的電子轉移方法之結果,這些產生 已知的電洞,其數目及移動性或多或少顯著改變基質 材料的導電率。 ⑧ 7 1287532 已知基質材料為如生狀化合物如4,4’,4,,-夫(二苯 胺)三苯胺(TDATA) ’ 4,4’,4”-參(3_曱基苯基苯胺)三苯 胺(m-MTDATA)及N,N,N’,N’-四個(4_ f氧基苯基)聯苯 胺(MeO-TPD)。 上述已知基質材料的化學結構為如下所示:129. The invention relates to the manufacture of organic semiconductor materials using organic matrix materials, and also to organic semiconductor materials comprising organic matrix materials and organic dopants, and also to electronic components. Pre-monthly technology • Doping is known to alter the electronic properties of organic semiconductors, especially *· their electrical conductivity, as is the case with inorganic semiconductors such as germanium semiconductors. In this case, the generation of the charge carrier in the matrix material increases the initially relatively low electrical conductivity, and the change in the semiconductor Fermi level is achieved depending on the form of the dopant used, and the doping causes an increase in the conductivity of the charge transport layer. This reduces the loss of electrical limits and creates improved charge carrier transport between the contact points and the organic layer. For the doping of such an organic semiconductor, a strong electron acceptor such as tetracyanoquinodimethane (TCNQ) or 2,3,5,6·tetrafluorotetracyanobenzoquinone-monomethylpyrene (F4-TCNQ) is Known; reference to M. Pfeiffer, A. Beyer, T. Fritz, Κ Leo, Applied Physics Letters, 73 (22) 3202-3204 (1998) and J. Blochwitz, M. Pfeiffer, T. Fritz, K. Leo , Applied Physics Letters, 73 (6) 729-732 (1998). As a result of electron transfer methods for electron-like donor substrate materials (hole transport materials), these produce known holes whose number and mobility significantly alter the conductivity of the matrix material. 8 7 1287532 It is known that the matrix material is a biological compound such as 4,4',4,,-di(diphenylamine)triphenylamine (TDATA) '4,4',4"-parade (3-nonylphenylaniline) Triphenylamine (m-MTDATA) and N,N,N',N'-tetrakis(4_foxyphenyl)benzidine (MeO-TPD) The chemical structure of the above known matrix materials is as follows:
然而,這些化合物為熱不穩定的,亦即它們具低 玻璃悲化>JDL度及傾向於在低'/Μ»結晶,此最終導致不穩 定的電子組件。 該玻璃態化溫度係認為是在材料自溶化快速冷 .春 卻的情況下分子移動因動力原因不再為可能的,及熱 力參數如熱容或膨脹係數突然自典型液體值變化為典 型固體值之溫度。當有機半導體材料與此種基質材料 一起使用時基質材料的熱穩定性特別是因形態原因而 更為重要,為防止在高操作溫度時於此種半導體材料 的慣用層結構上粗糙度的形成。而且,熱穩定性為重 要的以限制基質材料内掺雜劑的擴散。 先前技藝亦揭示熱穩定基質材料如2,2,,7,7,-四個 8 Ί287532 " ) • (N,N_二苯胺)-9,9’-螺雙芴(螺-TAD),然而,因為它們 的最高佔據分子域(HOMOs)的能階位置,它們無法被 掺雜。However, these compounds are thermally unstable, i.e. they have a low glass deficient > JDL degree and tend to crystallize at low '/Μ», which ultimately leads to unstable electronic components. The glass transition temperature is considered to be in the case of rapid auto-melting of the material, and the molecular movement is no longer possible due to the dynamic reasons, and the thermal parameters such as heat capacity or expansion coefficient suddenly change from the typical liquid value to the typical solid value. The temperature. The thermal stability of the matrix material when used with such a matrix material is particularly important, especially for morphological reasons, to prevent the formation of roughness on the conventional layer structure of such semiconductor materials at high operating temperatures. Moreover, thermal stability is important to limit the diffusion of dopants within the matrix material. The prior art also discloses thermally stable matrix materials such as 2, 2, 7, 7, and 4 8 Ί 287 532 " ) • (N,N-diphenylamine)-9,9'-spirobifluorene (spiro-TAD), However, because of their energy-rich positions in the highest occupied molecular domains (HOMOs), they cannot be doped.
