Highly crystalline bilayer electron transport layer for efficient conjugated polymer solar cells

Solution processed solar cells are a promising renewable energy technology due to the low fabrication costs. The most commonly used electron transport layer for solution processed organic solar cells is ZnO. However, sol-gel derived ZnO is amorphous, which limits interfacial charge transport. In this study, we demonstrate a ZnO bilayer, composed of a nanoparticle ZnO and sol-gel derived ZnO layer, as the electron transport layer in polymer solar cells incorporating the novel polymer poly [(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3‴-di (2-octyldodecyl)-2,2′; 5′,2″; 5″,2‴-quaterthiophen-5,5‴-diyl)] (PffBT4T-2OD). Compared with the single layer sol-gel ZnO, the bilayer displayed enhanced crystallinity. Consequently, the interfacial transport from the active layer was improved, as evidenced by dark J-V and PL spectroscopy measurements. Solar cells incorporating this bilayer ZnO layer achieved PCE values exceeding 10%, a relative improvement of 25% compared to the sol-gel ZnO devices.     

2,7-Carbazole and thieno[3,4-c]pyrrole-4,6-dione based copolymers with deep highest occupied molecular orbital for photovoltaic cells

Three kinds of donor–acceptor (D–A) type photovoltaic polymers were synthesized based on 2,7-carbazole and thieno[3,4-c]pyrrole-4,6-dione (TPD). The conjugation of weakly electron (e)-donating 2,7-carbazole and strongly e-accepting TPD moieties yielded a deep highest occupied molecular orbital (HOMO) and its energy level was fine-controlled to be −5.72, −5.67 and −5.57 eV through the incorporation of thiophene (T), thieno[3,2-b]thiophene (TT) and bithiophene (BT) as a π-bridge. Polymer:[6,6]-phenyl-C₇₁ butyric acid methyl ester (PC₇₁BM) based bulk heterojunction solar cells exhibited a high open-circuit voltage (V_OC) in the range, 0.86–0.94 V, suggesting good agreement with the measured HOMO levels. Despite the high V_OC, the thiophene (or thienothiophene)-containing PCTTPD (or PCTTTPD) showed poor power conversion efficiency (PCE, 1.14 and 1.25%) because of the very low short-circuit current density (J_SC). The voltage-dependent photocurrent and photoluminescence quenching measurements suggested that hole transfer from PC₇₁BM to polymer depends strongly on the HOMO level of the polymer. The PCTTPD and PCTTTPD devices suffered from electron–hole recombination at the polymer/PC₇₁BM interfaces because of the insufficient energy offset between the HOMOs of the polymer and PC₇₁BM. The PCBTTPD:PC₇₁BM device showed the best PCE of 3.42% with a V_OC and J_SC of 0.86 V and 7.79 mA cm⁻², respectively. These results show that photovoltaic polymers should be designed carefully to have a deep HOMO level for a high V_OC and sufficient energy offset for ensuring efficient hole transfer from PC₇₁BM to the polymer.     

Effect of an Al-doped ZnO electron transport layer on the efficiency of inverted bulk heterojunction solar cells

Doping is a widely-implemented strategy for enhancing the inherent electrical properties of metal oxide charge transport layers in photovoltaic devices because higher conductivity of electron transport layer (ETL) can increment the photocurrent by reducing the series resistance. To improve the conductivity of ETL, in this study we doped the ZnO layer with aluminum (Al), then investigated the influence of AZO on the performance of inverted bulk heterojunction (BHJ) polymer solar cells based on poly [[4,8-bis [(2-ethylhexyl)oxy]benzo [1,2-b:4,5-b’]dithiophene-2,6-diyl]-[3-fluoro-2[(2-ethylhexyl)-carbonyl]-thieno-[3,4-b]thiophenediyl ]] (PTB7):[6,6]-phenyl C71 butyric acid methyl ester (PC₇₁BM). The measured conductivity of AZO was ~10⁻³ S/cm, which was two orders of magnitude higher than that of intrinsic ZnO (~10⁻⁵ S/cm). By decreasing the series resistance (R_s) in a device with an AZO layer, the short circuit current (J_sc) increased significantly from 15.663 mA/cm² to 17.040 mA/cm². As a result, the device with AZO exhibited an enhanced power conversion efficiency (PCE) of 8.984%.     

