Donor–acceptor–acceptor–donor small molecules for solution processed bulk heterojunction solar cells

We report on the optical and electrochemical characterization (experimental and theoretical) of two donor substituted benzothiadiazole with different cyano based acceptor π-linkers, tetracyanobutadiene (TCBD) SM1 and dicyanoquinomethane (DCNQ) SM2, and explore them as the donor component for solution processed bulk heterojunction organic solar cells, along with PC₇₁BM as the electron acceptor. The solution bulk heterojunction (BHJ) solar cells based on dichloromethane (DCM) processed active layer with SM1 and SM2 as donor and PC₇₁BM as acceptor achieve power conversion efficiency (PCE) of 2.76% and 3.61%, respectively. The solar cells based on these two small molecules exhibit good Voc, which is attributed to their deep HOMO energy level. The higher PCE of the device based on SM2 compared to SM1 is attributed to the its small bandgap, broader absorption profile and enhanced hole mobility. Additionally, the PCE of the SM2:PC₇₁BM based solar cells processed with 1-chloronaphthalene CN (3 v%)/DCM is further improved reaching upto 4.86%. This increase in PCE has been attributed to the improved nanoscale morphology and more balanced charge transport in the device, due to the solvent additive.     

Efficient bilayer heterojunction polymer solar cells with bumpy donor–acceptor interface formed by facile polymer blend

We demonstrated a facile method for the fabrication of bilayer polymer solar cells with a controlled heterojunction structure via simple polymer blends. The spontaneous phase separation of poly(3-hexylthiophene)/polyethylene glycol blends provides a bumpy electron-donor layer with characteristic circular depressions. The diameter and depth of the circular depressions can be controlled by varying the PEG content of the blend. The deposition of -phenyl-C61-butyric acid methyl ester as an electron-acceptor layer then creates an interpenetrating donor–acceptor interface for bilayer heterojunction polymer solar cells. The bumpy morphology of the interface results in a significant enhancement in the power conversion efficiency over that of the bilayer polymer solar cells with a typical planar interface, which is mainly due to an increase of photocurrent. An estimation of the field-dependent possibility of charge separation indicates that charge extraction is more efficient than charge recombination in the bilayer devices and the increase in the interfacial area of solar cells with a bumpy-interface leads to generate more electron-hole pairs at the interface.     

Role of the donor material and the donor–acceptor mixing ratio in increasing the efficiency of Schottky junction organic solar cells

Schottky junction organic solar cells (OSCs) employ a high work-function anode and an active layer comprised of fullerene and low concentrations of donor. In this study, the roles of the donor material and the donor–acceptor mixing ratio in Schottky junction OSCs are explored. The results show that the high short circuit current (J_sc) seen in Schottky junction OSCs at low donor concentrations arises primarily from photocurrent contributions from charge-transfer intermolecular states in C₆₀ aggregates. These aggregates absorb light at 400–600 nm and are thus well matched to the solar spectrum. The presence of the donor molecules is shown to be necessary for the dissociation of the C₆₀ aggregate excitons, which ultimately allows for enhanced photocurrents. The exciton dissociation process is governed primarily by the highest occupied molecular orbial (HOMO) energy level difference between the donor and C₆₀, and is only efficient when this difference is large enough for the energetically favorable transfer of holes from C₆₀ to the donor material. Increasing the donor concentration beyond a certain threshold hinders C₆₀ aggregate formation and thus removes its contribution to photocurrent completely. Furthermore, the V_oc is shown to be strongly influenced by the choice of donor material, indicating that it is not set by the Schottky junction barrier height as previously thought. In spite of this influence on V_oc, the choice of donor in the active layer does not appear to play a significant role in the extraction of holes from the Schottky junction organic solar cells. Optimized chlorine indium phthalocyanine (ClInPc) doped C₇₀ Schottky cells were fabricated to demonstrate a peak power conversion efficiency of 3.6%.     

Modeling the structure–property relations in pillar-structured organic donor/acceptor solar cells

Recently, organic solar cells with ordered morphologies in the form of vertical, interpenetrating donor- and acceptor-pillars have been demonstrated with various fabrication techniques. In order to find the optimal shape and size of these pillar structures, the conventional computational method requires simulating and comparing across different pillar designs; this may be time consuming since the pillar designs could have a large number of variations. In this paper, we establish a theoretical and computational framework that allows for efficient optimization of pillar-type morphologies. We first capture the effects of two key morphological parameters – the specific donor/acceptor interfacial area and the donor/acceptor volume ratio – with closed-form structure–property relations. We then illustrate through three-dimensional device modeling that the photovoltaic behavior of these pillar-structured cells is essentially determined by these two morphological parameters. The cross-sectional pattern of the pillar structures, on the other hand, has no major influence on the cell performance. Finally, we demonstrate a fast procedure to generate a power-density map that can aid in designing the optimal pillar structures.     

