1236312 九、發明說明： 【發明所屬之技術領域】 本發明係與發光裝置有關，更詳而言之是指一種可產 生白光的有機電激發光裝置及其製作方法。 5【先前技術】 。月參閱第圖所不之習用可產生白光的有機電激發光 裝置1’其係利用於-陽極2與一陰極3之間設置有三個以 不同發光材料所形成的有機層4a、4b與4c，各該有機層在 陽極2與陰極3受到一外加偏壓作用時，分別產生紅光、 1〇綠光與藍光，且在紅、綠與藍三種色光的發光強度相當並 互為混合後，即可獲得白色光源。 惟，由於各獨立發光的有機層(4a、4b與4c)各需不同 的驅動電壓，且其等發光效率及使用壽命不同，例如可產 生紅光的有機層4a使料命相較其他二者為短，間接導致 15該發光裝置1可使用壽命縮短，受制於上述因素，使得該 發光裝置1在製作與控制方面更顯不易。 凊再參閱第二圖所示之另一習用可產生白光的有機電 激發光裝置5(中華民國公告第556，楊號專利），其用以產 2〇 ^光發射的主要積層為一以DPVBi構成的第一主體材料層 與-以CBP構成的第二主體材料層7，於第一主體材料 層6中並摻雜有可投射藍光的DSA物質，於該第二主體材 料層7中則摻雜有可投射綠光的斤(附)3物質及可投射紅光 $ 〇CM2物質，各該主體材料層(6、7)在該發光裝置5之 陽極與陰極受_外加偏壓作用時，可投射出 紅、綠與藍三 1236312 種色光，並於互為混合後形成白光。 誠然，該發光裝置5可提供所需的白色光源，但，由 於各主體材料層（6、7)皆係以小分子(m〇lecules)材料所構 ^以及發光裝置5之電洞/電子傳輸層（8、9)亦是選擇小 分子材料(如：CuPc/Alq3)製得，因此，在各積層的成膜製 作^面，係採真空蒸鍍方式製作，惟，在蒸鍍過程中，、^ 在著有機分子摻雜濃度不易控制及製程繁瑣等缺失。 有鑒於此，本案發明人乃經詳思細索，並積多年從事 有機發光元件之研究開發經驗，終而有本發明之產生。 【發明内容】 15 其製在於提供—種有機電激發光裝置及 '八有製輊簡易、成臈因素易於控制的優點。 $明之次要目的在於提供—财機電激發光裝 忒=二較低電壓即可獲得較高電力效率與發 其製财魏歸光裝置及 笋 ，、、/"侍知疋性鬲及色純度佳的白色光源。 發光裝置及其製作:步驟如下 述.取一、上表 ' * ' 板做為支擇#上表面具有陽極之基 層、將高分子㈣=為電洞傳輸 材料做為摻雜物溶於右二 至^種小分子發光 傳輸層上形成—絲射詞巾’復經濕式製程於該電洞 成紅射層、於該光發射層上形成一電洞阻 20 1236312 隔層、於該電洞阻隔層上形成一電子注入層、最後再於該 電子注入層上製作一陰極。 【實施方式】 以下’紙列舉本發明之較佳實施例，並配合下列圖示 洋細說明於后，其中·· 第一圖係習用有機電激發光裝置之結構剖視圖。 第二圖係另一習用有機電激發光裝置之結構圖。 第三圖係本發明之製作流程圖。 第四圖係本發明一較佳實施例之結構圖。 第五圖係本發明之發光裝置產生白光時之光波長示意 圖。 第六圖係一種彩色濾光片的光透射比示意圖，該濾光 片係可與本發明之發光裝置搭配應用。 請參閱第三、四圖所示，本發明可產生白色光源的有 機電激發光裝置100之製作方法如下所述·· 備料： 取一上表面具有陽極12的基板10做為支撐材， 前述基板10可為玻璃基板、可捲曲的塑膠基板、具 可導電性質的金屬基板或是以有機材料直接製成的 基板，而該陽極12係由銦錫氧化物(IT〇)、銦鋅氧化 物(ΙΖΟ)或鋁鋅氧化物(ΑΖΟ)等材料擇一製成厚度在 1000至6000埃(Α)之間的薄膜所構成。 -6- 1236312 製作電洞傳輪層20 : 係以高分子材料(如：PED〇T、p〇iyaniUne等）溶於 有機/谷以中’經屬於濕式製程(Wetpr〇cess)的旋轉被 覆方法(spin coating)塗佈於該基板1〇後，再於充滿 惰性氣體的環境下進行烘烤而形成厚度在5至2500 埃(A)之間的薄膜；於本實施例中，係以pED〇T為 例，並利用摻雜有機酸pSS以提高電洞注入性，且 該電洞傳輸層20厚度在700埃(人)為佳；前述濕式製春 程當然包括有喷墨塗佈(Ink lnject printing)、滾輪塗 佈（roller coating)、網版印刷（screen ρΓ|ηί_)、到刀 塗佈（doctor blade coating)及轉貼層壓(—„η〇ρΓΜη§) 等。 製作光發射層30 : 係以高分子發光材料做為宿主(host)，二種小分子 發光材料做為摻雜物(dopant)，依一定重量比例混合 後一同溶於有機溶劑(如：二甲苯、CH2C12或THF) _ 中，之後，經濕式製程塗佈於該電洞傳輸層2〇上， 且於充滿惰性氣體的環境下進行烘烤以形成厚度在 5至2500埃(A)之間的薄膜；本實施例所採用之濕式 製程為旋轉被覆方法，前述高分子發光材料係可選自 聚{2,7-[(9,9·二院基）苟]、苯乙稀（para-phenylene ethylene，PPV)、聚乙稀口坐(p〇iy-(N_vinylcarbazole)5PVK) 或是陶氏化學公司（DOW Chemical)所生產的glue J 材料，而小分子發光材料則可選自C545T、Ir(ppy)3、 -7- 1236312 DCJTB、Rubrene 或 PtOEP 等材料； 在本實施例中，於高分子發光材料方面係選用陶 氏化學公司（DOW Chemical)可產生藍光的Bhje j材 料，在小分子發光材料方面則分別選擇可產生綠光的 C545T及可產生紅光的DCJTB材料，且Biue j與 C545T及DCJTB的混合比例為1 : 〇 〇7 ·· 〇 〇4，且該 光發射層30厚度在600埃(A)為佳。 製作電洞阻隔層40 : 10 在材料選擇方面，可以小分子材料或高分子材料 製成，前者如BCP、TPBI，後者如F8_TFB ;而於本 實施例中，係選擇TPBI小分子材料經成膜加工(如： 蒸鍍、濺鍍)於該光發射層3〇上製得一厚度在5至 1000埃(A)之間並可將電洞侷限於該光發射層3〇内 的薄膜’該電洞阻隔層40的厚度在埃(A)為佳； 另外，當以高分子材料製作時，其成膜方式則採如上 述之濕式製程為之。 製作電子注入層50 : 以小分子材料經成膜加工(如：蒸鑛、濺鑛)而於該 電洞阻隔層40上形成—厚度在5至雇〇埃⑹之間 的薄膜=本實施例中，係以·為例做 洞阻隔層40的材料。 製作陰極60 : 係以蒸鑛或_方法於該電子注入層5〇上製得厚 又在1000至5_埃(A)之間的單層或多層結構前 20 1236312 述形成單層結構所選用的材料可為鋁(A1)或銀(Ag). 等金屬材質，而形成多層結構所選用的材料則可為鈣 (Ca)/銘(A1)、鋇(Ba)/銘(A1)、約(Ca)/鎂鋁混合物(Mg : A1)或鋇(Ba)/鎂鋁混合物(Mg : A1)等複合金屬材質； 5 於本實施例中，係以鈣(CaV鋁(A1)複合金屬製成該 陰極60 ,且妈(Ca)的厚度在4〇〇埃(A)，紹(A〗)的厚 度在1000埃(A)為佳。 以上即為本發明有機電激發光裝置1〇〇之結構與製 法’而在元成有機層的成膜製作後，接著，復進行封裝作 ίο業以防止外部大氣中的水分與電極接觸而導致氧化，進一 步保護内部有機層的性能，於前述封裝作業中，更可利用 增汉一層隔水氧薄膜(desiccant)以強化防止電極氧化之效 本發明之有機電激發光裝置1〇〇在其陽極12與陰極6〇 15受到一外加偏壓作用時（電壓為10V，電流強度為 50mA/cm2)，將促使電洞與電子在以高分子材料與小分子材 料依一疋重罝比例混合製成的光發射層3〇中產生再結合 (recombination)，進而激發別此：材料發出藍光同時造成 C545T材料與DCJTB材料發出綠光與紅光，該三種色光在 2〇混合後可獲得具有三段波長特性的連續全波長白光(圖五參 照），β亥白光的CIE座仏為X-〇·3〇，y=〇 33 ’即白光的色純 度佳，另說明的是，本發明有機電激發光裝置1〇〇之發光 輝度(luminance)可達6500cd/m2，且具有以較低電壓即可獲 得較高電力效率(5·61 m/w)的優點。 -9« 1236312 紅上所述，本發明之有機電激發光裝置1〇〇在成臈作 業的刚段製作方面（包括電洞傳輸層與光發射層的製作），因 以濕式製㈣之而具有簡化製程與成朗素易於控制的優 點，改善以蒸鑛製作存在著有機分子換雜濃度不易控制的 缺失，並且，本發明之有機電激發光裝置1〇〇所發出的白 光不易隨著轉電壓的變麵產生偏色情形，具良好 性。 "另外，本發明之光發射層3(M系以適當比例的高分子發 光材料摻雜二種光色具互媽性的小分子發光材料製成， 於產生自糾，所得級錢為具有三個波峰的連續全波 長（圖五參照），各該波峰位置恰與彩色濾光片之光透射比 圖六參照），因此’本發明之有機電激發 顯L _搭配應用後’即可獲得全彩色的 #、、、貝不面板。 15 是以，本發明於同類產品中著實具有進步性， 明於申請前並無相同製程與結構見於刊物或如 二 上所述者’僅為本伽之較佳可行實關％ ^ =發明說明書及申請專利範圍所為之等，：： 含在本發明之專利範圍内。 應匕 -10- 20 1236312 【圖式簡單說明】 第一圖係習用有機電激發光裝置之結構剖視圖。 第二圖係另一習用有機電激發光裝置之結構圖。 第三圖係本發明之製作流程圖。 第四圖係本發明一較佳實施例之結構圖。 第五圖係本發明之發光裝置產生白光時之光波長示意 第六圖係一種彩色濾光片的光透射比示意圖，該濾光 片係可與本發明之發光裝置搭配應用。1236312 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to light-emitting devices, and more specifically refers to an organic electro-luminescent device capable of generating white light and a method for manufacturing the same. 5 [Prior art]. Referring to the figure, the conventional organic electroluminescent device 1 ′ capable of generating white light is used in that three organic layers 4a, 4b, and 4c formed of different light-emitting materials are provided between the anode 2 and a cathode 3, Each of the organic layers generates red light, 10 green light, and blue light when the anode 2 and the cathode 3 are subjected to an external bias, and the three light colors of red, green, and blue are equivalent and mixed with each other, that is, A white light source is available. However, since each of the independently emitting organic layers (4a, 4b, and 4c) requires a different driving voltage, and their luminous efficiency and service life are different, for example, the organic layer 4a that can generate red light makes the material life as compared to the other two. Short, indirectly, the life span of the light-emitting device 1 is shortened. 15 Subject to the above factors, the light-emitting device 1 is more difficult to manufacture and control.凊 Refer to another conventional organic electroluminescent device 5 that can generate white light as shown in the second figure (Republic of China Publication No. 556, Patent No. Yang). The main layer used to produce 20 ^ light emission is DPVBi. The first host material layer and the second host material layer 7 made of CBP are doped in the first host material layer 6 and doped with a DSA substance capable of projecting blue light, and the second host material layer 7 is doped with Mixed with a substance that can project green light (attachment) 3 and a substance that can project red light $ 0CM2, each of the main material layers (6, 7) when the anode and cathode of the light-emitting device 5 are subjected to an external bias, It can project red, green and blue colors of 1,363,312 colors, and form white light after mixing with each other. It is true that the light-emitting device 5 can provide the required white light source, but since each of the host material layers (6, 7) is composed of small molecule materials, and the holes / electron transmission of the light-emitting device 5 The layers (8, 9) are also made by selecting small molecular materials (such as: CuPc / Alq3). Therefore, the film formation surface of each layer is made by vacuum evaporation. However, during the evaporation process, , ^ In the organic molecule doping concentration is not easy to control and tedious process and other defects. In view of this, the inventor of this case has carefully considered and accumulated many years of experience in research and development of organic light-emitting devices, and finally the invention has emerged. [Summary of the invention] 15 The system is to provide an organic electro-excitation light device and the advantages of simple and easy to