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WO2017152354A1 - Motif donneur d'électrons, son copolymère et leurs procédés de préparation, ainsi que leurs utilisations - Google Patents

Motif donneur d'électrons, son copolymère et leurs procédés de préparation, ainsi que leurs utilisations Download PDF

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WO2017152354A1
WO2017152354A1 PCT/CN2016/075839 CN2016075839W WO2017152354A1 WO 2017152354 A1 WO2017152354 A1 WO 2017152354A1 CN 2016075839 W CN2016075839 W CN 2016075839W WO 2017152354 A1 WO2017152354 A1 WO 2017152354A1
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mixture
electron
polymer
conducted
thiophene
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Xugang GUO
Xiaojie GUO
Qiaogan LIAO
Yongye Liang
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Southwest University of Science and Technology
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Definitions

  • the present invention belongs to the field of semiconductor material, in particular to an electron-donating unit, a copolymer thereof and their preparation methods, as well as their uses.
  • Polymer semiconductors have received great attention due to their potential for fabricating diverse opto-electrical devices using solution-based processing techniques, such as coating and printing 1-3 .
  • the solution processability enables the fabrication of cost-effective, large area, and mechanically flexible electronic devices, such as organic thin-film transistors (OTFTs) and polymer solar cells (PSCs) 2, 4-6 .
  • OFTs organic thin-film transistors
  • PSCs polymer solar cells
  • the semiconducting materials should possess well-tailored bandgaps, energetically optimized frontier molecular orbitals (FMOs) , a desirable film morphology, and good solubility 4, 7-15 .
  • FMOs frontier molecular orbitals
  • polymer semiconductors are typically functionalized with solubilizing alkyl side chain substituents.
  • alkylation patterns must be strategically manipulated to minimize steric hindrance, hence head-to-head (HH) linkages should be avoided in semiconducting polymer design to minimize accompanying backbone torsion, which reduces conjugation along the polymer chain, compromises film crystallinity/order, and diminishes charge carrier mobility 16-19 .
  • HH head-to-head
  • the backbone In order to achieve high degrees of macromolecular backbone planarity for enhanced charge carrier delocalization, the backbone must be designed to energetically favor planar conformations versus any twisted alternatives. Although in principal conjugated backbones should be energetically favored in planar conformations, adverse steric interactions, mainly from side substituents, often prevent realization of this ideal case.
  • two materials design strategies are widely employed in polymer electronics, 1) reducing steric hindrance by inserting spacers (or bridges) along the chain 17, 20 , and 2) conformation locking with covalent bonds 21, 22 or non-covalent.
  • spacers mainly unsubstituted thiophene (or thiazole) derivatives
  • PBTTT and PQT 20 have yielded great success in high-performance semiconductors such as PBTTT and PQT 20, 23-27 .
  • the spacer incorporation requires additional steps in the monomer synthesis 28-30 and could also dilute the concentration of key building blocks, typically the acceptor units, in the polymeric backbones, risking sub-optimal opto-electronic properties for the resulting semiconductors 31-34 .
  • such spacers are typically nonalkylated, which could reduce polymer solubilities 17, 35, 36 .
  • Form 2 Conformation locking through covalent bonds (Formula 2) has also provided great success as a planarizining design strategy, however, the sp 3 orbital hybridization of the bridging atoms, such as C, Si, and Ge, leads to out-of-plane substituent orientation, thereby enlarging intermolecular stacking distances, reducing interchain ⁇ - ⁇ orbital overlap, and lowering carrier mobilities 21, 22, 37 . Therefore, polymer semiconductors containing cyclopentadithiophene or dithienosilole (germole) frequently have limited OTFT mobilities and suboptimal fill factors (FFs; ⁇ 70%) in bulk heterojunction (BHJ) PSCs 38-41 .
  • FFs suboptimal fill factors
  • Poly (3, 4-ethylenedioxythiophene) (PEDOT) is a widely used conducting polymer with high doped state conductivity 42, 43 which is partially attributed to substantial backbone planarity 44 .
  • PEDOT polyethylenedioxythiophene
  • 2-bis (3, 4-ethylenedioxythiophene) the distance between the (thienyl) sulfur and (3, 4-ethylenedioxy) oxygen atoms (S...O) is substantially below the sum of the S and O van der Waals radii
  • This intramolecular non-covalent S...O interaction promotes a planar backbone conformation and charge carrier delocalizations 41, 46, 47 .
  • Yoshimura developed an electron rich 5H-dithieno [3, 2-b: 2’ , 3’ -d] pyran (DTP, Figure 1c) 62 , which has greater electron-donating capacity than cyclopentadithiophene 63 .
  • DTP Figure 1c
  • the resulting polymer semiconductor exhibits a smaller bandgap than the cyclopentadithiophene counterpart but maintains a decent V oc of 0.7 V.
  • the PSCs show promising power conversion efficiencies (PCEs) of 8.0% 62 and 10.6% 64 in single junction and tandem cells, respectively.
