Cumulative energy demand for small molecule and polymer photovoltaics

Organic photovoltaics (OPVs) are expected to be a low cost, environmentally friendly energy solution with advantageous properties such as flexibility and light weight that enable their use in new applications. Considerable progress in power conversion efficiencies has brought OPV technology closer to commercialization. However, little consideration has been given to potential environmental impact associated with their production. Although environmental life cycle studies of OPV exist, their scope is narrow or too reliant on outdated technologies. Some of the most significant recent improvements are the result of new semiconductors materials, which have not yet been assessed from a life cycle perspective. Therefore, this study calculates life cycle embodied energy for 15 new materials encompassing a variety of donor, acceptor, and interface compounds showing the most promise in organic electronics. With the use of new inventory data, life cycle energy impact associated with production of both single junction and multi‐junction architectures has been calculated including bulk heterojunction polymer, planar small molecule, and planar‐mixed small molecule devices. The cumulative energy demand (CED) required to fabricate small molecule and polymer photovoltaics were found to be similar from 2.9 to 5.7 MJ/Wp. This CED is on average of 50% less than for conventional inorganic photovoltaics, motivating the continued development of both technologies. The use of fullerenes was shown to have a dramatic impact on polymer solar cells, comprising 18–30% of the CED, despite only being present in small quantities. Increases in device efficiency are shown to marginally reduce CED for both small molecule and polymer designs. Copyright © 2012 John Wiley & Sons, Ltd.     

Enhanced storage/operation stability of small molecule organic photovoltaics using graphene oxide interfacial layer

Graphene and graphene oxide (GO) have been applied in flexible organic electronic devices with enhanced efficiency of polymeric photovoltaic (OPV) devices. In this work, we demonstrate that storage/operation stability of OPV can be substantially enhanced by spin-coating a GO buffer layer on ITO without any further treatment. With a 2 nm GO buffer layer, the power conversion efficiency (PCE) of a standard copper phthalocyanine (CuPc)/fullerene (C₆₀) based OPV device shows about 30% enhancement from 1.5% to 1.9%. More importantly, while the PCE of the standard device drop to 1/1000 of its original value after 60-days of operation-storage cycles; those of GO-buffered device maintained 84% of initial PCE even after 132-days. Atomic force microscopy studies show that CuPc forms larger crystallites on the GO-buffered ITO substrate leading to better optical absorption and thus photon utilization. Stability enhancement is attributed to the diffusion barrier of the GO layer which slow down diffusion of oxygen species from ITO to the active layers.     

Synthesis of organic molecule donor for efficient organic solar cells with low acceptor content

A new planar A-D-A structured organic small molecule semiconductor (O-SMS) with dialkyl-thiophene substituted benzodithiophene (BDT) as central electron-rich core flanked by relatively electron-deficient units of [1,2,5]thiadiazolo[3,4-c]pyridine (PTz) and terminated with alkyl-bithiophene as π-conjugated end-caps, BDTDPTz, was designed and synthesized for the application as donor material in organic solar cells (OSCs). BDTDPTz possesses wider absorption spectra with an optical bandgap of 1.65 eV, lower the highest occupied molecular orbital (HOMO) energy level of −5.42 eV and highly crystalline structures in solid films. The OSCs based on BDTDPTz:PC₇₁BM blend film with a lower PC₇₁BM content of 40% demonstrate a power conversion efficiency (PCE) of 6.28% with a relatively higher open-circuit voltage of 0.868 V and short circuit current density of 12.83 mA cm⁻². These results indicate that highly coplanar and crystalline structure of BDTDPTz can effectively reduce the content of fullerene acceptor in the active layer and then enhance the absorption and PCE of the OSCs.     

