A D-A copolymer donor containing an alkylthio-substituted

Transcription

1 Electronic upplementry Mteril (EI) for New Journl of Chemistry. This journl is The Royl ociety of Chemistry nd the Centre Ntionl de l Recherche cientifique 2017 upporting Informtion A D-A copolymer donor contining n lkylthio-sustituted thieno[3,2-]thiophene unit Rui Kong,, Zuo Xio, Fngyun Xie, Jixing Jing* nd Liming Ding* hnxi Key Lortory for Advnced Energy Devices, chool of Mterils cience nd Engineering, hnxi Norml University, Xi'n , Chin. E-mil: jixing@snnu.edu.cn CA Center for Excellence in Nnoscience, CA Key Lortory of Nnosystem nd Hierrchicl Friction, Ntionl Center for Nnoscience nd Technology, Beijing , Chin. E-mil: ding@nnoctr.cn R. Kong nd Z. Xio contriuted eqully to this work. 1. Generl chrcteriztion 2. ynthesis 3. NMR 4. CV 5. XRD 6. Device friction nd mesurements 7. ptimiztion of device performnce 8. CLC 1

2 1. Generl chrcteriztion 1 H nd 13 C NMR spectr were mesured on Bruker Avnce-400 spectrometer. Asorption spectr were recorded on himdzu UV-1800 spectrophotometer. Gel permetion chromtogrphy (GPC) ws performed on Wters series GPC coupled with differentil refrctive index detector using THF s eluent nd polystyrenes s stndrds. Thermogrvimetric nlysis ws done y using Perkin Elmer Dimond TG/DTA therml nlyzer under nitrogen. Cyclic voltmmetry ws done y using hnghi Chenhu CHI620D voltmmetric nlyzer under rgon in n nhydrous cetonitrile solution of tetr-n-utylmmonium hexfluorophosphte (0.1 M). A glssy-cron electrode ws used s the working electrode, pltinumwire ws used s the counter electrode, nd Ag/Ag + electrode ws used s the reference electrode. The polymer ws coted onto glssy-cron electrode nd ll potentils were corrected ginst Fc/Fc +. AFM ws performed on Multimode microscope (Veeco) using tpping mode. X-ry diffrction (XRD) of thin films ws performed on Rigku D/mx-2500 X-ry diffrctometer in reflection mode y using Cu Kα rdition (40 kv, 200 ma). 2. ynthesis All regents were purchsed from J&K Co., Alddin Co., Innochem Co. nd other commercil suppliers. All rections deling with ir- or moisture-sensitive compounds were crried out using stndrd chlenk techniques. 3,6-Dimethoxythieno[3,2- ]thiophene [1] nd (3,3'-difluoro-[2,2'-ithiophene]-5,5'-diyl)is(trimethylstnnne) [2] were prepred ccording to literture. 2-Hexyldecne-1-thiol. To solution of 7-(romomethyl)pentdecne (1.43 g, 4.68 mmol) in THF (10 ml) were dded hexmethyldisilthine (1 g, 5.6 mmol) nd tetrutylmmonium fluoride (44.0 ml, 44.0 mmol, 1.0 M in THF with 5% wter) t -10 C. The rection mixture ws wrmed to room temperture nd stirred overnight. 2

