A Simple and Effective Modification of PCBM for Use as an Electron Acceptor in Efficient Bulk Heterojunction Solar Cells

[6,6]‐phenyl‐C‐61‐butyric acid methyl ester (PCBM) and poly(3‐hexylthiophene) (P3HT) are the most widely used acceptor and donor materials, respectively, in polymer solar cells (PSCs). However, the low LUMO (lowest unoccupied molecular orbital) energy level of PCBM limits the open circuit voltage (V_oc) of the PSCs based on P3HT. Herein a simple, low‐cost and effective approach of modifying PCBM and improving its absorption is reported which can be extended to all fullerene derivatives with an ester structure. In particular, PCBM is hydrolyzed to carboxylic acid and then converted to the corresponding carbonyl chloride. The latter is condensed with 4‐nitro‐4’‐hydroxy‐α‐cyanostilbene to afford the modified fullerene F . It is more soluble than PCBM in common organic solvents due to the increase of the organic moiety. Both solutions and thin films of F show stronger absorption than PCBM in the range of 250–900 nm. The electrochemical properties and electronic energy levels of F and PCBM are measured by cyclic voltammetry. The LUMO energy level of F is 0.25 eV higher than that of PCBM. The PSCs based on P3HT with F as an acceptor shows a higher V_oc of 0.86 V and a short circuit current (J_sc) of 8.5 mA cm^?2, resulting in a power conversion efficiency (PCE) of 4.23%, while the PSC based on P3HT:PCBM shows a PCE of about 2.93% under the same conditions. The results indicate that the modified PCBM, i.e., F , is an excellent acceptor for PSC based on bulk heterojunction active layers. A maximum overall PCE of 5.25% is achieved with the PSC based on the P3HT: F blend deposited from a mixture of solvents (chloroform/acetone) and subsequent thermal annealing at 120 °C.     

High-performance inverted polymer solar cells with lead monoxide-modified indium tin oxides as the cathode

The photovoltaic stability of polymer solar cells (PSCs) can be greatly improved by adopting an inverted device structure. This paper reports high-performance inverted PSCs with lead monoxide (PbO)-modified indium tin oxide (ITO) as the cathodes. A thin PbO layer can effectively lower the work function of ITO from 4.5 to 3.8 eV. The optimal inverted PSCs with poly(3-hexylthiophene) (P3HT) as the donor and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as the acceptor exhibited high photovoltaic performance: open-circuit voltage of 0.59 V, short-circuit current density of 10.8 mA cm⁻², fill factor of 0.632, and power conversion efficiency of 4.00% under simulated AM1.5G illumination (100 mW cm⁻²). The photovoltaic efficiency is significantly higher than that of the control inverted PSCs with unmodified ITO as the cathode. It is even better than that of the control PSCs with normal architecture, which have an optimal efficiency of 3.5%. The lowering in the work function by the PbO modification is attributed to the charge transfer between PbO and ITO, as evidenced by the X-ray photoelectron spectra.     

High-performance ITO-free spray-processed polymer solar cells with incorporating ink-jet printed grid

Highly efficient ITO-free polymer solar cells (PSCs) based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) have been fabricated by a combination of inkjet-printing and spray processes. A hybrid transparent conducting electrode consisting of printed silver (Ag) grids and highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PH1000) was used as an alternative to indium-tin oxide (ITO). Spray process incorporating with printed Ag grids played a critical role in improving the interfacial contact between Ag grids and photoactive layer, and thus enhanced the performance of ITO-free large-area PSC. The ITO-free PSC (device area = 0.3 cm²) prepared here has a comparable performance of 2.86%. The average PCE of 2.34% was achieved in the ITO-free PSC with a large electrode area (8 cm²) fabricated herein by the combination of inkjet-printed grid and spray processes. This result is much better than ITO-based large-area PSC generally reported.     

Alcohol soluble titanium(IV) oxide bis(2,4-pentanedionate) as electron collection layer for efficient inverted polymer solar cells

We demonstrate efficient inverted polymer solar cells (PSCs) based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) by using solution-processed titanium(IV) oxide bis(2,4-pentanedionate) (TOPD) as electron collection layer (ECL) between the indium tin oxide (ITO) electrode and photoactive layer. The TOPD buffer layer was prepared by spin-coating isopropanol solution of TOPD on ITO and then baked at 140 °C for 5 min. The power conversion efficiency (PCE) of the inverted PSC with TOPD buffer layer reaches 4% under the illumination of AM1.5G, 100 mW/cm², which is increased by 76% in comparison with that (2.27%) of the inverted device without TOPD ECL. The results indicate that TOPD is a promising electron collection layer for inverted PSCs.     