Charge transfer in thin films of donor–acceptor complexes studied by infrared spectroscopy

The degree of charge transfer in thin films of organic charge transfer (CT)-complexes, which are deposited via thermal evaporation, is examined via infrared-spectroscopy. We demonstrate a linear relationship between the shift in the excitation energy of the CN-stretching mode of CT-complexes with the acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ) and the charge transfer. The measured correlation corresponds very well with DFT calculations. For Na-TCNQ we observe a splitting in the peak of the CN-stretching mode, which can be explained by the coupling of two modes and was confirmed by the calculations. In CT-complexes with partial charge transfer the appearance of an electronic excitation is demonstrated.     

Linear and propeller-like fluoro-isoindigo based donor–acceptor small molecules for organic solar cells

Two donor–acceptor type fluoro-isoindigo based small molecule semiconductors are synthesized and their optical, electrochemical, thermal, and charge transport properties are investigated. The two molecular chromophores differ by their architecture, linear (M1) vs propeller-like (M2). Both molecules present a broad absorption in the visible range and a low optical HOMO–LUMO gap (∼1.6 eV). AFM images of solution-processed thin films show that the trigonal molecule M2 forms highly oriented fibrils after a few seconds of solvent vapor annealing. The materials are evaluated as electron donor components in bulk heterojunction organic solar cells using PC₆₁BM as the electron acceptor. The devices based on the propeller-like molecule M2 exhibit a high open-circuit voltage (around 1.0 V) and a power conversion efficiency of 2.23%.     

Improved power conversion efficiency by insertion of RGO–TiO2 composite layer as optical spacer in polymer bulk heterojunction solar cells

We report that the power conversion efficiency (PCE) can be enhanced in polymer bulk heterojunction solar cells by inserting an interfacial electron transporting layer consisting of pristine TiO₂ or reduced graphene oxide–TiO₂ (RGO–TiO₂) between the active layer and cathode Al electrode. The enhancement in the PCE has been analyzed through the optical absorption, current–voltage characteristics under illumination and estimation of photo-induced charge carrier generation rate. It was found that either TiO₂ or RGO–TiO₂ interfacial layers improve the light harvesting, as well as the charge extraction efficiency, acting as a blocking layer for holes, and also reducing charge recombination. The combined enhancement in light harvesting property and charge collection efficiency improves the PCE of the organic solar cell up to 4.18% and 5.33% for TiO₂ and RGO–TiO₂ interfacial layer, respectively, as compared to a value of 3.26% for the polymer solar cell without interfacial layer.     

Capacitance–voltage characteristics of P3HT:PCBM bulk heterojunction solar cells with ohmic contacts and the impact of single walled carbon nanotubes on them

Capacitance–voltage (C–V) characteristics of P3HT:PCBM devices of two different thicknesses are correlated with current density–voltage (J–V) characteristics. The rising portion of the C–V characteristics coincides with the exponential current density below the built-in voltage. The negative capacitance (NC) of these devices is a low frequency phenomenon and it occurs in trap-free space charge limited current (SCLC) regime. The onset frequencies of NC for devices with and without SWNTs also do not follow direct relation with effective mobility. The NC in thin devices has non-monotonic change with voltage for thin devices showing that interface state kinetics can be the reason for its occurrence. The NC of thick devices, on the other hand, increases monotonically with voltage showing that bulk properties dominate in these. Addition of SWNTs to these devices for efficiency improvement does not modify their built-in voltage. Also, the SWNTs do not affect the forward NC behaviour. However, the devices containing SWNTs show NC in reverse bias also which has different frequency dependence with voltage. The reverse bias NC is attributed to the large non-linear reverse current by charge injection into the additional energy levels introduced by SWNTs.     

Synthesis of ZnO and Fe2O3 nanoparticles by sol–gel method and their application in dye-sensitized solar cells

ZnO and Fe₂O₃ nanoparticles have been formed in a silica matrix, through the sol–gel method and were used as a photoanode to fabricate dye-sensitized solar cells (DSCs). The obtained oxides were characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscope and UV–visible absorption spectroscopy. The results indicate that ZnO and Fe₂O₃ prepared by this method may be used as photoanodes in photo-electro-chemical energy conversion systems. DSSCs have been built using eosin Y as photosensitizer and their photocurrent, open-circuit voltage, fill factor and efficiency have been measured under direct sunlight illumination (1000 Wcm^?2). A ZnO-film solar cell had the best performance with an open-circuit voltage of V_oc=0.7 V and short-circuit current density of I_sc=490 μA/cm². This was attributed to high optical gap energy and transparency of ZnO compared to Fe₂O₃. The effects of annealing temperature and concentration of Fe₂O₃ on conversion efficiency of the Fe₂O₃ based solar cell were also studied.     