  • the present invention provides the design and synthesis of the novel electron-donating 3-alkyl-3’ -alkoxy-2, 2’ -bithiophene (TRTOR) unit ( Figure 1e) and that its incorporation into copolymers affords semiconductors (Formula 4) with good materials solubility, high degrees of backbone planarity, appropriately placed FMOs, and ordered film morphologies.
  • TRTOR novel electron-donating 3-alkyl-3’ -alkoxy-2, 2’ -bithiophene
  • R 1 is a straight or branched alkyl, preferably having 5-15 carbon atoms, and more preferably having 7-12 carbon atoms
  • R 2 is a straight or branched alkyl, preferably having 5-15 carbon atoms, and more preferably having 7-12 carbon atoms
  • R 1 and R 2 are same or different.
  • TRTOR is a 2H-pyran ring opened DTP, hence TRTOR should have electronic properties comparable to those of DTP.
  • Density functional theory (DFT) computation demonstrates a planar backbone conformation for TTOR unit ( Figure 1d) , which is functionalized with a single solubilizing alkoxy chain. The introduction of an extra alkyl chain on the 3-position of thiophene should not be detrimental to the TRTOR backbone planarity. Indeed this is confirmed by the DFT computation, which indicates that a TRTOR-containing HH linkage maintains a planar conformation enabled by the single planarizing alkoxy side chain ( Figure 1e) 46, 50 .
  • TRTOR is a more promising building block since it contains more solubilizing substituent chains and has a more symmetrical structure.
  • the asymmetric single-chain functionalized bithiophene based polymer exhibits poor PSC device performance 32 .
  • TRTOR has a low-lying HOMO at -4.92 eV --0.25 eV below that of BTOR (-4.67 eV) and comparable to that of DTP (-4.97 eV; Figure 1) . Therefore, TRTOR-based copolymers should have lower-lying HOMOs versus the BTOR-based counterparts, which will benefit both OTFT and PSC device performance.
  • TRTOR is a promising building block for polymer semiconductor construction due to its planar conformation, solubilizing characteristics, appropriately lying HOMO, and centrosymmetric geometry.
  • the present invention provides a copolymer of the electron-donating unit described herein having the Formula 4,
  • R 1 is a straight or branched alkyl, preferably having 5-15 carbon atoms, and more preferably having 7-12 carbon atoms
  • R 2 is a straight or branched alkyl, preferably having 5-15 carbon atoms, and more preferably having 7-12 carbon atoms
  • R 1 and R 2 are same or different
  • ⁇ is an electron-deficient group
  • n depends on the desired solubility of the copolymer, preferably being 5-80.
  • ⁇ is selected from the following group:
  • R is a straight or branched alkyl, preferably having 5-15 carbon atoms, and more preferably having 7-12 carbon atoms.
  • phthalimide 10, 57, 66 was chosen as the in-chain acceptor unit for constructing a copolymer semiconductor series. It will be seen that the resulting phthalimide-TRTOR polymers exhibit promising device performance in both ogranic thin-film transistors and polymer solar cells, with the PCE (6.3%) of the phthalimide-TRTOR polymer being among the highest reported to date for phthalimide-based polymers 10 . These results demonstrate that a single planarizing alkoxy substituent to reduce steric emcumbrance and an S...O interaction to lock the polymer backbone toward planarity render TRTOR a promising building block for polymer semiconductor construction. Materials structure-property-device performance correlations are established here, and offer useful insights into organic electronics materials design. We believe that more promising performance can be realized by optimizing the chemical structures of TRTOR-based materials.
  • the present invention provides a preparation method of the electron-donating unit described herein wherein R 1 and R 2 are straight alkyls comprising:
  • the mole ratio of the 2-bromo-3-alkoxy-thiophene to the alkali carbonate is 1: 0.5-2, for example, 1: 0.8, 1: 1.2, 1: 1.7 and so on, preferably 1: 0.7-1.5, more preferably 1: 1.
  • the ratio of the organic solvent or water to the 2-bromo-3-alkoxy-thiophene is 2-10 mL/mmol, for example, 3 mL/mmol, 5 mL/mmol, 8 mL/mmol and so on, preferably 3-7 mL/mmol; the ratio of the THF or water to the 2-bromo-3-alkoxy-thiophene may be same or different.
  • the alkali carbonate is selected from K 2 CO 3 , Na 2 CO 3 , Li 2 CO 3 or a mixture of at least two of them.
  • the organic solvent is selected from THF, EtOH, dioxane, DMF, toluene or a mixture of at least two of them.
  • time of the purging is more than 10 minutes, preferably more than 20 minutes, more preferably 30 minutes.
  • the mixture is heated to 50-80 °C, for example, 55 °C, 57 °C, 65 °C, 74 °C and so on; preferably to 70 °C;
  • the inert gas is selected from any one of Ar, N 2 , He, Ne, or a mixture of at least two of them.
  • the mole ratio of the Pd (PPh 3 ) 4 to the 2-bromo-3-alkoxy-thiophene is 1: 5-20, for example, 1: 7, 1: 11, 1: 16 and so on, preferably 1: 8-15, more preferably 1: 10.