control, and easy to control the formation factors. The main purpose of $ 明 Secondary is to provide-CaiMei's excitation light equipment = two lower voltages can achieve higher power efficiency and the development of financial equipment and shoots. Pure white light source. Light-emitting device and its production: The steps are as follows. Take one, the above table * * as the option # the base layer with the anode on the top surface, the polymer ㈣ = as a hole transport material as a dopant dissolved in the second right Formed on the light-emitting transmission layer of a small molecule-the silk-spun word towel is re-wet-processed to form a red-emitting layer on the hole, and a hole resistance 20 1236312 is formed on the light-emitting layer, and the hole is formed. An electron injection layer is formed on the barrier layer, and a cathode is finally formed on the electron injection layer. [Embodiment] The following 'paper lists the preferred embodiments of the present invention, and the following diagrams are described in detail below, where the first picture is a cross-sectional view of the structure of a conventional organic electroluminescent device. The second figure is a structural diagram of another conventional organic electro-optic device. The third figure is a manufacturing flowchart of the present invention. The fourth figure is a structural diagram of a preferred embodiment of the present invention. The fifth diagram is a schematic diagram of light wavelengths when the light emitting device of the present invention generates white light. The sixth diagram is a schematic diagram of the light transmittance of a color filter, which can be used in combination with the light-emitting device of the present invention. Please refer to the third and fourth figures. The manufacturing method of the organic electroluminescent device 100 capable of generating a white light source according to the present invention is as follows. Material Preparation: A substrate 10 having an anode 12 on its upper surface is used as a supporting material. 10 can be a glass substrate, a rollable plastic substrate, a metal substrate with conductive properties, or a substrate made directly from organic materials, and the anode 12 is made of indium tin oxide (IT〇), IZO) or aluminum zinc oxide (AZO) and other materials are made of thin films with a thickness between 1000 and 6000 Angstroms (A). -6- 1236312 Fabrication of hole transmission wheel layer 20: It is made of polymer materials (such as PEDOT, p0iyaniUne, etc.) dissolved in organic / valley, and it is covered by spinning which is a wet process (Wetpr〇cess). The method (spin coating) is applied to the substrate 10, and then baked in an environment filled with an inert gas to form a thin film having a thickness between 5 and 2500 angstroms (A); in this embodiment, pED is used. 〇T is taken as an example, and doped organic acid pSS is used to improve hole injectivity, and the thickness of the hole transport layer 20 is preferably 700 angstroms (person); of course, the aforementioned wet spring manufacturing process includes inkjet coating ( Ink lnject printing), roller coating, screen printing (screen ρΓ | ηί_), doctor blade coating, and transfer lamination (—η〇ρΓΜη§), etc. Production of light emitting layer 30: The polymer light-emitting material is used as a host, and two small-molecular light-emitting materials are used as dopants. They are mixed in a certain weight ratio and dissolved in organic solvents (such as xylene, CH2C12, or