發明内容 、 本發明目的為提供使用有機基質材料製造有機半 =體材料’該基質材料為熱穩定的及可掺雜的,以提 七、具同電洞傳導性的電洞傳遞層以用於有機半導體組 而且’應可能由氣相沉積施用該有機基質以藉由 ^蒸發在減壓下以強的有機電子接收體提供具相對應 兩電洞電導率的層。 目的係藉由包括至少一部份分子式⑴的螺雙芴化合 物的有機基質材料 Ί287532SUMMARY OF THE INVENTION It is an object of the present invention to provide an organic half-body material that is made of an organic matrix material. The matrix material is thermally stable and can be doped to provide a hole transport layer having the same hole conductivity for use in The organic semiconductor group and 'should be possible to apply the organic matrix by vapor deposition to provide a layer having a corresponding two-hole conductivity with a strong organic electron acceptor under reduced pressure by evaporation. The object is by an organic matrix material comprising at least a portion of a spirobiguanide compound of formula (1) Ί287532
(I; R-螺-TAD } 其中R為於苯基自由基上的至少一個取代基,但並非 所有R同時為氫。 及/或分子式(II)(I; R-spiro-TAD } wherein R is at least one substituent on the phenyl radical, but not all R are simultaneously hydrogen. And/or formula (II)
其中R為除氫以外的取代基及R’為取代基, 有機基質材料的玻璃態化溫度為至少120〇C及該基質 材料的最高佔據分子域(HOMOs)係位於5.4電子伏特 的最大能階位準。在分子式(I),苯基自由基可因而提 Ί287532 ' 供為具一或更多取代基。 • 較佳為在分子式(I)及(II)的每一個R及/或R’係獨 立地由氳、曱基、乙基、正丙基、異丙基、正丁基、 異丁基、第三丁基、NH2、N(CH4)2及NPh2所組成族 - 群選出,並非在分子式(I)的所有R同時為氳。 特佳為該螺雙8化合物由Wherein R is a substituent other than hydrogen and R' is a substituent; the glass transition temperature of the organic matrix material is at least 120 ° C and the highest occupied molecular domain (HOMOs) of the matrix material is at a maximum energy level of 5.4 eV. Level. In the formula (I), the phenyl radical can thus be provided as having one or more substituents. • Preferably each of R and/or R' in formulas (I) and (II) is independently fluorenyl, fluorenyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, The group consisting of the third butyl group, NH2, N(CH4)2 and NPh2 is selected, and not all of the R of the formula (I) are simultaneously ruthenium. Particularly good for this snail double 8 compound by
11 Ί287532 所組成族群選出。 同樣地較佳為該螺雙苟化合物的玻璃態化溫度位 . 於120〇C及250〇C之間,及該化合物的最高佔據分子 域係位於4.5電子伏特及5.4電子伏狀間的能階位 準,較佳為介於4.8電子伏特及5.2 Λ目的亦可由包含有機基質材料及有機掺雜劑的 有機半導體材料達到’該有機基質材料至少部分包括 » 用做根據本發明基質材料的一或更多化人物。 -· 同樣較佳地是該捧雜劑為2,3,5,6-σ四氟°_7,7,8,8,_ 四氰基醌二曱烷或是其衍生物。然而,具類似接受體 作用及相等或較大分子量的其他楱雜劑為可能的;參 考’如’德國專利10357044.6。特佳為掺雜劑對基質 材料的摩爾掺雜比為介於1:1及1:1〇 〇〇〇之間。 §玄目的可由一種電子組件進一步達到,其中使用 有機基質材料,其係包括至少-部份直覺做為根據本 發明基質材料的螺雙芴化合物。 .φ 最後提供的是以有機發光二極體(OLED)、光電 池、有機太陽能電池、有機二極體或有機場效電晶體 形式的電子組件。 本發明係基於所欽述用於產生有機半導體材料的 有機基質材料之使用提供熱穩疋及經掺雜電洞傳遞層 以用於有機半導體組件之驚人發現。