PEDOT:PSS薄膜的丝网印刷、后处理改性及在染料敏化太阳能电池中的应用
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摘要
运用丝网印刷的方式在导电玻璃基底表面涂覆了聚(3,4-乙烯二氧噻吩)(PEDOT):聚苯乙烯磺酸盐混合物(PSS)薄膜,并采用稀H_2SO_4加甲醇混合溶液后处理的方式对其进行了改性.使用扫描电子显微镜(SEM)和原子力显微镜(AFM)观察处理前后薄膜的表面形貌及厚度的变化,对比了处理前后薄膜的电导率,并结合X射线衍射(XRD)和X射线光电子能谱(XPS)分析探讨了导致电导率变化的原因.最后,将PEDOT:PSS薄膜作为对电极组装了染料敏化太阳能电池(DSSC),运用电化学阻抗谱(EIS)研究了对电极的催化性能,并测试了DSSC的光伏性能.结果显示,经过后处理改性后,由于PSS被部分去除,PEDOT:PSS薄膜的表面形貌发生了显著改变,厚度变薄,粗糙度升高,电导率提升至原始的3倍以上,对I_3~–还原的催化活性升高,且组装的DSSC的性能也有了显著提高,光电转换效率由5.12%提升至6.64%.
Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate(PEDOT:PSS) films were coated on fluorinedoped tin oxide(FTO) conductive glass substrates via facile screen printing,followed by a modification.The modification was realized through post-treatment,i.e.,immersing the as-printed films into a mixed solution consisting of diluted H_2SO_4 and methanol,and baking at 120 °C after 10 min of dipping.Scanning electron microscopy(SEM) and atomic force microscopy(AFM) were used to investigate the surface morphology and the thickness changes of the films before and after treating.Electrical conductivity of the pristine and that of the treated films were calculated and compared,using sheet resistance and thickness,and the result was discussed based on X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS) analysis.Finally,PEDOT:PSS films were used as counter electrodes of dye-sensitized solar cells(DSSCs).The catalytic activity of the PEDOT:PSS films toward I_3~– reduction reaction was characterized by electrochemical impedance spectroscopy(EIS),and the photovoltaic performance of DSSCs assembled by the films was evaluated under the irradiation of simulated AM 1.5G condition.The results demonstrate that,the amorphous PEDOT:PSS films are uniformly coated on FTO substrates after screen printing,and the surface morphology of PEDOT:PSS experiences significant change after the modification by post-treatment,with significantly decreased thickness and slightly increased roughness.The electrical conductivity has been enhanced to more than three times of that in the pristine film,due to the partial removal of PSS rather than the improvement of crystallinity.The catalytic activity toward I_3~– reduction reaction is greatly enhanced,and the photovoltaic performance of the DSSCs assembled is also obviously improved,with the photo conversion efficiency increases from 5.12% to 6.64%.The increased PEDOT/PSS mass ratio,electrical conductivity and roughness of the PEDOT:PSS films after post-treatment is believed to be responsible for the improvedment of the photovoltaic performance of the DSSCs.
Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate(PEDOT:PSS) films were coated on fluorinedoped tin oxide(FTO) conductive glass substrates via facile screen printing,followed by a modification.The modification was realized through post-treatment,i.e.,immersing the as-printed films into a mixed solution consisting of diluted H_2SO_4 and methanol,and baking at 120 °C after 10 min of dipping.Scanning electron microscopy(SEM) and atomic force microscopy(AFM) were used to investigate the surface morphology and the thickness changes of the films before and after treating.Electrical conductivity of the pristine and that of the treated films were calculated and compared,using sheet resistance and thickness,and the result was discussed based on X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS) analysis.Finally,PEDOT:PSS films were used as counter electrodes of dye-sensitized solar cells(DSSCs).The catalytic activity of the PEDOT:PSS films toward I_3~– reduction reaction was characterized by electrochemical impedance spectroscopy(EIS),and the photovoltaic performance of DSSCs assembled by the films was evaluated under the irradiation of simulated AM 1.5G condition.The results demonstrate that,the amorphous PEDOT:PSS films are uniformly coated on FTO substrates after screen printing,and the surface morphology of PEDOT:PSS experiences significant change after the modification by post-treatment,with significantly decreased thickness and slightly increased roughness.The electrical conductivity has been enhanced to more than three times of that in the pristine film,due to the partial removal of PSS rather than the improvement of crystallinity.The catalytic activity toward I_3~– reduction reaction is greatly enhanced,and the photovoltaic performance of the DSSCs assembled is also obviously improved,with the photo conversion efficiency increases from 5.12% to 6.64%.The increased PEDOT/PSS mass ratio,electrical conductivity and roughness of the PEDOT:PSS films after post-treatment is believed to be responsible for the improvedment of the photovoltaic performance of the DSSCs.
引文
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9Huang P,Liu Y,Zhang K,Yuan L,Li D,Hou G,Dong B,Zhou Y,Song B,Li Y.J Mater Chem A,2017,5(46):24275-24281
10Xue Q,Liu M,Li Z,Yan L,Hu Z,Zhou J,Li W,Jiang X F,Xu B,Huang F,Li Y,Yip H L,Cao Y.Adv Funct Mater,2018,28(18):1707444
11Anothumakkool B,Soni R,Bhange S N,Kurungot S.Energy Environ Sci,2015,8(4):1339-1347
12Cysewska K,Karczewski J,Jasiński P.Electrochim Acta,2015,176:156-161
13Du X,Wang Z.Electrochim Acta,2003,48(12):1713-1717