  • time of the purging is more than 5 minutes, preferably more than 10 minutes, more preferably 20 minutes.
  • the mixture is heated to 50-80 °C, for example, 55 °C, 57 °C, 65 °C, 74 °C and so on; preferably to 70 °C.
  • the inert gas is selected from any one of Ar, N 2 , He, Ne, or a mixture of at least two of them.
  • step (3) the 2- (3-alkylthiophen-2-yl) -4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolane is added with a mole ratio to the 2-bromo-3-alkoxy-thiophene of 1: 3-15, for example, 1: 4, 1: 7, 1: 14 and so on, preferably 1: 5-10, more preferably 1: 6.3.
  • the 2- (3-alkylthiophen-2-yl) -4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolane is added dropwise.
  • the mixture is refluxed at 50-80 °C, for example, 55 °C, 57 °C,65 °C, 74 °C and so on; preferably at 70 °C.
  • step (4) the reaction mixture is extracted with organic solvent, preferably with DCM.
  • the washing is conducted with water and brine.
  • step (5) the concentrating is conducted under reduced pressure.
  • the purifying is conducted by column chromatography using petroleum ether as an eluent.
  • the present invention provides a preparation method of the electron-donating unit described herein wherein R 1 or/and R 2 is (are) branched alkyl comprising:
  • step (1) the ratio of the 2-bromo-3-alkoxy-thiophene to 2- (3-alkylthiophen-2-yl) -4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolane is 1: 0.5-1, preferably 1: 0.7-0.9, more preferably 1: 0.8.
  • the mixture is stirred and purged with an inert gas.
  • the inert gas is selected from any one of Ar, N 2 , He, Ne, or a mixture of at least two of them.
  • the ratio of the solvent to the 2-bromo-3-alkoxy-thiophene is 10-80 mL/g, preferably 20-50 mL/g.
  • step (2) the mixture is heated to 100-120 °C for 10-20 h, more preferably the mixture is heated to 100-110 °C for 13-18 h.
  • the Aliquat is in toluene.
  • the alkali carbonate is selected from K 2 CO 3 , Na 2 CO 3 , Li 2 CO 3 or a mixture of at least two of them.
  • the mass ratio of [Pd (PPh 3 ) 4 ] , Aliquat, and alkali carbonate is 1: 1-5: 2-10, for example, 1: 2: 5, 1: 4: 9, 1: 3: 4 and so on, preferably 1: 2-3: 3-8, more preferably 1: 2.5: 5.
  • step (4) the reaction mixture is extracted with organic solvent, preferably with DCM.
  • the washing is conducted with water.
  • the drying is conducted over MgSO 4 .
  • step (5) the concentrating is conducted under reduced pressure.
  • the purifying is conducted by column chromatography or silica gel using petroleum ether as an eluent.
  • the present invention provides a preparation method of the copolymer described herein comprising:
  • step (4) drying the solid precipitate obtained in step (4) to give the crude product, and then extracting the crude product;
  • the electron-deficient material is selected from the following group:
  • the mole ratio of the electron-donating unit of claim 1 to the electron-deficient material is 1: 0.5-2, for example, 1: 0.8, 1: 1.2, 1: 1.8 and so on, preferably 1: 0.8-1.5, more preferably 1: 1.
  • the mole ratio of the tris (dibenzylideneacetone) dipalladium (0) (Pd 2 (dba) 3 ) to tris (o-tolyl) phosphine (P (o-tolyl) 3 ) is 1: 4-15, for example, 1: 6, 1: 9, 1: 13 and so on, preferably 1: 6-10, more preferably 1: 8; the Pd loading is 0.005-0.1 equiv, preferably 0.01-0.06.
  • reaction vessel and the mixture are subjected to 1-5 pump/purge cycles with Ar.
  • the inert gas is selected from any one of Ar, N 2 , He, Ne, or a mixture of at least two of them.
  • the inert gas is selected from any one of Ar, N 2 , He, Ne, or a mixture of at least two of them.
  • the organic solvent is selected from any one of anhydrous toluene, benzene, chlorobenzene, DMF, or a mixture of at least two of them.
  • the ratio of the organic solvent to the electron-donating unit is 10-75 mL/mmol, preferably 5-50 mL/mmol.
  • the heating is conducted at 50-170 °C for 1-72h, preferably at 80-150 °C for 3-50h.
  • the heating is conducted under microwave irradiation.
  • the heating is conducted by 80 °C for 10 minutes, 100 °C for 10 minutes, and 140 °C for 3 h under microwave irradiation.
  • step (3) the heating is conducted at 80-170 °C for more than 0.2 h, preferably at 100-160 °C for more than 0.4 h.
  • the heating is conducted under microwave irradiation.
  • the heating is conducted under microwave irradiation at 140 °C for 0.5 h;finally, adding 2-bromothiophene and stirring the reaction mixture at 140 °C for another 0.5 h.