Dicyano-functionalized chlorophyll derivatives with ambipolar characteristic for organic photovoltaics

Two ambipolar chlorophyll derivatives, namely, 3²,3²-dicyano-pyropheophorbide-a (Chl-1) and methyl 13¹-deoxo-13¹-(dicyanomethylene) pyropheophorbide-a (Chl-2), were synthesized for use as either the electron acceptor or the electron donor in organic planar-heterojunction solar cells. Despite the higher electron mobilities of these chlorophyll derivatives compared with their hole mobilities, devices using them as the electron donor with fullerene C₇₀ give much better photovoltaic performance than when they are used as the electron acceptor with copper phthalocyanine. In these Chl-based solar cells, the energy gap between the LUMO levels of the donor and acceptor molecules substantially affects the charge separation and resultant photocurrent and photovoltaic performance. The highest solar energy-to-electricity conversion efficiency of up to 2.3% has been achieved using the Chl-2/C₇₀ solar cell, under AM1.5 solar illumination (100 mW/cm²) after thermal annealing of the device. It was also confirmed that the electron mobility of blend films containing Chls and fullerene derivative PC₇₀BM was determined not only by the electron mobility of PC₇₀BM but also by that of Chls.     

An effective bilayer cathode buffer for highly efficient small molecule organic solar cells

Novel organic/ultrathin low work function metal bilayer cathode buffers for small molecule organic solar cells are proposed. Ultrathin low work function metal layers possess a high built-in electric field for effective carrier extraction and a high cathode reflectivity for maximum absorption in the photoactive layers. This leads to a significant increase of short circuit current density and fill factor of cells. By integrating this bilayer cathode buffer with DTDCTB:C₆₀ small molecular heterojunction, the device exhibits a high power conversion efficiency of up to 5.28%, which is an improvement of 22% compared to a device with a traditional single organic layer buffer.     

Low bandgap polymers based on bay-annulated indigo for organic photovoltaics: Enhanced sustainability in material design and solar cell fabrication

Although research in the field of organic photovoltaics (OPV) still merely focuses on efficiency, efforts to increase the sustainability of the production process and the materials encompassing the device stack are of equally crucial importance to fulfil the promises of a truly renewable source of energy. In this study, a number of steps in this direction are taken. The photoactive polymers all contain an electron-deficient building block inspired on the natural indigo dye, bay-annulated indigo, combined with electron-rich thiophene and 4H-dithieno[3,2-b:2′,3′-d]pyrrole units. The synthetic protocol (starting from indigo) is optimized and the final materials are thoroughly analyzed. MALDI-TOF mass spectrometry provides detailed information on the structural composition of the polymers. Best solar cell efficiencies are obtained for polymer:fullerene blends spin-coated from a pristine non-halogenated solvent (o-xylene), which is highly recommended to reduce the ecological footprint of OPV and is imperative for large scale production and commercialization.     

Rapid and green synthesis of complementary D-A small molecules for organic photovoltaics

Two push-pull molecules with close molecular structures have been synthesized through two green steps, direct heteroarylation and Knoevenagel condensation. The electronic properties and the basic bilayer heterojunction solar cells demonstrate that the two molecules are complementary in term of light absorption. Thus solar cells using a blend of the two molecules present higher power conversion efficiencies, reaching 3%, than the cells made from each compound alone.     

Revealing the effect of donor/acceptor intermolecular arrangement on organic solar cells performance based on two-dimensional conjugated small molecule as electron donor

A series of solution processed organic solar cells (OSCs) were fabricated with a two-dimensional conjugated small molecule SMPV1 as electron donor and fullerene derivatives PC₇₁BM or ICBA as electron acceptor. The champion power conversion efficiency (PCE) of OSCs arrives to 7.05% for the cells with PC₇₁BM as electron acceptor. A relatively large open circuit voltage (V_OC) of 1.15 V is obtained from cells using ICBA as electron acceptor with an acceptable PCE of 2.54%. The fill factor (FF) of OSCs is 72% or 61% for the cells with PC₇₁BM or ICBA as electron acceptor, which is relatively high value for small molecule OSCs. The relatively low performance of OSCs with ICBA as electron acceptor indicates that ICBA cannot play positive role in photoelectric conversion processes, which is very similar to the phenomenon observed from the OSCs with high efficient narrow band gap polymers other than P3HT as electron donor, the underlying reason is still in debate. The SMPV1 has strong self-assemble ability to form an ordered two dimensional lamellar structure, which provides an effective platform to investigate the effect of electron acceptor chemical structure on the performance of OSCs. Experimental results exhibit that ICBA molecules may prefer to vertical cross-intercalation among side chains of SMPV1, PC₇₁BM molecules may have better miscibility with SMPV1 in the active layer. The different donor/acceptor (D/A) intermolecular arrangement strongly influences photon harvesting, exciton dissociation and charge carrier transport, which may provide a new sight on performance improvement of OSCs by adjusting D/A intermolecular arrangements.     