Morphological modification induced by external electric field during solution process of organic solar cells

An electric field was externally applied on the poly(3-hexylthiophene)/[6,6]-phenyl C₆₁ butyric acid methyl ester (P3HT:PCBM) blend film during the fabrication of the bulk-heterojunction (BHJ) solar cells to induce morphological modification. It influences the vertical ratio of P3HT:PCBM molecules. Because the field is applied externally to the device, its direction can be altered. When the electric field of 5.0 × 10⁵ V m⁻¹ was applied with the specific direction, it formed a P3HT-rich and rougher surface, compared with that of pristine active layer, to improve the performance of the inverted polymer solar cells. Hence, the current density was improved from 9.15 mA cm⁻² to 9.83 mA cm⁻², and power conversion efficiency increased from 3.16% to 3.51%. This finding provides guidance for morphology engineering in organic materials for higher power conversion efficiency of organic solar cells.     

Elaboration of P3HT/CNT/PCBM Composites for Organic Photovoltaic Cells

This Full Paper focuses on the preparation of single‐walled or multi‐walled carbon nanotube solutions with regioregular poly(3‐hexylthiophene) (P3HT) and a fullerene derivative 1‐(3‐methoxycarbonyl) propyl‐1‐phenyl[6,6]C₆₁ (PCBM) using a high dissolution and concentration method to exactly control the ratio of carbon nanotubes (CNTs) to the P3HT/PCBM mixture and disperse the CNTs homogeneously throughout the matrix. The CNT/P3HT/PCBM composites are deposed using a spin‐coating technique and characterized by absorption and fluorescence spectroscopy and by atomic force microscopy to underline the structure and the charge transfer between the CNTs and P3HT. The performance of photovoltaic devices obtained using these composites as a photoactive layer mainly show an increase of the short circuit current and a slight decrease of the open circuit voltage which generally leads to an improvement of the solar cell performances to an optimum CNT percentage. The best results are obtained with a P3HT/PCBM (1 : 1) mixture with 0.1 wt % multi‐walled carbon nanotubes with an open circuit voltage (V_oc) of 0.57 V, a current density at the short‐circuit (I_sc) of 9.3 mA cm^–2 and a fill factor of 38.4 %, which leads to a power conversion efficiency of 2.0 % (irradiance of 100 mW cm^–2 spectroscopically distributed following AM1.5).     

Efficient bulk heterjunction solar cells based on a low-bandgap polyfluorene copolymers and fullerene derivatives

A low-bandgap polymer (PF-PThCVPTZ) consisted of fluorene and phenothiazine was designed and synthesized. With the donor–acceptor segment, the partial charge transfer can be built in the polymer backbone leading to a wide absorbance. The absorption spectrum of PF-PThCVPTZ exhibits a peak at 510 nm and an absorption onset at 645 nm in the visible range. As blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as an electron acceptor, narrow bandgap PF-PThCVPTZ as electron donor shows significant solar cell performance. Under AM 1.5 G, 100 mA/cm² illumination, a power conversion efficiency (PCE) of 1.85% was recorded, with a short circuit current (J_SC) of 5.37 mA/cm², an open circuit voltage (V_OC) of 0.80 V, and a fill factor (FF) of 43.0%.     

Enhanced performance in inverted polymer solar cells via solution process: Morphology controlling of PEDOT:PSS as anode buffer layer by adding surfactants

Inverted polymer solar cells were fabricated by adding the amphiphilic surfactant ‘Surfynol 104 series’ to Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as a anode buffer layer by solution process. With the introduction of Surfynol 104 series-added PEDOT:PSS, it was able to form a homogeneous film by adjusting the wettability of a hydrophobic poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C₆₁-butyric acid methyl ester (PCBM) film. With decrease in series resistance (R_S) and increase in shunt resistance (R_SH), as a result, the short circuit current density (J_SC), open circuit voltage (V_OC) and fill factor (FF) of the optimized device were 10.2 mA/cm², 0.63 V and 61.3%, respectively, calculated the power conversion efficiency (PCE) was 4.0%. In addition, the air stability of the fabricated device was improved.     