Effect of the chemical composition of Cu–In–Ga–Se layers on the photoconductivity and conversion efficiency of CdS/CIGSe solar cells

The effect of the [Ga]/[In+Ga] ratio of gallium and indium on the microwave photoconductivity of Cu–In–Ga–Se (CIGSe) films and on the efficiency of solar cells fabricated in accordance with the same technology is investigated. According to the observations of a field-emission scanning electron microscopy (FESEM), the grain size decreases with increasing Ga content. With increasing gallium content in the samples, the photogenerated-electron lifetime and the activation energy of the microwave photoconductivity also decrease. The changes in the activation energy of the through conduction in darkness are less than 20%. Analysis of the obtained data shows that the known effect of the gallium gradient on the efficiency should be associated with modification of the internal structure of grains instead of with their boundaries.     

Bridging donor–acceptor energy offset using organic dopants as energy ladders to improve open-circuit voltages in bulk-heterojunction solar cells

A systematic way to improve the open circuit voltage of bulk-heterojunction (BHJ) organic photovoltaics is demonstrated by incorporating energy ladder material to form a ternary blend with cascade energy structures. We propose that doping organic molecules with appropriate energetic alignment to bridge the donor–acceptor energy offset can facilitate exciton dissociation and hence improve open-circuit voltage (V_oc) and power conversion efficiency. The cascade energy alignment structure is measured via ultraviolet photoemission spectroscopy. The V_oc and power conversion efficiency of devices using the proposed schemes can be enhanced by 10% and 20%, respectively. The results provide a new path toward higher power conversion efficiency in BHJ systems by engineering the energy structures of the materials in the active layers.     

Investigation of the blue–green emission and UV photosensitivity of Cu-doped ZnO films

Cu-doped zinc oxide (ZnO:Cu) films were deposited on p-Si (100) substrates using radio-frequency reactive magnetron sputtering. The structure and optical properties of the films were characterized by X-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and fluorescence spectroscopy. XRD and SEM results revealed that ZnO:Cu film had a better preferential orientation along the c-axis compared with pure ZnO film. The chemical state of copper and oxygen in ZnO:Cu films was investigated by XPS. The results suggest that the Cu ion has a mixed univalent and bivalent state. The integrated Cu²⁺/Cu⁺ intensity ratio increased with the O₂ partial pressure. Photoluminescence measurements at room temperature revealed a double peak in the blue regions and a green emission peak. The close relationship between the valence state of Cu ions and the blue–green emission is discussed in detail. A higher photocurrent was observed for ZnO:Cu films under UV illumination. UV photodetectors based on ZnO:Cu films have high sensitivity and fast response and recovery times. Under periodic UV illumination at 380 nm the ZnO:Cu films showed stable photocurrent growth and decay, so the films are potential candidate materials for UV photodetectors.     

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 open-circuit voltage polymer solar cells based on D–A copolymer of indacenodithiophene and fluorine-substituted benzotriazole

A medium band gap D–A copolymer of indacenodithiophene (IDT) and fluorinated dithienylbenzotriazole (FBTA), PIDT-FBTA, was synthesized for the application as donor material in polymer solar cells (PSCs). PIDT-FBTA showed deeper highest occupied molecular orbital (HOMO) energy level due to the strong electron-withdrawing difluorine substitution on benzotriazole acceptor unit in the D–A copolymer. The PSCs based on PIDT-FBTA:PC₇₀BM (1:3) exhibited a high V_oc of 0.90 V and a power conversion efficiency (PCE) of 3.62% under the illumination of AM 1.5G, 100 mW cm⁻². The device performance was further improved by methanol treatment with PCE increased to 4.90% and V_oc increased to 0.92 V.     

Direct comparison of charge transport and electronic traps in polymer–fullerene blends under dark and illuminated conditions

A direct comparison of charge transport and electronic traps in representative polymer–fullerene blend, poly (3-hexylthiophene) (P3HT) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 (PCBM), is carried out in dark and illuminated conditions based on the measurements of temperature-dependent current–voltage characteristics. In dark condition, the charge transport presents a transition from Ohmic to trap-limited current. While the trap-filled space charge limited current is observed under illumination at the same applied bias. From evaluations of trap density and energy distribution by a differential method, it is reveal that the diverse charge transport in dark and illuminated conditions is mainly caused by the different trap states distribution, which strongly affects the space charges and the electrical field in P3HT: PCBM blends.     

