Ultrafast Coherent Hole Injection at the Interface between CuSCN and Polymer PM6 Using Femtosecond Mid-Infrared Spectroscopy.

Tracking the dynamics of ultrafast hole injection into copper thiocyanate (CuSCN) at the interface can be experimentally challenging. These challenges include restrictions in accessing the ultraviolet spectral range through transient electronic spectroscopy, where the absorption spectrum of CuSCN is located. Time-resolved vibrational spectroscopy solves this problem by tracking marker modes at specific frequencies and allowing direct access to dynamical information at the molecular level at donor-acceptor interfaces in real time. This study uses photoabsorber PM6 (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))]) as a model system to explore and decipher the hole transfer dynamics of CuSCN using femtosecond (fs) mid-infrared (IR) spectroscopy. The time-resolved results indicate that excited PM6 exhibits a sharp vibrational mode at 1599 cm-1 attributed to the carbonyl group, matching the predicted frequency position obtained from time-dependent density functional theory (DFT) calculations. The fs mid-IR spectroscopy demonstrates a fast formation (<168 fs) and blue spectral shift of the CN stretching vibration from 2118 cm-1 for CuSCN alone to 2180 cm-1 for PM6/CuSCN, confirming the hole transfer from PM6 to CuSCN. The short interfacial distance and high frontier orbital delocalization obtained from the interfacial DFT models support a coherent and ultrafast regime for hole transfer. These results provide direct evidence for hole injection at the interface of CuSCN for the first time using femtosecond mid-IR spectroscopy and serve as a new investigative approach for interfacial chemistry and solar cell communities.

High-Performance Near-Infrared Absorbing n-Type Porphyrin Acceptor for Organic Solar Cells.

While the outstanding charge transport and sunlight-harvesting properties of porphyrin molecules are highly attractive as active materials for organic photovoltaic (OPV) devices, the development of n-type porphyrin-based electron acceptors has been challenging. In this work, we developed a high-performance porphyrin-based electron acceptor for OPVs by substitution of four naphthalene diimide (NDI) units at the perimeter of a Zn-porphyrin (PZn) core using ethyne linkage. Effective π-conjugation between four NDI wings and the PZn core significantly broadened Q-band absorption to the near infrared region, thereby achieving the narrow band gap of 1.33 eV. Employing a windmill-structured tetra-NDI substituted PZn-based acceptor ( PZn-TNDI) and mid-band gap polymer donor (PTB7-Th), the bulk heterojunction OPV devices achieved a power conversion efficiency (PCE) of 8.15% with an energy loss of 0.61 eV. The PCE of our PZn-TNDI-based device was the highest among the reported OPVs using porphyrin-based acceptors. Notably, the amorphous characteristic of PZn-TNDI enabled optimization of the device performance without using any additive, which should make industrial fabrication simpler and cheaper.

Development of n-Type Porphyrin Acceptors for Panchromatic Light-Harvesting Fullerene-Free Organic Solar Cells.

The development of n-type porphyrin acceptors is challenging in organic solar cells. In this work, we synthesized a novel n-type porphyrin acceptor, PZn-TNI, via the introduction of the electron withdrawing naphthalene imide (NI) moiety at the meso position of zinc porphyrin (PZn). PZn-TNI has excellent thermal stability and unique bimodal absorption with a strong Soret band (300-600 nm) and weak Q-band (600-800 nm). The weak long-wavelength absorption of PZn-TNI was completely covered by combining the low bandgap polymer donor, PTB7-Th, which realized the well-balanced panchromatic photon-to-current conversion in the range of 300-800 nm. Notably, the one-step reaction of the NI moiety from a commercially available source leads to the cheap and simple n-type porphyrin synthesis. The substitution of four NIs in PZn ring induced sufficient n-type characteristics with proper HOMO and LUMO energy levels for efficient charge transport with PTB7-Th. Fullerene-free organic solar cells based-on PTB7-Th:PZn-TNI were investigated and showed a promising PCE of 5.07% without any additive treatment. To the best of our knowledge, this is the highest PCE in the porphyrin-based acceptors without utilization of the perylene diimide accepting unit.

11% Organic Photovoltaic Devices Based on PTB7-Th: PC71BM Photoactive Layers and Irradiation-Assisted ZnO Electron Transport Layers.

The enhancement of interfacial charge collection efficiency using buffer layers is a cost-effective way to improve the performance of organic photovoltaic devices (OPVs) because they are often universally applicable regardless of the active materials. However, the availability of high-performance buffer materials, which are solution-processable at low temperature, are limited and they often require burdensome additional surface modifications. Herein, high-performance ZnO based electron transporting layers (ETLs) for OPVs are developed with a novel g-ray-assisted solution process. Through careful formulation of the ZnO precursor and g-ray irradiation, the pre-formation of ZnO nanoparticles occurs in the precursor solutions, which enables the preparation of high quality ZnO films. The g-ray assisted ZnO (ZnO-G) films possess a remarkably low defect density compared to the conventionally prepared ZnO films. The low-defect ZnO-G films can improve charge extraction efficiency of ETL without any additional treatment. The power conversion efficiency (PCE) of the device using the ZnO-G ETLs is 11.09% with an open-circuit voltage (VOC), short-circuit current density ( JSC), and fill factor (FF) of 0.80 V, 19.54 mA cm-2, and 0.71, respectively, which is one of the best values among widely studied poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)]: [6,6]-phenyl-C71-butyric acid methyl ester (PTB7-Th:PC71BM)-based devices.