THF). ) _, Then, coated on the hole transport layer 20 by a wet process, and filled with inert gas Baking is performed under a green environment to form a thin film with a thickness between 5 and 2500 Angstroms (A); the wet process used in this embodiment is a spin coating method, and the aforementioned polymer light-emitting material may be selected from poly {2, 7-[(9,9 · 二 院 基) Gou], para-phenylene ethylene (PPV), polyethylene mouth (p0iy- (N_vinylcarbazole) 5PVK) or Dow Chemical Company (DOW Chemical J), and small molecule light-emitting materials can be selected from materials such as C545T, Ir (ppy) 3, -7-1236312 DCJTB, Rubrene, or PtOEP; in this embodiment, in terms of polymer light-emitting materials Department of Dow Chemical Company (DOW Chemical) can produce blue light Bhje j material, in the small molecule light-emitting materials are selected to produce green light C545T and red light DCJTB materials, and Biue j and C545T and DCJTB materials The mixing ratio is 1: 〇07 · · 〇〇04, and the thickness of the light emitting layer 30 is preferably 600 angstroms (A). Making the hole barrier layer 40: 10 In terms of material selection, small molecular materials or polymers can be used. Made of materials, the former such as BCP, TPBI, the latter such as F8_TFB; and in this embodiment The TPBI small-molecule material is selected by film-forming processing (such as: evaporation, sputtering) on the light-emitting layer 30 to obtain a thickness between 5 and 1000 Angstroms (A), and the hole can be limited to the light emission. The thickness of the thin film in the layer 30 is better than the thickness of the hole barrier layer 40 in Angstrom (A). In addition, when it is made of a polymer material, the film formation method is the same as the wet process described above. Fabrication of electron injection layer 50: a small molecule material is formed on the hole barrier layer 40 through a film forming process (such as steam ore or sputtering) —a thin film with a thickness between 5 and 5 angstroms = this embodiment In the example, the material of the hole blocking layer 40 is taken as an example. Fabrication of cathode 60: The single-layer or multi-layer structure with a thickness of 1000 to 5 Angstroms (A) and a thickness of 1000 to 5 Angstroms (A) is prepared on the electron injection layer 50 by steaming or _ method. The material can be aluminum (A1) or silver (Ag). And other metal materials, and the material used to form the multilayer structure can be calcium (Ca) / Ming (A1), barium (Ba) / Ming (A1), about ( Ca) / magnesium-aluminum mixture (Mg: A1) or barium (Ba) / magnesium-aluminum mixture (Mg: A1) and other composite metal materials; 5 In this embodiment, it is made of calcium (CaV aluminum (A1) composite metal The thickness of the cathode 60 is 400 Angstroms (A), and the thickness of Shao (A) is preferably 1000 Angstroms (A). The above is the organic electroluminescent device of the present invention. Structure and manufacturing method 'and after the film formation of the organic layer, the encapsulation process is repeated to prevent the moisture in the external atmosphere from contacting with the electrode to cause oxidation, and further protect the performance of the internal organic layer. In addition, a layer of desiccant can be used to enhance the effect of preventing electrode oxidation. The organic electroluminescent device 100 of the present invention has an anode 12 and a cathode 6. 