銀粉含量對(duì)印刷型聚合物發(fā)光器件的影響

曾文進(jìn)，趙春燕，李詠華，李冬梅，李　雪，張　赤，

彭俊彪2，賴文勇1，牛巧利1，閔永剛1

1) 南京郵電大學(xué)材料學(xué)院，江蘇南京 210023；2)華南理工大學(xué)發(fā)光材料與器件教育部重點(diǎn)實(shí)驗(yàn)室，廣東廣州 510641

?

Received：2015-06-14；Accepted：2015-11-13

Foundation：National Natural Science Foundation of China (61504066); Natural Science Foundation of Jiangsu Higher Education Institutions of China (15KJB430024); Natural Science Foundation of Jiangsu Province (BK20150838)

? Corresponding author：Professor Min Yonggang. E-mail: iamygmin@njupt.edu.cn

Citation：Zeng Wenjin, Zhao Chunyan, Li Yonghua, et al. Effect of Ag content on the performance of cathode-printed PLEDs[J]. Journal of Shenzhen University Science and Engineering, 2016, 33(1): 18-24.

【Chemistry and Chemical Engineering / 化學(xué)與化工】

Effect of Ag content on the performance of

cathode-printed PLEDs

Zeng Wenjin1, Zhao Chunyan1, Li Yonghua1, Li Dongmei1, Li Xue1,

Zhang Chi2, Peng Junbiao2, Lai Wenyong1,

銀粉含量對(duì)印刷型聚合物發(fā)光器件的影響

曾文進(jìn)1，趙春燕1，李詠華1，李冬梅1，李雪1，張赤2，

彭俊彪2，賴文勇1，牛巧利1，閔永剛1

1) 南京郵電大學(xué)材料學(xué)院，江蘇南京 210023；2)華南理工大學(xué)發(fā)光材料與器件教育部重點(diǎn)實(shí)驗(yàn)室，廣東廣州 510641

摘要：研究銀粉含量和印刷陰極型聚合物發(fā)光二極管(polymer light-emitting diode，PLED)之間的構(gòu)-效關(guān)系．實(shí)驗(yàn)比較兩種不同銀粉含量的導(dǎo)電銀膠，通過(guò)刮涂法制備PLED的陰極．兩種銀膠的膠體基底相同，區(qū)別在于銀粉顆粒的含量不同．實(shí)驗(yàn)研究銀粉的分布狀態(tài)與器件性能之間的關(guān)系．結(jié)果表明，銀膠中的銀粉含量越高，器件的性能越好，主要體現(xiàn)在驅(qū)動(dòng)電壓更低、電流密度更大和量子效率更高．偏光顯微鏡圖片顯示，提高銀膠中銀粉的含量，可以優(yōu)化銀粉在印刷陰極/電子傳輸層之間的分布．通過(guò)銀粉覆蓋率的數(shù)據(jù)模擬也證明了這一點(diǎn)．為確定銀粉覆蓋率的提高能夠優(yōu)化器件效率，在器件中通過(guò)蒸鍍添加薄銀層．結(jié)果表明，由于薄銀層的插入，器件的驅(qū)動(dòng)電壓隨之下降，器件性能也得到優(yōu)化．因此，在印刷型的PLED器件中，提高銀膠中銀粉的含量可以有效減低載流子的注入勢(shì)壘，達(dá)到器件優(yōu)化的效果．

關(guān)鍵詞：化學(xué)物理學(xué)；聚合物發(fā)光二極管；導(dǎo)電銀膠；刮涂工藝；印刷式電極；相界面電阻

The polymer light-emitting diode (PLED) has attracted tremendous attention due to its superiorities in solution processability, low cost, richness of display colors and its potential applications in large-area display panels and solid state light source, etc. Moreover, PLED can be fabricated by the technique of full-printing[1-4]. Until now, the series of novel electroluminescent polymers, which are suitable for solution-processing, have been developed since electronic luminescence was reported from devices made of conjugated polymers[5-9].