CdSe-sensitized inorganic–organic heterojunction solar cells: The effect of molecular dipole interface modification and surface passivation

CdSe-sensitized heterojunction solar cells composed of mesoscopic TiO₂/CdSe/P3HT (poly-3-hexylthiophene) were constructed, and the negative molecular dipole of 4-methoxybenzenethiol (MBT) and the ZnS passivation layer were used as interface modifiers to improve device performance. Through the interface modification between TiO₂/CdSe and P3HT using MBT and by ZnS surface passivation, the power conversion efficiency of the modified solar cell was greatly enhanced from 1.02% to 1.62% under 1 sun illumination.     

Interrelation of the construction of the metamorphic InAlAs/InGaAs nanoheterostructures with the InAs content in the active layer of 76–100% with their surface morphology and electrical properties

The influence of the construction of a metamorphic buffer on the surface morphology and electrical properties of InAlAs/InGaAs/InAlAs nanoheterostructures with InAs content in the active layer from 76 to 100% with the use of the GaAs and InP substrates is studied. It is shown that such parameters as the electron mobility and the concentration, as well as the root-mean-square surface roughness, substantially depend on the construction of the metamorphic buffer. It is established experimentally that these parameters largely depend on the maximal local gradient of the lattice constant of the metamorphic buffer in the growth direction of the layers rather than on its average value. It is shown that, with selection of the construction of the metamorphic buffer, it is possible to form nanostructured surfaces with a large-periodic profile.     

Molecular dipole,dye structure and electron lifetime relationship in efficient dye sensitized solar cells based on donor–π–acceptor organic sensitizers

In this work we report the synthesis and characterization of two new push–pull organic dyes (LC95 and LC107) to be employed as sensitizers in solar cells. Both molecules contain the bis(4-hexyloxyphenylamino)styril unit as the donor group, the cyanoacrylate acid as the acceptor, and the selenophene–thiophene (LC95 dye) and thiophene–selenophene (LC107 dye) moieties as the conjugated linkers. Dye sensitized solar cells employing these two photosensitizers and the cobalt(II/III) redox electrolyte exhibit good solar to energy conversion efficiencies of 6.3% and 6.5% measured under the 100 mW cm⁻² simulated AM1.5 sunlight. The efficiencies are slightly lower with the iodine/iodide electrolyte. The performance of these two dyes has been discussed and compared to three closely related sensitizers, i.e. C214, C216 and C218, by means of experimental measurements and quantum chemistry computations, with special attention to differences on their geometries, molecular dipoles and electron recombination lifetimes.     

D–A copolymer with high ambipolar mobilities based on dithienothiophene and diketopyrrolopyrrole for polymer solar cells and organic field-effect transistors

Donor–acceptor (D–A) type conjugated polymers have been developed to absorb longer wavelength light in polymer solar cells (PSCs) and to achieve a high charge carrier mobility in organic field-effect transistors (OFETs). PDTDP, containing dithienothiophene (DTT) as the electron donor and diketopyrrolopyrrole (DPP) as the electron acceptor, was synthesized by stille polycondensation in order to achieve the advantages of D–A type conjugated polymers. The polymer showed optical band gaps of 1.44 and 1.42 eV in solution and in film, respectively, and a HOMO level of 5.09 eV. PDTDP and PC₇₁BM blends with 1,8-diiodooctane (DIO) exhibited improved performance in PSCs with a power conversion efficiency (PCE) of 4.45% under AM 1.5G irradiation. By investigating transmission electron microscopy (TEM), atomic force microscopy (AFM), and the light intensity dependence of J_SC and V_OC, we conclude that DIO acts as a processing additive that helps to form a nanoscale phase separation between donor and acceptor, resulting in an enhancement of μ_h and μ_e, which affects the J_SC, EQE, and PCE of PSCs. The charge carrier mobilities of PDTDP in OFETs were also investigated at various annealing temperatures and the polymer exhibited the highest hole and electron mobilities of 2.53 cm² V⁻¹ s⁻¹ at 250 °C and 0.36 cm² V⁻¹ s⁻¹ at 310 °C, respectively. XRD and AFM results demonstrated that the thermal annealing temperature had a critical effect on the changes in the crystallinity and morphology of the polymer. The low-voltage device was fabricated using high-k dielectric, P(VDF-TrFE) and P(VDF-TrFE-CTFE), and the carrier mobility of PDTDP was reached 0.1 cm² V⁻¹ s⁻¹ at V_d = −5 V. PDTDP complementary inverters were fabricated, and the high ambipolar characteristics of the polymer resulted in an output voltage gain of more than 25.