An Organic–Inorganic Hybrid Material Based on Benzo[ghi]perylenetri-imide and Cyclic Titanium-Oxo Cluster for Efficient Perovskite and Organic Solar Cells

• DOI: 10.31635/ccschem.021.202100825
• Publication Date: 2021-04-07T03:56:32Z
• Authors: Zhou Zhang; Faming Han; Jie Fang; Chaowei Zhao; Shuai Li; Yonggang Wu; Yuefeng Zhang; Shengyong You; Binghui Wu; Weiwei Li
• Keywords: Imide

Open AccessCCS ChemistryCOMMUNICATION1 Mar 2022An Organic–Inorganic Hybrid Material Based on Benzo[ghi]perylenetri-imide and Cyclic Titanium-Oxo Cluster for Efficient Perovskite Organic Solar Cells Zhou Zhang†, Faming Han†, Jie Fang†, Chaowei Zhao, Shuai Li, Yonggang Wu, Yuefeng Zhang, Shengyong You, Binghui Wu Weiwei Li Zhang† Institute of Applied Chemistry, Jiangxi Academy Sciences, Nanchang 330096 College Chemistry Environmental Science, Hebei University, Baoding 071002 , Han† State Key Laboratory Physical Solid Surfaces, Pen-Tung Sah Micro-Nano Science Technology, Chemical Engineering, Xiamen 361005 Guangxi Low Carbon Energy Materials, Pharmaceutical Normal Guilin 541004 Fang† Zhao *Corresponding authors: E-mail Address: [email protected] Zhang You Beijing Advanced Innovation Center Soft Matter Engineering Composites, University 100029 https://doi.org/10.31635/ccschem.021.202100825 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail organic solar cells usually require electron-transport interlayers efficiently transport electrons from the photoactive layer metal electrode. In general, pure or inorganic materials are applied into interlayers, but organic–inorganic hybrid have been rarely reported this application. work, we report using first titanium-oxo cluster-based as interlayer material by introducing large π-conjugated benzo[ghi]perylenetriimides an part via a simple ligand-exchange reaction. This new showed excellent solubility, well-aligned energy levels, electron mobilities, enabling its great potential application in such perovskite cells, providing high power conversion efficiencies <20% 16%, respectively. Therefore, claim that our present work introduces class exhibit promising electronics. Download figure PowerPoint Introduction Titanium oxide (TiO2) nanomaterials commonly adopted layers (ETLs) different thin-film dye-sensitized (DSSCs), (PSCs), (OSCs).1–10 The suitable level alignment between TiO2 light-harvesting semiconductors endows ability extract block holes with reducing series recombination.11–14 Meanwhile, photovoltaics is still inhibited low mobility rough surface amount defects,15–17 which unfavorable ohmic contact organic/inorganic layers. Consequently, causes severe accumulation recombination at interface, resulting (PCEs) evident hysteresis planar PSCs.18 To smooth interface reduce defect layer, some materials, including perylene diimide (PDI) derivative PDI2,19 well-known fused-ring acceptor 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene (ITIC),20 conjugated polymer electrolyte,21 were introduced active layers, improved PSCs OSCs. However, these difficulty forming tight perfect levels TiO2. developed solution-processed could be compatible both act universal interfacial We used Ti-oxo clusters (TOCs) component construct material. As molecular analogue TiO2, TOCs atomically precise structures attracted increasing attention due their constructing assemblies models studying correlation structure function.22–25 date, mainly photocatalysis, host–guest ions selectivity, supporting single-atom site/metallic nanomaterials, porous materials.26–38 Although chromophore appending exhibited efficient communication considerable photocurrent model DSSCs,39–41 there only few reports about high-performing photovoltaics.42,43 One challenge how attach dyes onto since trial-and-error one-pot approach relatively inefficient bulky dye ligands protecting TOCs.44 A feasible way functionalize as-synthesized ligand exchange labile sites.45–47 protocol has proven rather ripe ligands,48–50 photoelectronic properties attached reported. previous synthesized stable cyclic (CTOCs) ligated –OH –COOH units, they highly exchangeable other alcohols.37 finding intrigued us introduce rational design. Herein, construction based benzo[ghi]perylenetriimide ( BPTI-OH, Supporting Information Scheme S1) TOC CTOC-3) (Scheme 1) it BPTI unit π-extended PDI exhibits deep frontier strong crystallinity, potentially electron-transporting material.51 targeted CTOC-3-BPTI was simply BPTI-OH ethylene glycolates CTOC-3. then OSCs, exhibiting enhanced PCEs over 20% 16%. also advanced techniques study physical material, revealing outstanding performance tune function cells. 1 | Synthetic route CTOC-3-BPTI. Results Discussion chemical CTOC-3-BPTI, synthetic depicted 1. hierarchical CTOC-3 simplified eight Ti4 cycles clarity. overall involving alcohol site shown Figure S1. detailed procedures presented Information. involatile monocoordinated glycol initially replaced volatile isopropanol recrystallization process, yielding CTOC-3- i OPr. Powder X-ray diffraction (XRD) indicated crystal maintained after S2). product mixed CH2Cl2 solution stirred room temperature. reaction process monitored UV–vis absorption spectra. 