200828641 九、發明說明： 【發明所屬之技術領域】 本發明係有關於-種發光二極體播，特別係有關於一種具 有有機無機複合材料之發光二極體元件。 【先前技術】 高分子有機電致發光材料的發展，自199〇年英國劍橋大學 Calvendish實驗團隊成功開發出具有共軛性質的高分子聚對苯乙 烯類（poly(p-Phenyleneyinylene); PPV)材料後，從此開拓高分子 •有機電致發光材料應用的新紀元。隨即，該實驗團隊於年成 立劍橋喊示技術公司(Cambridge Display Technology ; CDT)，同時 積極地授權相關技術予國際各大高分子電致發光顯示器製造公 司。 此後，陸續有各種類型的發光材料不間斷地發表公佈，繼之 而起的是以苐（fluorene)為主鏈結構之高分子電致發光材料的開 發。例如，2000 年 I. S. Millard 在’’Synth Met. ’’期刊第 ηι_Η2 卷 第 119 至 123 頁，發表主題為”High Efficiency P〇lyflUOTene200828641 IX. Description of the Invention: [Technical Field] The present invention relates to a kind of light-emitting diode broadcasting, and particularly relates to a light-emitting diode element having an organic-inorganic composite material. [Prior Art] The development of polymer organic electroluminescent materials. Since 199, the Calvendish experimental team at the University of Cambridge in the UK has successfully developed a poly-p-Phenylene-in-silicon (PPV) material with conjugate properties. After that, a new era of polymer and organic electroluminescent materials was developed. Immediately afterwards, the experimental team established Cambridge Display Technology (CDT) and actively licensed the technology to major international polymer electroluminescent display manufacturers. Since then, various types of luminescent materials have been published uninterruptedly, followed by the development of polymer electroluminescent materials with fluorene as the main chain structure. For example, in 2000, I. S. Millard published the theme "High Efficiency P〇lyflUOTene" in the ’’Synth Met.’’ journal, ηι_Η2, pp. 119-123.
Polymers Suitable for RGB Applications”之論文，便是利用苐 (fluorene)單體分別與 benzothiodiozyl group、胺類（amine group) 及蔥類 （anthracene group)共聚合，形成以烷寡聚芴 (alkylfluorene)為主體之紅、藍、綠高分子電致發光材料。同時， 陶氏化學（Dow Chemical)、德國Coivon及美國ADS等公司亦積 極開發南分子電致發光材料，發表一系列以烧基第(alkylfluorene) 200828641 為主脰之南刀子黾致發光材料。陶氏化學公司更 進-步地細7L件結構之設計與製程改良，有效提升其^件之操 作可π與光私4寸性。ADS (American Dye Source)公司更將奈米材 料導入高奸紐發光材料之分子鏈末端赠善高分子魏集之 效應，提升高分子電致發光特性。 所明的共軛高分子（conJugated p〇lymers)，係為一個主鏈上具 男里複出現雙鍵的高分子，主要藉由高分子主鏈上未定域之Η鍵 ，（b—ng) * Π*反鍵結（antib〇nding)執域形成價帶和傳導 π ’可提供帶電的載子（carriers)移動，由於獨特的光電特性，且 易於製備並具有加卫特性，可製得大面積高品f的_，近年來 成為受人注目的研究領域。 由々上较共轭型高分子主鏈平面性較大，分子鏈之間容易 產生激發雙體(excimer)、激發複合體(exciplex)或聚集 =象’_職生的激子(exdton)純人分子鏈巾的缺陷位置而被 汗熄（q職hing)，致使發光效率降低。然而，透過電致發光圖级 ”最大發光波峰外尚會生成肩峰，使其光譜波長分： ，圍較寬，元件色純度下降。過去為解決高分子聚集之研究已有 多篇文獻發表，當巾包含化學修飾和物理方式改良。由於以物理 理可明免化學合成上之複雜反應，故讀上有不少以捧 妨八將無機奈储料加人高分子發光材料當巾以改善元件之特 性。-般常用的無機奈米材料包含二氧化石夕(Si〇2)、二氧化鈦 (丁!02)、奈米碳管(carb〇n咖〇此’· cnt)及金⑽)等。雖然無機 200828641 奈米材料可請錢發雙體㈣黯)、錄複合體（exdplex)或 聚集（aggregation)現象的產生，但是與高分子有機溶液混合會產 生相分離，降低元件的操作穩定性。 近年來多立面倍半石夕氧燒寡聚體㈣yhedral 〇lig〇silsqu職脇，· P0SS)成為一種新興的無機奈米材料來源、，因為具有觸的籠狀 讀結構’當其存在高分子鏈科，便能有效關分子鏈之間距 而減少糾_機會。但由於無機P0SS材料仍存在著相分離的問 題，一般掺雜比例偏低，大約僅有重量百分比5%以下，因此所能 2善的效果纽’麟作於縫電場就下時元件料產生不穩^ 定的表現。 … 【發明内容】 先前技術中由於存在於發光區域之高分子鏈間易產生聚集現 象’ ¥致所座生的激子（excit〇n)在分子鍵間因泮媳(q職㈣ 喊減，進轉致發光二鋪元件的亮度蘭， : 的發光效率。 ⑤曰轉 料之2料上述_題’本發贿出―種具有有機無機複合材 ，其包含有—陽極、—陰細及-發光區域。 每先區域配設於陽極與陰極之間，其中包含有 機可溶性宫能基之核無機複合材料。 糾及，、有有 斗有機無機複合材料係由具有籠狀立體結構之無機？收 办所組成，此無機P0SS奈米材料上具有至少_種_取代基，、 以促進有機她复合㈣在有機發光材射獲得良好的分妓 200828641 果。 =:1有私可溶,时能基之有機無機複合材料掺入發光 H 了錯低騎技術巾分子賴糾_縣，並使益機 ㈣中展現_分散效果，避免產生= Γ 進而提升發光二極體元件的發光強度及功率效 千。 於本翻魄之說·以下之實施方式之說明係用 本發明之精神與原理，並且提供本發明之專利申請 孳巳圍更進一步之解釋。 【實施方式】 以下在實施方式中詳細敘述本發明之詳細特徵以及優點，i 内谷足以使任何熟f _技藝者了解本發明之技_容並據以實 %，且根據本朗書所揭露之内容、申請專利棚及圖式，任何 熟習相關縣者可輕易地理解本發日糊社目的及優點。 