1265968 九、發明說明： 【發明所屬之技術領域】 本發明係、關於-種$合物及其單層電致光薄M，特別是 係關於-種非全共輛接枝聚合物及其可調變光色之單 致光薄膜。 … 【先前技術】 電致發光元件（例如發光二極體等）在施加電場時可發射 出光束。目可產業上的分子發光二極體主要係利用小分子 或聚合物的有機物質製造成發光元件之多層電致光薄膜。 相較於使用無機材料（例如氮化鎵或神化鎵等）製備電致光 薄膜之發光元件，這類使用有機聚合物之發光元件的製程 較簡單且可產生大面積全彩顯示器。特而言之，有機聚合 物易於從溶液製備可撓曲的薄膜，有利於 ^ 顯示器之製造和應用。 铫曲 應用於發光元件之聚合物主要係全共㈣合物，其骨架 (backbone)具有連續延伸之兀鍵電子軌域網路其中連續延伸 之π鍵網路可依著聚合物骨架來傳遞電子。目前產業界使 用=全共輛聚合物主要有聚對苯基伸乙烯基（PPV)、聚二烧 基苟（PF)、聚對-伸苯基（ρρρ)及聚嗟吩等聚合物。 【發明内容】 本^月之主要目的係提供—種非全共1厄接枝聚合物及其 可調變光色之單層電致光發光薄膜。 為了達成上述之目的，本發明揭示一種非全共軛接枝聚 合物及其可調變光色之單層電致光薄膜。該非全共輛接枝 H.AHU\HYG\ 中山大學\93862\93862.加(： 1265968 聚合物具有下列之分子結構：1265968 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a compound and a single layer electro-optic thin film M, in particular to a non-common carrier graft polymer and A monochromatic film that modulates light color. [Prior Art] An electroluminescence element (e.g., a light-emitting diode or the like) emits a light beam when an electric field is applied. Molecular light-emitting diodes in the industrial field are mainly made of a multi-layer electroluminescent film of a light-emitting element using an organic substance of a small molecule or a polymer. Such a light-emitting element using an organic polymer is simpler in process and can produce a large-area full-color display than a light-emitting element in which an electroluminescent film is prepared using an inorganic material such as gallium nitride or gallium arsenide. In particular, organic polymers are easy to prepare flexible films from solutions, which facilitates the manufacture and application of displays. The polymer applied to the illuminating element is mainly a total (four) compound, and the backbone has a continuously extending 兀 bond electronic trajectory network. The continuously extending π-bond network can transfer electrons according to the polymer skeleton. . At present, the industry uses = all of the polymer mainly includes poly(p-phenylene vinylene) (PPV), polydialkyl fluorene (PF), poly-p-phenylene (ρρρ) and polybenzazole. SUMMARY OF THE INVENTION The main purpose of this month is to provide a single-layer electroluminescent film which is not a total of 1 angstrom graft polymer and its tunable color change color. In order to achieve the above object, the present invention discloses a non-fully conjugated graft polymer and a single layer electroluminescent film of which a variable color is tunable. The non-common vehicle graft H.AHU\HYG\ Zhongshan University\93862\93862. Plus (: 1265968 polymer has the following molecular structure:
該聚合物包含一具有懸垂基R1、R2之第一單體以及一具 有懸垂基R3、R4之第二單體，而仍值係該第一單體的莫耳 分率。懸接於該聚合物之骨架上的三氟甲基（CF3)中斷了該 聚合物之電荷共軛結構，因此該聚合物的電荷共軛結構僅 為局部性並不延伸到整個分子鏈。較佳地，R1係為羥基， R2係氫，R3與R4則為癸基氧基。實質上，該聚合物亦可視 為含有不同懸垂基之均聚物。此外，該聚合物之黏度係 取决於懸接在笨環上之懸垂基種類以及該第一單體與該第 一單體之莫耳分率（即二者之含量）。 本發明的可調變光色之單層電致光薄膜係由該非全共軛 接枝聚合物構成。當該第一單體之莫耳分率大於或等於〇 5 時，該單層電致光薄膜可發射出綠色光或近藍色光。當該 第-單體之莫耳分率小於0.5時，該單層電致㈣膜可發射 出白光。因此，發明了可調變光色及發白色光的單層Μ 共輛發光二極體。 相較於習知技藝使用全共軛聚合物製備多層電致光薄 膜，本發明係使用非全共輛接枝聚合物製備可調變光色之 單層電致光薄膜。藉由改變懸接於苯環上之懸垂基種類以 及該第-單體之莫耳分率，本發明可調整該單層電致光薄 胺之發光波長'產生不同的發光顏色，並發出照明通用的 H:\HU\HYG\ 令山大學仞862仞862 d〇c 1265968 白色光。 【實施方式】 圖1顯示本發明之非全共軛接枝聚合物20〇w2-fUlly conjugated graft polymer)之分子結構。該聚合物20係由二個相同 骨架（backbone)之第一單體22與第二單體24共聚合而成，而 該第一單體22與第二單體24具有不同的懸垂基（pendant)。懸 接於該聚合物20的骨架上之三氟甲基（trifluoromethyl，CF3)中 斷了該聚合物20之電荷共軛結構，因此該聚合物20僅具有 局部之電荷共軛。換言之，該聚合物20之分子單體具有二 個局部電荷共軛的分子結構。特而言之，該聚合物20係一 非全共軛接枝共聚合物0⑽-folly conjugated graft copolymer)。 懸垂基R1、R2、R3及R4係選自氫、羥基（hydroxy，OH)及 烧氧基（alkoxy)組成之化學基團。烧氧基之分子式為 CKCnHh-i)，例如：η = 1時之甲基氧基（methoxy)或η = 2之乙 基氧基（ethoxy)。較佳地，R1係為經基，R2係氫，而R3與R4 則為癸基氧基（decyloxyl，〇C10H21)。分子結構中之m值係代 表該第一單體22之莫耳分率（m〇lar fraction)，而（1 -m)代表該第 二單體24之莫耳分率。當m值等於1時，即表示該聚合物20 係完全地由該第一單體22聚合而成，如圖2(a)所示。相對 地，當m值等於0時，表示該聚合物20係完全地由該第二單 體24聚合而成，如圖2(b)所示。此外，該聚合物20之黏度係 取決於懸接在苯環上之懸垂基種類和該第一單體22與該第 二單體24之莫耳分率（即二者之含量）。 圖3係本發明之發光二極體之光激光（photoluminescence，PL) H:\HU\HYG\ 中山大學\93862\93862.(1〇〇 1265968 光4圖’纟中该光激光薄膜為_單層聚合物薄膜。該單層 光致光薄膜係由該聚合物20構成，其係將不同莫耳分率 所值）之第一單體22與第二單體24以化學合成方式聚合成聚 合物，再以旋轉塗佈方式分佈於一石英基板上形成該聚合 物20的光激光樣品。之後，再以波長為363奈米之激發光照 射該單層光致光薄膜，並量測其受光激發而發射之光激光 發射強度。如圖所示，當該第一單體22之莫耳分率大於或 等於〇.5(即1、0.75及0_5)時，該單層光致光薄膜在波長54〇 奈米附近有一強訊號峰，產生綠色光或近藍色光。而當該 第一單體22之莫耳分率小於0.5時，該光致光薄膜在波長介 於400至700奈米之間形成一連續之可見光譜，即產生白光。 圖4係本發明之發光二極體4〇之示意圖。如圖4所示，該 發光二極體包含一氧化銦錫（Indium Tin Oxide，ITO)基板42、 一没置於該氧化銦錫基板42上之單層電致光薄膜44以及一 設置於該單層電致光薄膜44上之鋁薄膜46。該單層電致光 薄膜44係由該聚合物20所構成，其係使用不同莫耳分率之 第一單體22與第二單體24經由化學聚合反應形成該聚合物 20，再以旋轉塗佈方式將該聚合物20塗佈於該氧化銦錫基 板42上以形成該單層電致光薄膜44，其中該氧化銦錫基板 42亦作為電洞注入極。之後，再以真空蒸鍍的方式形成該 鋁薄膜46於該單層電致光薄膜44上，作為電子注入極。 圖5及圖6係本發明之發光二極體40之電激光 (electroluminescence，EL)光譜圖與電壓-電流的電性關係圖。如 圖5所示，當該第一單體22之之莫耳分率為1時，該發光二 H:\HU\HYG\ 中山大學\93862\93862.(1<^: 1265968 極體40之電激光發射光波長為㈣奈米 光。當該第-單體22之莫耳分率由丨漸減為。時 極體4〇之發射㈣度在波長為彻奈域料漸增加，接近 白光。如圖6所示，該發光二極體4〇具有一般二極體之啟始 電性，且其啟始電壓約為6伏特。 圖係么明之發光一極體40之CIE色度座標圖（c正 ehK)matidtydiagram)’其中施加之電壓為9伏特。如圖7所示， 當該第-單體22之莫耳分率為5時，對應之色度 座標分別為為(0.25, 〇.53)、（0.23, 〇 一綠色光或近籃色光。當該第-單體22之莫耳分率^2為5 及0時’對應之色度座標分別為（〇.24,〇 3 〇及（〇·24,〇 3〇) ’ 位於白光區域中。 換言之，若該單層電致光薄膜44之第一單體“的莫耳分 率大於或等於G.5日^ ’該單層電致光薄膜44可發出綠色光戍 近藍色光’而當該第-單體22之莫耳分率小㈣辦，該單 層電致光薄膜44可發出白光。特而言之，當該單層電致光 薄膜44之第—單體22的莫耳分率為_，該單層電致光薄膜 44所發射之白光的色度座標（g.24,g.3g)非常接近純白光之 (0.33,0.33) 〇 相車乂於自知技藝使用全共概聚合物製# μ 膜本^月係使用该非全共輛接枝聚合物製備該單層電 ，光，膜44。藉由改變懸接於苯環上之懸垂基種類以㈣ 弟-早體22之莫耳分率，本發明除了可調整該聚合物⑼之 黏度外’亦可調整該單層電致光薄膜44之發光波長，並達 H:\HU\HYG\ 中山大學\93862\93862.£1〇£： -10 - 1265968 到發出白光的功能。 【圖式簡單說明】 圖1、圖2(a)及圖2(b)顯示本發明之非全共軛接枝聚合物 之分子結構； 圖3係本發明之發光二極體之光激光（PL)光譜圖； 圖4係本發明之發光二極體之示意圖； 圖5及圖6係本發明之發光二極體之電激光（EL)光譜圖與 電壓-電流關係圖，以及 圖7係發明之發光二極體之CIE色度座標圖。 【主要元件符號說明】 20聚合物 22第一單體 24第二單體 40發光二極體 42氧化銦錫基板 44單層電致光薄膜 46鋁薄膜 H:\HU\HYG\ 中山大學\93862\93862.