1a, when equiv OPr treated 17 intensity peaks significantly reduced h. After 24 h, onset spectra red-shifted 486 509 nm. Besides, ratio second peak (∼434 nm) third (∼465 enhanced. consistent change film S3), indicating aggregation during process. continuously 48 no apparent 72 finished Column chromatography purify yellow solid. It solubility nonpolar polar solvents n-hexane (Figure 1b), facile photovoltaic devices. (a) Reaction (b) molar coefficient CH2Cl2, n-hexane. (c) 1H NMR chloroform-d1. proton nuclear magnetic resonance (1H NMR) 1c, shifts 9.1–10.3 ppm assigned aromatic Hs upshifted 8.5–9.6 integral H atoms those C–CH2CH2-O CTOC 16:1, BPTI:CTOC S4). confirmed further thermogravimetric analyses (TGA, S5). tried obtain single-crystal XRD perform mass spectroscopy data deduce convincing structural information, attempts failed. coexistence diffusion-ordered (DOSY), where signals unified diffusion (D) 1.51 × 10−10 m2/s (log D = −9.82) S6). When added volume methanol-d4 (50 μL) unload all BPTI, unique dissociated two individual species 1.23 −9.91) 2.45 −9.61), corresponding respectively S7). These measurements illustrated equilibrium existed utilized enough time, obtained, decomposed volumes alcohol. demonstrated device configuration fluorine-doped tin (FTO)/TiO2/ CTOC-3-BPTI/perovskite/Spiro/Au 2a). fabrication described cation Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3, cesium formamidinium methylammonium lead halide [(CsFAMA)PbX3] layer. prepared devices without comparison. current density–voltage (J–V) curves best performing 2b S8, parameters summarized Table PSC directly deposited PCE 16.02%. interlayer, open-circuit voltages (Vocs) short-circuit densities (Jscs) slightly enhanced, fill factors (FFs) almost unchanged so increased 16.82% 17.21%. Surprisingly, simultaneously improved, boosting 20.14%. Jscs reflected incident photon-to-current (IPCEs, 2c), photoresponse range 300–800 Moreover, phenomena CTOC-contained S8), unlike interlayer. core responsible suppression. histograms 30 2d revealed reproducibility fabricated study. 2 PSCs. Comparison reverse scan J–V IPCE interlayers. (d) Histograms forward scans among Photovoltaic Parameters Best CTOC-3, Interlayers Voc (V) Jsc (mA/cm2) FF (%) Without 1.022 21.60 72.57 16.02 1.070 21.78 72.13 16.82 1.035 22.80 72.96 17.21 1.119 23.81 75.58 20.14 Next, studied origination Jsc, Voc, First, scanning microscopy (SEM, Figures S9 S10) (XRD, S11) measurement found similar grain size varied interface. Kelvin probe force (KPFM) difference (CPD), inherently correlated variation (Figures 3a–3c, S12–S15).52–54 Measured same tip, CPD −2.3 mV bare 86.2 CTOC-3-BPTI-modified elevation ∼90 mV. For comparison, 30.8 9.3 3c). results indicate altered function, partially explaining possible intramolecular charge transfer amorphous nature generated dense S2), function. led localize middle underlayer (−4.10 eV) (CsFAMA)PbX3 (−3.93 eV), promoting S16). clear suppression CTOC-containing might correlate trap passivation, optimized 3 (a b) Two-dimensional topography spatial maps CTOC-3-BPTI/TiO2. TRPL films substrates. steady-state time-resolved photoluminescence (TRPL) evaluate charge-transfer kinetics across TiO2/interlayer/perovskite interfaces. primary PL 760 presence ETL, especially S17. associated effective ETL. From measurement, average lifetime cast FTO 59.9 ns, while value 37.2 ns FTO/TiO2 16.7 FTO/TiO2/ 3d). supported significant Additionally, charge-carrier characterized electrochemical impedance (EIS). Nyquist plots subjected one sun illumination bias testing S18. introduction resulted increase observed arcs intermediate frequency region 1000 kHz. Since perovskite/hole-selective interfaces identical cases, higher belongs more through lower related recombination. All synergistically contributed OSCs ITO/poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT-PSS)/poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b′]dithiophene))-alt-(5,5-(1′,3′-di-2-thienyl-5′,7′-bis(2-ethylhexyl)benzo[1′,2′-c:4′,5′-c′]dithiophene-4,8-dione)] (PM6):2,2′-((2Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (Y6)/ CTOC-3-BPTI/Ag. electrolyte 2,9-bis[3-(dimethyloxidoamino)propyl]anthra[2,1,9-def:6,5,10-d′e′f′]diisoquinoline-1,3,8,10(2H,9H)-tetrone PDINO) comparison.55 OSC 4a 4b. obtained 15.43% than PDINO (15.84%), 4c 2. FFs, although external quantum (EQE, 4d). CTOC-3-BPTI/ double applied, 16.71% 27.22 mA/cm2, 0.845 V, 72.66% (Table 2). 4 PM6, Y6, PDINO. Device architecture OSC. EQE single PDINO, CTOC-3-BPTI/PDINO EH, 2-ethylhexyl. Single Double Respectively Calculated μe (cm2/V S) 0.823 (0.831) 25.75 (25.57) 24.49 74.76 (73.57) 15.84 (15.64) 0.00317 0.820 (0.821) 26.20 (25.98) 25.20 71.79 (71.68) 15.43 (15.30) 0.0212 (0.837) (26.64) 25.93 72.66 (73.75) 16.71 (16.47) 0.0894 Values brackets six independent investigated fabricating electron-only ITO/ZnO/Y6/ETL/Ag. S19 2, cm2/V S, S remarkable enhancement mobilities able improve electrode.56 Conclusion 16% obtained. attributed tuning injection Also, intend emphasize combining molecule enhance adhesion electrode possibly PCEs. envision oxo-clusters would open avenue available includes general procedure characterization Conflict Interest There conflict interest report. Funding jointly MOST (nos. 2018YFA0208504 2017YFA0204702) NSFC (51773207, 52073016, 5197030531, 21801213) China. 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