3 The rection mixture ws diluted with dichloromethne nd wshed with sturted NH 4 Cl. The orgnic lyer ws dried over nhydrous Mg 4. After removl of the solvent, the crude product ws purified vi column chromtogrphy (silic gel) using petroleum ether s eluent to give 2-hexyldecne-1-thiol s colorless oil (1.05 g, 88%). 1 H NMR (CDCl 3, 400 MHz, δ/ppm): 2.53 (d, J = 5.7 Hz, 2H), (m, 26H), 0.88 (m, 6H). 13 C NMR (CDCl 3, 100 MHz, δ/ppm): 40.10, 32.34, 32.33, 31.92, 31.88, 29.95, 29.61, 29.34, 28.58, 26.62, 26.59, 22.69, 22.68, 14.12, ,6-Bis((2-hexyldecyl)thio)thieno[3,2-]thiophene (TT). To solution of 3,6- dimethoxythieno[3,2-]thiophene (200 mg, 1 mmol) nd 2-hexyldecne-1-thiol (1.3 g, 5.03 mmol) in toluene (20 ml) ws dded p-toluenesulfonic cid (40 mg, 0.20 mmol). The rection mixture ws heted to reflux for 12 h. After removl of the solvent, the crude product ws purified vi column chromtogrphy (silic gel) using petroleum ether s eluent to give TT s colorless oil (458 mg, 70%). 1 H NMR (CDCl 3, 400 MHz, δ/ppm): 7.23 (s, 2H), 2.91 (d, J = 5.8 Hz, 4H), 1.58 (m, 2H), (m, 48H), 0.88 (s, 12H). 13 C NMR (CDCl 3, 100 MHz, δ/ppm): , , , 39.38, 37.84, 32.97, 31.92, 31.85, 29.90, 29.59, 29.57, 29.34, 26.50, 26.47, 22.71, 22.68, 14.15, MALDI-TF M (m/z): (M + ). 2,5-Diromo-3,6-is((2-hexyldecyl)thio)thieno[3,2-]thiophene (TT-Br). To solution of TT (400 mg, 0.61 mmol) in chloroform (5 ml) ws dded NB (240 mg, 1.35 mmol) t room temperture. The mixture ws stirred for 3h. After removl of the solvent, the crude product ws purified vi column chromtogrphy (silic gel) using petroleum ether s eluent to give TT-Br s colorless oil (450 mg, 90%). 1 H NMR (CDCl 3, 400 MHz, δ/ppm): 2.86 (d, J = 3.8 Hz, 4H), (m, 50H), 0.88 (s, 12H). 13 C NMR (CDCl 3, 100 MHz, δ/ppm): , , , 39.18, 38.18, 32.81, 31.93, 31.85, 29.88, 29.59, 29.54, 29.34, 26.49, 26.46, 22.72, 22.68, 14.16, MALDI-TF M (m/z): (M + ). PTTF2T. To mixture of TT-Br (101.5 mg, mmol), (3,3'-difluoro-[2,2'- 3

4 ithiophene]-5,5'-diyl)is(trimethylstnnne) (66.1 mg, mmol), Pd 2 (d) 3 (5.7 mg, mmol) nd P(o-Tol) 3 (15.2 mg, mmol) in chlenk flsk ws dded toluene (3 ml) under rgon. The mixture ws heted to reflux for 28 h. Then the solution ws cooled to room temperture nd dded into 150 ml methnol dropwise. The precipitte ws collected nd further purified vi oxhlet extrction using methnol, hexne, chloroform nd chloroenzene in sequence. The chloroenzene frction ws concentrted nd dded into methnol dropwise. The precipitte ws collected nd dried under vcuum overnight to give PTTF2T s lck solid (45 mg, 41%). 1 H NMR (CDCl 3, 400 MHz, δ/ppm): 7.13 (r, romtic protons), 2.90 (r, liphtic protons), (r, liphtic protons). Elementl nlysis (%) clcd for C 46 H 68 F 2 6 : C, 64.89; H, Found: C, 64.43; H, F Me Me H PTA Tol NB Br Br n n F Pd 2 (d) 3, P(o-Tol) 3 Tol F F n TT TT-Br PTTF2T cheme 1 ynthetic route for PTTF2T. 3,6-Bis((2-hexyldecyl)oxy)thieno[3,2-]thiophene (TT). To solution of 3,6- dimethoxythieno[3,2-]thiophene (200 mg, 1 mmol) nd 2-hexyl-1-decnol (1.21 g, 5 mmol) in toluene (20 ml) ws dded p-toluenesulfonic cid (40 mg, 0.20 mmol). The rection mixture ws heted to reflux for 12 h. After removl of the solvent, the crude product ws purified vi column chromtogrphy (silic gel) using petroleum ether s eluent to give TT s colorless oil (380 mg, 67%). 1 H NMR (CDCl 3, 400 MHz, δ/ppm): 6.23 (s, 2H), 3.94 (d, J = 5.7 Hz, 4H), 1.81 (m, 2H), (m, 48H), (m, 12H). 13 C NMR (CDCl 3, 100 MHz, δ/ppm): , , 97.61, 73.53, 37.84, 31.94, 31.88, 31.41, 30.03, 29.70, 29.61, 29.37, 26.88, 26.85, 22.71, MALDI-TF M (m/z): (M - H + ). 4