Efficient and stable inverted polymer solar cells using TiO2 nanoparticles and analysized by Mott-Schottky capacitance

The performance of both inverted and conventional polymer solar cells (PSCs) were examined with a low-temperature, solution-processed synthesized TiO₂ nanoparticles (TiO₂ NPs) as the electron extraction layer. The performance of inverted PSCs based on P3HT:PCBM bulk-heterojunction with a TiO₂ NPs layer was dramatically improved and the highest power conversion efficiency (PCE) of 4.56% was achieved via 24 h exposure in air, which is one of the highest PCEs for P3HT:PCBM bulk-heterojunction PSCs using TiO₂ as electron extraction layer. Meanwhile, the performance of inverted PSCs was superior to regular PSCs. Mott-Schottky capacitance analysis was carried out for both inverted and regular PSCs to obtain the built-in potential, the depletion width, as well as the doping level of the active layer, which all support the performance improvement of PSCs devices with inverted structure. In addition, inverted PSCs show excellent stability in air without encapsulation. The PCE can retain 87% of its original values after 400 h exposure in air, which is much better than that of regular PSCs. The results indicate that solution-processed TiO₂ NPs shows great potential applications in the fabrication of highly efficient and stable inverted PSCs as well as large-area, flexible printed PSCs.     

Understanding the role of organic polar solvent induced nanoscale morphology and electrical evolutions of P3HT:PCBM composite film

We investigated the effect of organic polar solvent on the properties of [6,6]-phenyl-C₇₁-butyric acid methyl ester (PCBM) films and poly(3-hexylthiophene) (P3HT):PCBM blend films employed as active layer in organic photovoltaic. The nanoscale morphology and the electrical characteristics of the P3HT:PCBM film can be controlled through organic polar solvent exposure, which exhibited with a short-circuit current density of 8.64 mA/cm², an open circuit voltage of 0.63 V, and a power conversion efficiency of 3.29% under AM 1.5 illumination with a light intensity of 100 mW/cm². By exposing the active layer films to organic polar solvent a favorable phase separation in the P3HT:PCBM films is obtained. The improved power conversion efficiency can be to the high conductivity and high surface area of the P3HT:PCBM layer treated with organic polar solvent.     

Enhanced performance of dye-sensitized solar cells with novel 2,6-diphenyl-4H-pyranylidene dyes

Novel 2,6-diphenyl-4H-pyranylidene derivatives were designed and synthesized as dyes for dye-sensitized solar cells (DSSC). Dyes 2a, b with a phenyl substituent showed high DSSC energy conversion efficiencies of 5.3% (J_sc = 10.3 mA/cm², V_oc = 0.72 V, FF = 0.72) and 4.7% (J_sc = 8.9 mA/cm², V_oc = 0.73 V, FF = 0.72) at 100 mW/cm² under simulated AM 1.5 G solar light conditions. These values are twice better than that of dye 1 without the phenyl substituent under the same conditions. Both the photocurrent density (J_sc) and open circuit voltage (V_oc) of DSSCs based on dyes 2a, b are increased compared with 1. It can be attributed to their twisted structures, absorption abilities and proper energy levels. This result shows that the tetraphenylpyranylidene is a promising electron-donor unit for high-efficiency DSSCs.     

Effects of incorporation of copper sulfide nanocrystals on the performance of P3HT: PCBM based inverted solar cells

It has been reported that performance of bulk heterojunction organic solar cells can be improved by incorporation of an additive like metal and semiconducting nanoparticles in the active layer. Here in, we have synthesized Cu₂S nanocrystals (NCs) by chemical route and studied its dispersion in poly (3-hexylthiophene) [6, 6]-phenyl C61-butyric acid methyl ester (P3HT: PCBM) matrix. Variation in the performance parameters with change in the concentration of Cu₂S NCs into the P3HT: PCBM matrix has also been studied and it was found that the inverted geometry device with concentration of 20 wt% of Cu₂S NCs and having the structure ITO/ZnO (NPs)/P3HT: PCBM:Cu₂S NCs/MoO₃/Al has shown maximum efficiency of 3.39% which is more than 100% increase in comparison with devices without Cu₂S NCs. Photoluminescence measurements studies unveiled that the incorporation of Cu₂S NCs into a P3HT: PCBM matrix has helped in quenching photoluminescence which suggests more effective exciton dissociation at the interfaces between the P3HT and PCBM domains. The Nyquist plots obtained from impedance spectroscopy at 1 V bias in the dark has suggested the effective lifetime and global mobilities for P3HT: PCBM as 0.267 ms and 1.17 × 10⁻³ cm²/V-S and for P3HT: PCBM:Cu₂S NCs (20 wt%) systems as 0.156 ms and 2.02 × 10⁻³ cm²/V-S respectively. Based on observed photoluminescence quenching, calculated effective lifetime and global mobility, we have tried to explain the possible reason for improvement in the efficiency with the very well dispersion of Cu₂S NCs into the P3HT: PCBM matrix.     

