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      PVK有機薄膜對PF?BT15聚合物發(fā)光二極管性能的影響

      2014-09-17 18:16:58祝秋香肖衛(wèi)初張學(xué)軍簡正波
      現(xiàn)代電子技術(shù) 2014年17期

      祝秋香 肖衛(wèi)初 張學(xué)軍 簡正波

      摘 要: 采用聚乙烯基咔唑(PVK)作為空穴傳輸層,PF?BT15作為發(fā)光層,制備了結(jié)構(gòu)為ITO/PEDOT/ PVK(0~60 nm)/PF?BT15/Cs2CO3/Al的聚合物發(fā)光二極管。通過測試器件的電流密度?電壓?發(fā)光亮度特性,研究了空穴傳輸層厚度對聚合物發(fā)光二級管器件性能的影響,優(yōu)化了器件功能層的厚度匹配。實驗結(jié)構(gòu)表明,聚合物發(fā)光二極管的光電性能與空穴傳輸層的厚度密切相關(guān),當(dāng)轉(zhuǎn)速約為2 000 r/s,濃度約為1%,膜厚約為40 nm時,其器件光電性能有較大的提高。

      關(guān)鍵詞: 聚乙烯基咔唑; FP?BT15; 聚合物發(fā)光二極管; 空穴傳輸層

      中圖分類號: TN710?34 文獻標(biāo)識碼: A 文章編號: 1004?373X(2014)17?0110?03

      Abstract: Taking polyvinyl carbazole as hole transport layer (HTL) and PF?BT15 as light?emitting layer, the polymer light?emitting diodes (PLEDs) with the structure of ITO/PEDOT/PVK(0~60 nm) / PF?BT15/Cs2CO3/Al were fabricated. By testing and analyzing the electric current density?voltage?luminance characteristics, influences of the thickness of HTL on PLED performance was investigated and the thickness matching of the device′s function layer was optimized. Experimental results show that optical and electrical properties of PLED are closely related to the thickness of HTL, and the photoelectric property of the device is improved more significantly when spin speed is about 2 000 r/s, concentration is about 1% and film thickness is 40 nm.

      Keywords: polyvinyl carbazole; FP?BT15; polymer light?emitting diode; HTL

      0 引 言

      聚合物發(fā)光二極管(Polymer Light?Emitting Diodes,PLEDs)是一種由多層有機薄膜結(jié)構(gòu)形成的電致發(fā)光器件,它的制作過程非常簡單,而且驅(qū)動電壓比較低 [1?3]。近年來,由于有機/聚合物發(fā)光材料具有一些特殊的優(yōu)點,比如低驅(qū)動電壓、高發(fā)光效率、能實現(xiàn)全色發(fā)光、良好的成膜性等,在發(fā)光管、平板顯示方面的應(yīng)用引起了人們的高度重視[4?5]。

      1936年,Destriau將有機熒光化合物分散在聚合物中制成薄膜,得到最早的電致發(fā)光器件[6]。在20世紀(jì)60—80年代中期,相繼有美國New York大學(xué)的Pope等人第一次發(fā)現(xiàn)有機材料單晶恩的電致發(fā)光現(xiàn)象[7],Partridge制作出第一個聚合物材料的發(fā)光器件[8],Vincett小組用真空蒸鍍法制成了0.6 μm厚的蒽薄膜[9],有機電致研究徘徊在一個高電壓、低亮度、低效率的水平上。直到1987年,美國柯達公司的C.W.Tang(鄧青云)和VanSlyke采用真空蒸鍍成膜制備出了一種高效的有機小分子發(fā)光二極管(OLED),其亮度達到了1 000 cd/m2,外量子效率高到1%,而驅(qū)動電壓在10 V以下[10]。1990年,Burroughs等人將聚苯撐乙烯(PPV)的預(yù)聚體旋涂成膜[11],制成了單層結(jié)構(gòu)的共軛聚合物電致發(fā)光器件。1992年,美國Uniax公司的Gustafsson、Y. Cao(曹鏞)和Heeger等人在柔性塑料基底上實現(xiàn)了可彎曲的聚合物發(fā)光二極管[12]。這些工作拉開了高分子材料及器件研究的序幕,從此開辟了發(fā)光器件的一個新領(lǐng)域——聚合物發(fā)光二極管(PLEDs)。

      在本文中,采用聚乙烯基咔唑(PVK)作為空穴傳輸層,PF?BT15作為發(fā)光層,制備了結(jié)構(gòu)為ITO/ PEDOT/PVK(0~60 nm)/PF?BT15/Cs2CO3/Al的聚合物發(fā)光二極管。初步研究表明,在空穴注入層和發(fā)光層之間加入一層空穴傳輸層,能提高電流效率,改善器件性能。