基質材料之使用 提供由氣相沉積所施用的電洞傳遞材料,使得它們 由以強有機電子接受體在減壓下共蒸發而產生具高電 12 1287532 洞電導率的層。 當使用所敘述的有機基質材料時,達到穩定、個別帶 陽電荷的陽離子狀態之電洞傳遞材料。 實施方式11 Ί 287532 selected group. Similarly, the glass transition temperature of the spirobiguanide compound is between 120 ° C and 250 ° C, and the highest occupied molecular domain of the compound is between 4.5 electron volts and 5.4 electron volts. The level, preferably between 4.8 eV and 5.2, can also be achieved by an organic semiconductor material comprising an organic matrix material and an organic dopant, the organic matrix material comprising at least a portion of the matrix material used in accordance with the present invention. More people. Also preferably, the dopant is 2,3,5,6-σtetrafluoro[7,7,8,8,-tetracyanoquinodioxane or a derivative thereof. However, other dopants having similar acceptor functions and equal or greater molecular weights are possible; reference is made to 'German Patent 10357044.6. It is particularly preferred that the molar doping ratio of the dopant to the matrix material is between 1:1 and 1:1 〇. The phantom may be further achieved by an electronic component in which an organic matrix material is used which comprises at least a portion of the intuition as a spirobiguanide compound according to the matrix material of the present invention. .φ Finally, electronic components in the form of organic light-emitting diodes (OLEDs), photovoltaic cells, organic solar cells, organic diodes or organic field-effect transistors are available. The present invention is based on the use of an organic matrix material for the production of organic semiconductor materials to provide a thermally stable and doped hole transport layer for the surprising discovery of organic semiconductor components. Use of Matrix Materials The hole transfer materials applied by vapor deposition are provided such that they are co-evaporated with a strong organic electron acceptor under reduced pressure to produce a layer having a high electrical conductivity of 12 1287532. When the described organic matrix material is used, a stable, individual positively charged cation state of the hole transport material is achieved. Implementation
實例 A· 2,2,,7,7,-四個(N,Nc_對-曱基苯胺)-9,9’_螺雙 苟(螺-TTB)的製備EXAMPLES Preparation of A·2,2,,7,7,-four (N,Nc_p-nonylaniline)-9,9'-spirobisindole (spiro-TTB)