The cathode of PLED can also be printed from the metal pastes, such as silver, copper or gold pastes. However it should be noted that high efficiency required the balanced injection of charge carriers from both the electrodes (anode and cathode) before we applied the metal pastes on the cathode as mentioned above[10]. In addition, metals with low work function, such as Ca, Ba and Mg, are not suitable for printing due to their high chemical activities. Currently, Ag paste is considered as the most promising material for the cathode printing in full-printed PLED based on the following three reasons: ① Silver paste can be achieved with comparable conductivity to evaporated metal after curing at room or moderate temperature, unlike CNTs or graphene which need super high temperature to achieve considerable conductivity. ② Ag paste possesses strong adhesive strength which leads to its wide application in the field of electronic circuits. ③ Ag paste is applicable to most printing techniques such as blade-coating, inkjet printing, screen printing, etc[11].

Due to the high work function of silver, generally an electron-transporting layer (ETL) is needed to match the energy levels of the polymer layer and the cathode. Amino-/ammonium-functionalized polyfluorene were synthesized ETL materials in the full-printed PLED by Cao and other groups[12-20].

However, we still notice that the performance of PLED with printed cathode needs further improvement, which mainly reflects its higher driving voltage and lower current density. It is necessary to investigate the injection barriers of the silver particles at the interface between the polymer layer and the Ag-paste cathode. And the injection barriers of the silver particles may be greatly affected by the distribution of silver particles in the paste, which arises from the particles size, the silver content and contact resistance at the interface of the polymer/silver paste.

In this study, PLED was fabricated with the cathode made from two kinds of Ag pastes, based on the same resin base but the different Ag contents. It was found that the Ag contents significantly influence the coverage of Ag particles at the polymer-cathode interface. The coverage of Ag particles is related to the interfacial resistance of the cathode. With the simulation of the polarized microscopic images by scientific image processing software, we can analyze the relationship between the distribution of Ag particles and the performance of the device.

1Experiment

1.1Materials

Indium tin oxide (ITO) glass with a surface resistance of ca. 25 Ω/sq was purchased from China South Glass Co. Ltd. Poly[2-(4-(3′,7′-dimethyloctyloxy)-phenyl)-p-phenylenevinylene] (P-PPV) and poly[9, 9-bis(3′-(N, N-dimethylamino)propyl)-2,7-fluorene-alt-2,7-(9,9-dioctylfluorene)] (PFN) were synthesized as reported elsewhere[21-22]. Poly (3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT ∶PSS) (Baytron P 4083) was purchased from Bayer company and used without further purification. The conducting Ag pastes with a viscosity of ca. 18 Pa·s and a conductivity higher than 3 × 103s·cm-1were prepared in laboratory. Two kinds of Ag pastes with different Ag content were applied in this study. Paste KD-1 has a mass fraction of 75% for the Ag content, while paste KD-2 has a higher mass fraction of 95%.

1.2Device fabrication

ITO glass was cleaned ultrasonically by a solvent bath of acetone, detergent, deionized water and isopropyl alcohol in sequence. Surface treatment by O2plasma was performed on ITO surface to remove the organic residue and improve the work function as well. The layers of PEDOT∶PSS, P-PPV solution (5.5 mg/mL inp-xylene) and PFN solution (4 mg/mL in methanol) were formed on the clean ITO glass in sequence by spin-coating. The optimum thickness for each layer was found to be 40 nm of PEDOT∶PSS, 80 nm of P-PPV and 20 nm of PFN. For the devices with the cathode made of Ag paste, the Ag paste was patterned on top of the PFN layer by the method of blade coating in a glove box under an inert atmosphere. The shape and thickness of the Ag paste were controlled by a plastic mask. For the control device using Ag as a cathode, 150 nm Ag was thermal evaporated at a rate of 0.2 nm/s under high vacuum below 3 × 10-4Pa, with the metal thickness controlled by a calibrated crystal oscillator. The architecture of electron-only device was ITO/Sn(30 nm)/ P-PPV(80 nm)/PFN(20 nm)/cathode. The 30 nm layer of Sn was thermally evaporated under high vacuum below 3 × 10-4Pa. The subsequent deposition of P-PPV, PFN and the cathode was same as that of the standard devices.

