【摘要】：有機(jī)發(fā)光二極管顯示器(OLED)具有自發(fā)光、強(qiáng)對(duì)比、大色域、廣視角、快響應(yīng)、高效率、低電壓等優(yōu)點(diǎn),而且適用環(huán)境廣、面板厚度薄、制程簡(jiǎn)單、可制作大尺寸與柔性面板,被譽(yù)為下一代的“夢(mèng)幻顯示器”�！叭芤褐苽洹奔夹g(shù)被認(rèn)為是OLED進(jìn)一步降低成本和實(shí)現(xiàn)大面積的有效途徑,但目前國(guó)際上溶液制備的主要工作和成果集中在有機(jī)功能層上,尚未有采用印刷金屬電極制備OLED顯示屏的相關(guān)技術(shù),因此還不能稱之為OLED的“全溶液制備”技術(shù)。采用完全省去真空蒸鍍環(huán)節(jié)的“全溶液制備”技術(shù)開發(fā)顯示屏,是一項(xiàng)嶄新的科學(xué)領(lǐng)域,更是一個(gè)世界級(jí)的技術(shù)難題。 遴選出高發(fā)光效率的材料是全溶液法制備OLED顯示屏的前提。固體有機(jī)薄膜的光致發(fā)光外量子效率(PLQE)是有機(jī)熒光材料最重要的性能參數(shù)之一。我們成功地設(shè)計(jì)了一套可靠的實(shí)驗(yàn)方法,通過直接推算樣品吸收的光子數(shù)和發(fā)射的光子數(shù),來測(cè)量有機(jī)發(fā)光材料的PLQE。由于取消了測(cè)定樣品吸收率的步驟并革新了算法思想,我們的方法不僅減少了操作步驟和數(shù)據(jù)處理,更避免了復(fù)雜模型和額外假設(shè)所可能帶來的系統(tǒng)誤差。我們的方法可以廣泛應(yīng)用于大部分有機(jī)發(fā)光材料,包括一些其他方法無法測(cè)量或者需要復(fù)雜數(shù)據(jù)處理的樣品,例如高散射薄膜樣品。結(jié)果顯示我們的方法能利用更簡(jiǎn)單的設(shè)備,更容易的操作,更少的數(shù)據(jù)處理來得到更準(zhǔn)確的實(shí)驗(yàn)結(jié)果和更小的偶然誤差區(qū)間。此外,有機(jī)材料的PLQE在不同襯底上的測(cè)量結(jié)果,也顯示了位于金屬/有機(jī)界面的導(dǎo)體對(duì)于PLQE具有強(qiáng)烈的q 滅效應(yīng)。 立足于高效率的聚合物發(fā)光材料,通過結(jié)合多功能緩沖層的制備和精細(xì)陰極的加工,我們首次成功實(shí)現(xiàn)了全溶液法制備高分辨率無源聚合物OLED顯示屏。與其它的印刷方法和印刷材料不同,噴墨打印制備的導(dǎo)電納米顆粒陰極能保證高分辨率的陰極圖案,以及精細(xì)的陰極線的良好導(dǎo)通,且加工過程中不會(huì)對(duì)有機(jī)層產(chǎn)生機(jī)械壓力。緩沖層位于印刷陰極和發(fā)光層之間,由水/醇溶性共軛聚合物——聚[9,9-二辛基芴-9,9-雙(N,N-二甲基胺丙基)芴](PFNR_2)與一種可固化的環(huán)氧樹脂粘合劑共混而成。它能阻止溶劑侵蝕,保證電子注入,并能與陰極墨水保持適當(dāng)?shù)挠H和能力。交聯(lián)結(jié)構(gòu)的緩沖層不僅提升了器件的性能,尤其是極大地降低了漏電流,還導(dǎo)致了一種“線性η-J衰減”的有趣現(xiàn)象,由之能推導(dǎo)出實(shí)用的結(jié)果。制得的紅、綠、藍(lán)單色OLED顯示屏和全彩色OLED顯示屏像素結(jié)構(gòu)為96×3×64,無壞點(diǎn)壞線。經(jīng)過最優(yōu)化的燒結(jié)工序后,納米銀墨水形成連續(xù)性好、無缺陷、低電阻的陰極行,且無任何形變。在紅、綠、藍(lán)顯示中,電流效率分別為0.62、4.38、0.93 cd/A,色坐標(biāo)分別為(0.63, 0.37)、(0.39, 0.57)、(0.18, 0.16)。全溶液加工消除了對(duì)高真空熱蒸鍍陰極金屬的依賴,為實(shí)現(xiàn)工業(yè)化的“卷對(duì)卷”方式生產(chǎn)平板顯示器鋪平了道路。 在噴墨打印OLED發(fā)光材料和電極材料的研究中我們發(fā)現(xiàn),固液界面的潤(rùn)濕性問題是全溶液技術(shù)面臨的一項(xiàng)重要科學(xué)問題。我們以超疏水表面上的水滴這種自然界最常見、最典型的不浸潤(rùn)現(xiàn)象為研究對(duì)象,對(duì)潤(rùn)濕性問題的本質(zhì)進(jìn)行了系統(tǒng)地觀測(cè)和分析。雖然人們普遍認(rèn)為水和超疏水表面之間囚陷著空氣,但一直未能有直接的實(shí)驗(yàn)證據(jù)表明這一微觀層次的空氣的存在。早在1944年Wenzel態(tài)和Cassie態(tài)就已被提出并用于分析超疏水表面,但也由于對(duì)包埋著的界面缺乏直接、定量的觀測(cè),對(duì)于不同情況下究竟哪種態(tài)占主導(dǎo)一直陷于熱議。我們利用激光共聚焦掃描顯微鏡,首次實(shí)現(xiàn)了一種原位的、無損的方法來對(duì)水滴與超疏水表面間的包埋界面進(jìn)行直接的三維成像。其界面間囚陷著的一層十微米級(jí)的空氣墊層被定量觀測(cè),并被證明與超低流動(dòng)阻力有關(guān)。一直以來都無法觀測(cè)和辨別的Wenzel態(tài)和Cassie態(tài),可以通過這種技術(shù)來清楚地觀測(cè)。我們的這種新觀測(cè)方法,可用于對(duì)發(fā)生在氣液固界面間的復(fù)雜現(xiàn)象和微妙過程進(jìn)行探索和調(diào)節(jié),為相應(yīng)的基礎(chǔ)研究和工業(yè)應(yīng)用開辟了一條新的道路。 全溶液法制備OLED的研究中最關(guān)鍵的技術(shù)在于導(dǎo)電陰極的溶液加工,由于目前最適合高分辨率陰極加工的是噴墨打印工藝,因此開發(fā)和優(yōu)化出適用的納米銀導(dǎo)電墨水也就成為首要任務(wù)之一。我們成功發(fā)展了一種環(huán)境友好的“綠色”溶液工藝,來實(shí)現(xiàn)多晶結(jié)構(gòu)的納米銀多面體的大規(guī)模、高產(chǎn)率合成。通過使用單寧酸和聚乙烯基吡咯烷酮(PVP),高質(zhì)量的納米銀多面體可在水相一鍋煮反應(yīng)中生成,而不需任何模板或輔助劑。將生成的納米銀顆粒在不同的溶劑中分散,可得到能滿足不同需要的各種導(dǎo)電墨水。使用導(dǎo)電墨水在剛性和柔性襯底上退火,可以得到高導(dǎo)電的納米銀膜。在玻璃襯底上的銀膜樣品能實(shí)現(xiàn)的最高導(dǎo)電率為8.5×104 S·cm~(-1)。而在PET襯底上,即使退火溫度僅為160°C,銀膜的導(dǎo)電率也能達(dá)到3.6×104 S·cm~(-1)。彎折測(cè)試表明,我們的納米銀膜在經(jīng)過50,000次的反復(fù)彎折后,仍保持導(dǎo)電率基本不變。由于能制成高機(jī)械強(qiáng)度、高導(dǎo)電率、低退火溫度、長(zhǎng)壽命的納米銀膜,我們研制的導(dǎo)電墨水在印刷電子學(xué)和柔性電子器件中具有廣闊應(yīng)用。至此,我們實(shí)現(xiàn)了全溶液法制備OLED中從上游原材料到下游整機(jī)的整個(gè)生產(chǎn)鏈都在本實(shí)驗(yàn)室內(nèi)完成,并將印刷陰極的成本降為使用進(jìn)口導(dǎo)電墨水時(shí)的1/10。