2,2,,7,7,-四溴_9,9,_螺雙芴(1〇公克,15.8毫莫 耳),二-對-甲苯胺(14.2公克,72.1毫莫耳)及第三丁 醇鈉(9.6公克,100毫莫耳)於loo毫升無水甲苯在氮 氣壓下於60〇C攪拌1小時。接著,加入三第三丁基膦 (2〇〇亳克,1·〇毫莫耳,6.3%基於四溴螺雙芴)及醋酸 1巴(11)(92毫克,0.4毫莫耳,2.6%基於四溴螺雙芴)及 在氮氣壓下加熱反應混合物並回流。反應的進行由薄 層層析法監測(溶離劑:50%己烷於二氯曱烷)。2·5小 時後,於TLC不再偵測到任何反應物。冷卻反應混合 物,與100毫克KCN於20毫升水的溶液掺合及於60〇c 13 Ί287532 另外攪拌1小時。在冷卻至室溫後,相分離,及有機 相於硫酸鈉上乾燥及溶液被移除,粗產物自二噁烷再 結晶兩次及接著自些微二氯甲烷於己烷再沉澱及在減 壓下乾燥。 產率:15·0公克(13·8毫莫耳,87%理論)的些微 淺綠色粉末。 1Η NMR(500 MHz,CDC13+水合肼):7.40(d,1Η, J=7.8),7.00(d,4H,J=8.3),6.88(d,4H,J=8.3),6.85(dd, 1H,J=8.3, J=2.0),6.67(d,1H,J=2.0),2.30(s,6H)。 13C NMR(127.5 MHz,CDC13+水合肼):149.8, 146.7, 145.3, 136·1,131·5, 129·5, 124.0, 123.2, 119.9, 119.3, 65.3, 20·6 〇 Β. 2,2’,7,7’-四個(Ν,Ν_二對異丙基苯胺)_9,9,·螺 雙苟(螺_iPr-TAD)的製備 4_異丙基埃苯2,2,,7,7,-tetrabromo-9,9,_spirobifluorene (1 gram, 15.8 millimoles), di-p-toluidine (14.2 grams, 72.1 millimoles) and third Sodium butoxide (9.6 g, 100 mmol) was stirred in loo ml of anhydrous toluene under nitrogen pressure at 60 ° C for 1 hour. Next, add tri-tert-butylphosphine (2 gram, 1 〇 millimolar, 6.3% based on tetrabromospirobiguanide) and 1 bar of ethanol (11) (92 mg, 0.4 mmol, 2.6%) The reaction mixture was heated and refluxed under nitrogen pressure based on tetrabromospiroindole. The progress of the reaction was monitored by thin layer chromatography (solvent: 50% hexane in dichloromethane). After 2·5 hours, no reactants were detected in TLC. The reaction mixture was cooled, blended with a solution of 100 mg of KCN in 20 ml of water and stirred for another hour at 60 〇c 13 Ί 287 532. After cooling to room temperature, the phases are separated, the organic phase is dried over sodium sulfate and the solution is removed. The crude product is recrystallized from dioxane twice and then re-precipitated from hexanes Dry down. Yield: slightly light green powder of 15·0 g (13·8 mmol, 87% theory). 1 NMR (500 MHz, CDC13 + hydrazine hydrate): 7.40 (d, 1 Η, J = 7.8), 7.00 (d, 4H, J = 8.3), 6.88 (d, 4H, J = 8.3), 6.85 (dd, 1H, J = 8.3, J = 2.0), 6.67 (d, 1H, J = 2.0), 2.30 (s, 6H). 13C NMR (127.5 MHz, CDC13 + hydrazine hydrate): 149.8, 146.7, 145.3, 136·1, 131·5, 129·5, 124.0, 123.2, 119.9, 119.3, 65.3, 20·6 〇Β. 2,2', Preparation of 7,7'-four (Ν,Ν_di-p-isopropylaniline)_9,9,·spirobiguanide (spiro_iPr-TAD) 4_isopropyl benzene
4·異丙基苯胺(49·5公克,366毫莫耳)懸浮於200 毫升蒸餾水及在冰浴下與200毫升半濃縮硫酸逐漸掺 合。接著’亞硝酸鈉(25·5公克,370毫莫耳)於2〇〇毫 升蒸餾水的溶液以一種速率逐滴加入使得溫度不會升 至高於2oC。在逐滴加入完成後,混合物於2〇。另外 14 1287532 攪拌20分鐘。所得清澈淡紅色重氮鹽類溶液現在經由 過濾器加至碟化鉀(135.0公克,813毫莫耳)於200毫 升蒸餾水的溶液。反應混合物於80〇C攪拌1小時,在 此進行期間,溶液變為黑色且劇烈氣體釋出及油狀有 機相分離出。冷卻後,移除有機相及水相以1〇〇毫升 乙醚萃取四次或更多。合併有機相以稀氫氧化鈉溶液 及蒸餾水清洗,於硫酸納上乾燥。在溶劑移除後,粗 產物於膜式粟真空蒸餾。該些微淺紅色標的產品於 100-105〇C的溫度(15毫巴)蒸餾。 產率:75.3公克(310毫莫耳,83%理論)的些微淺 紅色液體。 