Effects of Postproduction Treatment on Plastic Solar Cells

Efficiencies of organic solar cells based on an interpenetrating network of a conjugated polymer and a fullerene as donor and acceptor materials still need to be improved for commercial use. We have developed a postproduction treatment that improves the performance of solar cells based on poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) by means of a tempering cycle at elevated temperatures in which an external voltage is simultaneously applied, resulting in a significant increase of the short‐circuit current. Using this postproduction treatment, an enhancement of the short‐circuit current density, I_sc, to 8.5 mA cm^–2 under illumination with white light at an illumination intensity of 800 W m^–2 and an increase in external quantum efficiency (IPCE, incident photon to collected electron efficiency) to 70 % are demonstrated.     

Electrical and photoelectrical properties of P3HT/n-Si hybrid organic–inorganic heterojunction solar cells

A detail analysis of electrical and photoelectrical properties of hybrid organic–inorganic heterojunction solar cells poly(3-hexylthiophene) (P3HT)/n-Si, fabricated by spin-coating of the polymeric thin film onto oxide passivated Si(1 0 0) surface, was carried out within the temperature ranging from 283 to 333 K. The dominating current transport mechanisms were established to be the multistep tunnel-recombination and space charge limited current at forward bias and leakage current through the shunt resistance at reverse bias. A simple approach was developed and successfully applied for the correct analysis of the high frequency C–V characteristics of hybrid heterojunction solar cells. The P3HT/n-Si solar cell under investigation possessed the following photoelectric parameters: J_sc = 16.25 mA/cm², V_oc = 0.456 V, FF = 0.45, η = 3.32% at 100 mW/cm² AM 1.5 illumination. The light dependence of the current transport mechanisms through the P3HT/n-Si hybrid solar cells is presented quantitatively and discussed in detail.     

High resolution electrical characterisation of organic photovoltaic blends

In this work, electrostatic force microscopy (EFM) and conductive atomic force microscopy (C-AFM) are applied to perform high-resolution electrical characterisation of organic photovoltaic films. These films are composed of the C₆₀-derivative PCBM blended with hole conductive conjugated polymers PPV derivatives or P3HT. It is demonstrated that both EFM and C-AFM are able to electrically evidence phase separation in the blends, suggesting in addition higher density of carriers along interfaces. Correlation between the EFM contrast and the photovoltaic properties of the blends was observed. Local spectroscopy (I-V curves) completes the C-AFM investigations, analysing charge transport mechanisms in the P3HT:PCBM blend. Significant modifications of the local electrical properties of P3HT are shown to occur upon blending. Space charge limited current is evidenced in the blend and a hole mobility of 1.7 × 10⁻² cm² V⁻¹ s⁻¹ is determined for P3HT.     

Interfacial layer material derived from dialkylviologen and sol–gel chemistry for polymer solar cells

Sol–gel processible organosilicate material based on dialkylviologen (1,1-(bis-trimethoxysilane)-[4,4′]bipyridium dibromide (bis-trimethoxypropylsilane)-yl-viologen, PV-Si) was synthesized and used as an interfacial layer material for polymer solar cells based on poly(3-hexylthiophene): [6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM). PV-Si is very good soluble in polar protic solvents because of two pyrinium bromide salts and PV-Si pre-polymer can be easily prepared by sol–gel chemistry under the mild acidic conditions. From the ultraviolet spectroscopy (UPS) study, the reduction of the work function of Al and ITO is observed by the formation of interface dipole, which is induced by the thin film of thermally cured PV-Si pre-polymer (cPV-Si) at 180 °C. The open circuit voltage (V_oc) of conventional type polymer solar cell (CPSC) with a structure of ITO/active layer (P3HT:PCBM)/cPV-Si(<5 nm)/Al is 0.58 V, which is higher than the CPSC without cPV-Si (0.55 V). This indicates that the favorable interface dipole is generated by the thin film of cPV-Si. Besides, the power conversion efficiency (PCE) of CPSC with cPV-Si reaches at 2.90%, which is higher than that of the device without cPV-Si (2.69%). Surprisingly, the PCE and the short circuit current (J_sc) of inverted type polymer solar cell (IPSC) with a structure of ITO/cPV-Si (<5 nm)/active layer/WO₃/Ag are 2.83% and ?9.19 mA/cm², respectively, which are higher than those of the device with ZnO (2.51% and ?8.63 mA/cm²) as an electron transporting/injecting layer. This is due to that the work function of ITO is also reduced by the formation of interface dipole. The IPSC with cPV-Si as an interfacial layer (IFL) shows very good rectification and a contact property as well. From the results, the thin layer of cPV-Si is potential material for an IFL for either CPSC or IPSC. Especially, ZnO can be replaced by cPV-Si because of their improved device performances and pretty low processing temperature.     