μ«第1目」，係為本翻具有有機錢複合材料之發 二極體树_。如「第1圖」所示，發光二極體树100依 序包含有-基板no、—陽極12G、_電洞傳輸層㈣、_發絲 域140、一電子傳輸層15〇及-陰極16〇。 田其中，基板110用以提供支禮功能，使各層結構得以依序堆 且於二、上適口作為基板110之材料包含玻璃、石英及聚合物材 枓寺’此聚合物材料包含有聚乙烯對苯二▼酸醋類 (p〇lye%leneterephthalates)、聚酯類㈤ 、聚碳酸I旨類 200828641 (polycarbonates) ^ g, §| ^ ^ ^ ^ ^ ^ _卿_)特料。再者，基板m之材料亦可選自於可提供有 效支撐各層結構而不干擾裝置功能運作的材料。 陽極则成於縣板⑽上，料電_子的供應來源， 適合作為雜12〇賭料，—般具有翻鱗透明躲，例如氧 化銦錫（md腿tin oxlde ; IT〇)或氧化錫(tm 〇χΜε)等金屬氧化 物。此外，陽極120材料亦可選擇功函數較大之金屬材料如金 (Au)、歸t)及!ε(Ρ(1傳（但非用以限定本發明之應用範_)，或是 π共軛高分子材料如聚乙烯二氧噻吩/聚笨乙烯絡酸 (PED0T/PSS)、聚苯胺及聚 電洞傳輸層130形成於陽極120上，用以將由陽極12〇所注 入的電洞載付穩地輸送至發战域14Q中，並可阻擋來自陰極 160的電子載子逸人陽極120。此外’作為電洞傳輸層13〇合適材 料的基本要求，必須使陽極120的費米(Fermi)能階和電洞傳輸之 最高佔據分子執域(HOMO)能階之間的電位差值減少，以利於電 洞載子的注入，並可同時防堵電子載子流入陽極12〇，因此，能 夠滿足上述條件的電洞傳輸層130材料包含有芳香胺(ar〇matic amines)化合物如Ν,Ν’-二苯基-N，N，-二(3-曱基笨基)-1，1 _聯笨_4,4，_ 二胺【Ny-diphenyl-NW-bisOmethylphenyD-lJ-biphenyl-W- diamine ; TPD】 及 4,4'，4〃-三 (Ν,Ν-二苯基氨基) 三苯基胺 【4,4，，4"_ tris(N，N-diphenylamino)triphenylamine ; TDATA】；味嗤(carbazoles) 化合物如 Ν，ΚΓ-咔唑基-4,4T-聯苯【N，Nf-dicarbazolyM，4，- biphenyl ; 9 200828641 CBP 】、4,4'-雙(3,6-二苯基咔唑基-9)-1,Γ-聯苯【4,4'-bis(3,6-diphenylcarbazol_9-yl)-l，r_biphenyl ; TPCB】及 4,4’-雙(9-ϋ卡口坐基)-Ι,Γ-聯苯【4,4’-bis(9-carbazolyl)-l，lf-biphenyl】等。此外，更包含 聚乙烯二氧17塞吩（PEDOT)、聚苯胺（poly aniline)、聚吼略 (polypyrrole)等材料。 發光區域140形成於電洞傳輸層130上，藉由所注入之電荷 載子於此發光區域140中進行電子電洞對的再結合反應，而以激 發光的型式發射出光線。發光區域140中包含有可產生電致發光 效果之發光材料，常見的共輛高分子發光材料包括聚對苯乙烯類 如聚對苯乙烯類【poly(p-phenylenevinylene) ; PPV】、聚(2-甲氧基 -5-(2-乙基己氧)1，4-伸苯乙烯）【p〇ly(2-me也OXy_5-(2-ethylhexyl〇xy)l，4-phenylenevinylene) ; MEHPPV 】及聚（2,5-二烷氧基苯乙烯） 【poly(2,5-dialkoxyphenylenevinylene) ; PDMeOPV】等。此外，更 包括聚苯類（p〇lyPhenylenes)材料如聚對苯【p〇ly(p_phenylene); PPP】、梯形?κ對本【ladder-p〇ly-para_phenylene ; LPPP】及聚(四 -氫芘)【p〇ly(tetra-hydr叩yrene); pTHP】等；聚苐類（p〇_^ 材料如 poly(9,94n-〇Ctylfluorene_257_diyl)、p〇ly(2,8_(从 tetraalkylm ^(fluorene)^iLiL^ 等此外由於上述之發光材料其分子鏈段之間容易產生堆疊， 形成南分子鏈的聚集(aggregati〇n)現象，以致降低量子效率。因 此，本實施例之發光區域刚中摻雜具有有機可溶性官能基之有 機無機複合·，如具有有機可溶性官能基之多立面倍半石夕氧烧 10 200828641 寡聚體（polyhedral oligosilsquioxanes ; POSS)結構，通式(I): 其具有下歹,jThe paper "Polymers Suitable for RGB Applications" uses fluorene monomers to copolymerize with benzothiodiozyl group, amine group and anthracene group to form alkylfluorene. Red, blue and green polymer electroluminescent materials. At the same time, Dow Chemical, Coivon and ADS are also actively developing southern molecular electroluminescent materials, and published a series of alkylfluorenes. 200828641 The main tool is the South Knife 黾 luminescent material. The Dow Chemical Company has further improved the design and process improvement of the 7L piece structure, effectively improving the operation of the π and the light private 4 inch. ADS (American Dye Source) introduced the nano-material into the end of the molecular chain of the high-tech luminescent material to give the effect of the polymer, and to enhance the electroluminescence properties of the polymer. Conjugated p〇lymers, It is a macromolecule with a double bond in the main chain, mainly by the unlocalized bond on the polymer backbone, (b-ng) * Π * anti-bonding (antib〇nding) The valence band and conduction π 'provide the movement of charged carriers. Due to the unique photoelectric characteristics, and easy to prepare and have the edging characteristics, it can produce a large area of high-quality _, which has become attracting attention in recent years. Research