1H NMR(500 MHz,CDC13) : 7.60(d,2H,J=8.3), 6.98(d,2H,J=8.3),2.85(q,1H,J=6.8),1.22(d,6H, J=6.8) o 13C NMR(127.5 MHz,CDC13): 148·4, 137·3, 128.6, 90·6, 33·7, 23·8。 正-乙醢基-4-異丙基苯胺4. Isopropylaniline (49. 5 grams, 366 millimoles) was suspended in 200 ml of distilled water and gradually mixed with 200 ml of semi-concentrated sulfuric acid in an ice bath. Then a solution of sodium nitrite (25. 5 grams, 370 millimoles) in 2 milliliters of distilled water was added dropwise at a rate such that the temperature did not rise above 2oC. After the dropwise addition was completed, the mixture was at 2 Torr. In addition, 14 1287532 was stirred for 20 minutes. The resulting clear reddish diazonium salt solution was now added via a filter to a solution of potassium (3.55 grams, 813 millimoles) in 200 milliliters of distilled water. The reaction mixture was stirred at 80 ° C for 1 hour, during which time the solution turned black and vigorous gas evolution and oily organic phase separated. After cooling, the organic phase and the aqueous phase were removed and extracted four times or more with 1 mL of diethyl ether. The combined organic phases were washed with dilute sodium hydroxide solution and distilled water and dried over sodium sulfate. After the solvent was removed, the crude product was vacuum distilled in a membrane type. The slightly light red standard products are distilled at a temperature of 100-105 ° C (15 mbar). Yield: 75.3 grams (310 millimoles, 83% theory) of slightly light red liquid. 1H NMR (500 MHz, CDC13): 7.60 (d, 2H, J = 8.3), 6.98 (d, 2H, J = 8.3), 2.85 (q, 1H, J = 6.8), 1.22 (d, 6H, J = 6.8) o 13C NMR (127.5 MHz, CDC13): 148·4, 137·3, 128.6, 90·6, 33·7, 23·8. n-Ethyl-4-isopropylaniline
醋酸酐(26·0公克,254毫莫耳)逐滴緩慢加入4-異丙基苯胺(17.2公克,127毫莫耳)於80毫升氯仿的 溶液。在此進行期間,反應混合物的強烈加熱發生。 1287532 在逐滴加入完成後,混合物於室溫另外攪拌2小時。 反應混合物濃縮至乾燥及所得淺紅色-白色固體自己 烧再結晶。 產率:21.1公克(120毫莫耳,94%理論)的白色固 體。 1H NMR(500 MHz,CDC13) : 7.88(s,1H),7.40(d, 2H,J=8.3),7.14(d,2H,J=8.3),2.86(q,1H,J=6.8), L21(d,6H,J=6.8)。 13C NMR(127.5 MHz,CDC13): 168.6, 144.9, 135·6, 126.7, 120.2, 33·5, 24·3, 23.9。 熔點:107〇C(文獻(Dyall,澳洲化學期刊17,1964, 419):104_105 oC) 〇 正-乙酸基-N,N —二(4-異丙基苯基)胺Acetic anhydride (26·0 g, 254 mmol) was slowly added dropwise to a solution of 4-isopropylaniline (17.2 g, 127 mmol) in 80 ml of chloroform. During this progress, intense heating of the reaction mixture takes place. 1287532 After the dropwise addition was completed, the mixture was stirred at room temperature for additional 2 hours. The reaction mixture was concentrated to dryness and the obtained pale red- white solid was evaporated and evaporated. Yield: 21.1 g (120 mmol, 94% theory) of a white solid. 