5 2,5-Diromo-3,6-is((2-hexyldecyl)oxy)thieno[3,2-]thiophene (TT-Br). To solution of TT (380 mg, 0.67 mmol) in chloroform (5 ml) ws dded NB (265 mg, 1.48 mmol) t room temperture. The mixture ws stirred for 3h. After removl of the solvent, the crude product ws purified vi column chromtogrphy (silic gel) using petroleum ether s eluent to give TT-Br s colorless oil (470 mg, 90%). 1 H NMR (CDCl 3, 400 MHz, δ/ppm): 4.09 (d, J = 5.5 Hz, 4H), 1.71 (m, 2H), (m, 48H), (m, 12H). 13 C NMR (CDCl 3, 100 MHz, δ/ppm): , , 95.30, 75.41, 38.54, 31.92, 31.85, 31.02, 31.01, 30.00, 29.67, 29.59, 29.35, 26.77, 26.75, 22.71, 22.69, MALDI-TF M (m/z): (M + ). PTTF2T. To mixture of TT-Br (102 mg, 0.13 mmol), (3,3'-difluoro-[2,2'- ithiophene]-5,5'-diyl)is(trimethylstnnne) (69.1 mg, 0.13 mmol), Pd 2 (d) 3 (6.0 mg, mmol) nd P(o-Tol) 3 (15.9 mg, mmol) in chlenk flsk ws dded toluene (3 ml) under rgon. The mixture ws heted to reflux for 28 h. Then the solution ws cooled to room temperture nd dded into 150 ml methnol dropwise. The precipitte ws collected nd further purified vi oxhlet extrction using methnol, hexne, nd chloroform in sequence. The chloroform frction ws concentrted nd dded into methnol dropwise. The precipitte ws collected nd dried under vcuum overnight to give PTTF2T s lck solid (85 mg, 77%). 1 H NMR (CDCl 3, 400 MHz, δ/ppm): 6.66 (r, romtic protons), 4.30 (r, liphtic protons), (r, liphtic protons). Elementl nlysis (%) clcd for C 46 H 68 F : C, 67.44; H, Found: C, 66.94; H,

6 3. NMR H Fig. 1 1 H NMR spectrum of 2-hexyldecne-1-thiol (CDCl 3, 298 K). H Fig C NMR spectrum of 2-hexyldecne-1-thiol (CDCl 3, 298 K). 6