1.3Characterization

The thickness of the polymer thin films was determined by a surface profiler (Tencor Alpha-Step 500). Current density-luminance-voltage (J-L-V) characteristic curves were collected on a semiconductor testing system consisting of a Keithley 236 source-meter and a calibrated silicon photodiode. The external quantum efficiency (QE) was calculated by measuring the light output in a calibrated integrated sphere (IS-080, Labsphere). The polarized microscopic images were collected on the polarized microscope (Nikon Eclips E600, Tokyo, Japan). The coverage of Ag particles was calculated using an image-processing software (Image J, a widely-used software to calculate the area of irregular shape).

2Results and discussions

The chemical structures of the polymers P-PPV and PFN are shown in Fig.1(a) and (b) respectively, in which the P-PPV acts as the emission layer (EML) and PFN as the electron-transporting layer (ETL). The amino group of PFN can induce dipoles under the applied electric filed, thus benefits the electron injection from the PLED cathode. As known, Ag is a noble metal with high work function, which is unfavorable for electron injection from the cathode. Therefore, the thin layer of PFN plays a very important role in the realization of using Ag metal as the cathode. Fig.1(c) indicates the device architecture has the optimum configuration of ITO/PEDOT∶PSS(40 nm)/P-PPV(80 nm)/PFN(20 nm)/Ag paste, which had been verified in previous study[18].

Fig.1　Chemical structures of P-PPV, PFN, and the device architecture with the configuration of ITO/PEDOT∶PSS(40 nm)/P-PPV(80 nm)/PFN(20 nm)/Ag paste圖1　P-PPV和PFN的化學(xué)結(jié)構(gòu)式以及器件結(jié)構(gòu)

In our previous study[15-16], it has been revealed that the thickness of PPV and PFN can affect device performance. The thickness of each film layer indicated in the structure has been optimized. For comparison, devices with evaporated Ag as cathodes were also fabricated in the same configuration as the control. For simplicity, devices with cathodes made of the above-mentioned materials were referred as device 1, device 2 and device 3, corresponding to evaporated Ag, Ag paste KD-1 and KD-2, respectively.

Fig.2　Electronic properties of P-PPV devices with two different Ag pastes (KD-1 and KD-2) as device cathodes. Performance of control device with evaporated Ag is also shown for comparison.圖2　兩種不同銀膠(KD-1和KD-2)制備的P-PPV發(fā)光二極管的電學(xué)性能曲線圖

It is expectable that there are differences between the electric properties of PLED with evaporated Ag and Ag paste as the cathode. Fig.2(a) and (b) respectively demonstrate the J-L-V characteristic curves and QE-Jcurves of P-PPV devices with different cathode materials. It can be seen that devices 1 and 3 have similar on-voltage, lower than that of device 2. However, when the luminance at a specified voltage is taken into account, device 1 possesses a higher value than device 2 and device 3. As a result, indicated in Fig.2(b), device 1 demonstrates the highest efficiency. More details are summarized in table 1. At a specific current density of 10 mA/cm2, device 1 achieves a luminance of 880 cd/m2at 7.9 V, with a QE of 3.8%, a QEmaxof 4.2% and a maximum luminance efficiency (LEmax) of 11.0 cd/A. For devices with two kinds of Ag paste as a cathode, such as device 2 and device 3, the latter has a much better performance, with a luminance of 740 cd/m2at 7.8 V, a QEmaxof 3.0% and a LEmaxof 7.8 cd/A.

Table 1　Performance comparison between P-PPV devices with Ag paste KD-1 and KD-2 as the cathode

Fig.3　In-situ polarized microscopic images collected from the ITO side to compare the distribution of Ag particles between the two Ag pastes圖3　兩種不同銀膠的偏光顯微鏡照片以及對(duì)應(yīng)的軟件模擬圖