Artificial light-harvesting n-type porphyrin for panchromatic organic photovoltaic devices.

A near-infrared-harvesting n-type porphyrin-based acceptor for organic photovoltaics (OPVs) was developed. The n-type acceptor, PDI-PZn-PDI, was designed by connecting a zinc porphyrin (PZn) core to two perylenediimide (PDI) wings through ethyne bridges. A narrow bandgap of 1.27 eV was achieved through the extended π-conjugation and intramolecular charge transfer between the strongly electron-donating PZn core and the electron-accepting PDI wings. A bulk heterojunction (BHJ) structured photovoltaic device fabricated from PDI-PZn-PDI with PTB7-Th exhibited panchromatic photon-to-current conversion from 350 to 900 nm. A power conversion efficiency of 5.25% with a remarkably low Eloss of 0.54 eV was achieved by optimizing the nanomorphology of the BHJ films by adding pyridine and by controlling the ZnO/BHJ interfacial properties.

Fullerene-Free Organic Solar Cells with an Efficiency of 10.2% and an Energy Loss of 0.59 eV Based on a Thieno[3,4-c]Pyrrole-4,6-dione-Containing Wide Band Gap Polymer Donor.

Although the combination of wide band gap polymer donors and narrow band gap small-molecule acceptors achieved state-of-the-art performance as bulk heterojunction (BHJ) active layers for organic solar cells, there have been only several of the wide band gap polymers that actually realized high-efficiency devices over >10%. Herein, we developed high-efficiency, low-energy-loss fullerene-free organic solar cells using a weakly crystalline wide band gap polymer donor, PBDTTPD-HT, and a nonfullerene small-molecule acceptor, ITIC. The excessive intermolecular stacking of ITIC is efficiently suppressed by the miscibility with PBDTTPD-HT, which led to a well-balanced nanomorphology in the PBDTTPD-HT/ITIC BHJ active films. The favorable optical, electronic, and energetic properties of PBDTTPD-HT with respect to ITIC achieved panchromatic photon-to-current conversion with a remarkably low energy loss (0.59 eV).

High-Efficiency Photovoltaic Devices using Trap-Controlled Quantum-Dot Ink prepared via Phase-Transfer Exchange.

Colloidal-quantum-dot (CQD) photovoltaic devices are promising candidates for low-cost power sources owing to their low-temperature solution processability and bandgap tunability. A power conversion efficiency (PCE) of >10% is achieved for these devices; however, there are several remaining obstacles to their commercialization, including their high energy loss due to surface trap states and the complexity of the multiple-step CQD-layer-deposition process. Herein, high-efficiency photovoltaic devices prepared with CQD-ink using a phase-transfer-exchange (PTE) method are reported. Using CQD-ink, the fabrication of active layers by single-step coating and the suppression of surface trap states are achieved simultaneously. The CQD-ink photovoltaic devices achieve much higher PCEs (10.15% with a certified PCE of 9.61%) than the control devices (7.85%) owing to improved charge drift and diffusion. Notably, the CQD-ink devices show much lower energy loss than other reported high-efficiency CQD devices. This result reveals that the PTE method is an effective strategy for controlling trap states in CQDs.

Improved performance of dye-sensitized solar cells using dual-function TiO(2) nanowire photoelectrode.

A unique, hierarchically structured, aggregated TiO(2) nanowire (A-TiO(2)-nw) is prepared by solvothermal synthesis and used as a dual-functioning photoelectrode in dye-sensitized solar cells (DSSCs). The A-TiO(2)-nw shows improved light scattering compared to conventional TiO(2) nanoparticles (TiO(2)-np) and dramatically enhanced dye adsorption compared to conventional scattering particles (CSP). The A-TiO(2)-nw is used as a scattering layer for bilayer photoelectrodes (TiO(2)-np/A-TiO(2)-nw) in DSSCs to compare the cell performance to that of devices using state-of-the-art photoelectrode architectures (TiO(2)-np/CSP). The DSSCs fabricated using bilayers of TiO(2)-np/A-TiO(2)-nw show improved power conversion efficiency (9.1%) and current density (14.88 mA cm(-2)) compared to those using single-layer TiO(2)-np (7.6% and 11.84 mA cm(-2)) or TiO(2)-np/CSP bilayer structures (8.7% and 13.81 mA cm(-2)). The unique contribution of the A-TiO(2)-nw layers to the device performance is confirmed by studying the incident photon-to-current efficiency. The enhanced external quantum efficiencies at approximately 520 nm and 650 nm clearly reveal the dual functionality of A-TiO(2)-nw. These unique properties of A-TiO(2)-nw may be applied in other devices utilizing light-scattering n-type semiconductor.