[Abstract]:The organic light-emitting diode display (OLED) has the advantages of self-luminescence, strong contrast, large color gamut, wide viewing angle, fast response, high efficiency, low voltage and the like, and is wide in application environment, thin in panel thickness and simple in process, and can be used for manufacturing large-size and flexible panels, and is regarded as the next-generation "Dream display". The "full solution preparation" technology is considered to be an effective way for the OLED to further reduce the cost and realize large area, but the main work and the result of the solution preparation at present are concentrated on the organic functional layer, and the related technology for preparing the OLED display screen by using the printed metal electrode is not provided, Therefore, it is also not possible to refer to the "full solution preparation" technology of the OLED. It is a brand-new field of science and a world-class technical problem by using the "full solution preparation" technology development display screen which completely omits the vacuum evaporation process. The method for selecting high light-emitting efficiency by the method of the invention is that the OLED display screen is prepared by a full-solution method, The photoluminescence external quantum efficiency (PLQE) of the solid organic thin film is the most important performance parameter of the organic fluorescent material. We have successfully designed a set of reliable experimental methods to measure the PL of the organic light-emitting material by directly calculating the number of photons absorbed by the sample and the number of photons emitted. QE. Our approach not only reduces operational steps and data processing, but also avoids the system that is likely to be brought about by complex models and additional assumptions, as a result of the elimination of the steps to determine the absorbance of the sample and to innovate the algorithm's mind The error. Our approach can be widely used in most of the organic light-emitting materials, including some other methods that are not measurable or require complex data processing, such as high-scattering films The results show that our method can take advantage of simpler equipment, easier operation and less data processing to get more accurate experimental results and less even error in addition, the measurement of the PLQE of the organic material on different substrates also shows that the conductor located at the metal/ machine interface has a strong q-out for the PLQE