Despite the obvious results that device 1 has attained the best performance among the three types of devices, it would be more interesting to make clear the reason why device 3 possesses a superior performance over device 2 merely arising from the different Ag contents in the paste. It can be taken for granted that pastes of different Ag content have different resistance, which can influence device performance. However, to further understand the mechanism, silver distribution of Ag particles should be investigated, especially at the interface between the cathode and the polymer layer. Therefore, polarized microscopy was applied in-situ to observe the distribution of the Ag particles within the actual device. The polarized images of the two pastes are presented in Fig.3(a) and (b), in which the brighter spots represent the Ag particles directly contacting the polymer layer, while the darker background is the opaque paste resin. By comparing the two images, it is clear that Ag particles have a richer distribution in device 3. As known, Ag particles are the effective components making an Ag paste conductive. The enrichment of Ag particles can facilitate better formation of an ohmic contact[23-24]between the cathode and the polymer layer and would thus effectively benefit the transporting and injection of electrons. To quantitatively evaluate the enrichment of Ag particles, the value of Ag particles coverage was calculated using simulation software. The simulated images are demonstrated in Fig.3(c) and (d), which correspond to the polarized images in (a) and (b). The coverage of Ag particles in Fig.3(a) was calculated to be 27.6%, less than 65.0% in Fig.3(b). Direct contact of silver particles with the polymer layer can reduce the internal resistance of the device since the resin of the silver paste is usually isolated[25]. Therefore, it is reasonable to speculate that the lower coverage of Ag particles in paste KD-1 led to its poorer device performance.Electron-only devices were prepared with tin (Sn) as the anode. The injection barrier height of different cathode configurations can be calculated according to the Fowler-Nordheim (FN) tunneling mechanism. In the FN model, the injection current density (J) is related to the magnitude of electric field (F) by the following equation[26-27],

where

Here φ is the barrier height, m the effective mass of electrons in the active materials, q is the charge of an electron, and h is Planck’s constant. The barrier heights were calculated to be 0.40, 0.51 and 0.44 eV, respectively, for the cathode configurations of Ag, Ag paste KD-1 and Ag paste KD-2, as indicated in Fig.4. The results indicate that higher coverage of Ag particles can lower the injection carrier of the electrons injecting from the cathode.

Fig.4　Characteristic curves of the injection current density related to the electric field圖4　不同電極材料的P-PPV器件的陰極注入勢(shì)壘計(jì)算曲線

Fig.5　Electronic properties of P-PPV devices with a thin layer of evaporated Ag in different thickness inserted between polymer layer and Ag paste cathode KD-1圖5　插層蒸鍍Ag后的P-PPV器件電學(xué)性能曲線

To further verify the speculation, a thin layer of Ag in a different thickness was thermally evaporated on top of the polymer layer before the coating of the Ag paste KD-1. With the thickness of the evaporated Ag increasing, the Ag particles can finally form a complete layer of Ag which can fully cover the polymer surface. The evaporated thin Ag film and the following coated Ag paste together constituted the device cathode. Therefore, the thermal evaporation of the inserted Ag film can be regarded as an analogous process in which the coverage of Ag particles in the paste can increase gradually with the growth of the evaporated Ag film. The J-V curves and L-V curves are shown in Fig.5(a) and (b). It can be seen that the electric behavior of the paste device, with the thickness of the evaporated Ag layer increasing from 0 to 30 nm, became more similar to that of the evaporated control one. And its performance also improves gradually towards that of the control device. Therefore, it is proved again that a low coverage of Ag particles in the paste is unfavorable to device performance. It is crucial to develop efficient methods to increase the coverage of Ag particles to achieve high-efficiency PLED with the cathode made of Ag paste.

Conclusions

In summary, we have undertaken an investigation on the relationship between the silver content in the paste and the device performance of the cathode-printed PLED. Our experiment results reveal that higher silver content in the paste facilitates better distribution of Ag at the interface of the cathode and the electron-transporting layer. According to the simulation results, higher coverage of Ag particles at the interface is favorable to the device performance, therefore it provides guidance to the further improvement of the printed PLED with Ag paste as cathode. As a result, the maximum QE of 3.0% are achieved for the devices with the cathode of higher silver contents.

趙春燕(1990—)，女，南京郵電大學(xué)碩士研究生．研究方向：有機(jī)光電器件. E-mail：1053179147@qq.com

曾文進(jìn)、趙春燕為共同第一作者．

引文：曾文進(jìn)，趙春燕，李詠華，等．銀粉含量對(duì)印刷型聚合物發(fā)光器件的影響[J]. 深圳大學(xué)學(xué)報(bào)理工版，2016，33(1)：18-24.(英文版)

參考文獻(xiàn)/ References：

[1] Friend R H, Gymer R W, Holmes A B, et al. Electroluminescence in conjugated polymers[J]. Nature, 1999, 397(6715): 121-128.

