疊層式有機(jī)發(fā)光二極管的電荷產(chǎn)生層及界面的研究
發(fā)布時(shí)間：2019-07-02 20:30
【摘要】：有機(jī)發(fā)光二極管(OLED)以其自發(fā)光,對(duì)比度大,視角廣,響應(yīng)時(shí)間快和工作溫度范圍寬的特點(diǎn)已被成功地應(yīng)用于平板顯示領(lǐng)域。為了降低顯示面板的制造成本,大尺寸化是當(dāng)前OLED技術(shù)應(yīng)用的發(fā)展趨勢(shì)。大尺寸OLED面板的全彩色顯示采用白光OLED(WOLED)與彩色濾光片組合的方式,其中WOLED為疊層式OLED,即由多個(gè)發(fā)光單元在垂直方向上用電荷產(chǎn)生層連接而成。相比傳統(tǒng)OLED,疊層式OLED的應(yīng)用可提高面板的發(fā)光效率和工作壽命,降低面板的短路幾率。電荷產(chǎn)生層是疊層式OLED的核心,其電荷產(chǎn)生與分離效率,工作穩(wěn)定性,透光性以及制備工藝關(guān)系到器件乃至整個(gè)面板的效率,壽命和成本。論文以發(fā)展用于大尺寸OLED顯示面板的高效穩(wěn)定的疊層式器件為目標(biāo),從結(jié)構(gòu),機(jī)理,材料和工藝方面對(duì)疊層式OLED的電荷產(chǎn)生層及界面做了深入的研究。首先,針對(duì)傳統(tǒng)有機(jī)n/p摻雜型電荷產(chǎn)生層的穩(wěn)定性差和工藝復(fù)雜的問(wèn)題,論文提出了基于有機(jī)p型摻雜層NPB:F4-TCNQ和超薄電子注入層Liq/Al的綜合性能優(yōu)異的新型電荷產(chǎn)生層Liq/Al/NPB:F4-TCNQ,電荷產(chǎn)生與分離效率高,可見(jiàn)光區(qū)域透光率超過(guò)90%,長(zhǎng)期工作穩(wěn)定性高,且制備工藝簡(jiǎn)單。通過(guò)對(duì)電荷產(chǎn)生與分離的機(jī)理研究,發(fā)現(xiàn)提高Al的蒸鍍速率,F4-TCNQ的摻雜濃度,以及增加界面層可以促進(jìn)能級(jí)匹配,降低電荷分離能壘,獲得優(yōu)化的電荷產(chǎn)生層liq/al/f4-tcnq/npb:f4-tcnq。將該電荷產(chǎn)生層應(yīng)用于基于蒸鍍和溶液法工藝的疊層式woled,不僅降低了woled的制備成本,而且可以通過(guò)改變有機(jī)p型摻雜層的厚度調(diào)節(jié)woled的光色。其次,針對(duì)n型銦鎵鋅氧化物薄膜晶體管與倒置式oled結(jié)合用于大尺寸顯示面板的特點(diǎn),論文著重研究了傳統(tǒng)的單發(fā)光單元的和疊層的倒置式oled的效率和穩(wěn)定性。傳統(tǒng)電子注入層cs2co3易被空氣氧化,電子注入穩(wěn)定性差,而論文提出的新型電子注入層al/cs2co3,通過(guò)簡(jiǎn)單地插入一層超薄的al,與cs2co3形成穩(wěn)定的al-o-cs化合物,大幅提高了倒置式oled的穩(wěn)定性。針對(duì)疊層的倒置式oled的特點(diǎn),論文提出了采用非摻雜型p/n異質(zhì)結(jié)moo3/al/cs2co3的電荷產(chǎn)生層,其中的p型組件采用moo3與咔唑類(lèi)主體材料的搭配,可同時(shí)又作為空穴傳輸層,簡(jiǎn)化了疊層式器件結(jié)構(gòu);中間1nm的插層al可顯著提高電荷產(chǎn)生層的電荷分離能力與穩(wěn)定性,這主要是由于插層al可以有效地防止cs2co3與moo3發(fā)生化學(xué)反應(yīng)形成耗盡層。最后,由于溶液法工藝相比熱蒸鍍工藝更易于實(shí)現(xiàn)大尺寸化且可柔性化的面板,論文對(duì)基于溶液法制備電荷產(chǎn)生層及疊層式oled器件的關(guān)鍵性問(wèn)題做了探索性研究,包括空穴注入層和電子注入層的溶液法制備,以及電荷產(chǎn)生層的溶液法工藝。空穴注入層由moo3粉末直接溶解在氨水中形成的澄清透明溶液,旋涂后在空氣中經(jīng)150°C低溫退火形成薄膜。此空穴注入層具有納米柱狀結(jié)構(gòu),可以獲得比PEDOT:PSS和蒸鍍的MoO3更好的空穴注入能力。另一種空穴注入材料是由HATCN溶解在乙腈溶劑中形成的透明溶液,采用該溶液制的薄膜也具有較強(qiáng)的空穴注入能力。電子注入層是由ZnO粉末與甲酸在氨水催化作用下制備而成,在空氣中經(jīng)低溫退火后具有很強(qiáng)的電子注入能力。X射線單晶衍射等結(jié)果表明薄膜中形成了金屬-有機(jī)骨架(MOF)[(H3O)Zn(HCOO)3]∞,具有強(qiáng)電負(fù)性和吸電子性的甲酸根吸附在電極表面,形成指向MOF薄膜的偶極子,降低了電極的表面功函數(shù)。以MOF[(H3O)Zn(HCOO)3]∞與PEIE混合作為n型組件,HATCN的乙腈溶液為p型組件,實(shí)現(xiàn)了溶液法電荷產(chǎn)生層MOF:PEIE/HATCN。電荷注入層和電荷產(chǎn)生的溶液法工藝,不僅降低了OLED的制備成本,而且在其他有機(jī)電子器件中也具有廣闊的應(yīng)用。
[Abstract]:The organic light-emitting diode (OLED) has been successfully applied to the field of flat panel display with its self-luminescence, high contrast, wide viewing angle, fast response time and wide operating temperature range. In order to reduce the manufacturing cost of the display panel, the large-size is the developing trend of the current OLED technology application. The full color display of the large-size OLED panel is in the form of a white light OLED (WOLED) and a color filter, wherein the WOLED is a stacked OLED, that is, a plurality of light emitting units are connected in a vertical direction with a charge generating layer. Compared with the traditional OLED, the application of the laminated OLED can improve the light-emitting efficiency and the working life of the panel, and reduce the short-circuit probability of the panel. The charge generation layer is the core of the laminated OLED, and the charge generation and separation efficiency, the working stability, the light transmission and the preparation process are related to the efficiency, the service life and the cost of the device and the whole panel. In order to develop a highly effective and stable laminated device for large-size OLED display panel, the charge generation layer and the interface of the laminated OLED are studied in terms of structure, mechanism, material and process. First, a novel charge generation layer Liq/ Al/ NPB: F4-TCNQ with excellent comprehensive performance of the organic p-type doped layer NPB: F4-TCNQ and the ultra-thin electron injection layer Liq/ Al is proposed for the problems of poor stability and complex process of the conventional organic n/ p-doped type charge generation layer, and the charge generation and separation efficiency are high, The