field: Since the conjugated polymer backbone has a large planarity, it is easy to generate excimers, exciplexes or aggregates like the excitons of the occupational traits. Exdton) is the position of the defect of the pure molecular chain towel and is extinguished by sweat (h), resulting in a decrease in luminous efficiency. However, through the electroluminescence pattern, the shoulder of the maximum luminescence peak is generated, and its spectral wavelength is divided into: The circumference is wider and the color purity of the component is decreased. In the past, many studies have been published to solve the problem of polymer aggregation, and the towel contains chemical modification and physical modification. Because of the complex reaction of chemical synthesis, there are many readings to add inorganic ray storage materials to human luminescent materials as a towel to improve the characteristics of components. The commonly used inorganic nanomaterials include cerium oxide (Si〇2), titanium dioxide (Ding! 02), carbon nanotubes (carb), and gold (10). Although inorganic 200828641 nanomaterials can be used for the production of double-body (four) 黯), exdplex or aggregation phenomena, mixing with a polymer organic solution will result in phase separation and reduce the operational stability of the element. In recent years, the multi-faceted sesame-spotted oxygen oligomer (4) yhedral 〇lig〇silsqu job threat, · P0SS) has become a new source of inorganic nanomaterials, because of the cage-like read structure of the touch 'when it exists in the polymer Chain department can effectively reduce the distance between molecular chains and reduce the number of opportunities. However, since the inorganic P0SS material still has the problem of phase separation, the general doping ratio is low, about 5% or less by weight, so that the effect of the good 2 is not generated when the crack electric field is under the component material. Steady performance. [Explanation] In the prior art, the aggregation phenomenon is easily generated between the polymer chains existing in the light-emitting region. The excitons (excit〇n) that are in the vicinity of the molecular bond are caused by the 职 (q job). The brightness of the light-emitting two-ply component is: Lan, the luminous efficiency of the material. The above-mentioned _ title 'this bribe--the organic-inorganic composite material, which contains - anode, - yin and - Light-emitting area. Each of the first areas is disposed between the anode and the cathode, and contains a nuclear-inorganic composite material of organic soluble uterine energy. Corrected, the organic-inorganic composite material having the organic structure of the cage is composed of an inorganic material having a cage-like three-dimensional structure. The composition of the office, the inorganic P0SS nanomaterial has at least _ kinds of substituents, in order to promote organic compounding (4) in the organic luminescent material to obtain a good distribution of 200828641 fruit. =: 1 privately soluble, time base The organic-inorganic composite material is incorporated into the luminescence H, and the low-riding technical towel molecule is used in the county, and the _ dispersion effect is exhibited in the benefit machine (4), thereby avoiding the generation