[2] Burroughes J H, Bradley D D C, Brown A R, et al. Light-emitting diodes based on conjugated polymers[J]. Nature, 1990, 347(6293): 539-541.

[3] Braun D, Heeger A J. Visible light emission from semiconducting polymer diodes[J]. Applied Physics Letters, 1991, 58(18):1982-1984.

[4] Wu Junbo, Becerril H A, Bao Zhenan, et al. Organic solar cells with solution-processed graphene transparent electrodes[J]. Applied Physics Letters, 2008, 92(26): 263302.

[5] Zhong Chengmei, Duan Chunhui, Huang Fei, et al. Materials and devices toward fully solution processable organic light-emitting diodes[J]. Chemistry of Materials, 2011, 23(3): 326-340.

[6] Zhang Lianjie, Hu Sujun, Chen Junwu, et al. A series of energy-transfer copolymers derived from fluorene and 4,7-dithienylbenzotriazole for high efficiency yellow, orange, and white light-emitting diodes[J]. Advanced Functional Materials, 2011, 21(19): 3760-3769.

[7] Grimsdale A C, Chan K L, Martin R E, et al. Synthesis of light-emitting conjugated polymers for applications in electroluminescent devices[J]. Chemical Reviews, 2009, 109(3):897-1091.

[8] Kamtekar K T, Monkman A P, Bryce M R, et al. Recent advances in white organic light-emitting materials and devices (WOLEDs)[J]. Advanced Materials, 2010, 22(5): 572-582.

[9] Farinola G M, Ragnia R. Electroluminescent materials for white organic light emitting diodes[J]. Chemical Society Reviews, 2011, 40(7): 3467-3482.

[10] Rozanski L J, Castaldelli E, Sam F L M, et al. Solution processed naphthalene diimide derivative as electron transport layers for enhanced brightness and efficient polymer light emitting diodes[J]. Journal of Materials Chemistry C, 2013, 13(7): 3347-3352.

[11] Hu Liangbing, Kim H S, Lee J Y, et al. Scalable coating and properties of transparent, flexible, silver nanowire electrodes[J]. ACS Nano, 2010, 4(5): 2955-2963.

[12] Huang Fei，Cheng Yenju，Zhang Yong，et al．Crosslinkable hole-transporting materials for solution processed polymer light-emitting diodes[J]. Journal of Materials Chemistry, 2008, 18(38): 4495-4509.

[13] Huang Fei, Wu Hongbin, Cao Yong, et al. Water/alcohol soluble conjugated polymers as highly efficient electron transporting/injection layer in optoelectronic devices[J]. Chemical Society Reviews, 2010, 39(7): 2500-2521.

[14] Ma Wanli, Iyer P K, Gong Xiong, et al. Water/methanol soluble conjugated copolymer as an electron transport layer in polymer light-emitting diodes[J]. Advanced Materials, 2005, 17(3): 274-277.

[15] Wu Hongbin, Huang Fei, Mo Yueqi, et al. Efficient elctron injection from a bilayer cathode consisting of aluminum and alchole-/water-soluble conjugated polymers[J]. Advanced Materials, 2004, 16(20): 1826-1830.

[16] Hoven C V, Garcia A, Bazan G C, et al. Recent applications of conjugated polyelectrolytes in optoelectronic devices[J]. Advanced Materials, 2008, 20(20): 3793-3810.

[17] Wu Hongbin, Huang Fei, Peng Junbiao, et al. High-efficiency electron injection cathode of Au for polymer light-emitting devices[J]. Organic Electronics, 2005, 6(3):118-128.

[18] Zhong Chengmei, Liu Shengjian, Huang Fei, et al. Highly efficient electron injection from indium tin oxide/cross-linkable amino-functionalized polyfluorene interface in inverted organic light emitting devices[J]. Chemistry of Materials, 2011, 23(21):4870-4876.