light transmittance of the visible light region is more than 90 percent, the long-term working stability is high, and the preparation process is simple. By studying the mechanism of charge generation and separation, it is found that increasing the deposition rate of Al, the doping concentration of F4-TCNQ, and increasing the interface layer can promote the energy level matching, reduce the charge separation energy base, and obtain the optimized charge generation layer liq/ al/ f4-tcnq/ npb: f4-tcnq. The application of the charge generation layer to a laminated type wled based on a vapor deposition and solution process process not only reduces the cost of preparation of the wled, but can adjust the light color of the oled by changing the thickness of the organic p-type doped layer. In this paper, the efficiency and stability of the conventional single-light-emitting unit and the laminated inverted-type oled are studied in this paper, for the characteristics of the n-type zinc-doped zinc oxide thin film transistor and the inverted-type oled for large-size display panel. The conventional electron injection layer cs2co3 is easily oxidized by air and the stability of the electron injection is poor, and the novel electron injection layer al/ cs2co3 proposed in the paper can form a stable al-o-cs compound with the cs2co3 by simply inserting a layer of ultra-thin al, and the stability of the inverted oled is greatly improved. In this paper, a charge generation layer with a non-doped p/ n heterojunction moov 3/ al/ cs2co3 is proposed in this paper. The p-type component is used with the combination of the moo3 and the bulk material, and can be used as the hole transport layer at the same time, and the structure of the stacked device is simplified. The intercalation al at the middle of 1 nm can significantly improve the charge separation ability and stability of the charge-generating layer, which is mainly due to the fact that the intercalation al can effectively prevent the c2co3 and the moo3 from being chemically reacted to form a depletion layer. In the end, due to the fact that the process of the solution process is easier to realize the large-size and flexible panel compared with the hot-vapor deposition process, the key problem of the charge generation layer and the laminated-type oled device prepared on the basis of the solution method is explored, Includes a hole injection layer and an electron injection layer, and a solution process process of the charge generation layer. The hole injection layer is directly dissolved in the clear transparent solution formed in the ammonia water by the moo3 powder, and the film is formed at a low temperature of 150 DEG C in the air after spin coating. The hole injection layer has a nano-columnar structure, and a better hole injection capability than that of the PEDOT: PSS and the vapor-deposited MoO3 can be obtained. The other hole injection material is a transparent solution formed by dissolving the HATCN in an acetonitrile solvent, and the film prepared by the solution also has a strong hole injection capability. The electron injection layer is prepared from ZnO powder and formic acid under the action of ammonia water, and has strong electron injection capability after low-temperature annealing in air. The results of X-ray single crystal diffraction show that the metal-organic framework (MOF)[(H3O) Zn (HCOO)3] is formed in the film, and a strong electronegativity and electron-absorbing formate is adsorbed on the surface of the electrode to form a dipole which is directed to the MOF film, and the surface work function of the electrode is reduced. The solution method charge generation layer MOF: PEE/ HATCN is realized by mixing the MOF[(H3O) Zn (HCOO)3] and the PEE as n-type components and the acetonitrile solution of the HATCN as the p-type component. The process of the charge injection layer and the charge generation solution method not only reduces the preparation cost of the OLED, but also has a wide application in other organic electronic devices.