  • the mole ratio of the 2- (tributylstanny) thiophene to the electron-donating unit is 0.1-0.5: 1, for example, 0.2: 1, 0.4: 1 and so on, preferably 0.2: 0.4-1.
  • the mole ratio of the 2-bromothiophene to the electron-donating unit is 0.2-1.5: 1, for example, 0.4: 1, 0.8: 1, 1.3: 1 and so on, preferably 0.4: 0.8-1; preferably, in step (4) , the methanol contains 0.5-10mL hydrochloric acid,preferably 0.5-10mLof 5-20 mol/L hydrochloric acid.
  • the dripping is conducted under vigorous stirring, preferably is conducted for at least 0.5 h, preferably at least 1 h.
  • step (6) the dripping is conducted under vigorous stirring.
  • the collecting is conducted by filtration.
  • the drying is conducted under reduced pressure.
  • the present invention provides an use of the copolymer according to the present invention in thin-film transistor or polymer solar cell.
  • the raw material used in above preparation method can be prepared by known method in the art or by the following method described below or buying on the market.
  • TRTOR head-to-head linakge containing electron-donating 3-alkyl-3’ -alkoxy-2, 2’ -bithiophene (TRTOR) unit for constructing high-performance polymer semiconductors.
  • TRTOR 3-alkyl-3’ -alkoxy-2, 2’ -bithiophene
  • BTOR 3’ -dialkoxy-2, 2’ -bithiophene (BTOR) unit having two alkoxy substituents, which utilizes the reduced steric hindrance of the O (versus CH 2 ) and conformation locking effect of intramolecular S...O non-covalent interactions to induce backbone planarity
  • TRTOR reported here has a single planarizing alkoxy substituent hence an optimized single S...O interaction.
  • TRTOR has comparable electronic properties but a centrosymmetric geometry, promoting a more compact and ordered structure than DTP, which is axisymmetric with out-of-plane substituents.
  • TRTOR is an effective building block for constructing high-performance polymer semiconductors due to its solubilizing ability, centrosymmetric geometry, backbone planarity, compact packing, and appropriate electron donating ability versus the previously reported BTOR and DTP units.
  • a head-to-head linkage containing one alkyl chain and one alkoxy substituent at the bithiophene 3-positions can achieve planar backbones due to reduced steric hindrance and intramolecular non-covalent S...O interactions, and strategically employing single S...O interactions is thus a promising strategy for materials design in organic electronics.
  • Figure 1 are chemical structures, optimized geometries, and energy levels of the frontier molecular orbitals of (a) 3, 3’ -dialkyl bithiophene (BTR) ; (b) 3, 3’ -dialkoxy bithiophene (BTOR) ; (c) 5H-dithieno [3, 2-b: 2’ , 3’ -d] pyran (DTP) ; (d) 3-alkoxy-2, 2’ -bithiophene (TTOR) , and (e) 3-alkyl-3’ -alkoxy-2, 2’ -bithiophene (TRTOR) ; calculations carried out at the DFT//B3LYP/6-31G**level, alkyl substituents truncated here to simplify the calculations.
  • FIG. 7 TEM images of P1 (aand h) , P2 (b and i) , P3 (c and j) , P4 (d and k) , P5a (e and l) , P5b (f and m) , and P5c (g and n) bulk heterojunction blend (polymer: PC 71 BM) films processed without (up row) and with (bottom row) processing additive, 1, 8-octanedithiol (ODT) . (Scale bar: 500 nm) .
  • Figure 10 Computed optimized geometry for the repeating units of DTP-based polymer P3 (a) and TRTOR-based polymer P5 (b) .
  • the calculations were carried out at the DFT//B3LYP/6-31G**level, alkyl substituents are truncated here to simplify the calculations.
  • FIG. 16 AFM topographical images of polymer: PC 71 BM blend films of P1 (a, h) , P2 (b, i) , P3 (c, j) , P4 (d, k) , P5a (e, l) , P5b (f, m) and P5c (g, n) processed without (1 st and 2 nd rows) and with (3 rd and 4 th rows) additive, 1, 8-octanedithiol.
  • the image size is 5 ⁇ m ⁇ 5 ⁇ m.
  • the monomer (5, 5-bis (3, 7-dimethyloctyl) -5H-dithieno [3, 2-b: 2’ , 3’ -d] pyran-2, 7-diyl) bis (tributylstan nane) was purchased from SunaTech Inc. (Suzhou, Jiangsu) , and 5, 5’ -bis (trimethylstannyl) -3, 3’ -bis (dodecyl-oxy) -2, 2’ -bithiophene was synthesized via the published procedures 88 . All other reagents were used as received except where noted. Unless otherwise stated, all manipulations and reactions were carried out under argon using standard Schlenk line techniques. Polymerizations were carried out on Initiator+ Microwave Synthesizer (Biotage, Sweden) .
  • TGA curves were recorded on a TA Instrument (Mettler, STAR e ) .
  • UV-Vis data were recorded on a Shimadzu UV-3600 UV-VIS-NIR spectrophotometer.