The effect of various solvent additives on the power conversion efficiency of polymer-polymer solar cells

We investigated the effect of three different additives (1-chloronaphthalene, 1,8-diiodooctane, diphenylether) on the performance of polymer-polymer solar cells based on a BHJ blend consisting of poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene-alt-3-fluorothieno[3,4-b]thiophene-2-carboxylate] (PTB7-Th) as a donor and poly[[N,N′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)] (P(NDI2OD-T2)) as an acceptor. A direct comparison of the efficiency of the solar cells with and without additive indicated that the device using the additive exhibited slightly improved performance. However, the efficiency enhancement was not significant. The optimal ratio of additive differed depending on the properties of the additive. In addition, the performances of polymer-polymer solar cells were not significantly dependent on the type of additive. Identifying the optimal fabrication condition was critical for achieving the highest performance. It is known that the general role of an additive in polymer solar cells based on a BHJ active layer was to induce good phase separation between the donor and acceptor by morphology modification. However, grazing-incidence wide-angle X-ray scattering results showed that no significant morphology change in polymer-polymer active layer was caused by the additive. Rather, our modulated impedance spectroscopy study showed that the performance enhancement in polymer-polymer solar cells with additive was because of improved recombination properties rather than improvements in crystalline morphology.     

Highly stable inverted poly (3-hexylthiophene):methano-fullerene [6,6]-phenyl C71-butyric acid methyl ester bulk heterojunction solar cell with thin oxide nano particle layer using solution process

We have investigated the inverted poly (3-hexylthiophene):methano-fullerene [6,6]-phenyl C71-butyric acid methyl ester (P3HT:PC₇₁BM) bulk heterojunction (IBHJ) solar cell with various n-type metal oxide nano particle layers on ITO and MoO₃ anode buffer layer underneath Al. The IBHJ solar cell with a tin oxide nano particle layer shows the power conversion efficiency (PCE) of 3.1% and better stability compared to conventional BHJ solar cell. The PCE of this cell decreases by 3% after 2 months in ambient air while the other cells show more degradation.     

Influence of bridging atom on the vertical phase separation of low band gap bulk heterojunction solar cells

Vertical phase separation of the polymer and fullerene molecules in bulk heterojunction organic solar cells influences the exciton dissociation, charge carrier transport and collection. This work compares the vertical phase separation of poly[2,1,3‐benzothiadiazole‐4,7‐diyl[4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta [2,1‐b:3,4‐b′]dithiophene‐2,6‐diyl]] (C‐PCPDTBT):[6,6]‐phenyl C71 butyric acid methyl ester (PC₇₁BM) and poly[2,1,3‐benzothiadiazole‐4,7‐diyl[4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta [2,1‐b:3,4‐b′]dithiophene‐siloe2,6‐diyl]] (Si‐PCPDTBT):PC₇₁BM blend films, using X‐ray photoemission spectroscopy depth profiles. The difference between the two polymers is the bridging atom, which is carbon for C‐PCPDTBT and silicon for Si‐PCPDTBT. Si‐PCPDTBT exhibits enhanced polymer chain packing and crystallinity. We believe this enhanced chain packing provides a driving force during film drying which alters the vertical morphology. The different nature of vertical phase separation plays a role in determining the increased device performance observed for Si‐PCPDTBT:PC₇₁BM solar cells. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Study on effect of substituents grafted on cyclopenta-fused anthracences as the cascade material for improving ternary bulk heterojunction photovoltaic cells

Searching alternatives to enhance the attainable conversion efficiency of organic photovoltaics is one of the most crucial issues toward renewable energy source. Here, the model ternary organic solar cells systems were designed to improve the performance of P3HT/PC₆₁BM organic solar cells which promise a potential to large area and flexible fabrication, based on a group of cyclopent[hi]aceanthrylenes (CPAs) derivatives as the third cascade component in active layer of the device. In all of these solar cells, although all ternary structures containing a group of cyclopent[hi]aceanthrylene derivatives demonstrate the improvement of open-circuit voltage (V_OC) compared to binary device of P3HT/PC₆₁BM, the conversion efficiencies of these devices can not all be improved. This indicates the different influence on observable device metrics attributed by the different substituents around cyclopent[hi]aceanthrylene core. By extension, these results suggest that the ternary system used a simple one single active layer processing step can provide a potentially effective way to optimize the performance in BHJ solar cells.     