【學(xué)位授予單位】：上海交通大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TN383.1
，
本文編號(hào)：2509209
[Abstract]:The organic light-emitting diode (OLED) has been successfully applied to the field of flat panel display with its self-luminescence, high contrast, wide viewing angle, fast response time and wide operating temperature range. In order to reduce the manufacturing cost of the display panel, the large-size is the developing trend of the current OLED technology application. The full color display of the large-size OLED panel is in the form of a white light OLED (WOLED) and a color filter, wherein the WOLED is a stacked OLED, that is, a plurality of light emitting units are connected in a vertical direction with a charge generating layer. Compared with the traditional OLED, the application of the laminated OLED can improve the light-emitting efficiency and the working life of the panel, and reduce the short-circuit probability of the panel. The charge generation layer is the core of the laminated OLED, and the charge generation and separation efficiency, the working stability, the light transmission and the preparation process are related to the efficiency, the service life and the cost of the device and the whole panel. In order to develop a highly effective and stable laminated device for large-size OLED display panel, the charge generation layer and the interface of the laminated OLED are studied in terms of structure, mechanism, material and process. First, a novel charge generation layer Liq/ Al/ NPB: F4-TCNQ with excellent comprehensive performance of the organic p-type doped layer NPB: F4-TCNQ and the ultra-thin electron injection layer Liq/ Al is proposed for the problems of poor stability and complex process of the conventional organic n/ p-doped type charge generation layer, and the charge generation and separation efficiency are high, The light transmittance of the visible light region is more than 90 percent, the long-term working stability is high, and the preparation process is simple. By studying the mechanism of charge generation and separation, it is found that increasing the deposition rate of Al, the doping concentration of F4-TCNQ, and increasing the interface layer can promote the energy level matching, reduce the charge separation energy base, and obtain the optimized charge generation layer liq/ al/ f4-tcnq/ npb: f4-tcnq. The application of the charge generation layer to a laminated type wled based on a vapor deposition and solution process process not only reduces the cost of preparation of the wled, but can adjust the light color of the oled by changing the thickness of the organic p-type doped layer. In this paper, the efficiency and stability of the conventional single-light-emitting unit and the laminated inverted-type oled are studied in this paper, for the characteristics of the n-type zinc-doped zinc oxide thin film transistor and the inverted-type oled for large-size display panel. The conventional electron injection layer cs2co3 is easily oxidized by air and the stability of the electron injection is poor, and the novel electron injection layer al/ cs2co3 proposed in the paper can form a stable al-o-cs compound with the cs2co3 by simply inserting a layer of ultra-thin al, and the stability of the inverted oled is greatly improved. In this paper, a charge generation layer with a non-doped p/ n heterojunction moov 3/ al/ cs2co3 is proposed in this paper. The p-type component is used with the combination of the moo3 and the bulk material, and can be used as the hole transport layer at the same time, and the structure of the stacked device is simplified. The intercalation al at the middle of 1 nm can significantly improve the charge separation ability and stability of the charge-generating layer, which is mainly due to the fact that the intercalation al can effectively prevent the c2co3 and the moo3 from being chemically reacted to form a depletion layer. In the end, due to the fact that the process of the solution process is easier to realize the large-size and flexible panel compared with the hot-vapor deposition process, the key problem of the charge generation layer and the laminated-type oled device prepared on the basis of the solution method is explored, Includes a hole injection layer and an electron injection layer, and a solution process process of the charge generation layer. The hole injection layer is directly dissolved in the clear transparent solution formed in the ammonia water by the moo3 powder, and the film is formed at a low temperature of 150 DEG C in the air after spin coating. The hole injection layer has a nano-columnar structure, and a better hole injection capability than that of the PEDOT: PSS and the vapor-deposited MoO3 can be obtained. The other hole injection material is a transparent solution formed by dissolving the HATCN in an acetonitrile solvent, and the film prepared by the solution also has a strong hole injection capability. The electron injection layer is prepared from ZnO powder and formic acid under the action of ammonia water, and has strong electron injection capability after low-temperature annealing in air. The results of X-ray single crystal diffraction show that the metal-organic framework (MOF)[(H3O) Zn (HCOO)3] is formed in the film, and a strong electronegativity and electron-absorbing formate is adsorbed on the surface of the electrode to form a dipole which is directed to the MOF film, and the surface work function of the electrode is reduced. The solution method charge generation layer MOF: PEE/ HATCN is realized by mixing the MOF[(H3O) Zn (HCOO)3] and the PEE as n-type components and the acetonitrile solution of the HATCN as the p-type component. The process of the charge injection layer and the charge generation solution method not only reduces the preparation cost of the OLED, but also has a wide application in other organic electronic devices.
【學(xué)位授予單位】：上海交通大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TN383.1
，
本文編號(hào)：2509209
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