  • Cyclic voltammetry measurements of polymers were carried out under argon atmosphere using a CHI760E voltammetric analyzer with 0.1 M tetra-n-butylammonium hexafluorophosphate in acetonitrile as supporting electrolyte.
  • a platinum disk working electrode, a platinum wire counter electrode and silver wire reference electrode were employed, and F c /F c+ was used as internal reference for all measurements.
  • the scan rate was 100 mV/S.
  • Polymer films were drop-coated from chloroform solutions on a Pt working electrode (2 mm in diameter) .
  • the supporting electrolyte solution was thoroughly purged with Ar before all CV measurements.
  • AFM measurements of polymer: PCBM blend films were performed by using a Dimension Icon Scanning Probe Microscope (Asylum Research, MFP-3D-Stand Alone) in tapping mode.
  • TEM specimens were prepared following identical conditions as the actual devices, but were drop-cast onto 40 nm PEDOT: PSS covered substrate. After drying, substrates were transferred to deionized water and the floated films were transferred to TEM grids.
  • TEM images were obtained on Tecnai Spirit (20 kV) TEM.
  • Reagents/conditions in Scheme 1 are: (i) NBS, chloroform, HOAc; (ii) n-BuLi, isopropoxyboronic acid pinacol ester, THF; (iii) ROH, PTSA, toluene, 110 °C; (iv) NBS, DMF; (v) Pd (PPh 3 ) 4 , K 2 CO 3 , THF, H 2 O; (vi) n-BuLi, Me 3 SnCl, THF (vii) Pd 2 (dba) 3 , P (o-tolyl) 3 , toluene, microwave, 140 °C.
  • 2-bromo-3-dodecyl-thiophene 2a (4.0 g, 12.07 mmol) was added into an oven dried flask and then dissolved in 90 mL anhydrous THF under argon. After cooling to -78 °C, n-BuLi (13.28 mmol, 8.30 mL, 1.6 M in hexane) was added dropwise and the whole was stirred at -78 °C for 50 min. Then 2-isopropoxy-4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolane (2.47 g, 13.28 mmol) was added in one portion and the reaction mixture was warmed to room temperature and stirred overnight.
  • NBS (1.83 g, 10.29 mmol) was added in one portion to 5a (2.5 g, 9.8 mmol) in 20 mL DMF at 0 °C and the whole was warmed to room temperature and stirred for 15 h.
  • the reaction mixture was diluted with ether (50 mL) and washed with water (2 ⁇ 20 mL) .
  • the organic layer was dried over MgSO 4 , concentrated under reduced pressure, and the residue was subjected to column chromatography (silica gel, petroleum ether) to give 6a as a colorless solid (3.02 g, 92.4 %) .
  • Monomer 10 was prepared and isolated as a colorless oil from 9 using the same procedures employed for monomer 8a (82 %) .
  • 1 H NMR (CDCl 3 , 400MHz, ppm) ⁇ 7.03 (s, 2H) , 2.52 (t, 4H) , 1.56 (m, 4H) , 1.25 (m, 36H) , 0.90 (t, 6H) , 0.38 (s, 18H) .
  • Monomer 12 was synthesized following the same procedure employed in synthesis of compound 8a.
  • 1 H NMR 400MHz, CDCl 3 , ppm) : 7.37 (d, 1H) , 7.11 (d, 1H) , 6.91 (s, 1H) , 4.15 (t, 2H) , 1.87 (m, 2H) , 1.56 (m, 2H) , 1.35 (m, 16H) , 0.91 (t, 3H) , 0.40 (s, 18H) .
  • the tube was sealed under argon flow and then stirred at 80 °C for 10 minutes, 100 °C for 10 minutes, and 140 °C for 3 h under microwave irradiation. Then, 0.1 mL of 2- (tributylstanny) thiophene was added and the reaction mixture was stirred under microwave irradiation at 140 °C for 0.5 h. Finally, 0.2 mL of 2-bromothiophene was added and the reaction mixture was stirred at 140 °C for another 0.5 h. After cooling to room temperature, the reaction mixture was slowly dripped into 100 mL of methanol (containing 5 mL 12 N hydrochloric acid) under vigorous stirring.
  • the solid precipitate was transferred to a Soxhlet thimble.
  • the crude product was subjected to sequential Soxhlet extraction with the choice of solvents and sequence depending on the solubility of the particular polymer.
  • the polymer solution was concentrated to approximately 20 mL, and then dripped into 100 mL of methanol under vigorous stirring. The polymer was collected by filtration and dried under reduced pressure to afford deep colored solid as the product.
  • P1 1 was synthesized by following Scheme 17.
  • Polymer P3 containing the 5H-dithieno [3, 2-b: 2’ , 3’ -d] pyran (DTP) 62 electron donor unit has a bandgap of 1.93 eV, which is between that of P1 (2.42 eV) and P2 (1.65 eV) .
  • the larger P3 bandgap (1.93 eV) is attributed to the weaker electron donating ability of DTP which contains one electron donating OR and one CH 2 versus two ORs in BTOR.
  • TRTOR should be a more effective unit for creating narrow bandgap polymers than DTP.