A comparative study on the performance of hybrid solar cells containing ZnSTe QDs in hole transporting layer and photoactive layer

In this paper, ZnSTe quantum dots-based hybrid solar cells (HSC) with two different device architectures have been investigated. The improved performance of the poly(3-hexylthiophene) (P3HT) and [6,6]phenyl C₇₁ butyric acid methyl ester (PC₇₁BM)-based bulk heterojunction (BHJ) solar cells by the incorporation of ZnSTe quantum dots (QDs) with an average size of 2.96 nm in PEDOT:PSS layer and active layer that have been demonstrated. Although the efficiency of both types of devices is almost the same, a close comparison reveals different reasons behind their improved performance. The device prepared with QDs in the HTL has shown reduced series resistance, increased shunt resistance, and improved mobility. On the other hand, QDs in the photoactive layer demonstrates increased photo-generation leading to improved efficiency.     

Photovoltaic performance of bifunctional low band gap conjugated copolymer

We have investigated the bifunctional properties using ambipolar low band gap conjugated copolymer in organic bulk-heterojunction (BHJ) solar cells. Ambipolar copolymer, poly[3,6-dithien-2-yl-2,5-di(2-decyltetradecanyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-5′,5′’-diyl-alt-benzo-2,1,3-thiadiazol-4,7-diyl] (PDTDPP-alt-BTZ), successfully works as the bifunctional material acting as both donor or acceptor. However, because of fast recombination nature and broken charge balance of hole and electron, solar cell performances were significantly limited. The results indicate that having distinct role of each component might be better for the high performance BHJ solar cells rather than bifunctional property based on good charge transport properties of both hole and electrons.     

Electronic processes at the interfaces between photoactive layers and TiO<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript> buffer layers in organic solar cells

The effect a layer of TiO_x located between a photoactive layer and a metallic Al electrode has on the photovoltaic properties of an organic solar cell based on P3HT:PC₇₀BM polymer is studied. The optimum thickness of the TiO_x layer at which the efficiency of the solar cells is highest and the TiO_x layer ensures the transfer of electrons from the photoactive polymer layer to the electrode while blocking vacancies is found to be 10 nm. The effect oxygen has on electronic processes during the operation of the photovoltaic cell is discussed.     

Fabrication and characterization of ZnTPP:PCBM bulk heterojunction (BHJ) solar cells

Bulk heterojunction (BHJ) solar cells were fabricated based on blended films of a porphyrin derivative 5,10,15,20-Tetraphenyl-21H,23H-porphine zinc (ZnTPP) and a fullerene derivative [6,6]-phenyl-C₆₁ butyric acid methyl ester (PCBM) as the active layer. The ZnTTP:PCBM BHJ solar cells were fabricated by spin-casting of the blended layer. The weight ratios of ZnTPP and PCBM were varied from 1:1 to 0:10. The electronic and optical properties of each cell were investigated. Optical density (OD) of the blended film for each cell was extracted from its reflection and transmission curves. OD and average absorption coefficients of the active materials were used to determine film thicknesses. Absorption spectra of each component material were compared with the spectra of the blended films. Current density–Voltage (J–V) characteristics were recorded under dark as well as under the illumination of AM 1.5G (1 sun) solar spectrum. The BHJ solar cell with ZnTPP:PCBM ratio of 1:9 showed the best performance . The values of RR, V_OC , J_SC , FF and η for these ratios were 106.3, 0.4 V, 1.316 mA/cm², 0.4 and 0.21%, respectively. The cross-section of this device using SEM was also examined.     

Au nanodot lattices with well‐controlled size and density for thin organic solar cells

Size, shape, and density‐controlled metal nanostructure, Au nanodot lattices fabricated by electron beam lithography, were embedded in thin organic solar cell consisting of PC₇₁BM:PCPDTBT. The effects of their size and density on device performance were examined. Even though dipole res‐onances of Au nanodots were consistent with the absorption range of the active materials, there were no improvements in device performance under any sizes and densities. In addition, under high volume density of Au nanodots to PEDOT:PSS layer, the device performance was deteriorated. These results indicated that not only size and density but also other factors which determine light scattering characteristics greatly affect the device performance of solar cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Förster-type energy transfer mechanism in PF2/6 to MEH-PPV conjugated polymers