Inkjet printed silver nanowire percolation networks as electrodes for highly efficient semitransparent organic solar cells

In this work, we demonstrate inkjet printing of silver nanowires (AgNW) with an average length of 10's of μm using industrial printheads with nozzle diameters in the same size range. The printed silver nanowire mesh reveals uniform distribution and a good balance between conductivity and transmittance, which is comparable to layers fabricated by conventional methods like slot-die or spray coating. Employing a novel AgNW ink formulation based on a high boiling alcohol allows printing directly on PEDOT:PSS and prevents nozzle clogging. Using silver nanowire meshes as bottom and top electrodes, a fully inkjet printed semitransparent organic solar cell with a power conversion efficiency of 4.3% for 1 cm² area is demonstrated, which is the highest value reported so far for fully inkjet printed organic photovoltaic cells.     

Comparison of short and long wavelength absorption electron donor materials in C60-based planar heterojunction organic photovoltaics

Buckminsterfullerene, C₆₀-based planar heterojunction (PHJ) organic photovoltaics (OPVs) have been created using a short wavelength absorption (λ_max = 490 nm) electron-donating bis(naphthylphenylaminophenyl)fumaronitrile (NPAFN). NPAFN exhibits a hole mobility greater than 0.07 cm² V⁻¹ s⁻¹ as determined by its field-effect transistor. It can be attributed to such hole mobility that enables a thin layer (<10 nm) NPAFN in PHJ OPV, ITO/NPAFN/C₆₀/bathocuproine/Al. Because of the low lying HOMO energy level (5.75 eV) of NPAFN and relatively high ionization potential ITO (∼5.58 eV), such OPVs exhibit a very high open circuit voltage of ∼1.0 V, relatively high fill factor of 0.60, and a relatively high shunt resistance of 1100 Ω cm⁻², which all compensate for a relatively low short circuit current of 3.15 mA cm⁻² due to the short absorption wavelength and inferred short exciton diffusion length of NPAFN. Altogether, NPAFN OPVs display a power conversion efficiency (η_PC) of 2.22%, which is better than other long wavelength absorption materials in similar PHJ OPVs, such as pentacene (λ_max 670 nm, HOMO 5.12 eV, η_PC 1.50%) and copper phthalocyanine (λ_max 624, 695 nm, HOMO 5.17 eV, η_PC 1.43%).     

A two-dimension-conjugated small molecule for efficient ternary organic solar cells

Ternary organic solar cells (OSCs) are burgeoning as one of the effective strategies to achieve high power conversion efficiencies (PCEs) by incorporating a third component with a complementary absorption into the binary blends. In this study, we presented a new two-dimension-conjugated small molecule denoted by DR3TBDTTVT, which alone gave rise to a best PCE of 5.71% with acceptor PC₇₁BM as active layer. Given the complementary absorption with PTB7-Th, DR3TBDTTVT was doped into (PTB7-Th:PC₇₁BM)-based binary blends, and ternary OSCs were developed. The ternary OSCs with 10 wt% of DR3TBDTTVT displayed improved hole-mobility, reduced device resistance and better phase separation of active layer, thus leading to an impressive PCE of 7.77% with open-circuit voltage of 0.77 V, short-circuit density of 14.52 mA cm⁻² and fill factor of 70.3%. Ternary OSCs well make up for the light-harvesting insufficiency of binary OSCs, and this research provides a new material for the improvement of PCEs for single-junction OSCs.     