Based on the high-efficiency polymer light-emitting material, by combining the preparation of the multi-function buffer layer and the processing of the fine cathode, we successfully realized the high-resolution passive polymer OL by the full solution method. the conductive nano-particle cathode prepared by the ink-jet printing can ensure the high-resolution cathode pattern and the fine cathode line in good conduction, and the organic layer can not be produced during the processing process, The buffer layer is located between the printing cathode and the light-emitting layer, and is bonded to a curable epoxy resin by a water/ alcohol-soluble co-polymer _ poly[9,9-dioctylphenyl-9,9-bis (N, N-dimethylamine propyl) benzene] (PFNR _ 2) It can prevent the solvent from being eroded, ensure the electron injection and keep the cathode ink suitable. The buffer layer of the cross-linking structure not only improves the performance of the device, but also greatly reduces the leakage current, and also leads to an interesting phenomenon of the "linear J-J attenuation", which can be deduced The prepared red, green, blue single-color OLED display screen and the full-color OLED display screen pixel structure are 96-3-64, the nano-silver ink forms a cathode row with good continuity, no defect and low resistance after the optimized sintering process, and The current efficiency is 0.62, 4.38, 0.93 cd/ A, respectively (0.63, 0.37), (0.39, 0.57), (0.18, 0.16). The full solution processing eliminates the dependence on the cathode metal for high vacuum thermal evaporation, and the flat panel display is produced for realizing the industrial "volume-to-volume" mode. The road is paved. In the study of ink-jet printing of OLED light-emitting materials and electrode materials, we have found that the wetting problem of the solid-liquid interface is the whole solution technology. The most common and typical non-wetting phenomenon of water droplets on the super-hydrophobic surface is the study object, and the essence of the wettability problem is Systematic observation and analysis. Although it is widely believed that air is trapped between water and superhydrophobic surfaces, there has been no direct experimental evidence that this micro- The existence of the air in the hierarchy has been proposed and used for the analysis of the super-hydrophobic surface in the Wenzel state and the Cassie state in 1944, but also because of the lack of direct and quantitative observation of the embedded interface, which state accounts for different situations The lead has been in hot debate. We use the laser confocal scanning microscope for the first time to realize an in-situ and non-destructive method to feed the embedded interface between the water droplets and the super-hydrophobic surface. a direct three-dimensional imaging. An air cushion layer of a ten-micron level that is trapped between