(1〇〇 -11 -The polymer comprises a first monomer having pendant groups R1, R2 and a second monomer having pendant groups R3, R4, while still being the molar fraction of the first monomer. The trifluoromethyl group (CF3) suspended on the backbone of the polymer interrupts the charge conjugated structure of the polymer, so that the charge conjugated structure of the polymer is only local and does not extend throughout the molecular chain. Preferably, R1 is a hydroxyl group, R2 is a hydrogen, and R3 and R4 are a mercaptooxy group. In essence, the polymer can also be considered as a homopolymer containing different pendant groups. In addition, the viscosity of the polymer depends on the type of pendant which is suspended on the abbreviated ring and the molar fraction of the first monomer and the first monomer (i.e., the content of both). The tunable color-changing single-layer electroluminescent film of the present invention is composed of the non-fully conjugated graft polymer. When the molar fraction of the first monomer is greater than or equal to 〇 5 , the single-layer electroluminescent film can emit green light or near-blue light. When the mole fraction of the first monomer is less than 0.5, the single-layer electro (tetra) film emits white light. Therefore, a single-layer Μ common light-emitting diode with adjustable light color and white light is invented. The use of a fully conjugated polymer to prepare a multilayer electroluminescent film compared to the prior art utilizes a non-commonly grafted polymer to produce a single layer electroluminescent film of variable color. By changing the type of the pendant group suspended on the benzene ring and the molar fraction of the first monomer, the present invention can adjust the light-emitting wavelength of the single-layer electroluminescent thin amine to generate different luminescent colors and emit illumination. General H:\HU\HYG\ Lingshan University 仞862仞862 d〇c 1265968 White light. [Embodiment] Fig. 1 shows the molecular structure of a 20〇w2-fUlly conjugated graft polymer of the present invention. The polymer 20 is formed by copolymerizing a first monomer 22 of two identical backbones with a second monomer 24, and the first monomer 22 and the second monomer 24 have different pendant groups (pendant) ). The trifluoromethyl (CF3) suspended on the backbone of the polymer 20 interrupts the charge conjugated structure of the polymer 20, so that the polymer 20 has only a partial charge conjugation. In other words, the molecular monomer of the polymer 20 has a molecular structure in which two partial charges are conjugated. In particular, the polymer 20 is a non-conjugated graft copolymer (0)-folly conjugated graft copolymer. The pendant groups R1, R2, R3 and R4 are selected from the group consisting of hydrogen, hydroxyl (OH) and alkoxy. The alkyl group of the alkoxy group is CKCnHh-i), for example, a methoxy group of η = 1 or an ethoxy group of η = 2. Preferably, R1 is a trans-group, R2 is hydrogen, and R3 and R4 are a decyloxyl (〇C10H21). The m value in the molecular structure represents the m〇lar fraction of the first monomer 22, and (1 - m) represents the molar fraction of the second monomer 24. When the m value is equal