  • P3 has a low-lying HOMO of -5.34 eV due to the moderate DTP electron donating ability 62 and torsional polymer backbone 20, 73 .
  • polymer P4 shows a slightly higher-lying HOMO at -5.28 eV, attributable to the higher degree of P4 conjugation due to more planar backbone and compact packing 74 .
  • replacement of one alkoxy substituent by an alkyl substituent lowers the P5a HOMO (-5.19 eV) by 0.26 eV vs that of P2 (-4.93 eV) .
  • Polymer P5c with a branched N-2-ethylhexyl group has a slightly lower HOMO (-5.25 eV) than P5a (-5.19 eV) and P5b (-5.18 eV) with linear N-alkyl substituents 74 .
  • polymers P5a-c have slightly higher HOMOs, likely due to the weak electron-donating P5 alkyl substituent.
  • reaction mixture was stirred at room temperature overnight.
  • the reaction was quenched with 2 M of hydrochloric acid (15mL) .
  • DCM was added and the organic layer was washed three times with water.
  • the organic layer was dried over MgSO 4 and the solvent was removed under reduced pressure.
  • the crude product was passed through silica gel using PE as an eluent to give colorless oil (3g, 39.6%) .
  • 3-methoxythiophene (3.0 g, 26.28 mmol) , 2-propylheptan-1-ol (4.159g, 26.28mmol) and anhydrous sodium hydrogen sulfate (0.5 g, 4.16 mmol) were charged into around bottom flask.
  • Toluene (100 mL) was then added, purged by argon for 30 min and the mixture was heated to 130 °Cfor 19 hr under argon protection. After cooling to room temperature, saturate NaHCO 3 water was added and extraction with ethyl acetate was done. The organic layer was dried over anhydrous MgSO 4 , filtered and concentrated for purification via column chromatography (silica gel, PE 100%) to afford compound 5c (3.5g, 55.4%) .
  • This compound was prepared with the same procedure according to 6c.
  • This compound was prepared with the same procedure according to 7c.
  • This compound was prepared with the same procedure according to 8c.
  • This compound was prepared with the same procedure according to 1c.
  • This compound was prepared with the same procedure according to 2c.
  • This compound was prepared with the same procedure according to 3c.
  • the tube was sealed under argon flow and then stirred at 80 °C for 10 minutes, 100 °C for 10 minutes, and 140 °C for 3 h under microwave irradiation. Then, 0.05 mL of 2- (tributylstanny) thiophene was added and the reaction mixture was stirred under microwave irradiation at 140 °C for 0.5 h. Finally, 0.10 mL of 2-bromothiophene was added and the reaction mixture was stirred at 140 °C for another 0.5 h. After cooling to room temperature, the reaction mixture was slowly dripped into 100 mL of methanol (containing 1 mL 12 N hydrochloric acid) under vigorous stirring.
  • the UV-Vis absorption spectra show bathochromic shifts due to the F atom influence. From solution to film state, the polymers show bathochromic shifts due to the increased backbone planarity and enhanced aggregation.
  • Top-gate/bottom-contact (TG/BC) device structure was used to investigate the charge transport property of polymers in organic thin-film transistors (OTFTs) .
  • OTFTs organic thin-film transistors
  • polymer solution was spin-coated at 1500 rpm for 120 sec in N 2 -purged glove box.
  • the polymer semiconductor films were then thermally annealed in a N 2 -purged glove box at 150, 175, 200, 225, 250, or 275 °C for 30 min.
  • PMMA poly (methyl methacrylate)
  • n-butyl acetate 80 mg/mL
  • Pre-patterned ITO-coated glass with a sheet resistance of ⁇ 10 ⁇ / ⁇ is used as the substrate, which is cleaned by sequential sonication in water containing detergent, deionized water, methanol, isopropanol, and acetone followed by UV/ozone (BZS250GF-TC, HWOTECH, Shenzhen) treatment for 20 min.
  • ZnO precursor was prepared according to the published procedure 89 .
  • the precursor solution was spin-coated (4000 rpm for 30 s) onto the pre-patterned ITO-coated glass.
  • the films were annealed at 200 °C for 30 min in air, and then transferred into a N 2 glovebox.
  • the ZnO film thickness is about 30 nm.
  • PC 71 BM blend (1: 1.6 w/w, 26 mg/mL)
  • P1 PC 71 BM
  • P2 PC 71 BM
  • P3 PC 71 BM
  • P4 PC 71 BM
  • P5a PC 71 BM
  • ODT 8-octanedithiol
  • Grazing incidence wide-angle x-ray scattering (GIWAXS) measurements were performed at Beamline 8-ID-E of the Advanced Photon Source at Argonne National Laboratory. Polymer samples were prepared on Si substrate using identical spin speeds, solvents, concentrations and annealing temperature and times to the relevant OTFT and PSC devices. All spectra were collected in air. The photon energy is 7.35 keV and data were collected on a Pilatus 1M pixel array detector at a sample-detector distance of 204 mm. Spectra were collected at an incidence angle of 0.2°; the films were exposure for 20 seconds. To account for the gaps in the detector array, two images were taken per sample, one with the detector in the standard position and the other translated 23 mm down to fill the gap, the two images are then merged.