15 When subjected to an external bias (voltage is 10V, current intensity is 50mA / cm2), it will promote holes and electrons in a light emitting layer made of polymer materials and small molecular materials in a weight ratio of 3%. Recombination occurs in the process, which in turn stimulates others: the blue light emitted by the material causes the C545T material and the DCJTB material to emit green and red light. After mixing the three color lights, a continuous full-wavelength white light with a three-band wavelength characteristic can be obtained. (Refer to Fig. 5), the CIE block of βHai white light is X- 0.30, y = 033 ', that is, the color purity of white light is good, and it is also explained that the organic electroluminescent device 100 of the present invention emits light The brightness can reach 6500cd / m2, and has the advantage of obtaining higher power efficiency (5 · 61 m / w) at a lower voltage. -9 «1236312 As mentioned above, the organic electro-excitation light of the present invention The device 100 has the advantages of simplifying the process and easy to control the production of the lysine in the production of rigid sections (including the production of the hole transmission layer and the light-emitting layer) by the wet process. Impurity concentration of organic molecules The lack of easy control, and the white light emitted by the organic electroluminescent device 100 of the present invention is not easy to produce a color cast with the change of the voltage conversion surface, which is good. &Quot; In addition, the light emitting layer 3 of the present invention 3 (M is made of polymer light-emitting materials with appropriate proportions and doped with two light-coloring and small-molecule light-emitting materials with mutual compatibility. In order to generate self-correction, the obtained grade is a continuous full wavelength with three peaks (refer to Figure 5 for reference) ), The position of each of the peaks is exactly the same as that of the light transmittance of the color filter (refer to FIG. 6), so 'the organic electro-excitation display L _ of the present invention can be used to obtain a full-color # ,, and Be panel. 15 Therefore, the present invention is really progressive in similar products. It is clear that there is no same process and structure before the application. Seen in the publication or as described in the above. And the scope of patent application is as follows :: It is included in the patent scope of the present invention. Ying Diao -10- 20 1236312 [Brief description of the drawings] The first figure is a cross-sectional view of the structure of a conventional organic electroluminescent device. The second figure is a structural diagram of another conventional organic electro-optic device. The third figure is a manufacturing flowchart of the present invention. The fourth figure is a structural diagram of a preferred embodiment of the present invention. The fifth diagram is a schematic diagram of the light wavelength when the light-emitting device of the present invention generates white light. The sixth diagram is a schematic diagram of the light transmittance of a color filter, which can be used in conjunction with the light-emitting device of the present invention.
10 【主要元件符號說明】 100 有機電激發光裝置 10 基板 12 陽極 20 電洞傳輸層 15 30 光發射層 40 電洞阻隔層 50 電子注入層 60 陰極 -11- 2010 [Description of main component symbols] 100 Organic electroluminescent device 10 Substrate 12 Anode 20 Hole transmission layer 15 30 Light emission layer 40 Hole barrier layer 50 Electron injection layer 60 Cathode -11- 20