14Koch L,Polek A,Rudd S,Evans D.ACS Appl Mater Interfaces,2017,9(1):65-70
15Zhao X,Dong M Y,Zhang J X,Li Y Z,Zhang Q H.Nanotechnology,2016,27(38):385705
16Li Xin(李昕),Xu Yingtao(许英涛),Zheng Yiping(郑一平),Zhang Yan(张焱),Li Congju(李从举),Chen Guangming(陈光明).Acta Polymerica Sinica(高分子学报),2017,(4):661-668
17Alhashmi Alamer F.J Alloys Compd,2017,702:266-273
18Liu J,Wang X J,Li D Y,Coates N E,Segalman R A,Cahill D G.Macromolecules,2015,48(3):585-591
19Lee I,Kim G W,Yang M,Kim T S.ACS Appl Mater Interfaces,2016,8(1):302-310
20Li W P,Zhang X L,Zhang X,Yao J N,Zhan C L.ACS Appl Mater Interfaces,2017,9(2):1446-1452
21Ouyang J Y,Chu C W,Chen F C,Xu Q F,Yang Y.Adv Funct Mater,2005,15(2):203-208
22Xia Y J,Ouyang J Y.Macromolecules,2009,42(12):4141-4147
23Zhang W F,Zhao B F,He Z C,Zhao X M,Wang H T,Yang S F,Wu H B,Cao Y.Energy Environ Sci,2013,6(6):1956-1964
24Beretta D,Barker A J,Maqueira-Albo I,Calloni A,Bussetti G,Dell’Erba G,Luzio A,DuòL,Petrozza A,Lanzani G,Caironi M.ACS Appl Mater Interfaces,2017,9(21):18151-18160
25Cheng T,Zhang Y Z,Yi J P,Yang L,Zhang J D,Lai W Y,Huang W.J Mater Chem A,2016,4(36):13754-13763
26Gomes L,Branco A,Moreira T,Feliciano F,Pinheiro C,Costa C.Sol Energy Mater Sol Cells,2016,144:631-640
27Istamboulie G,Sikora T,Jubete E,Ochoteco E,Marty J L,Noguer T.Talanta,2010,82(3):957-961
28Cho S,Kim M,Jang J.ACS Appl Mater Interfaces,2015,7(19):10213-10227
29Krebs F C.Sol Energy Mater Sol Cells,2009,93(4):465-475
30Yohannes T,Ingan?s O.Sol Energy Mater Sol Cells,1998,51(2):193-202
31Fan X,Xu B G,Liu S H,Cui C H,Wang J Z,Yan F.ACS Appl Mater Interfaces,2016,8(22):14029-14036
32Xu S J,Luo Y F,Liu G W,Qiao G J,Zhong W,Xiao Z H,Luo Y P,Ou H.Electrochim Acta,2015,156:20-28
33Pringle J M,Armel V,MacFarlane D R.Chem Commun,2010,46(29):5367-5369
34Li H G,Xiao Y M,Han G Y,Hou W J.J Power Sources,2017,342:709-716
35 Ellis H,Vlachopoulos N,H?ggman L,Perruchot C,Jouini M,Boschloo G,Hagfeldt A.Electrochim Acta,2013,107:45-51
36 Li Yuyu(李昱煜),Shen Hujiang(沈沪江),Liu Yan(刘岩),Wang Wei(王炜),Yuan Huihui(袁慧慧),Xie Huaqing(谢华清).Mater Rev(材料导报),2017,31:19-25
37 Song D D,Li M C,Jiang Y J,Chen Z,Bai F,Li Y F,Jiang B.J Photochem Photobiol A,2014,279:47-51
38 Ke C R,Chang C C,Ting J M.J Power Sources,2015,284:489-496
39 Wu K Z,Ma J,Cui W Z,Ruan B,Wu M X.J Photochem Photobiol A,2017,340:29-34
40 Huang J,Miller P F,de Mello J C,de Mello A J,Bradley D D C.Synth Met,2003,139(3):569-572
41 Alemu D,Wei H Y,Ho K C,Chu C W.Energy Environ Sci,2012,5(11):9662-9671
42 McGillivray D,Thomas J P,Abd-Ellah M,Heinig N F,Leung K T.ACS Appl Mater Interfaces,2016,8(50):34303-34308