      1 實 驗

      聚合物發(fā)光二極管的基本結(jié)構(gòu)屬于夾層式的“三明治式”結(jié)構(gòu),并且一側(cè)為透明電極,以便獲得面發(fā)光,如圖1所示。

      PLEDs的基本結(jié)構(gòu)主要由透明導(dǎo)電玻璃ITO陽極、聚合物發(fā)光層和金屬陰極構(gòu)成。根據(jù)發(fā)光層的構(gòu)成,PLEDs器件又可以分為單層器件[13?14]、雙層器件[15?16]和多層器件[17?18]。當(dāng)加上足夠的直流電壓時,電子從低功函數(shù)的金屬陰極,空穴從高功函數(shù)的ITO陽極分別向發(fā)光層注入。這兩種載流子在外加電場作用下在有機層中遷移和復(fù)合形成激子,然后激子向基態(tài)躍遷而輻射發(fā)光。本文制備的器件采用多層結(jié)構(gòu)??偟膩碚f,旋涂了PVK的PLEDs器件的電流效率要高于沒有旋涂PVK的電流效率。在電流為3 mA時,PVK厚度為40 nm的PLEDs器件的電流效率最高,接近0.6 cd/A。較大的電流效率意味著達到同樣的亮度需要較小的電流,這樣會減小器件在工作時候所釋放的焦耳熱,從而提高器件的穩(wěn)定性和壽命。

      通過以上的圖表分析可以得知,聚合物發(fā)光二極管的光電性能與空穴傳輸層的厚度密切相關(guān),當(dāng)轉(zhuǎn)速為2 000 r/m,濃度為1%,膜厚約為40 nm時,其器件光電性能有較大的提高。雖然旋涂了PVK的PLEDs器件并沒有降低器件的開啟電壓,但是卻提高了器件的發(fā)光亮度和電流效率,改善了器件的性能。

      3 結(jié) 論

      在PLEDs的空穴注入層PEDOT與發(fā)光層PF?BT15之間插入一層空穴傳輸層PVK,使發(fā)光器件具有較好的電壓電流特性,改善了發(fā)光性能,優(yōu)化了器件功能層的厚度匹配。當(dāng)轉(zhuǎn)速約為2 000 r/s,濃度約為1%,膜厚約為40 nm時,其電流效率較高,而且亮度較高。

      參考文獻

      [1] ADACHI C, TOKIO S, TSUTSUI T, et al. Electroluminescence in organic films with three?layer structure [J]. Japanese Journal of Applied Physics, part 2, 1988, 27: L269?L271.

      [2] YANG Y, HEEGER A J. Polyaniline as a transparent electrode for polymer light?emitting diodes: lower operating voltage and higher efficiency [J]. Applied Physics Letters, 1994, 64, 1245?1247.

      [3] BERNIUS M T, INBASEKARAN M, BRIEN J O, et al. Pro?gress with light?emitting polymers [J]. Advanced Materials, 2000, 12(23): 1737?1750.

      [4] 王立軍,劉星元,寧永強,等.有機/聚合物激光[J].光機電信息, 2002(9):8?12.

      [5] KRAFT A, GRIMSDALE A C, HOLMES A B. Electroluminescent conjugated polymers?seeing polymers in a new light [J]. Angewandte Chemie International Edition, 1998, 37(4): 402?428.

      [6] DESTRIAU G. Reserches sur les Scintillations des Zinc aux Rayons [J]. Journal of Chem Phys, 1963, 33: 587?625.

      [7] POPE M, KALLMANN H P, MAGNANTE P. Electroluminescence in organic crystals [J]. Journal of Chem Phys, 1963, 38: 2042?2043.

      [8] PARTRIDGE R H. Radiation sources: US, 3 995 299 [P]. 1976?11?30.

      [9] VINCETT P S, BARLOW W A, HANN R A, et al. Electrical conduction and low voltage blue electroluminescence in vacuum?deposited organic films [J]. Thin Solid Films, 1982, 94: 171?183.

      [10] TANG C W, VAN SLYKE S A. Organic electroluminescent diodes [J]. Applied Physics Letters, 1987, 51: 913?915.

      [11] BURROUGHES J H, BRADLEY D D C, BROWN A R, et al. Light?emitting diodes based on conjugated polymers [J]. Nature, 1990, 347: 539?541.

      [12] GUSTAFSSON G, CAO Y, TREACY G M, et al. Flexible light?emitting diodes made from soluble conducting polymers [J]. Nature, 1992, 357: 477?479.