1H NMR (500 MHz, CDC13): 7.88 (s, 1H), 7.40 (d, 2H, J = 8.3), 7.14 (d, 2H, J = 8.3), 2.86 (q, 1H, J = 6.8), L21 (d, 6H, J = 6.8). 13C NMR (127.5 MHz, CDC13): 168.6, 144.9, 135·6, 126.7, 120.2, 33·5, 24·3, 23.9. Melting point: 107 〇C (Document (Dyall, Australian Chemical Journal 17, 1964, 419): 104_105 oC) 〇 n-acetic acid-N,N-bis(4-isopropylphenyl)amine
4-異丙基碘苯(29.2公克,118毫莫耳),正-乙醯 基-4-異丙基苯胺(21·0公克,118毫莫耳),銅粉末(15.0 公克,237毫莫耳),碳酸鉀(65.4公克,474毫莫耳) 及18-冠-6 (2.9公克,12毫莫耳)於200毫升1,2-二氯 苯加熱回流。反應由薄層層析法監測(溶離劑:l〇%THF 於二氯曱烷)。48小時後,熱反應混合物過濾,徹底清 洗過濾器餘留物及溶劑於旋轉蒸發器移除。粗產物使 1287532 用10%THF於m切膠上色層分析。濃縮產物 部分至乾燥,自己烧再結晶及於減壓下乾燥。 產率· 14.31公克(48毫莫耳,41%理論)些微淡 棕色固體。 1H NMR(500 MHz,CDC13): 7.21(m,8H), 2.90(s(br·),2H),2.04(s,3H),1.23(s(br),12H)。 N,N—二(4-異丙基苯基)胺4-isopropyl iodobenzene (29.2 g, 118 mmol), n-ethinyl-4-isopropylaniline (21·0 g, 118 mmol), copper powder (15.0 g, 237 mmol) Ear), potassium carbonate (65.4 grams, 474 millimoles) and 18-crown-6 (2.9 grams, 12 millimoles) were heated to reflux in 200 milliliters of 1,2-dichlorobenzene. The reaction was monitored by thin layer chromatography (solvent: 1% THF in dichloromethane). After 48 hours, the hot reaction mixture was filtered and the filter residue and solvent were thoroughly purged and removed on a rotary evaporator. The crude product was analyzed by 1287532 using 10% THF in m-gel. The product was concentrated to dryness, then recrystallized and dried under reduced pressure. Yield 14.31 g (48 mmol, 41% theory) slightly light brown solid. 1H NMR (500 MHz, CDC13): 7.21 (m, 8H), 2.90 (s (br.), 2H), 2.04 (s, 3H), 1.23 (s (br), 12H). N,N-bis(4-isopropylphenyl)amine
正-乙醯基-N,N—二(4-異丙基苯基)胺(5·4公 克,18·4毫莫耳)於100毫升20%水相乙醇加熱回流。 反應由薄層層析法監測’ 3 0小時後,沒有任何反應物 可於TLC偵測出。乙醇溶液倒至蒸餾水,且淡棕色沉 澱物以吸力濾出,溶解於二氣曱烷及以硫酸鈉乾燥, 濃縮溶液及以50%二氯甲烧於己烧經由短石夕膠枉層 # 析。產物部分濃縮至乾燥及產品於減壓下乾燥。 產率:4·0公克(16毫莫耳,86%理論)的淡棕色固 1Η NMR(500 MHz,CDC13) : 7.12(d,4Η,J=8.3), 6.99(d,4H,J=8.3),5.55(s(br·),1H),2.86(q,2H, J=6.8), 1.24(d,12H,J=6.8)。 13C NMR(127.5 MHz, CDC13) : 141.3,127.1, 117.7, 33.4, 24.1。 17 1287532n-Ethyl-N,N-bis(4-isopropylphenyl)amine (5.4 g, 18.4 mmol) was heated to reflux in 100 ml of 20% aqueous ethanol. After the reaction was monitored by thin layer chromatography, no reaction was detected by TLC after 30 hours. The ethanol solution was poured into distilled water, and the pale brown precipitate was filtered off with suction, dissolved in dioxane and dried over sodium sulfate, concentrated solution and burned with 50% dichloromethane in a sinter. . The product was partially concentrated to dryness and the product was dried under reduced pressure. Yield: 4·0 g (16 mmol, 86% theory) of light brown solid 1 NMR (500 MHz, CDC13): 7.12 (d, 4 Η, J = 8.3), 6.99 (d, 4H, J = 8.3 ), 5.55 (s(br·), 1H), 2.86 (q, 2H, J = 6.8), 1.24 (d, 12H, J = 6.8). 13C NMR (127.5 MHz, CDC13): 141.3, 127.1, 117.7, 33.4, 24.1. 17 1287532