Effects of iodine doping on small molecule organic semiconductors for high charge carrier mobility and photoconductivity

Here we report the effects of iodine doping on small molecule organic semiconductors. Thin films of semiconducting p-DTS(FBTTh₂)₂ doped with 1–5 wt% iodine were fabricated and their photo-physical, crystallographic, morphological, and electrical properties were systematically analyzed. The doping significantly increased the energetic distance between the highest occupied molecular orbital (HOMO) and Fermi level of p-DTS(FBTTh₂)₂, typical for p-type doping. In addition, depletion mode transistor measurements showed an increase in the hole concentration with increasing dopant concentration. From grazing incidence X-ray diffraction (GIXD) analyses of iodine-doped p-DTS(FBTTh₂)₂ films, we observed significant changes in the crystal orientation at the optimal doping ratio of 1 wt%. Atomic force microscopy (AFM) analyses showed morphological changes with respect to dopant concentrations, which were in good agreement with the GIXD results. As a result, accumulation mode transistor measurements demonstrated an increase in the hole mobility by 54% at the optimized doping concentration compared to an undoped device. Furthermore, photoconductive device operation revealed that iodine-doping can induce dramatically enhanced photo-responsivity as high as 2.08 A/W. We demonstrate that iodine doping can be a simple and effective method for enhancing the performance of small molecule-based electronic devices, by optimizing the energy level configuration as well as enhancing intermolecular interactions.     

Novel organic dye employing dithiafulvenyl-substituted arylamine hybrid donor unit for dye-sensitized solar cells

In order to increase electron-donating ability of the donor part of the organic dye, two dithiafulvenyl (DTF) units were introduced into a triphenylamine unit to form dithiafulvenyl-substituted triphenylamine hybrid donor for dye-sensitized solar cells (DSSCs) for the first time. Novel donor–acceptor organic dye WD-10 containing this hybrid donor and 2-cyanoacetic acid acceptor has been designed, synthesized and applied in DSSCs. The influence of the substituent unit DTF in the dye on the device performance has been investigated. It was found that the dye with dithiafulvenyl-substituted triphenylamine hybrid donor gave higher photocurrent, open-circuit voltage, and efficiency value. The DSSC based on organic dye WD-10 displayed a short-circuit current (J_sc) of 9.58 mA cm^?2, an open-circuit voltage (V_oc) of 648 mV, and a fill factor (ff) of 0.71, corresponding to an overall conversion efficiency of 4.41%. An increase in η of about 79% was obtained from simple triphenylamine dye L0 to WD-10. The different photovoltaic behaviors of the solar cells based on the organic dyes were further elucidated by the electrochemical impedance spectroscopy. This work identifies that the introduction of DTF unit into the simple triphenylamine dye could significant improve the photovoltaic performance.     

Hydrophilic polyurethane acrylate and its physical property for efficient fabrication of organic photovoltaic cells via stamping transfer

Recently, stamping transfer process using by soft mold or film has been considered by promising technology to solve the drawbacks of spin coating such as deposition of large area and specific region, reducing the material loss, and multi-staking device structures. For the previous researches, polyurethane acrylate (PUA) stamp was essentially treated the 1H, 1H, 2H, 2H-Perfluorooctyltrichlorosilane (FOTS) for self-assembled monolayer (SAM) onto the Si wafer to modify surface energy. Because the FOTS is known as corrosive material, it is necessary to develop the intrinsic property of PUA with environment friendly. In this research, we investigates non-FOTS based PUA stamping transfer and the different surface energy properties that result in various physical phenomena when used for organic photovoltaics. To transfer the material, the energy release rate (G) between the PUA and the coated material should be smaller than the G between the coated material and the substrate. As a result, hydrophilic PUA was used to reduce the interaction between the PUA and the organic bulk heterojunction (BHJ) layer to transfer the BHJ layer from the PUA stamp to a PEDOT:PSS-coated ITO-substrate. 2-Hydroxyethyl methacrylate (HEMA) is included as the reactive diluent to reduce the PUA viscosity, and the contact angle was measured to compare the surface property between the reference PUA and the HEMA-PUA. The stamping-transferred BHJ device exhibits a 95% relative efficiency (2.9%) when compared to that obtained when using a spin-coating process, which is considered as a good alternative to fabricate optoelectronic devices. More importantly, we have found a decrease in the fill factor (64%–58%) and a comparable performance (3.0%–2.9%) derived from the increase in the charge recombination and resistance during the stamping transfer.     