Energy transfer mechanism between Poly[9,9-di-(2′-ethylhexyl)fluorenyl-2,7-diyl] (PF_2/6) as a donor and poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) as an acceptor in different solvents has been studied using steady-state emission measurements. Four different solvents namely, tetrahydrofuran (THF), toluene, chlorobenzene (C.B) and benzene have been used in this study. The absorption and luminescence behaviors of the samples are measured at a fixed concentration of donor (0.1 μM) while the concentrations for acceptor are kept in the range of 0.1–1.0 μM. Based on these measurements, the energy transfer properties namely quenching rate constant (k_SV), energy transfer rate constant (k_ET), energy transfer probability (P_DA), transfer efficiency (η) and critical distance of energy transfer (R_o) are calculated. The use of THF resulted in the highest energy transfer. Long range dipole–dipole interaction between the excited donor and ground state acceptor molecules is the dominant mechanism responsible for the energy transfer as proven by the large values of R_o.     

Novel fabrication route for carbon-free and dense CuInSe2 (CIS) thin films via a non-vacuum process for solar cell application

Carbon-free CuInSe₂ (CIS) thin film with a dense microstructure has been prepared using a novel non-vacuum based fabrication route. Cu_xS_y and In₂Se₃ binary nanoparticles, approximately 10 nm in size, were synthesized by a low temperature colloidal process. The precursor film was deposited using the coating ink formulated with the binary nanoparticles and pyridine, and then annealed in the rapid thermal annealing (RTA) chamber at 540 °C for 15 min under selenium (Se) atmosphere. Scanning electron micrographs, X-ray diffraction patterns and Raman spectra showed a phase pure carbon-free and dense CIS thin film was prepared in this method. A solar cell device fabricated using this CIS thin film showed the following photovoltaic characteristics: V_OC = 350 mV, J_SC = 24.72 mA cm⁻², FF = 38.73% and η = 3.36% under standard AM 1.5 condition.     

Extending the response spectrum of organic photodetectors by quaternary active layer method with complementary absorption spectra

In this work, we report a new method for extending the response spectra of organic photodetectors (OPDs) by incorporating PBDT-TT-C and PBDT-TT-F in the P3HT:PC₆₁BM. The effects of PBDT-TT-C and PBDT-TT-F incorporation on the optical and electrical properties of OPDs were investigated, It was found that when the mass ratio of P3HT:PBDT-TT-F:PBDT-TT-C:PC₆₁BM was 12:2:2:8, the response spectrum of the active layer was extended to 780 nm. The responsivity (R) and external quantum efficiency (EQE) of the OPDs reached 340, 376, 315 mA/W and 67%, 88%, 85% under 630, 530, and 460 nm illumination and −1 V bias, respectively, and the detectivity (D*) reached 10¹² Jones. The results show that the inclusion of an appropriate amount of donor material with similar chemical structure and complementary absorption spectrum can reduce the influence of the doping material on the micro-morphology of the original film while improving the absorption of the spectrum. The interaction between the donor materials promotes the generation of photogenerated carriers and increases the photocurrent of the OPDs. In addition, the incorporation of the different component promotes crystallization of the film, resulting in a reduction in dark current of the OPDs.     

Influence of vacuum annealing on the structural and photoelectrochemical properties of nanocrystalline MoBi2S5 thin films

In the present paper we report structural, optical, morphological and electrical properties of thin films of MoBi₂S₅ prepared by facile self organized arrested precipitation technique (APT) from aqueous alkaline bath. X-ray diffraction study on thin films suggests orthorhombic and rhombohedral mixed phase structure. The samples are further annealed under vacuum at 373 and 473 K. The EDS pattern shows minor loss of sulphur upto 473 K. The optical absorption in visible region shows direct allowed transition with band gap variation over 1.2–1.1 eV. Post-heat treated samples exhibit n-type electrical conductivity. SEM images show uniform distribution of spherical grains with diameter ∼200 nm for as-synthesized MoBi₂S₅ thin film. The grain size increases with annealing temperature and morphology becomes more compact due to crystallization of thin film. The surface roughness deduced from AFM, was in the range of 1.29–1.92 nm. The MoBi₂S₅ thin films are employed for the fabrication of photoelectrochemical solar cells as all the samples exhibit strong absorption in visible to near IR region. Due to vacuum annealing it gives a significant enhancement of power conversion efficiency (η) upto 0.14% as compared to as-synthesized MoBi₂S₅ thin film.     