of Γ, thereby improving the luminous intensity and power efficiency of the light-emitting diode element. In this translation The following description of the embodiments of the present invention is intended to provide a further explanation of the embodiments of the present invention. i 内谷 is enough for any skilled person to understand the technology of the present invention and according to the actual content, and according to the contents disclosed in this book, the patent application shed and the schema, any familiar county can easily understand The purpose and advantages of this book are as follows: μ«第1目, which is a hair-emitting diode tree with organic money composite material. As shown in Figure 1, the LED tree 100 is sequentially The substrate 110 includes a substrate substrate, an anode 12G, a hole transport layer (4), a hairpin field 140, an electron transport layer 15〇, and a cathode 16〇. The substrate 110 is used to provide a support function for each layer structure. The glass material, the quartz and the polymer material are contained in the material of the substrate 110. The polymer material comprises polyethylene terephthalate phthalic acid (polyfluorene phthalate). Ester (5), polycarbonate I 200828641 (polycarbonates) ^ g, §| ^ ^ ^ ^ ^ ^ _ Qing _) Specialties. Furthermore, the material of the substrate m may also be selected from materials which provide effective support for the various layer structures without interfering with the functional operation of the device. The anode is formed on the county board (10). The source of the electricity supply is suitable as a miscellaneous 12-inch gambling material. It has a transparent scale, such as indium tin oxide (ITd) or tin oxide ( Metal oxide such as tm 〇χΜ ε). In addition, the material of the anode 120 may also select a metal material having a large work function such as gold (Au), return to t), and ! ε (Ρ (but not to limit the application of the invention), or π A yoke polymer material such as polyethylene dioxythiophene/polystyrene acid (PED0T/PSS), polyaniline and polyelectron transport layer 130 is formed on the anode 120 for carrying the holes injected by the anode 12〇. It is stably transported into the battle domain 14Q, and can block the electron carrier from the cathode 160 to the anode 120. In addition, as the basic requirement of the suitable material for the hole transport layer 13, the Fermi of the anode 120 must be made. The potential difference between the highest occupied molecular domain (HOMO) energy level of the energy level and the hole transmission is reduced to facilitate the injection of the hole carrier, and at the same time, the electron carrier is prevented from flowing into the anode 12〇, thereby being able to satisfy The hole transport layer 130 material of the above condition contains an aromatic amine (ar〇matic amines) compound such as hydrazine, Ν'-diphenyl-N,N,-bis(3-indolyl)-1,1 _ Stupid _4,4, _ diamine [Ny-diphenyl-NW-bisOmethylphenyD-lJ-biphenyl-W- diamine; TPD] and 4,4',4〃-tris(Ν,Ν-diphenyl Triphenylamine [4,4,,4"_tris(N,N-diphenylamino)triphenylamine;TDATA]; carbazoles compounds such as hydrazine, ΚΓ-carbazolyl-4,4T-biphenyl [ N,Nf-dicarbazolyM,4,- biphenyl ; 9 200828641 CBP 】, 4,4'-bis(3,6-diphenyloxazolyl-9)-1, fluorene-biphenyl [4,4'-bis (3,6-diphenylcarbazol_9-yl)-l,r_biphenyl; TPCB] and 4,4'-double (9-ϋ bayonet)-Ι,Γ-biphenyl [4,4'-bis(9-carbazolyl -l, lf-biphenyl, etc. In addition, it further comprises materials such as polyethylene dioxygen 17 (PEDOT), polyaniline, polypyrrole, etc. The light-emitting region 140 is formed in the hole transport layer. 