  • GIWAXS Grazing incidence wide-angle x-ray scattering
  • 1D line cuts were taken from the 2D scattering spectra in the in-plane and out-of-plane directions using the GIXSGUI software package developed by the beamline scientists. To account for air scatter, the line cuts were background subtracted utilizing an exponential fit. The background-subtracted peaks were fit using the multipeak fit function in igor pro. Scherrer analysis was performed utilizing the method by Smiglies 90 to account for instrumental broadening and detection limits in the 2d detector. The values presented represent a lower limit for correlation length, as the Scherrer analysis does not account for broadening due to defects in the crystallites.
  • the data are the average value calculated from 5 devices at least.
  • BTR-based polymer P1 is inactive in OTFTs, which is attributed to the very low-lying HOMO (-5.66 eV) , twisted polymer backbone, limited conjugation, and low degree of crystallinity 79 .
  • P2 shows a high hole mobility ( ⁇ h ) of 1.45 cm 2 /Vs, which is almost 10x than in bottom-gate/bottom-contact OTFTs (0.17 cm 2 /Vs) 57 .
  • the high P2 mobility can be partially ascribed to facile hole injection from the gold electrode to the high-lying HOMO, since the bottom-contact gold electrode has lower work function of ca. -4.5 –-4.7 eV.
  • P5a shows a > 1000x smaller off-current (10 -12 –10 -11 A) and ⁇ 100x higher I on /I off (10 5-6 ) in the linear region ( Figure 4a) , primarily ascribable to the lower-lying P5a HOMO. Due to the enhanced solubility, P5b and P5c containing short alkyl substituents are also sufficiently soluble for OTFT fabrication, and the resulting OTFTs has appreciable ⁇ h s of 0.043 and 0.030 cm 2 /Vs, respectively.
  • the enhanced P5a mobility with longer alkyl substituents could be attributed to the smaller ⁇ - ⁇ stacking and more ordered microstructure derived from the side chain crystallization 47 as revealed by the grazing incidence wide-angle X-ray scattering (GIWAXS, vide infra) .
  • GIWAXS grazing incidence wide-angle X-ray scattering
  • P5a films have lower carrier mobility, which is likely due to the lower-lying HOMO and hence a larger charge injection barrier.
  • the large V oc is ascribed to the twisted polymer backbone 73 , and the small J sc to the sub-optimal blend film morphology (vide infra) and the negligible carrier mobility as measured from both OTFT/in-plane (Table 2) and space-charge limited current (SCLC, Table 5) /out-of-plane techniques.
  • the J sc s integrated from external quantum efficiency (EQE, Figure 12) vs an AM1.5 reference spectrum are within ⁇ 5%of those acquired from the J-V data, showing good internal consistency.
  • TRTOR-based P5 shows greatly increased PSC performance in V oc s, EQE, and FFs.
  • the V oc enhancement is attributed to the depressed HOMO achieved by replacing one alkoxy with an alkyl substituent, and in comparison to P3, the substantially enhanced J sc and FF are ascribed to the smaller P5 bandgap, closer packing, and higher mobility.
  • VOC of PSC is proportional to the difference between the HOMO level of polymer and the LUMO level of PC71BM, therefore,the F atom could lower the polymer LUMO and HOMO, so the polymer P1’ have lower HOMO than P2’ a nd P3’ , and the lower lying HOMO level of P1’ compare with P2’ a nd P3’ .
  • the hole-only and electron-only devices with a structure of ITO/PEDOT: PSS/polymer: PC 71 M/MoO 3 /Ag and Al/polymer: PC 71 BM/Ca/Al, respectively, are fabricated with or without using the processing additive, 1, 8-octanedithiol (ODT) .
  • Grazing incidence wide-angle X-ray scattering was carried out at beamline 8-ID-E of the advanced photon source to examine polymer film microstructure and morphology.
  • the polymer films were prepared neat on octyldecyltrichlorosilane (OTS) -modified Si substrates, blended with PC 71 BM, and blended with PC 71 BM processed with 3% (v/v) ODT as the processing additive on bare Si.
  • OTS octyldecyltrichlorosilane
  • 2D images for the blend films processed with ODT are presented in Figure 7 and the 2D images for the neat films and the blend films without using processing additive are shown in the Supporting Information ( Figures 13 and 14 ) .
  • 1 indicates a preferential face-on domain.
  • 2 indicates a preferential edge-on domain.
  • the neat polymer films exhibit a range of differing preferred orientations and relative crystallinities (Figure 5) .
  • Polymers P2 and P5 featuring intramolecular S...O interaction show similar lamellar and ⁇ - ⁇ stacking structures, while polymers P1, P3, and P4 appear to have more disparate stacking structures.
  • the BTR-based polymer P1 demonstrates in-plane (q xy ) peaks that each would be consistent with a face-on lamellar structure.