Photoinduced C70 radical anions in polymer:fullerene blends

Photoinduced polarons in solid films of polymer:fullerene blends were studied by photoluminescence (PL), photoinduced absorption (PIA) and electron spin resonance (ESR). The donor materials used were P3HT and MEH‐PPV. As acceptors we employed PC₆₀BM as reference and various soluble C₇₀‐derivates: PC₇₀BM, two different diphenylmethano‐[70]fullerene oligoether (C₇₀‐DPM‐OE) and two dimers, C₇₀–C₇₀ and C₆₀–C₇₀. Blend films containing C₇₀ revealed characteristic spectroscopic signatures not seen with C₆₀. Light‐induced ESR showed signals at g ≥ 2.005, assigned to an electron localized on the C₇₀ cage. The formation of C₇₀ radical anions also leads to a subgap PIA band at 0.92 eV, hidden in the spectra of C₇₀‐based P3HT and MEH‐PPV blends, which allows for more exact studies of charge separated states in conjugated polymer:C₇₀ blends. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Anionic nonconjugated polyelectrolyte as an anode interfacial layer for polymer solar cells

Since the most high-performing donor polymers in polymer solar cells (PSCs) possessed the deep highest occupied molecular orbital (HOMO) level, interfacial engineering on anode contact is becoming increasingly important. Herein, we demonstrated efficient PSCs using an anionic poly(styrene sulfonate) (PSS) as an anode interfacial layer (AIL). With the formation of the dipole layer, the effective work function (WF) of indium tin oxide (ITO) electrode is significantly increased from 4.8 to 5.3 eV, providing favorable energetic alignment to the quasi-Fermi level of various donor polymers. Moreover, by incorporating cationic polyelectrolytes as a cathode interfacial layer, a pair of electric dipole layers induces a strong built-in electric field across the photoactive layer to drive efficient sweep-out of photogenerated charges. Consequently, the device with PSS AIL exhibited high power conversion efficiencies of 9.2 and 14.8% in PTB7-Th:PC₇₁BM- and PM6:Y6-based PSCs, respectively, both of which are higher than those of the devices with PEDOT:PSS.     

Humidity controlled crystallization of thin CH3NH3PbI3 films for high performance perovskite solar cell

Control of crystallization of a solution‐processed perovskite layer is of prime importance for high performance solar cells. In spite of the negative effect of water on perovskite solar energy conversion in several previous works, we observed that humidity plays a critical role to develop a thin uniform, dense perovskite film with preferred crystals, in particular, in a device with architecture of ITO/PEDOT:PSS/CH₃NH₃PbI₃/ PC₇₁BM/LiF/Al fabricated by two‐step sequential spin‐coating process. Humidity controlled spin‐coating of CH₃NH₃I on the pre‐formed PbI₂ layer was the most influential process and systematic structural investigation as a function of humidity revealed that grains of CH₃NH₃PbI₃ perovskite crystals increase in size with their preferred orientation while film surface becomes roughened as the humidity increases. The performance of a device was closely related to the humidity dependent film morphology and in 40% relative humidity, the device exhibited the maximum power conversion efficiency of approximately 12% more than 10 times greater than that of a device fabricated at 20% humidity. The results suggest that our process with controlled humidity can be another efficient route for high performance and reliable perovskite solar cells. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Spin-dependent recombination of the charge-transfer state in photovoltaic polymer/fullerene blends

ABSTRACT

Q-band electron spin echo (ESE) spectroscopy was applied for studying the spin-dependent recombination of charge transfer (CT) states in the benchmark organic photovoltaics (OPV) blend of poly(3-hexylthiophene-2,5-diyl) and [6,6]-phenyl C61 butyric acid methyl ester (P3HT/PC₆₀BM). Selective microwave excitation and a special protocol for ESE data treatment allowed to suppress the ESE signal of thermalised polarons and weakly coupled CT states and to address CT states with a relatively short distance between positive and negative polarons (1.5 nm < r?<?2.5 nm). Inversion of the in-phase ESE signal with increase of the delay after laser flash was observed for the regioregular P3HT^?+/PC₆₀BM^?? CT state at a temperature of 40 K. This effect is very similar to the inversion of the time resolved (TR) EPR spectrum of the same system obtained previously. Both effects can be explained by spin-dependent recombination of the CT state, with the recombination via the triplet channel proceeding much slower than via the singlet channel. For the regiorandom P3HT^?+/PC₆₀BM^?? CT state no ESE sign inversion was observed in an analogous experiment. The result suggests the importance of CT state formation via a triplet exciton, a process which was not considered previously for the P3HT/PC₆₀BM blend.