      [13] SCOTT J C, KAUFMAN J H, BROCK P J, et al. Degradation and failure of MEH?PPV light?emitting diodes [J]. Journal of Applied Physics, 1996, 79: 2745?2751.

      [14] CAMPBELL LAN H, FERRARIS J P, HAGLER T W, et al. Measuring internal electric fields in organic light?emitting diodes using electroabsorption spectroscopy [J]. Polym Advan Technol, 1997, 8: 417.

      [15] CHAO Q L, CHEN S A. White light emission from exciplex in a bilayer device with two blue light?emitting polymers [J]. Applied Physics Letters, 1998, 73: 426?428.

      [16] CAO Y, YU G, ZHANG C, et al. Polyer light?emitting diodes with polyethylene dioxythiophene?polystyrene sulfonate as the transparent anode [J]. Synth Met, 1997, 87: 171?174.

      [17] FRIEND R H, GYMER R W, HOLMES A B, et al. Electroluminescence in conjugated polymers [J]. Nature, 1999, 397: 121?128.

      [18] KIM D Y, CHO H N, KIM C Y. Blue light emitting polymers [J]. Progress in Polymer Science, 2000, 25: 1089?1139.

      [19] BRAUN D, HEEGER A J. Visible light emission from semiconducting polymer diodes [J]. Applied Physics Letters, 1991, 58: 1982?1984.

      3 結(jié) 論

      在PLEDs的空穴注入層PEDOT與發(fā)光層PF?BT15之間插入一層空穴傳輸層PVK,使發(fā)光器件具有較好的電壓電流特性,改善了發(fā)光性能,優(yōu)化了器件功能層的厚度匹配。當(dāng)轉(zhuǎn)速約為2 000 r/s,濃度約為1%,膜厚約為40 nm時,其電流效率較高,而且亮度較高。

      參考文獻

      [1] ADACHI C, TOKIO S, TSUTSUI T, et al. Electroluminescence in organic films with three?layer structure [J]. Japanese Journal of Applied Physics, part 2, 1988, 27: L269?L271.

      [2] YANG Y, HEEGER A J. Polyaniline as a transparent electrode for polymer light?emitting diodes: lower operating voltage and higher efficiency [J]. Applied Physics Letters, 1994, 64, 1245?1247.

      [3] BERNIUS M T, INBASEKARAN M, BRIEN J O, et al. Pro?gress with light?emitting polymers [J]. Advanced Materials, 2000, 12(23): 1737?1750.

      [4] 王立軍,劉星元,寧永強,等.有機/聚合物激光[J].光機電信息, 2002(9):8?12.

      [5] KRAFT A, GRIMSDALE A C, HOLMES A B. Electroluminescent conjugated polymers?seeing polymers in a new light [J]. Angewandte Chemie International Edition, 1998, 37(4): 402?428.

      [6] DESTRIAU G. Reserches sur les Scintillations des Zinc aux Rayons [J]. Journal of Chem Phys, 1963, 33: 587?625.

      [7] POPE M, KALLMANN H P, MAGNANTE P. Electroluminescence in organic crystals [J]. Journal of Chem Phys, 1963, 38: 2042?2043.

      [8] PARTRIDGE R H. Radiation sources: US, 3 995 299 [P]. 1976?11?30.

      [9] VINCETT P S, BARLOW W A, HANN R A, et al. Electrical conduction and low voltage blue electroluminescence in vacuum?deposited organic films [J]. Thin Solid Films, 1982, 94: 171?183.

      [10] TANG C W, VAN SLYKE S A. Organic electroluminescent diodes [J]. Applied Physics Letters, 1987, 51: 913?915.

      [11] BURROUGHES J H, BRADLEY D D C, BROWN A R, et al. Light?emitting diodes based on conjugated polymers [J]. Nature, 1990, 347: 539?541.

      [12] GUSTAFSSON G, CAO Y, TREACY G M, et al. Flexible light?emitting diodes made from soluble conducting polymers [J]. Nature, 1992, 357: 477?479.

      [13] SCOTT J C, KAUFMAN J H, BROCK P J, et al. Degradation and failure of MEH?PPV light?emitting diodes [J]. Journal of Applied Physics, 1996, 79: 2745?2751.

      [14] CAMPBELL LAN H, FERRARIS J P, HAGLER T W, et al. Measuring internal electric fields in organic light?emitting diodes using electroabsorption spectroscopy [J]. Polym Advan Technol, 1997, 8: 417.

      [15] CHAO Q L, CHEN S A. White light emission from exciplex in a bilayer device with two blue light?emitting polymers [J]. Applied Physics Letters, 1998, 73: 426?428.