Carbazole-based small molecules for vacuum-deposited organic photovoltaic devices with open-circuit voltage exceeding 1 V

Fabrication of vacuum deposited small molecules organic solar cell with open-circuit voltage (V_oc) exceeding 1 V is crucial in advancing the applications of organic photovoltaics (OPVs). Here, a novel carbazole-based donor-π bridge-acceptor (D-π-A) of p-type material (F-series) in combination with fullerene derivative C₆₀ or C₇₀ as n-type material for bulk-heterojunction OPVs with the structure of ITO/MoO₃ (15 nm)/F-series donor: C₆₀ or C₇₀ (40 or 80 nm)/BCP (7 nm)/Ag (120 nm) have been proposed. The vacuum deposited small molecules OPV with the donor layer consisting of F1 combined with the electron acceptor C70 exhibits a high power conversion efficiency (PCE) of 4.93%. The higher PCE of the OPV is attributed to the large V_oc value of 1.02 V. The analysis of photophysical properties using a time-dependent density functional theory model and the B3LYP functional corroborates the experimental results and provides the evidence on increasing the V_oc of OPVs.     

A small molecule with selenophene as the central block for high performance solution-processed organic solar cells

A solution-processable A–D–A structure small molecule donor material called DRCN7T-Se with selenophene as the central block was synthesized. Conventional bulk-heterojunction solar cell devices based on DRCN7T-Se and PC₇₁BM were optimized by thermal annealing and an excellent power conversion efficiency of 8.30% was achieved under AM 1.5G irradiation (100 mW cm⁻²).     

Two different donor subunits substituted unsymmetrical squaraines for solution-processed small molecule organic solar cells

Two unsymmetrical squaraines (USQs) with different donor (D) subunits as photovoltaic materials, namely USQ-11 and USQ-12, were designed and synthesized to investigate the effect of different D subunits on the optoelectronic properties of USQs for the first time. The two USQs compounds were characterized for optical, electrochemical, quantum chemical and optoelectronic properties. By changing the two different D subunits attached to the squaric acid core from 2,3,3-trimethylindolenine to 2-methylbenzothiazole, the HOMO energy levels could be tuned with a stepping of 0.07 eV, and quite different solid state aggregations (H- or J-aggregation) were observed in the thin film by UV-Vis absorption spectra, which were attributed to their distinct steric effects and dipole moments. Solution-processed bulk-heterojunction small molecule organic solar cells fabricated with the USQ-11/PC₇₁BM (1:5, wt%) exhibited extremely higher PCE (4.27%) than that of the USQ-12/PC₇₁BM (2.78%). The much enhanced PCE should be attributed to the simultaneously improved V_oc, J_sc and FF.     

An asymmetric small molecule based on thieno[2,3-f]benzofuran for efficient organic solar cells

A new asymmetric small molecule, named R3T-TBFO, with 4,8-bis(2-ethylhexyloxy)-substituted thieno[2,3-f]benzofuran (TBF) as central donor block, has been synthesized and used as donor material in organic solar cells (OSCs). With thermal annealing (TA) and solvent vapor annealing (SVA) treatment, the blend of R3T-TBFO/PC₇₁BM shows a higher hole mobility of 1.37 × 10⁻⁴ cm² V⁻¹ s⁻¹ and a more balanced charge mobilities. Using a structure of ITO/PEDOT:PSS/R3T-TBFO:PC₇₁BM/ZrAcac/Al, the device with TA treatment delivered a moderate power conversion efficiency (PCE) of 5.63%, while device after TA + SVA treatment showed a preferable PCE of 6.32% with a high fill factor (FF) of 0.72.     

Scaling down of organic complementary logic gates for compact logic on foil

In this work, we realize complementary circuits with organic p-type and n-type transistor integrated on polyethylene naphthalate (PEN) foil. We employ evaporated p-type and n-type organic semiconductors spaced side by side in bottom-contact bottom-gate coplanar structures with channel lengths of 5 μm. The area density is 0.08 mm² per complementary logic gate. Both p-type and n-type transistors show mobilities >0.1 cm²/V s with V_on close to zero volt. Small circuits like inverters and 19-stage ring oscillators (RO) are fabricated to study the static and the dynamic performance of the logic inverter gate. The circuits operate at V_dd as low as 2.5 V and the inverter stage delay at V_dd = 10 V is as low as 2 μs. Finally, an 8 bit organic complementary transponder chip with data rate up to 2.7 k bits/s is fabricated on foil by successfully integrating 358 transistors.