Cong Trinh

A fullerene-based organic exciton blocking layer with high electron conductivity

We demonstrate the concentration dependence of C60 absorption in solid solutions of C60 and bathocuprione (BCP), revealing a nonlinear decrease of the C60 charge transfer (CT) state absorption. These blends are utilized to study the photocurrent contribution of the CT in bilayer organic photovoltaics (OPVs); 1:1 blends produce 40% less photocurrent. As exciton blocking electron transporting layers, the blends achieve power conversion efficiencies of 5.3%, an increase of 10% compared to conventional buffers.

Symmetry-breaking charge transfer in a zinc chlorodipyrrin acceptor for high open circuit voltage organic photovoltaics.

Low open-circuit voltages significantly limit the power conversion efficiency of organic photovoltaic devices. Typical strategies to enhance the open-circuit voltage involve tuning the HOMO and LUMO positions of the donor (D) and acceptor (A), respectively, to increase the interfacial energy gap or to tailor the donor or acceptor structure at the D/A interface. Here, we present an alternative approach to improve the open-circuit voltage through the use of a zinc chlorodipyrrin, ZCl [bis(dodecachloro-5-mesityldipyrrinato)zinc], as an acceptor, which undergoes symmetry-breaking charge transfer (CT) at the donor/acceptor interface. DBP/ZCl cells exhibit open-circuit voltages of 1.33 V compared to 0.88 V for analogous tetraphenyldibenzoperyflanthrene (DBP)/C60-based devices. Charge transfer state energies measured by Fourier-transform photocurrent spectroscopy and electroluminescence show that C60 forms a CT state of 1.45 ± 0.05 eV in a DBP/C60-based organic photovoltaic device, while ZCl as acceptor gives a CT state energy of 1.70 ± 0.05 eV in the corresponding device structure. In the ZCl device this results in an energetic loss between E(CT) and qV(OC) of 0.37 eV, substantially less than the 0.6 eV typically observed for organic systems and equal to the recombination losses seen in high-efficiency Si and GaAs devices. The substantial increase in open-circuit voltage and reduction in recombination losses for devices utilizing ZCl demonstrate the great promise of symmetry-breaking charge transfer in organic photovoltaic devices.

Symmetry-Breaking Charge Transfer of Visible Light Absorbing Systems: Zinc Dipyrrins

Zinc dipyrrin complexes with two identical dipyrrin ligands absorb strongly at 450–550 nm and exhibit high fluorescence quantum yields in nonpolar solvents (e.g., 0.16–0.66 in cyclohexane) and weak to nonexistent emission in polar solvents (i.e., <10–3, in acetonitrile). The low quantum efficiencies in polar solvents are attributed to the formation of a nonemissive symmetry-breaking charge transfer (SBCT) state, which is not formed in nonpolar solvents. Analysis using ultrafast spectroscopy shows that in polar solvents the singlet excited state relaxes to the SBCT state in 1.0–5.5 ps and then decays via recombination to the triplet or ground states in 0.9–3.3 ns. In the weakly polar solvent toluene, the equilibrium between a localized excited state and the charge transfer state is established in 11–22 ps.

Efficient energy sensitization of C60 and application to organic photovoltaics.

Fullerenes are currently the most popular electron-acceptor material used in organic photovoltaics (OPVs) due to their superior properties, such as good electron conductivity and efficient charge separation at the donor/acceptor interface. However, low absorptivity in the visible spectral region is a significant drawback of fullerenes. In this study, we have designed a zinc chlorodipyrrin derivative (ZCl) that absorbs strongly in the visible region (450-600 nm) with an optical density 7-fold higher than a C60 film. ZCl efficiently transfers absorbed photoenergy to C60 in mixed films. Application of ZCl as an energy sensitizer in OPV devices leads to an increase in the photocurrent from the acceptor layer, without changing the other device characteristics, i.e., open circuit voltage and fill factor. For example, C60-based OPVs with and without the sensitizer give 4.03 and 3.05 mA/cm(2), respectively, while both have V(OC) = 0.88 V and FF = 0.44. Our ZCl sensitization approach improves the absorbance of the electron-acceptor layer while still utilizing the beneficial characteristics of C60 in OPVs.

Power losses in bilayer inverted small molecule organic solar cells

Inverted bilayer organic solar cells using copper phthalocyanine (CuPc) as a donor and C60 as an acceptor with the structure: glass/indium tin oxide (ITO)/ZnO/C60/CuPc/MoO3/Al, in which the zinc oxide (ZnO) was deposited by atomic layer deposition, are compared with a conventional device: glass/ITO/CuPc/C60/bathocuproine/Al. These inverted and conventional devices give short circuit currents of 3.7 and 4.8 mA/cm2, respectively. However, the inverted device gives a reduced photoresponse from the CuPc donor compared to that of the conventional device. Optical field models show that the arrangement of organic layers in the inverted devices leads to lower absorption of long wavelengths by the CuPc donor; the low energy portion of the spectrum is concentrated near the metal oxide electrode in both devices.

Multichromophoric energy sensitization of C60 for organic photovoltaics

In organic photovoltaics (OPVs), photocurrent generation is limited by absorption and exciton diffusion in the active layer. In this work, we describe the energy sensitization of C60 simultaneously by two chromophores at high volume concentrations (50%). This sensitization strategy takes advantage of the intense absorption of the sensitizers and the exceptional electron conduction and exciton diffusion length of C60 resulting in a 30% increase in photoresponse of the C60-based sensitized acceptor layer between λ = 450 nm and 670 nm and power conversion efficiency under simulated AM 1.5 G illumination. In (2,4-bis[4-(N,N-diphenylamino)-2,6-dihydroxyphenyl] squaraine)/C60 devices, sensitization results in an increase in JSC from 6.5 ± 0.2 mA/cm2 to 8.6 ± 0.2 mA/cm2 without compromising VOC or FF. These results demonstrate the robust nature of this sensitization scheme and its broad potential for application in OPVs.