      [16] CAO Y, YU G, ZHANG C, et al. Polyer light?emitting diodes with polyethylene dioxythiophene?polystyrene sulfonate as the transparent anode [J]. Synth Met, 1997, 87: 171?174.

      [17] FRIEND R H, GYMER R W, HOLMES A B, et al. Electroluminescence in conjugated polymers [J]. Nature, 1999, 397: 121?128.

      [18] KIM D Y, CHO H N, KIM C Y. Blue light emitting polymers [J]. Progress in Polymer Science, 2000, 25: 1089?1139.

      [19] BRAUN D, HEEGER A J. Visible light emission from semiconducting polymer diodes [J]. Applied Physics Letters, 1991, 58: 1982?1984.

      3 結(jié) 論

      在PLEDs的空穴注入層PEDOT與發(fā)光層PF?BT15之間插入一層空穴傳輸層PVK,使發(fā)光器件具有較好的電壓電流特性,改善了發(fā)光性能,優(yōu)化了器件功能層的厚度匹配。當(dāng)轉(zhuǎn)速約為2 000 r/s,濃度約為1%,膜厚約為40 nm時,其電流效率較高,而且亮度較高。

      參考文獻

      [1] ADACHI C, TOKIO S, TSUTSUI T, et al. Electroluminescence in organic films with three?layer structure [J]. Japanese Journal of Applied Physics, part 2, 1988, 27: L269?L271.

      [2] YANG Y, HEEGER A J. Polyaniline as a transparent electrode for polymer light?emitting diodes: lower operating voltage and higher efficiency [J]. Applied Physics Letters, 1994, 64, 1245?1247.

      [3] BERNIUS M T, INBASEKARAN M, BRIEN J O, et al. Pro?gress with light?emitting polymers [J]. Advanced Materials, 2000, 12(23): 1737?1750.

      [4] 王立軍,劉星元,寧永強,等.有機/聚合物激光[J].光機電信息, 2002(9):8?12.

      [5] KRAFT A, GRIMSDALE A C, HOLMES A B. Electroluminescent conjugated polymers?seeing polymers in a new light [J]. Angewandte Chemie International Edition, 1998, 37(4): 402?428.

      [6] DESTRIAU G. Reserches sur les Scintillations des Zinc aux Rayons [J]. Journal of Chem Phys, 1963, 33: 587?625.

      [7] POPE M, KALLMANN H P, MAGNANTE P. Electroluminescence in organic crystals [J]. Journal of Chem Phys, 1963, 38: 2042?2043.

      [8] PARTRIDGE R H. Radiation sources: US, 3 995 299 [P]. 1976?11?30.

      [9] VINCETT P S, BARLOW W A, HANN R A, et al. Electrical conduction and low voltage blue electroluminescence in vacuum?deposited organic films [J]. Thin Solid Films, 1982, 94: 171?183.

      [10] TANG C W, VAN SLYKE S A. Organic electroluminescent diodes [J]. Applied Physics Letters, 1987, 51: 913?915.

      [11] BURROUGHES J H, BRADLEY D D C, BROWN A R, et al. Light?emitting diodes based on conjugated polymers [J]. Nature, 1990, 347: 539?541.

      [12] GUSTAFSSON G, CAO Y, TREACY G M, et al. Flexible light?emitting diodes made from soluble conducting polymers [J]. Nature, 1992, 357: 477?479.

      [13] SCOTT J C, KAUFMAN J H, BROCK P J, et al. Degradation and failure of MEH?PPV light?emitting diodes [J]. Journal of Applied Physics, 1996, 79: 2745?2751.

      [14] CAMPBELL LAN H, FERRARIS J P, HAGLER T W, et al. Measuring internal electric fields in organic light?emitting diodes using electroabsorption spectroscopy [J]. Polym Advan Technol, 1997, 8: 417.

      [15] CHAO Q L, CHEN S A. White light emission from exciplex in a bilayer device with two blue light?emitting polymers [J]. Applied Physics Letters, 1998, 73: 426?428.

      [16] CAO Y, YU G, ZHANG C, et al. Polyer light?emitting diodes with polyethylene dioxythiophene?polystyrene sulfonate as the transparent anode [J]. Synth Met, 1997, 87: 171?174.

      [17] FRIEND R H, GYMER R W, HOLMES A B, et al. Electroluminescence in conjugated polymers [J]. Nature, 1999, 397: 121?128.

      [18] KIM D Y, CHO H N, KIM C Y. Blue light emitting polymers [J]. Progress in Polymer Science, 2000, 25: 1089?1139.

      [19] BRAUN D, HEEGER A J. Visible light emission from semiconducting polymer diodes [J]. Applied Physics Letters, 1991, 58: 1982?1984.

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