130, the recombination reaction of the electron hole pair is performed in the light-emitting region 140 by the injected charge carrier, and the light is emitted in the form of the excitation light. The light-emitting region 140 includes an electroluminescence effect. Luminescent materials, common common polymer luminescent materials include poly-p-styrenes such as poly-p-phenylenevinylene; PPV, poly(2-methoxy-5-(2-ethylhexyl) Oxygen) 1,4-strength styrene) [p〇ly (2-me also OXy_5-(2-ethylhexyl〇xy)l,4-phenylenevinylene); MEHPPV] and poly(2,5-dialkoxystyrene) [poly(2,5-dialkoxyphenylenevinylene); PDMeOPV]. In addition, polyphenylene (P〇lyPhenylenes) materials such as polyparaphenylene [p〇ly (p_phenylene); PPP], trapezoidal? kappa pair [ladder-p〇ly-para_phenylene; LPPP] and poly(tetrahydropyrene) [p〇ly(tetra-hydr叩yrene); pTHP], etc.; polyfluorenes (p〇_^ materials such as poly(9,94n-〇Ctylfluorene_257_diyl), p〇ly(2,8_(from tetraalkylm ^(fluorene) ^iLiL^, etc. In addition, due to the above-mentioned luminescent materials, stacking between molecular segments is easy, and agglomeration phenomenon of the south molecular chain is formed, so that quantum efficiency is lowered. Therefore, the luminescent region of the embodiment is just incorporated. An organic-inorganic composite having an organically soluble functional group, such as a multi-faceted sesquiterpene oxide 10200828641 oligomer (polyhedral oligosilsquioxanes; POSS) structure having an organically soluble functional group, having the formula (I): Oh, j
其中 R!、R2、R3、R4、R5、r6、尺7 及團，且至少有一係選自於下列有機可溶性義 (I) R8係為相同或相異茂Wherein R!, R2, R3, R4, R5, r6, uldent 7 and agglomerate, and at least one selected from the group consisting of the following organic soluble (I) R8 is the same or different
⑴ (2) °、sr HsC' XCH: (1，2_epoxy_4 - ethylcydohexyD-dimethylsiloxy(1) (2) °, sr HsC' XCH: (1,2_epoxy_4 - ethylcydohexyD-dimethylsiloxy
(3) 2-(phenyl)ethyl-dimethylsilyloxy(3) 2-(phenyl)ethyl-dimethylsilyloxy
(4) Η3。/、ch3 2-(4-cyclohexenyl)ethyl- dimethylsilyloxy h2 h2 h2 h2 一C一C—C—c—〇H 3-hydroxypropyl (5) —ch2-ch-ch3 ch3 (6) 〇、a’\/'OH Η3。/、ch3 isobutyl (3-hydroxypropyl)- dimethylsiloxy 11 200828641 (Sis〇12)的核， 一無機最小單元(4) Η3. /,ch3 2-(4-cyclohexenyl)ethyl- dimethylsilyloxy h2 h2 h2 h2 C-C-C-c-〇H 3-hydroxypropyl (5) —ch2-ch-ch3 ch3 (6) 〇, a'\/ 'OH Η3. /, ch3 isobutyl (3-hydroxypropyl)- dimethylsiloxy 11 200828641 (Sis〇12) core, an inorganic minimum unit
此多立面倍半矽氧烷寡聚體結構具有 (Si8〇12)的核，其結構類似特定沸石(zeolite)與多 silica)中的主要立體結構，由於所具備之 為本發明發統域之雜物，非僅限於上述㈣舉。再者，發光 區域140巾有機無機複合材料之含量可具有較大的掺混比例範 圍，例如重量百分比濃度範圍在大於〇%到小於1〇〇%之間。 本實施例之電子傳輸層15〇係形成於發光區域14〇上，用以 將由陰極160所注入的電子載子平穩地輸送至發光區域14〇中， 並可阻擋來自1%極120的電洞載子逸入陰極HQ。常見的電子傳 輸層150材料包含有鋁錯化物如三(8_羥基喹琳)鋁化物【恤(8_ hydroxyquinoline)aluminum ; Alq3】、口惡二唾類(oxadiazoles)如 2-(4_ 聯苯基 _5-(4·三級 _丁基苯基)]，3,4_ i:i【2_(4_biphenylyl-5-(4-tert-butylphenyl；M，3,4-oxadiazole ; PBD】、三唑類（triaz〇ies)如 4,4f-bis_[2-(4,6·二苯基 三唑基]_ 1，Γ_ 聯苯【4,4%^[2-(4,6- diphenyl-l，3,5_triazinyl)]-l，l’-biphenyl ； ΤΙ 】以及啡琳類 (phenanthrolines)如 2,9-二曱基-4,7-二苯基-1,10-，^【2,9-dimethyl- 4,7-diphenyl-l，10_phenanthroline ; BCP】等。 