43 Liu G,Xie X,Liu Z,Cheng G,Lee E C.Nanoscale,2018,10(23):11043-11051
44 Huang L Q,Cheng X F,Yang J,Zhang L F,Zhou W H,Xiao S Q,Tan L C,Chen L,Chen Y W.ACS Appl Mater Interfaces,2016,8(40):27018-27025
45 Kim N,Kee S,Lee S H,Lee B H,Kahng Y H,Jo Y R,Kim B J,Lee K.Adv Mater,2014,26(14):2268-2272
46 Xia Y J,Sun K,Ouyang J Y.Adv Mater,2012,24(18):2436-2440
47 Yao B W,Wang H Y,Zhou Q Q,Wu M M,Zhang M,Li C,Shi G Q.Adv Mater,2017,29(28):1700974
48 Yu W,Wang K,Guo B,Qiu X,Hao Y,Chang J,Li Y.J Power Sources,2017,358:29-38
49 Li Y,Hong N.J Mater Chem A,2015,3(43):21537-21544
50 Wu Y,Wang J,Qiu X,Yang R,Lou H,Bao X,Li Y.ACS Appl Mater Interfaces,2016,8(19):12377-12383
51 Gueye M N,Carella A,Massonnet N,Yvenou E,Brenet S,Faure-Vincent J R M,Pouget S P,Rieutord F O,Okuno H,Benayad A,Demadrille R,Simonato J P.Chem Mater,2016,28(10):3462-3468
52 Mukherjee S,Singh R,Gopinathan S,Murugan S,Gawali S,Saha B,Biswas J,Lodha S,Kumar A.ACS Appl Mater Interfaces,2014,6(20):17792-17803
53 Yuan H,Wang W,Xu D,Xu Q,Xie J,Chen X,Zhang T,Xiong C,He Y,Zhang Y,Liu Y,Shen H.Sol Energy,2018,165:233-239
54 Wang W,Yuan H,Zhang Y,Xie J,Xu D,Chen X,He Y,Zhang T,Chen Z,Shen H.Sens Actuators,A,2018,275:148-153
55 Wang W,Yuan H,Xu D,Xie J,Chen X,He Y,Zhang T,Chen Z,Zhang Y,Shen H.J Photochem Photobiol A,2018,357:85-89
56 Wang W,Yuan H H,Xie J J,Xu D,Chen X Y,He Y L,Zhang T,Chen Z Q,Zhang Y M,Shen H J.Mater Res Bull,2018,100:434-439
57 He X,He R H,Lan Q M,Wu W J,Duan F,Xiao J D,Zhang M,Zeng Q G,Wu J H,Liu J Y.Materials,2017,10(3):220-229
58 Kim N,Kang H,Lee J H,Kee S,Lee S H,Lee K.Adv Mater,2015,27(14):2317-2323
59 Zotti G,Zecchin S,Schiavon G,Louwet F,Groenendaal L,Crispin X,Osikowicz W,Salaneck W,Fahlman M.Macromolecules,2003,36(9):3337-3344
60 Hu A,Tan L,Hu X,Hu L,Ai Q,Meng X,Chen L,Chen Y.J Mater Chem C,2017,5(2):382-389
61 Liu Weiqing(刘伟庆),Kou Dongxing(寇东星),Cai Molang(蔡墨朗),Hu Linhua(胡林华),Dai Songyuan(戴松元).Prog Chem(化学进展),2012,24:722-736
62 Meng X,Yu C,Song X,Liu Z,Lu B,Hao C,Qiu J.J Mater Chem A,2017,5(5):2280-2287
2Cheng T,Zhang Y Z,Lai W Y,Chen Y,Zeng W J,Huang W.J Mater Chem C,2014,2(48):10369-10376
3Worfolk B J,Andrews S C,Park S,Reinspach J,Liu N,Toney M F,Mannsfeld S C B,Bao Z N.Proc Natl Acad Sci U S A,2015,112(46):14138-14143
4Shi H,Liu C C,Jiang Q L,Xu J K.Adv Electron Mater,2015,1(4):1500017
5Xu Di(许頔),Shen Hujiang(沈沪江),Yuan Huihui(袁慧慧),Wang Wei(王炜),Xie Junjie(解俊杰).Prog Chem(化学进展),2018,30:252-271
6Wen Y P,Xu J K.J Polym Sci,Part A:Polym Chem,2017,55(7):1121-1150
7Yu Xiaowei(俞孝伟),Zhang Shanlin(张山林),He Weiwei(贺伟伟),Zhang Zhigang(张志刚),Guo Fengqi(郭丰启),Zhan Chuanlang(詹传郎),Huang Yan(黄彦).Chin J Org Chem(有机化学),2012,32:1981-1987