to 1, it means that the polymer 20 is completely polymerized from the first monomer 22, as shown in Fig. 2(a). In contrast, when the m value is equal to 0, it means that the polymer 20 is completely polymerized from the second monomer 24, as shown in Fig. 2(b). Further, the viscosity of the polymer 20 depends on the type of the pendant group suspended on the benzene ring and the molar fraction of the first monomer 22 and the second monomer 24 (i.e., the contents of both). 3 is a photoluminescence (PL) of the light-emitting diode of the present invention. H:\HU\HYG\ Sun Yat-sen University\93862\93862. (1〇〇1265968 光4图'纟 The light laser film is _ single a layered polymer film. The single layer photo-photo film is composed of the polymer 20, which is obtained by chemically synthesizing the first monomer 22 and the second monomer 24 of different molar fractions into a polymerization. The light laser sample of the polymer 20 is formed by spin coating on a quartz substrate. Thereafter, the single-layer photo-photosensitive film is irradiated with an excitation light having a wavelength of 363 nm, and the intensity of the laser light emitted by the light-excited light is measured. As shown, when the Mohr fraction of the first monomer 22 is greater than or equal to 〇.5 (ie 1, 0.75 and 0_5), the single-layer photo-photo film has a strong signal near the wavelength of 54 〇 nanometer. Peak, producing green or near-blue light. When the Mohr fraction of the first monomer 22 is less than 0.5, the photo-photosensitive film forms a continuous visible spectrum at a wavelength of from 400 to 700 nm, i.e., produces white light. Fig. 4 is a schematic view showing a light-emitting diode of the present invention. As shown in FIG. 4, the LED includes an Indium Tin Oxide (ITO) substrate 42 , a single-layer electro-optic film 44 not disposed on the indium tin oxide substrate 42 , and a The aluminum film 46 on the single layer electroluminescent film 44. The single-layer electroluminescent film 44 is composed of the polymer 20, which is formed by chemical polymerization of the first monomer 22 and the second monomer 24 having different molar fractions, and then rotated. The polymer 20 is coated on the indium tin oxide substrate 42 to form the single-layer electro-optic film 44, wherein the indium tin oxide substrate 42 also serves as a hole injection electrode. Thereafter, the aluminum thin film 46 is formed on the single-layer electroluminescent film 44 by vacuum evaporation as an electron injecting electrode. Fig. 5 and Fig. 6 are diagrams showing the electrical relationship between the electroluminescence (EL) spectrum and the voltage-current of the light-emitting diode 40 of the present invention. As shown in FIG. 5, when the Mohr fraction of the first monomer 22 is 1, the illuminating two H:\HU\HYG\ Zhongshan University\93862\93862. (1<^: 1265968 polar body 40 The wavelength