12 200828641 4,7-diphenyl，l，10_phenanthroline ; BCP】等。 形成於電子傳輸層150上之陰極160係用以提供電子載子的 來源，其材質甚為廣泛，可包含任何適用的材料如金屬材料。一 般係採用功函數較小的金屬材料，例如：鹼金屬如鋰(Li)或鈉 (Na); Π A族或鹼土金屬如鈹(Be)、鎂(Mg)、鈣(Ca)及鋇(Ba); DIA 族金屬、稀土金屬及锕類金屬如銃(Sc)、釔⑺、鑭(La)、鈽(Ce)、 銪(Eu)、铽(Tb)及荆(Ac)等。此外，上述金屬材料之合金也是陰極 ’ 材料的選用來源，例如鋰合金等。 本發明另一實施例中係以 PSS-Octaj>(4_cydohexenyl)etiiyl drniethykilyloxy]Substituted作為摻雜於發光區域14〇中之有機無 機複合材料，其中發光區域140含有MEHPPV共軛高分子材料， 以作為電致發光材料。 以卜將以具有不同摻雜濃度之有機無機複合材料 PSS-Octa[2_(4_cycl〇hexenyl)ethyl dimethylsilyloxy^ … 百分比濃度分別為〇%、5%、10%及30%之有機無機發光二極體 兀件進行光電特性測試，藉以探討摻雜濃度對發光效率之影響。 一明苳閱第2圖」及「第3圖」，分別為本實施例有機無機發 光二極體元件之紫外線_可見光吸收光譜圖/螢光光譜圖及電激發 光光。曰圖。如「第2圖」所示，左半部波形係為紫外線-可見光譜 图”、、員示卩返者接雜濃度的增加，其能隙值並無明顯的變化現象。 …、 第2圖」所示之右半部波形係為螢光光譜圖分析，圖 中所示鲞光波長接近於596 nm及630 nm之波岭係分別由 13 200828641 ΜΕΗ-PPV之主鏈及側鏈產生激子所發射之波峰，隨著有機無機複 合材料摻雜濃度的增加，側鏈所產生的發錢度呈現明顯地下^ 趨勢’這種趨勢代表著主鏈的堆疊程度伴隨逐漸增加的有機無機 複合材料彳錄量而獲得改善，以概電荷在高分子主鏈上進行非 定域化的財d械，後麵㈣㈣的触、效應(㈣c㈣ 伽）’進而提升發光二極體元件的發光效率。相同的關係圖形^ 勢亦^現在「第3圖」所示之電激發光光譜圖，如「第3圖」所 不，隨著有機無機複合材料摻雜濃度的增加，可明顯地發現由侧 鏈所產生的發光強度亦隨之降低，同時主鏈的發光鱗產生些微 ，藍轉現象，更加證明了有機無機複合#料足以降低發生在^ 卞鍵丨日]的〉午熄效應(quenching effect)。 請參閱「第4圖」及「第5圖」，係分別為本實施例有機無機 發光二極體元狀電流對電壓轉g及亮度/效率對電壓曲線 圖’、中各有機热機發光一極體元件係以氧化銦錫(汀〇)作為陽 極’賴Ca)/銀⑽複合層作為陰極，發光區域中係以廳化聊 作為發光材料並掺雜有不同濃度的 PSS-〇cta[2-(4-cydohexenyl)ethyl d血ethyls 百分比濃度分別為G%、5%、10%及3G%。如「第4圖」及「第$ 圖」所示，摻雜濃度為〇%之元件其啟動大約為Μ伏特，當 操作魏達丨3.8伏特時，其電流密度為每平方公分撕毫安^ 亮度則為每平方公尺测濁光；逐漸增加摻雜濃度至s%之元件 其啟動電Μ大約為2.5伏特，當操作魏達13·8伏特時，其電流 14 200828641 密，為每平方公分438毫安培，亮度為每平方公尺迦燭光；推 雜濃度增加為㈣之树其啟動霞大約為Μ伏特，當操作電 Cie U伏特時’電流雄、度為每平方公分4〇5毫安培，亮度則為 每平方公尺3749濁光。由此可見，ρ4著有機無機複合材料^度: 例的〜加’於作糕下，可有效降低電流密度並同時提 升4 H此外，隨讀統域巾有機無機複合材料的增加， 使得=件的最大發光效率由每安培_濁光（_濃度㈧ 升至每安培U0燭光（摻雜濃度3〇%)。 藉由本發财發光_情人具討射溶时能基之有機 無機稷合補，湘特殊的立體結構以撐__分子鍵，可丄 碰低高分子鏈_聚集縣。此外，由於有機無機複合封料^ 可溶性官能基的存在’避免先前技術中f產生的相分離情形，使 無機P0SS奈料料在有機發光#料中具有均勻的分散相，、 人為攸升發光二極體元件的放射強度及發光效率。 因此本發 明之專利保護範騎視本_書·之申請翔朗所界定料 雖然本發日⑽前述之健實補揭露如上，然其並非用以限 定本發=，任何熟習相像技藝者，在不脫離本發明之精神和蘇圍 内，所為之更動與潤飾，均屬本發明之專利保護範圍. 準 [圖式簡單說明】 第1圖係為本發批麵域發光二極體之 第2圖係為翻之她峨二極體元件之=可見 15 譜圖 ΖυυδΖδ〇41 光吸收光譜圖/螢光光譜圖，· 第3圖係為本發明 • 有钱m機發光二極體 元件之電激發光光 f4圖係為样3疑_麵發光二極 曲線圖；以及 體 元件之電流對電壓 第5圖係為本發％有機無機發光. 電壓曲線圖 、極體 元件之亮度/效率對 【主要元件符號說明】 100 110 120 130 140 150 160 發光二極體元件 基板 陽極 電洞傳輪層 發光區域 電子傳輪層 陰極 16The multi-faceted sesquiterpene oligomer structure has a (Si8〇12) core, and its structure is similar to that of a specific zeolite (zeolite) and polysilica, since it is provided as a domain of the present invention. The sundries are not limited to the above (4). Furthermore, the content of the organic-inorganic composite material in the light-emitting region 140 may have a larger blending ratio range, for example, the weight percentage concentration ranges from more than 〇% to less than 〇〇%. The electron transport layer 15 of the present embodiment is formed on the light-emitting region 14A to smoothly transport the electron carriers injected by the cathode 160 into the light-emitting region 14A, and block the hole from the 1% pole 120. The carrier escapes into the cathode HQ. Common electron transport layer 150 materials include aluminum complexes such as tris(8-hydroxyquinoline) aluminide [8-hydroxyquinoline aluminum; Alq3], oxadiazoles such as 2-(4-diphenyl) _5-(4·三级_butylphenyl)],3,4_ i:i[2_(4_biphenylyl-5-(4-tert-butylphenyl; M,3,4-oxadiazole; PBD], triazole (triaz〇ies) such as 4,4f-bis_[2-(4,6·diphenyltriazolyl]_ 1,Γ_biphenyl [4,4%^[2-(4,6- diphenyl-l, 3,5_triazinyl)]-l,l'-biphenyl ; ΤΙ 】 and phenanthrolines such as 2,9-dimercapto-4,7-diphenyl-1,10-,^[2,9- Dimethyl-4,7-diphenyl-l,10_phenanthroline; BCP], etc. 12 200828641 4,7-diphenyl,l,10_phenanthroline; BCP], etc. The cathode 160 formed on the electron transport layer 150 is used to provide an electron carrier. Source, its material is very wide, can contain any suitable materials such as metal materials. Generally, it uses metal materials with small work function, such as alkali metal such as lithium (Li) or sodium (Na); Π Group A or alkaline earth metal Such as beryllium (Be), magnesium (Mg), calcium (Ca) and barium (Ba); DIA group metals, rare earth metals and Metals such as strontium (Sc), strontium (7), lanthanum (La), cerium (Ce), lanthanum (Eu), lanthanum (Tb) and cerium (Ac), etc. In addition, the alloy of the above metal materials is also the choice of the cathode 'material Source, such as lithium alloy, etc. In another embodiment of the invention, PSS-Octaj>(4_cydohexenyl)etiiyl drniethykilyloxy]Substituted is used as the organic-inorganic composite material doped in the light-emitting region 14〇, wherein the light-emitting region 140 contains the MEHPPV conjugate Polymer material, as an electroluminescent material. The concentration of organic-inorganic composite PSS-Octa[2_(4_cycl〇hexenyl)ethyl dimethylsilyloxy^ ... with different doping concentrations is 〇%, 5%, 10 % and 30% of organic-inorganic light-emitting diodes were tested for photoelectric properties to investigate the effect of doping concentration on luminous efficiency. I see Figure 2 and Figure 3, respectively, for this example. Ultraviolet-visible absorption spectrum/fluorescence spectrum and electroluminescence of inorganic light-emitting diode elements. Cutout. As shown in the "Fig. 2", the left half of the waveform is an ultraviolet-visible spectrum, and the increase in the density of the contacts is shown, and the gap value does not change significantly. ..., Figure 2 The right half of the waveform shown is a fluorescence spectrum analysis. The Boro system with wavelengths close to 596 nm and 630 nm is excitons generated by the main chain and side chains of 13 200828641 ΜΕΗ-PPV. The peak of the emission, with the increase of the doping concentration of the organic-inorganic composite material, the degree of the money generated by the side chain shows a clear underground trend. This trend represents the degree of stacking of the main chain with the increasing organic-inorganic composite material. The amount of the recording is improved, and the energy of the light-emitting diode element is improved by the touch (effect) (4) c (four) gamma of the subsequent (4) (4). The same relationship graph ^ potential is also now the "electron excitation spectrum" shown in "3", as shown in "3", as the doping concentration of organic and inorganic composites increases, the side can be clearly found The luminescence intensity produced by the chain is also reduced, and the illuminating scale of the main chain produces a slight, blue-turn phenomenon, which further proves that the organic-inorganic composite material is sufficient to reduce the quenching effect occurring in the 卞 卞 。 