  • the DTP-based polymer P3 is almost completely amorphous with only a broad peak at and no further intermolecular order, which is attributed to its slightly twisted polymer backbone and the out-of-plane side chain orientation.
  • P4 demonstrates a clear edge-on orientation with a lamellar (100) spacing of and a ⁇ - ⁇ stacking distance of Therefore on the basis of the ⁇ - ⁇ stacking distance, the use of TTOR leads to more compact packing for P4 versus the BTR-based polymer P1, which could be attributed to the reduced steric hindrance and the planarizing intramolecular S...O interaction.
  • the diffraction patterns show that none of polymers P2, P5a, P5b and P5c demonstrate a clear preference for edge-on or face-on orientation in neat films as they show lamellar (100) and ⁇ - ⁇ stacking (010) diffractions in both the in-plane (q xy ) and out-of-plane (q z ) directions ( Figure 5) .
  • P5a shows the largest (010) correlation lengths (5.8 nm; Table 8) , which in combination with its smallest ⁇ - ⁇ stacking distance is likely contributed to its highest mobility among the polymers P5a-c.
  • the cells have a structure of ITO/ZnO/polymer: PC 71 M/MoO 3 /Al and are fabricated without using processing additive, 1, 8-octanedithiol.
  • the high planarity of the TRTOR unit enabled by the inclusion of the alkoxy side chains allows for very strong face-on (010) orientation. Due to the reduced side chain bulk breaking up domains on P5b, Scherrer analysis reveals larger face-on (010) domains in P5b than P5a, P5c, and P2 in both blends with and without ODT. This extended ⁇ - ⁇ periodicity helps explain the increased FF and J sc in P5b leading to its peak PSC performance in this polymer series.
  • the replacement of one alkoxy chain with an alkyl chain can result in a better mixing between the polymer donors P5 and the acceptor PC 71 BM.
  • the higher J sc and FF in combination of the much larger V oc lead to the substantial higher PCE (6.31%) for P5b PSCs versus that (3.38%) of P2 cells.
  • the introduction of alkyl chain on the 3-position of bithiophene in TRTOR leads to crystalline packing more favorable to device performance with a standard lamellar and close ⁇ - ⁇ stacking morphology and favorable polymer orientation for TRTOR-based polymers.
  • the TRTOR-based polymers show greatly improved J sc , FF, and PCE due to their more planar backbone, higher degree of crystallinity with favorable backbone orientation, and higher charge carrier mobility.
  • Figure 19 shows J-V curves of the photovoltaic devices based on the five polymers P1’ -P6’ with PC 71 BM.
  • P1’ s hows the optimized device performance and the polymer for comparison.
  • the photovoltaic performance of corresponding device is listed in table 4.
  • the device based on P1’ exhibited a significantly improved PCE of 7.86%with a J SC of 17.984mA cm -2 , a V oc of 0.663V, and a FF of 66.0%.
  • the Voc is decreased from 0.663 to 0.533V, and through change the dialkyl side chain, the Voc have a small change, the dialkyl side chain is long, and then the Voc is increase, because the long dialkyl side chain have steric hindrance, so the HOMO is low, and follow with high Voc.
  • TRTOR novel electron donor unit
  • TRTOR contains a head-to-head linkage and hence possesses good solubilizing capability.
  • TRTOR shows well-tailored opto-electrical property and high degree of backbone planarity enabled by the use of a single alkoxy side chain, which reduces side chain steric bulk near the backbone (versus dialkyl bithiophene in BTR) and leads to an optimized single intramolecular S...O interaction.
  • TRTOR has comparable electrical properties but with easy materials accessbility, centrosymmetric geometry, and more compact structure than DTP, which is axisymmetric and contains out-of-plane sidechains.
  • the incorporation of the single alkoxy side chain and optimizing the S...O interaction affords the resulting TRTOR polymers with low-lying HOMO, close intermolecular ⁇ - ⁇ stacking, high degree of crystallinity, and enhanced materials processability.

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Abstract

L'invention concerne un motif donneur d'électrons de formule, son copolymère et leurs procédés de préparation, ainsi que leurs utilisations dans un transistor en couches minces ou une cellule solaire à polymères. Le motif donneur d'électrons est un bloc de construction efficace pour construire des semi-conducteurs polymères haute performance en raison de sa capacité de solubilisation, de sa géométrie centrosymétrique, de sa planéité de squelette, de son emballage compact, et de sa capacité à donner des électrons appropriée par rapport aux motifs BTOR et DTP précédemment rapportés.
PCT/CN2016/075839 2016-03-08 2016-03-08 Motif donneur d'électrons, son copolymère et leurs procédés de préparation, ainsi que leurs utilisations Ceased WO2017152354A1 (fr)

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US20140167002A1 (en) * 2010-11-22 2014-06-19 The Regents Of The University Of California Organic small molecule semiconducting chromophores for use in organic electronic devices
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CN115636925A (zh) * 2022-09-19 2023-01-24 湖南松井新材料股份有限公司 稠环噻吩型电致变色聚合物、制备方法及应用

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