[19] Zeng Wenjin, Wu Hongbin, Zhang Chi, et al. Polymer light-emitting diodes with cathodes printed from conducting Ag paste[J]. Advanced Materials, 2007, 19(6): 810-814.

[20] Zheng Hua, Zheng Yina, Liu Nanliu, et al. All-solution processed polymer light-emitting diode displays[J]. Nature Communications, 2013, 4(7): 1971-1978.

[21] Mo Yueqi, Huang Jian, Jiang Jiaxin, et al. Influence of traces of water on the synthesis and electrolumi-nescence propties of poly(2-methoxy,5-(2′-ethylhexylo-xy)-1,4-phenylene vinylene)[J]. Chinese Journal of Polymer Science, 2002, 20(5): 461-465.

[22] Huang Fei, Hou Lintao,Wu Hongbin, et al. High-efficiency, environment-friendly electroluminescent polymers with stable high work function metal as a cathode: green- and yellow-emitting conjugated polyfluorene polyelectrolytes and their neutral precursors[J]. Journal of the American Chemical Society, 2004, 126(31): 9845-9853.

[23] Vinod P N. Specific contact resistance and metallurgical process of the silver-based paste for making ohmic contact structure on the porous silicon/p-Si surface of the silicon solar cell[J]. Journal of Materials Science: Materials in Electronics, 2010, 21(7): 730-736.

[24] Kulushich G, Bazer-Bachi B, Takahashi T, et al. Contact formation on 100 Ω/sq emitter by screen printed silver paste[J]. Energy Procedia, 2012, 27: 485-490.

[25] Strümpler R, Glatz-Reichenbach J. Conducting polymer composites[J]. Journal of Electroceramics, 1999, 3(4): 329-346.

[26] Parker I D, Glatz-Reichenbach J. Carrier tunneling and device characteristics in polymer light-emitting diodes[J]. Journal of Applied Physics, 1994, 75(3): 1656-1660.

[27] Kumar A, Srivastava R, Tyagi P, et al. Effect of doping of 8-hydroxyquinolinatolithium on electron transport in tris(8-hydroxyquinolinato) aluminum[J]. Journal of Applied Physics, 2011, 109(11): 114511.

【中文責(zé)編：方圓；英文責(zé)編：木南】

Niu Qiaoli1, and Min Yonggang1?

1) School of Materials Science and Engineering, Nanjing University of Posts and Telecommunications,

Nanjing 210023, Jiangsu Province, P.R.China

2) State Key Lab of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640,

Guangdong Province, P.R.China

Abstract：The structure-activity relationship of the cathode-printed polymer light-emitting diodes (PLEDs) is investigated. Two kinds of Ag pastes on the same paste resin but with different content of Ag particles were applied to prepare the cathodes of PLEDs by the blade-coating. The relationship between the distribution of Ag particles and the performance of PLEDs was investigated. The results indicate that the paste with a higher silver content exhibites better performances, including a lower driving voltage, higher current density and quantum efficiency. In-situ polarized microscopic images reveal that a higher silver content in the paste could lead to a better distribution of Ag at the interface of the cathode and the electron-transporting layer (ETL), which can also be proved by the simulation of the coverage percentage. A thin layer of Ag was inserted by evaporation between the ETL and Ag-paste cathode, which is regarded as equivalent to the increase of Ag coverage at the interface. As expected, the driving voltage of the devices was reduced and the performance improved after the thin layer of thermally-deposited Ag was inserted. Therefore, large Ag contents at the interface benefits the performance of PLED due to the low injection barriers.

Key words：chemical physics; polymer light-emitting diodes; Ag paste; blade-coating; printed cathode; interface resistance

作者簡(jiǎn)介：曾文進(jìn)(1981—)，男，南京郵電大學(xué)講師、博士．研究方向：有機(jī)光電器件．E-mail：iamwjzeng@njupt.edu.cn

基金項(xiàng)目：國(guó)家自然科學(xué)基金資助項(xiàng)目 (61504066)；江蘇省高校自然科學(xué)研究資助項(xiàng)目(15KJB430024)；江蘇省自然科學(xué)基金資助項(xiàng)目 (BK20150838)

doi：CLC number: O 472+.8Document code: A10.3724/SP.J.1249.2016.01018