7 Fig. 3 1 H NMR spectrum of TT (CDCl 3, 298 K). Fig C NMR spectrum of TT (CDCl 3, 298 K). 7

8 Br Br Fig. 5 1 H NMR spectrum of TT-Br (CDCl 3, 298 K). Br Br Fig C NMR spectrum of TT-Br (CDCl 3, 298 K). 8

9 Fig. 7 1 H NMR spectrum of TT (CDCl 3, 298 K). Fig C NMR spectrum of TT (CDCl 3, 298 K). 9

10 Br Br Fig. 9 1 H NMR spectrum of TT-Br (CDCl 3, 298 K). Br Br Fig C NMR spectrum of TT-Br (CDCl 3, 298 K). 10

11 F n F Fig H NMR spectrum of PTTF2T (CDCl 3, 298 K). F n F Fig H NMR spectrum of PTTF2T (CDCl 3, 298 K). 11

12 4. CV Fig. 13 Cyclic voltmmogrms for the polymers. 12

13 5. XRD Fig. 14 XRD ptterns for PTTF2T nd PTTF2T films. 13

14 6. Device friction nd mesurements Inverted solr cells The Zn precursor solution ws prepred ccording to literture. [3] It ws spin-coted onto IT glss (4000 rpm for 30 s). The films were nneled t 200 C in ir for 30 min. Zn film thickness is ~30 nm. A polymer: cceptor lend in chloroenzene (CB) with or without DI dditive ws spin-coted onto Zn lyer. Mo 3 (~6 nm) nd Ag (~80 nm) ws successively evported onto the ctive lyer through shdow msk (pressure c P). The effective re for the devices is 4 mm 2. The thicknesses of the ctive lyers were mesured y using KLA Tencor D-120 profilometer. J-V curves were mesured y using computerized Keithley 2400 ourcemeter nd Xenon-lmp-sed solr simultor (Enli Tech, AM 1.5G, 100 mw/cm 2 ). The illumintion intensity of solr simultor ws determined y using monocrystlline silicon solr cell (Enli RC2020, 2cm 2cm) clirted y NIM. The externl quntum efficiency (EQE) spectr were mesured y using QE-R3011 mesurement system (Enli Tech). Hole-only devices The structure for hole-only devices is IT/PEDT:P/ctive lyer/mo 3 /Al. A 30 nm thick PEDT:P lyer ws mde y spin coting n queous dispersion onto IT glss (4000 rpm for 30 s). PEDT sustrtes were dried t 150 C for 10 min. A polymer:cceptor lend in CB with or without DI dditive ws spin-coted onto PEDT lyer. Finlly, Mo 3 (~6 nm) nd Al (~100 nm) ws successively evported onto the ctive lyer through shdow msk (pressure c P). J-V curves were mesured y using computerized Keithley 2400 ourcemeter in the drk. 14

15 7. ptimiztion of device performnce Tle 1 ptimiztion of D/A rtio for PTTF2T:PC 71 BM inverted solr cells. D/A [w/w] 1: (1.93) 1: (4.30) 1: (4.58) 1: (4.60) 1: (4.12) Blend solution: 12 mg/ml in CB with 2 vol% DI; spin-coting: 1600 rpm for 60 s. Dt in prentheses stnd for the verge s for 10 cells. Tle 2 ptimiztion of the ctive lyer thickness for PTTF2T:PC 71 BM inverted solr cells. Thickness [nm] (3.91) (4.29) (4.32) (4.60) (4.32) D/A rtio: 1:2.5 (w/w); lend solution: 12 mg/ml in CB with 2 vol% DI. Dt in prentheses stnd for the verge s for 10 cells. 15

16 Tle 3 ptimiztion of DI content for PTTF2T:PC 71 BM inverted solr cells. DI [vol%] (0.54) (3.57) (4.60) (4.02) (3.99) (3.94) D/A rtio: 1:2.5 (w/w); lend solution: 12 mg/ml in CB; spin-coting: 1600 rpm for 60 s. Dt in prentheses stnd for the verge s for 10 cells. Tle 4 ptimiztion of D/A rtio for PTTF2T:ITIC inverted solr cells. D/A [w/w] 1: (3.80) 1: (4.62) 1: (4.02) Blend solution: 12 mg/ml in CB; spin-coting: 1600 rpm for 60 s. Dt in prentheses stnd for the verge s for 10 cells. 16