8Qin Mimi(秦咪咪),Li Xin(李昕),Zheng Yiping(郑一平),Zhang Yan(张焱),Li Congju(李从举).Acta Chimica Sinica(化学学报),2015,73:1161-1166
9Huang P,Liu Y,Zhang K,Yuan L,Li D,Hou G,Dong B,Zhou Y,Song B,Li Y.J Mater Chem A,2017,5(46):24275-24281
10Xue Q,Liu M,Li Z,Yan L,Hu Z,Zhou J,Li W,Jiang X F,Xu B,Huang F,Li Y,Yip H L,Cao Y.Adv Funct Mater,2018,28(18):1707444
11Anothumakkool B,Soni R,Bhange S N,Kurungot S.Energy Environ Sci,2015,8(4):1339-1347
12Cysewska K,Karczewski J,Jasiński P.Electrochim Acta,2015,176:156-161
13Du X,Wang Z.Electrochim Acta,2003,48(12):1713-1717
14Koch L,Polek A,Rudd S,Evans D.ACS Appl Mater Interfaces,2017,9(1):65-70
15Zhao X,Dong M Y,Zhang J X,Li Y Z,Zhang Q H.Nanotechnology,2016,27(38):385705
16Li Xin(李昕),Xu Yingtao(许英涛),Zheng Yiping(郑一平),Zhang Yan(张焱),Li Congju(李从举),Chen Guangming(陈光明).Acta Polymerica Sinica(高分子学报),2017,(4):661-668
17Alhashmi Alamer F.J Alloys Compd,2017,702:266-273
18Liu J,Wang X J,Li D Y,Coates N E,Segalman R A,Cahill D G.Macromolecules,2015,48(3):585-591
19Lee I,Kim G W,Yang M,Kim T S.ACS Appl Mater Interfaces,2016,8(1):302-310
20Li W P,Zhang X L,Zhang X,Yao J N,Zhan C L.ACS Appl Mater Interfaces,2017,9(2):1446-1452
21Ouyang J Y,Chu C W,Chen F C,Xu Q F,Yang Y.Adv Funct Mater,2005,15(2):203-208
22Xia Y J,Ouyang J Y.Macromolecules,2009,42(12):4141-4147
23Zhang W F,Zhao B F,He Z C,Zhao X M,Wang H T,Yang S F,Wu H B,Cao Y.Energy Environ Sci,2013,6(6):1956-1964
24Beretta D,Barker A J,Maqueira-Albo I,Calloni A,Bussetti G,Dell’Erba G,Luzio A,DuòL,Petrozza A,Lanzani G,Caironi M.ACS Appl Mater Interfaces,2017,9(21):18151-18160
25Cheng T,Zhang Y Z,Yi J P,Yang L,Zhang J D,Lai W Y,Huang W.J Mater Chem A,2016,4(36):13754-13763
26Gomes L,Branco A,Moreira T,Feliciano F,Pinheiro C,Costa C.Sol Energy Mater Sol Cells,2016,144:631-640
27Istamboulie G,Sikora T,Jubete E,Ochoteco E,Marty J L,Noguer T.Talanta,2010,82(3):957-961
28Cho S,Kim M,Jang J.ACS Appl Mater Interfaces,2015,7(19):10213-10227
29Krebs F C.Sol Energy Mater Sol Cells,2009,93(4):465-475
30Yohannes T,Ingan?s O.Sol Energy Mater Sol Cells,1998,51(2):193-202
31Fan X,Xu B G,Liu S H,Cui C H,Wang J Z,Yan F.ACS Appl Mater Interfaces,2016,8(22):14029-14036
32Xu S J,Luo Y F,Liu G W,Qiao G J,Zhong W,Xiao Z H,Luo Y P,Ou H.Electrochim Acta,2015,156:20-28
33Pringle J M,Armel V,MacFarlane D R.Chem Commun,2010,46(29):5367-5369
34Li H G,Xiao Y M,Han G Y,Hou W J.J Power Sources,2017,342:709-716
35 Ellis H,Vlachopoulos N,H?ggman L,Perruchot C,Jouini M,Boschloo G,Hagfeldt A.Electrochim Acta,2013,107:45-51
36 Li Yuyu(李昱煜),Shen Hujiang(沈沪江),Liu Yan(刘岩),Wang Wei(王炜),Yuan Huihui(袁慧慧),Xie Huaqing(谢华清).Mater Rev(材料导报),2017,31:19-25