its interfaces is quantitatively observed and is demonstrated to Ultra-low flow resistance. It has been impossible to observe and distinguish the Wenzel state and the Cassie state all the time, and this can be done by this This new method of observation can be used to explore and adjust the complex phenomena and delicate processes occurring in the gas-liquid solid interface, and to open the corresponding basic research and industrial application. A new road is developed. The most critical technique in the preparation of OLED by the solution process is that the solution of the conductive cathode is processed, and since the most suitable for high-resolution cathode processing is the ink-jet printing process, the applicable nano-silver conductive ink is developed and optimized. Water has also become one of the top priorities. We have successfully developed an environment-friendly "green" solution process to realize the nano-silver multi-face of the polycrystalline structure The high-quality nano-silver polyhedra can be generated in a one-pot boiling reaction of the water phase by using tannic acid and polyethylene-based polydioxanone (PVP), and the generated nano-silver particles are dispersed in different solvents, so that the nano-silver particles can be obtained, various conductive inks are required to be annealed on a rigid and flexible substrate using conductive ink, The high conductivity of the silver film sample on the glass substrate is 8.5%. 04S 路 cm ~ (-1). On the PET substrate, even if the annealing temperature is only 160 擄 C, the conductivity of the silver film can reach 3.6%. 04S 路 cm ~ (-1). The bending test shows that our nano-silver film has been bent over 50,000 times. because the nano-silver film with high mechanical strength, high conductivity, low annealing temperature and long service life can be made, the conductive ink developed by the method has the advantages of high mechanical strength, high conductivity, low annealing temperature and long service life, In that electronic device, the whole production chain from the upstream raw material to the downstream complete machine is complete in the laboratory, and the cost of the printing cathode is reduced to the use of the whole production chain of the whole solution method for preparing the OLED from the upstream raw material to the downstream complete machine.
【學(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2011
【分類號(hào)】：TN383.1

【引證文獻(xiàn)】

相關(guān)博士學(xué)位論文 前2條

1 薛善鋒;有機(jī)熒光分子的溶液加工薄膜及器件[D];吉林大學(xué);2012年

2 馮姝;濕法制備的有機(jī)電致發(fā)光小分子薄膜性質(zhì)研究[D];清華大學(xué);2012年

相關(guān)碩士學(xué)位論文 前3條

1 吳緒虎;幾種微納米環(huán)境功能材料的水熱法制備、表征及應(yīng)用[D];安徽大學(xué);2012年

2 柏松虎;基于金屬氧化物TFT的AMOLED顯示屏驅(qū)動(dòng)技術(shù)的研究[D];華南理工大學(xué);2012年

3 王春阜;基于氧化物TFT技術(shù)的AMOLED顯示屏驅(qū)動(dòng)與測(cè)試研究[D];華南理工大學(xué);2013年

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本文編號(hào)：2492204