2,2’,7,7’-四個(N,N-二-對·異丙基苯胺)_9,9,-螺雙芴(螺 -iPr-TAD)2,2',7,7'-tetra(N,N-di-p-isopropylaniline)_9,9,-spirobiguanide (spiro-iPr-TAD)
2,2,,7,7’_四溴-9,9,_螺雙芴(ι·7公克,2·6毫莫 耳),Ν,Ν—二-4-異丙基苯基胺(3·〇公克,12.0毫莫耳) 及第三丁醇鈉(1·6公克,17毫莫耳)於1〇〇毫升無水甲 苯在氮氣壓下於60〇C攪拌1小時。接著,加入三第三 丁基膦(4.8毫克,0.24毫莫耳,9.2%基於四溴螺雙芴) 及醋酸鈀(11)(27毫克,0.12毫莫耳,4.6%基於四溴螺 雙芴)及在氮氣壓下加熱反應混合物並回流。反應的進 行由薄層層析法監測(溶離劑:20%二氯甲烷於己烷)。 3·5小時後,於TLC不再偵測到任何反應物。冷卻反 應混合物,與100毫克KCN於20毫升水的溶液掺合, 及於60〇C另外攪拌1小時。在冷卻至室溫後,相分離, 及有機相於硫酸納上乾燥及溶液被移除,粗產物自二 11惡烧再結晶兩次及接者在減壓下乾燥。 產率·· 2.8公克(2.1毫莫耳,81%理論)的些微淡 黃色,微結晶粉末。 1H NMR(500 MHz,CDC13) : 7.41(d,1H,:Γ=8·3), 1287532 7.05(d,4H,J=8.3),6·90(ιη,5H),6.72(s(br·),1H),2.85(q, 2H,J=6.8),1.24(d,12H,J=6.8)。 13C NMR(127.5 MHz,CDC13) : 150.7,147.5, 146.3, 143.3, 137.2, 127.6, 125.3, 123.8, 120·8, 120.7, 66·2, 34·1,24·8。2,2,,7,7'_tetrabromo-9,9,_spirobifluorene (ι·7 g, 2.6 mmol), hydrazine, hydrazine-di-4-isopropylphenylamine ( 3·〇克, 12.0 mmol, and sodium butoxide (1.6 g, 17 mmol) in 1 ml of anhydrous toluene were stirred at 60 ° C for 1 hour under nitrogen pressure. Next, add tri-tert-butylphosphine (4.8 mg, 0.24 mmol, 9.2% based on tetrabromospirobiguanide) and palladium acetate (11) (27 mg, 0.12 mmol, 4.6% based on tetrabromospirobiguanide). And heating the reaction mixture under nitrogen pressure and refluxing. The reaction was monitored by thin layer chromatography (solvent: 20% dichloromethane in hexane). After 3 hours, no reactants were detected in TLC. The reaction mixture was cooled, blended with a solution of 100 mg of KCN in 20 ml of water, and stirred at 60 ° C for an additional hour. After cooling to room temperature, the phases were separated, and the organic phase was dried over sodium sulfate and the solution was removed. The crude product was recrystallized from hexanes and then dried under reduced pressure. Yield · · 2.8 g (2.1 mmol, 81% theory) of slightly yellowish, slightly crystalline powder. 1H NMR (500 MHz, CDC13): 7.41 (d, 1H,: Γ=8·3), 1287532 7.05 (d, 4H, J=8.3), 6·90 (ιη, 5H), 6.72 (s ), 1H), 2.85 (q, 2H, J = 6.8), 1.24 (d, 12H, J = 6.8). 13C NMR (127.5 MHz, CDC13): 150.7, 147.5, 146.3, 143.3, 137.2, 127.6, 125.3, 123.8, 120·8, 120.7, 66·2, 34·1, 24·8.