37 Song D D,Li M C,Jiang Y J,Chen Z,Bai F,Li Y F,Jiang B.J Photochem Photobiol A,2014,279:47-51
38 Ke C R,Chang C C,Ting J M.J Power Sources,2015,284:489-496
39 Wu K Z,Ma J,Cui W Z,Ruan B,Wu M X.J Photochem Photobiol A,2017,340:29-34
40 Huang J,Miller P F,de Mello J C,de Mello A J,Bradley D D C.Synth Met,2003,139(3):569-572
41 Alemu D,Wei H Y,Ho K C,Chu C W.Energy Environ Sci,2012,5(11):9662-9671
42 McGillivray D,Thomas J P,Abd-Ellah M,Heinig N F,Leung K T.ACS Appl Mater Interfaces,2016,8(50):34303-34308
43 Liu G,Xie X,Liu Z,Cheng G,Lee E C.Nanoscale,2018,10(23):11043-11051
44 Huang L Q,Cheng X F,Yang J,Zhang L F,Zhou W H,Xiao S Q,Tan L C,Chen L,Chen Y W.ACS Appl Mater Interfaces,2016,8(40):27018-27025
45 Kim N,Kee S,Lee S H,Lee B H,Kahng Y H,Jo Y R,Kim B J,Lee K.Adv Mater,2014,26(14):2268-2272
46 Xia Y J,Sun K,Ouyang J Y.Adv Mater,2012,24(18):2436-2440
47 Yao B W,Wang H Y,Zhou Q Q,Wu M M,Zhang M,Li C,Shi G Q.Adv Mater,2017,29(28):1700974
48 Yu W,Wang K,Guo B,Qiu X,Hao Y,Chang J,Li Y.J Power Sources,2017,358:29-38
49 Li Y,Hong N.J Mater Chem A,2015,3(43):21537-21544
50 Wu Y,Wang J,Qiu X,Yang R,Lou H,Bao X,Li Y.ACS Appl Mater Interfaces,2016,8(19):12377-12383
51 Gueye M N,Carella A,Massonnet N,Yvenou E,Brenet S,Faure-Vincent J R M,Pouget S P,Rieutord F O,Okuno H,Benayad A,Demadrille R,Simonato J P.Chem Mater,2016,28(10):3462-3468
52 Mukherjee S,Singh R,Gopinathan S,Murugan S,Gawali S,Saha B,Biswas J,Lodha S,Kumar A.ACS Appl Mater Interfaces,2014,6(20):17792-17803
53 Yuan H,Wang W,Xu D,Xu Q,Xie J,Chen X,Zhang T,Xiong C,He Y,Zhang Y,Liu Y,Shen H.Sol Energy,2018,165:233-239
54 Wang W,Yuan H,Zhang Y,Xie J,Xu D,Chen X,He Y,Zhang T,Chen Z,Shen H.Sens Actuators,A,2018,275:148-153
55 Wang W,Yuan H,Xu D,Xie J,Chen X,He Y,Zhang T,Chen Z,Zhang Y,Shen H.J Photochem Photobiol A,2018,357:85-89
56 Wang W,Yuan H H,Xie J J,Xu D,Chen X Y,He Y L,Zhang T,Chen Z Q,Zhang Y M,Shen H J.Mater Res Bull,2018,100:434-439
57 He X,He R H,Lan Q M,Wu W J,Duan F,Xiao J D,Zhang M,Zeng Q G,Wu J H,Liu J Y.Materials,2017,10(3):220-229
58 Kim N,Kang H,Lee J H,Kee S,Lee S H,Lee K.Adv Mater,2015,27(14):2317-2323
59 Zotti G,Zecchin S,Schiavon G,Louwet F,Groenendaal L,Crispin X,Osikowicz W,Salaneck W,Fahlman M.Macromolecules,2003,36(9):3337-3344
60 Hu A,Tan L,Hu X,Hu L,Ai Q,Meng X,Chen L,Chen Y.J Mater Chem C,2017,5(2):382-389
61 Liu Weiqing(刘伟庆),Kou Dongxing(寇东星),Cai Molang(蔡墨朗),Hu Linhua(胡林华),Dai Songyuan(戴松元).Prog Chem(化学进展),2012,24:722-736
62 Meng X,Yu C,Song X,Liu Z,Lu B,Hao C,Qiu J.J Mater Chem A,2017,5(5):2280-2287
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