Improving the Power Conversion Efficiency of Organic Solar Cell by Blending with CdSe/ZnS Core–Shell Quantum Dots

We have blended poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) with CdSe/ZnS core–shell quantum dots (QDs) as the active layer to produce organic solar cells (OSC). The size of the CdSe/ZnS core–shell QDs was determined to be about 4 nm using transmission electron microscopy. The OSC were characterized by measuring the absorption spectra, current–voltage characteristics, and external quantum efficiency (EQE) spectra. The samples doped with 0.5 wt.% CdSe/ZnS core–shell QDs exhibited higher power conversion efficiency (PCE) than samples doped with other concentrations of QDs. The PCE of the OSC increases from 2.10% to 2.38% due to an increase of the short circuit current density (J _sc) from 6.00 mA/cm² to 6.25 mA/cm². The open circuit voltage (V _oc) was kept constant when comparing OSC that were undoped and doped with 0.5 wt.% CdSe/ZnS core–shell QDs. These CdSe/ZnS core–shell QDs can increase optical absorption as well as provide extra exciton dissociation and additional electric pathways in hybrid OSC.     

Non-peripheral octahexylphthalocyanine doping effects in bulk heterojunction polymer solar cells

The improvement of long-wavelength sensitivity in bulk heterojunction organic thin-film solar cells based on poly(3-hexylthiophene) (P3HT) by the addition of the soluble phthalocyanine derivative, 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH₂) is reported. C6PcH₂ possesses near-infrared absorption and can be mixed with a P3HT:1-(3-methoxy-carbonyl)-propyl-1-1-phenyl-(6,6)C61 (PCBM) bulk heterojunction active layer. By doping C6PcH₂, the photosensitivity in the long-wavelength region was improved, and the energy conversion efficiency reached 3.0% at a composition ratio of P3HT:C6PcH₂:PCBM = 10:3:10. We discuss the principle of photoconversion in the bulk heterojunction solar cell based on the P3HT:C6PcH₂:PCBM active layer by taking into consideration the existence of both highly ordered P3HT domains and hexagonal columnar structures of C6PcH₂, and the microphase separation of P3HT and C6PcH₂ in the active layer.     

Solution-processable star-shaped photovoltaic organic molecule with triphenylamine core and thieno[3,2-b]thiophene–dicyanovinyl arms

A new solution-processable star-shaped D-π-A molecule with triphenylamine (TPA) as core and donor unit, dicyanovinyl (DCN) as end group and acceptor unit, and 3,6-dihexyl-thieno[3,2-b]thiophene (DHT) as π bridge, S(TPA-DHT-DCN) was synthesized for the application as donor material in solution-processed bulk-heterojunction organic solar cells (OSCs). The compound exhibits broad absorption in the visible region with suitable energy levels, which are desirable for application as a donor material in organic solar cells. The OSC devices based on S(TPA-DHT-DCN) as the donor and PC₇₁BM as the acceptor (1:2, w/w) exhibited power conversion efficiency (PCE) of 2.87%, with high open circuit voltage (V_oc) of 0.96 V, short circuit current density (J_sc) of 6.80 mA/cm², and fill factor (FF) of 43.5%, under the illumination of AM.1.5, 100 mW/cm². The V_oc of 0.96 V for S(TPA-DHT-DCN) is among the top values for the solution-processed molecular-based OSCs reported so far.     

Performance Analysis of Printed Bulk Heterojunction Solar Cells

In this paper we report on printed bulk heterojunction solar cells from poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl C₆₁ butyric acid methyl ester (PCBM) with power efficiencies of over 4 %. Devices have been produced by doctor blading, which is a reel‐to‐reel compatible large‐area coating technique. Devices exhibit a short‐circuit current of over 11.5 mA cm^–2, a fill factor of 58 %, and an open‐circuit voltage of 615 mV, resulting in an AM1.5 power efficiency of over 4.0 % at 25 °C and under 100 mW cm^–2. The mismatch factor of the solar simulator is cross‐calibrated by determining the spectral quantum efficiency of organic devices as well as of a calibrated Si device, and by the combination of outdoor tests; these efficiencies are precise within less than 3 % relative variation. Although the devices are regarded as fairly optimized, analysis in terms of a one‐diode equivalent circuit reveals residual losses and loss mechanisms. Most interestingly, the analysis points out the different properties of spin‐coated versus bladed devices. Based on this analysis, the future efficiency potential of P3HT–PCBM solar cells is analyzed.