Tg:144oC,Tk:166 oC,Tm:363 oC。 該兩種有機物質螺-TTB及螺-iPr-TAD每一個以 F4-TCNQ掺雜及於電傳導性測量測試。對這些測量, 該經掺雜層係藉由於減壓下共蒸發而施用於兩個約5 毫米-寬接觸點(由氧化銦錫,ITO製造),接觸點係以 彼此相距1毫米的距離施用於玻璃基材。該接觸點係 外部連接至電流-電壓測量儀器,其允許侧向電流於固 定施用電壓測量,由此侧向電流,該層的電傳導性接 著由簡單電阻關係式計算,該電傳導性係在下列方程 式協助下決定: 電傳導性=(側向電流*距離)/(寬度*層厚度) 第1及2圖每一個顯示對該兩個經掺雜基質材料 側向電流隨層厚度之增加,以2.5% F4_TCNQ掺雜的 50奈米厚的螺-TTB層之電傳導性約為1.6E-5S/公分, 且以5%F4-TCNQ掺雜的50奈米厚的螺-iPr_TAD層之 電傳導性約為8E-7S/公分。 以具有機基質材料的OLED形式的本發明電子 組件的一個具體實施例,如要根據本發明所使用,可 被製造及包含,在經由基材發射的一般設計之情況 19 -1287532 德拉/安培及45坎德拉/安培光產生的電流效率同樣地 為非常高及固定的。因為此穩定電洞傳遞層,此OLED 可在相當高溫度(高至100〇C)穩定操作而不會造成光 電性質的降低。 揭示於上列敘述、申請專利範圍及圖式中的本發明特 徵基本上可個別或以任何組合以其不同具體實施例實 現本發明。 1287532 圖式簡單說明 第1圖顯示侧向電流在有機基質材料螺_ΤΤΒ(以 F4-TCNQ掺雜)的傳遞層的層厚度的相依性; 第2圖顯示側向電流在有機基質材料螺-iPr-TAD (以 F4-TCNQ掺雜)的傳遞層的層厚度的相依性; 第3圖顯示具經掺雜傳遞層及螺-TTB(以F4-TCNQ掺 雜)做為P-掺雜劑的有機發光二極體之亮度信號電壓 及功率效率電壓特徵。 元件符號說明 無 22Tg: 144oC, Tk: 166 oC, Tm: 363 oC. The two organic substances, spiro-TTB and spiro-iPr-TAD, were each doped with F4-TCNQ and tested for electrical conductivity measurements. For these measurements, the doped layers were applied to two approximately 5 mm-wide contact points (made of indium tin oxide, ITO) by co-evaporation under reduced pressure, and the contact points were applied at distances of 1 mm from each other. On glass substrates. The contact point is externally connected to a current-voltage measuring instrument that allows the lateral current to be measured at a fixed applied voltage, whereby the lateral current, the electrical conductivity of the layer is then calculated from a simple resistance relationship, the electrical conductivity being The following equations are assisted by the decision: Conductivity = (lateral current * distance) / (width * layer thickness) Figures 1 and 2 each show the increase in lateral current of the two doped matrix materials as a function of layer thickness, The 50 nm thick spiro-TTB layer doped with 2.5% F4_TCNQ has an electrical conductivity of about 1.6E-5S/cm, and the 50 nm thick spiro-iPr_TAD layer doped with 5% F4-TCNQ The conductivity is about 8E-7S/cm. A specific embodiment of the electronic component of the invention in the form of an OLED having an organic matrix material, as used in accordance with the present invention, can be fabricated and contained in the case of a general design that is emitted via a substrate 19 -1287532 draels per ampere The current efficiency produced by the 45 cd/ampere light is also very high and fixed. Because of this stable hole transport layer, the OLED can operate stably at relatively high temperatures (up to 100 〇C) without causing a decrease in photo-electric properties. The invention as set forth in the above description, the scope of the invention, and the features of the invention may be embodied in various specific embodiments in various embodiments. 1287532 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the dependence of the lateral current on the layer thickness of the transfer layer of the organic matrix material ΤΤΒ_ΤΤΒ (F4-TCNQ doped); Figure 2 shows the lateral current in the organic matrix material snail - The dependence of the layer thickness of the transfer layer of iPr-TAD (doped with F4-TCNQ); Figure 3 shows the doped transfer layer and spiro-TTB (doped with F4-TCNQ) as a P-dopant Luminance signal voltage and power efficiency voltage characteristics of the organic light-emitting diode. Component Symbol Description None 22
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