17 Tle 5 ptimiztion of the ctive lyer thickness for PTTF2T:ITIC inverted solr cells. Thickness [nm] (2.76) (3.95) (4.65) (4.94) (4.00) D/A rtio: 1:1.5 (w/w); lend solution: 12 mg/ml in CB. Dt in prentheses stnd for the verge s for 10 cells. Tle 6 ptimiztion of DI content for PTTF2T:ITIC inverted solr cells. DI [vol%] (4.94) (3.26) (0.64) D/A rtio: 1:1.5 (w/w); lend solution: 12 mg/ml in CB; spin-coting: 2000 rpm for 60 s. Dt in prentheses stnd for the verge s for 10 cells. 17

18 Tle 7 ptimiztion of D/A rtio for PTTF2T:PC 71 BM inverted solr cells. D/A [w/w] 1: (1.28) 1: (1.65) 1: (1.79) 1: (1.86) 1: (1.95) 1: (1.84) Blend solution: 18 mg/ml in CB with 2 vol% DI; spin-coting: 1200 rpm for 60 s. Dt in prentheses stnd for the verge s for 10 cells. Tle 8 ptimiztion of the ctive lyer thickness for PTTF2T:PC 71 BM inverted solr cells. Thickness [nm] (1.25) (1.62) (1.81) (2.00) (1.99) (1.88) D/A rtio: 1:1.8 (w/w); lend solution: 18 mg/ml in CB with 2 vol% DI. Dt in prentheses stnd for the verge s for 10 cells. 18

19 Tle 9 ptimiztion of DI content for PTTF2T:PC 71 BM inverted solr cells. DI [vol%] (0.27) (1.76) (2.03) (1.92) (1.95) D/A rtio: 1:1.8 (w/w); lend solution: 18 mg/ml in CB; spin-coting: 1400 rpm for 60 s. Dt in prentheses stnd for the verge s for 10 cells. Tle 10 ptimiztion of D/A rtio for PTTF2T:ITIC inverted solr cells. D/A [w/w] 1: (1.53) 1: (1.63) 1: (1.41) Blend solution: 12 mg/ml in CB; spin-coting: 2000 rpm for 60 s. Dt in prentheses stnd for the verge s for 10 cells. 19

20 Tle 11 ptimiztion of the ctive lyer thickness for PTTF2T:ITIC inverted solr cells. Thickness [nm] (1.67) (1.80) (1.70) (1.63) (1.59) D/A rtio: 1:1.5 (w/w); lend solution: 12 mg/ml in CB. Dt in prentheses stnd for the verge s for 10 cells. Tle 12 ptimiztion of DI content for PTTF2T:ITIC inverted solr cells. DI [vol%] (1.80) (1.26) (0.47) (0.14) D/A rtio: 1:1.5 (w/w); lend solution: 12 mg/ml in CB; spin-coting: 1600 rpm for 60 s. Dt in prentheses stnd for the verge s for 10 cells. 20

21 8. CLC Chrge crrier moility ws mesured y CLC method. The moility ws determined y fitting the drk current to the model of single crrier CLC, which is descried y: J 9 V 8 d 2 0 r 3 where J is the current density, μ is the zero-field moility of holes (μ h ), ε 0 is the permittivity of the vcuum, ε r is the reltive permittivity of the mteril, d is the thickness of the lend film, nd V is the effective voltge, V = V ppl V i, where V ppl is the pplied voltge, nd V i is the uilt-in potentil determined y electrode work function difference (here, V i = 0.1 V [4] ). The moility ws clculted from the slope of J 1/2 -V plots. 21

22 References [1] N. Hergué, P. Frère nd J. Roncli, rg. Biomol. Chem., 2011, 9, 588. [2] J. W. Jo, J. W. Jung, H.-W. Wng, P. Kim, T. P. Russell nd W. H. Jo, Chem. Mter., 2014, 26, [3] Y. un, J. H. eo, C. J. Tkcs, J. eifter nd A. J. Heeger, Adv. Mter., 2011, 23, [4] C. Dun, W. Ci, B. Hsu, C. Zhong, K. Zhng, C. Liu, Z. Hu, F. Hung, G. C. Bzn, A. J. Heeger nd Y. Co, Energy Environ. ci., 2013, 6,