of the electric laser emitting light is (four) nanometer light. When the molar fraction of the first monomer 22 is gradually reduced from 丨, the emission (four) degree of the polar body 4 渐 gradually increases in the wavelength of the Chennai domain, and is close to white light. As shown in FIG. 6, the light-emitting diode 4 has the initial electrical conductivity of a general diode, and its starting voltage is about 6 volts. The CIE chromaticity coordinate diagram of the light-emitting diode 40 of the system is shown. Positive ehK) matidtydiagram) 'The voltage applied is 9 volts. As shown in FIG. 7, when the Mohs fraction of the first unit 22 is 5, the corresponding chromaticity coordinates are (0.25, 〇.53), (0.23, 〇1 green light or near basket color light, respectively. When the Mohr fraction of the first unit 22 is 5 and 0, the corresponding chromaticity coordinates are (〇.24, 〇3 〇 and (〇·24, 〇3〇)' are located in the white light region. In other words, if the first monomer of the single-layer electroluminescent film 44 has a molar fraction greater than or equal to G.5 days, the single-layer electroluminescent film 44 can emit a green light near blue light. When the moiety fraction of the first monomer 22 is small (four), the single-layer electroluminescent film 44 can emit white light. In particular, when the monolayer electro-optic film 44 is the first monomer 22 The ear fraction is _, and the chromaticity coordinates (g.24, g.3g) of the white light emitted by the single-layer electroluminescent film 44 are very close to that of pure white light (0.33, 0.33). The whole composite polymer system #μ膜本本月 uses this non-common vehicle graft polymer to prepare the single layer of electricity, light, film 44. By changing the type of suspension base suspended on the benzene ring to (4) - the molar fraction of the early body 22, in addition to the present invention The viscosity of the polymer (9) can be adjusted to adjust the light-emitting wavelength of the single-layer electro-optic film 44 to H:\HU\HYG\ Zhongshan University\93862\93862. £1〇£: -10 - 1265968 The function of emitting white light. [Simple description of the drawings] Fig. 1, Fig. 2(a) and Fig. 2(b) show the molecular structure of the non-fully conjugated graft polymer of the present invention; FIG. 4 is a schematic diagram of the light-emitting diode of the present invention; FIG. 5 and FIG. 6 are diagrams showing the relationship between the electric laser (EL) spectrum and the voltage-current of the light-emitting diode of the present invention. Figure 7 and Figure 7 show the CIE chromaticity coordinate diagram of the light-emitting diode of the invention. [Main component symbol description] 20 polymer 22 first monomer 24 second monomer 40 light-emitting diode 42 indium tin oxide substrate 44 single Layer electro-optic film 46 aluminum film H:\HU\HYG\ Zhongshan University\93862\93862.(1〇〇-11 -