New D-A-A'-Configured Small Molecule Donors Employing Conjugation to Red-shift the Absorption for Photovoltaics.

Four new donor-acceptor-acceptor' (D-A-A')-configured donors, CPNT, DCPNT, CPNBT, and DCPNBT equipped with naphtho[1,2-c:5,6-c']bis([1,2,5]-thiadiazole) (NT) or naphtho[2,3-c][1,2,5]thiadiazole (NBT) as the central acceptor (A) unit bridging triarylamine donor (D) and cyano or dicyanovinylene acceptor (A'), were synthesized and characterized. All molecules exhibit bathochromic absorption shifts as compared to those of the benzothiadiazole (BT)-based analogues owing to improved electron-withdrawing and quinoidal character of NT and NBT cores that lead to stronger intramolecular charge transfer. Favorable energy level alignments with C70 , together with the good thermal stability and the antiparallel dimeric packing render CPNT and DCPNT suitable donors for vacuum-processed organic photovoltaics (OPV)s. OPVs based on DCPNT : C70 active layers displayed the best power conversion efficiency (PCE)=8.3%, along with an open circuit voltage of 0.92 V, a short circuit current of 14.5 mA cm-2 and a fill factor of 62% under 1 sun intensity, simulated AM1.5G illumination. Importantly, continuous light-soaking with AM 1.5G illumination has verified the durability of the devices based on CPNT:C70 and DCPNT : C70 as the active blends. The devices were examined for their feasibility of indoor light harvesting under 500 lux illumination by a TLD-840 fluorescent lamp, giving PCE=12.8% and 12.6%, respectively. These results indicate that the NT-based D-A-A'-type donors CPNT and DCPNT are potential candidates for high-stability vacuum-processed OPVs suitable for indoor energy harvesting.

Centimetre-scale electron diffusion in photoactive organic heterostructures.

The unique properties of organic semiconductors, such as flexibility and lightness, are increasingly important for information displays, lighting and energy generation. But organics suffer from both static and dynamic disorder, and this can lead to variable-range carrier hopping, which results in notoriously poor electrical properties, with low electron and hole mobilities and correspondingly short charge-diffusion lengths of less than a micrometre. Here we demonstrate a photoactive (light-responsive) organic heterostructure comprising a thin fullerene channel sandwiched between an electron-blocking layer and a blended donor:C70 fullerene heterojunction that generates charges by dissociating excitons. Centimetre-scale diffusion of electrons is observed in the fullerene channel, and this can be fitted with a simple electron diffusion model. Our experiments enable the direct measurement of charge diffusivity in organic semiconductors, which is as high as 0.83 ± 0.07 square centimetres per second in a C60 channel at room temperature. The high diffusivity of the fullerene combined with the extraordinarily long charge-recombination time yields diffusion lengths of more than 3.5 centimetres, orders of magnitude larger than expected for an organic system.

High Efficiency Near-Infrared and Semitransparent Non-Fullerene Acceptor Organic Photovoltaic Cells.

The absence of near-infrared (NIR) solar cells with high open circuit voltage (Voc) and external quantum efficiency (EQE) has impeded progress toward achieving organic photovoltaic (OPV) power conversion efficiency PCE > 15%. Here we report a small energy gap (1.3 eV), chlorinated nonfullerene acceptor-based solar cell with PCE = 11.2 ± 0.4%, short circuit current of 22.5 ± 0.6 mA cm-2, Voc = 0.70 ± 0.01 V and fill factor of 0.71 ± 0.02, which is the highest performance reported to date for NIR single junction OPVs. Importantly, the EQE of this NIR solar cell reaches 75%, between 650 and 850 nm while leaving a transparency window between 400 and 600 nm. The semitransparent OPV using an ultrathin (10 nm) Ag cathode shows PCE = 7.1 ± 0.1%, with an average visible transmittance of 43 ± 2%, Commission d'Eclairage chromaticity coordinates of (0.29, 0.32) and a color rendering index of 91 for simulated AM1.5 illumination transmitted through the cell.

Large Absorption Enhancement in Ultrathin Solar Cells Patterned by Metallic Nanocavity Arrays.

A new type of light trapping structure utilizing ring-shaped metallic nanocavity arrays is proposed for the absorption enhancement in ultrathin solar cells with few photonic waveguide modes. Dozens of times of broadband absorption enhancement in the spectral range of 700 to 1100 nm is demonstrated in an ultrathin Si3N4/c-Si/Ag prototype solar cell by means of finite-difference time-domain (FDTD) simulation, and this dramatic absorption enhancement can be attributed to the excitation of plasmonic cavity modes in these nanocavity arrays. The cavity modes optimally compensate for the lack of resonances in the longer wavelength range for ultrathin solar cells, and eventually a maximum Jsc enhancement factor of 2.15 is achieved under AM 1.5G solar illumination. This study opens a new perspective for light management in thin film solar cells and other optoelectronic devices.

Regioisomeric Effects of Donor-Acceptor-Acceptor' Small-Molecule Donors on the Open Circuit Voltage of Organic Photovoltaics.

Donor-acceptor-acceptor' small-molecule donors are synthesized to investigate regioisomeric effects on organic photovoltaic device performance. Cross-conjugation in 2-((7-(N-(2-ethylhexyl)-benzothieno[3,2-b]thieno[3,2-d]pyrrol-2-yl)benzo[c][1,2,5]thiadiazol-4-yl)methylene)malononitrile leads to an increased open-circuit voltage compared with its isomer 2-((7-(N-(2-ethylhexyl)-benzothieno[3,2-b]thieno[2,3-d]pyrrol-2-yl)benzo[c][1,2,5]thiadiazol-4-yl)methylene)malononitrile. A correlation is then established between molecular conjugation length and orbital energies, and hence open-circuit voltage.

Charge trapping in mixed organic donor-acceptor semiconductor thin films.

A pump-probe method, whereby trapped charges are optically induced to contribute to the total photocurrent, is applied to quantitatively determine the trap density in small-molecule organic semiconductor thin films and donor-acceptor blends used in organic solar cells. The trapped charge density is correlated to the cell performance, and the dependence of charge trapping on the presence of nanocrystalline domains is discussed.