。. Please refer to "Figure 4" and "Figure 5" for the organic-inorganic light-emitting diode current-to-voltage conversion and brightness/efficiency versus voltage curve for the present embodiment, respectively. The polar body element is made of indium tin oxide (Ting), which is used as the anode 'La"/silver (10) composite layer as the cathode, and the light-emitting area is used as the luminescent material and doped with different concentrations of PSS-〇cta[2] The percentage concentrations of -(4-cydohexenyl)ethyl d blood ethyls were G%, 5%, 10% and 3G%, respectively. As shown in Figure 4 and Figure 00, the component with a doping concentration of 〇% starts at about ΜV, and when operating 3.8 volts, it has a current density of mAh per square centimeter. The turbidity is measured per square meter; the component whose doping concentration is gradually increased to s% has a starting voltage of about 2.5 volts. When operating Weida 13·8 volts, the current is 14 200828641, which is 438 millimeters per square centimeter. Ampere, the brightness is the candlelight per square meter; the pusher concentration is increased to (4) the tree's starting glow is about volts, when operating the electricity Cie U volts, the current is male, the degree is 4〇5 milliamperes per square centimeter, brightness It is 3,749 turbid light per square meter. It can be seen that ρ4 is based on the organic-inorganic composite material: in the case of the addition of the cake, it can effectively reduce the current density and simultaneously increase the 4 H. In addition, with the increase of the organic-inorganic composite material of the reading domain, the The maximum luminous efficiency is increased from ampere- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The special three-dimensional structure of Xiang can support the low molecular chain _ aggregation county. In addition, due to the existence of soluble functional groups of organic-inorganic composite seals, 'avoiding the phase separation caused by f in the prior art, The inorganic P0SS nanomaterial has a uniform dispersed phase in the organic light-emitting material, and the radiation intensity and luminous efficiency of the artificially-increasing light-emitting diode element. Therefore, the patent protection of the present invention is applicable to the application of the book. Although the above definitions (10) are as described above, they are not intended to limit the present invention. Anyone who is familiar with the art will be modified and retouched without departing from the spirit of the present invention and Suwei. This is a hair The patent protection scope of the Ming. The quasi [simplified description of the diagram] The first picture is the second picture of the surface area of the light-emitting diode. The second picture is the flip-flop of the diode element = visible 15 spectrum ΖυυδΖδ〇41 light Absorption spectrum/fluorescence spectrum, · Fig. 3 is the invention: The electric excitation light f4 diagram of the rich m machine LED component is a sample 3 suspected _ surface illuminating dipole graph; The current versus voltage is shown in Figure 5. This is the % organic-inorganic luminescence. Voltage graph, brightness/efficiency of the polar body. [Main component symbol description] 100 110 120 130 140 150 160 Luminous diode substrate anode hole Passing layer light emitting area electron transfer layer cathode 16