The field of organic photovoltaics has recently produced highly efficient single-junction cells with power conversion efficiency >10%, yet the open-circuit voltage (V_OC) remains relatively low in many high performing systems. An accurate picture of the density of states (DOS) in working solar cells is crucial to understanding the sources of voltage loss, but remains difficult to obtain experimentally. Here, the tail of the DOS is characterized in a number of small molecule bulk heterojunction solar cells from the charge density dependence of V_OC, and is directly compared to the disorder present within donor and acceptor components as measured by Kelvin probe. Using these DOS distributions, the total energy loss relative to the charge transfer state energy (E_CT)—ranging from ≈0.5 to 0.7 eV—is divided into contributions from energetic disorder and from charge recombination, and the extent to which these factors limit the V_OC is assessed.

The light intensity dependence of the main photoelectrical parameters of the nonfullerene small-molecule bulk heterojunction (BHJ) solar cells p-DTS(FBTTh₂)₂:perylene diimide (T1:PDI) shows that the nongeminate recombination losses play an important role in this system. A simple approach for the quantitative analysis of capacitance spectroscopy data of the organic BHJ solar cells, which allows to determine the density of free charge carriers as a function of applied bias under standard working conditions, is demonstrated. Using the proposed capacitance spectroscopic technique, the nongeminate recombination losses in the T1:PDI solar cells are quantitatively characterized in the scope of the bimolecular- and trap-assisted recombination mechanisms. Their contributions are separately analyzed within a wide range of the applied bias.

Whereas the role of molecularly mixed domains in organic photovoltaic devices for charge generation is extensively discussed in the literature, the impact on charge recombination and thus fill factor is largely unexplored. Here, a combination of soft X-ray techniques enables the quantification of phases at multiple length scales to reveal their role regarding charge recombination in a highly efficient solution processed small molecule system 7,7′-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b′]dithiophene-2,6-diyl)bis(6-fluoro-4-(5′-hexyl-[2,2′-bithiophen]-5-yl)benzo[c][1,2,5]thiadiazole) (p-DTS(FBTTh₂)₂) . A quantitative (linear) relationship between the average composition variations and the device fill-factor is observed. The results establish the complex interrelationship between average phase purity, domain size, and structural order and highlight the requirement of achieving sufficient phase purities to diminish bimolecular and geminate recombination in solution processed small molecule solar cells.

The driving forces and processes associated with the development of phase separation upon thermal annealing are investigated in solution-processed small molecule bulk heterojunction (BHJ) organic solar cells utilizing a diketopyrrolopyrrole-based donor molecule and a fullerene acceptor (PCBM). In-situ thermal annealing X-ray scattering is used to monitor the development of thin film crystallization and phase separation and reveals that the development of blend phase separation strongly correlates with the nucleation of donor crystallites. Additionally, these morphological changes lead to dramatic increases in blend electron mobility and solar cell figures of merit. These results indicate that donor crystallization is the driving force for blend phase separation. It is hypothesized that donor crystallization from an as-cast homogeneous donor:acceptor blend simultaneously produces donor-rich domains, consisting largely of donor crystallites, and acceptor-rich domains, formed from previously mixed regions of the film that have been enriched with acceptor during donor crystallization. Control of donor crystallization in solution-processed small molecule BHJ solar cells employing PCBM is thus emphasized as an important strategy for the engineering of the nanoscale phase separated, bicontinuous morphology necessary for the fabrication of efficient BHJ photovoltaic devices.

Organic solar cells utilizing the small molecule donor 7,7′-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b′]dithiophene-2,6-diyl)bis(6-fluoro-4-(5′-hexyl-[2,2′-bithiophen]-5-yl)benzo[c][1,2,5] thiadiazole) (p-DTS(FBTTh₂)₂ and the polymer acceptor poly{[N,N′-bis(2-octyldodecyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)}(P(NDI2OD-T2)) are investigated and a power conversion efficiency of 2.1% is achieved. By systematic study of bulk heterojunction (BHJ) organic photovoltaic (OPV) quantum efficiency, film morphology, charge transport and extraction and exciton diffusion, the loss processes in this blend is revealed compared to the blend of [6,6]-phenyl-C71-butyric acid methyl ester (PC₇₁BM) and the same donor. An exciton diffussion study using Förster resonant energy transfer (FRET) shows the upper limit of the P(NDI2OD-T2) exciton diffusion length to be only 1.1 nm. The extremely low exciton diffusion length of P(NDI2OD-T2), in combination with the overlap in donor and acceptor absorption, is then found to significantly limit device performance. These results suggest that BHJ OPV devices utilizing P(NDI2OD-T2) as an acceptor material will likely be limited by its low exciton diffusion length compared to devices utilizing functionalized fullerene acceptors, especially when P(NDI2OD-T2) significantly competes with the donor molecule for photon absorption.

A mechanistic study of the DNA interfacial layer that enhances the photoresponse in n-type field-effect transistors (FET) and lateral photoconductors using a solution-processed fullerene derivative embedded with disperse-red dye, namely PCBDR, is reported. Incorporation of the thin DNA layer simultaneously leads to increasing the electron injection from non-Ohmic contacts into the PCBDR active layer in dark and to increasing the photocurrent under irradiation. Such features lead to the observation of the enhancement of the photoresponsivity in PCBDR FETs up to 10³. Kelvin probe microscopy displays that in the presence of the DNA layer, the surface potential of PCBDR has a greater change in response to irradiation, which is rationalized by a larger number of photoinduced surface carriers. Transient absorption spectroscopy confirms that the increase in photoinduced carriers in PCBDR under irradiation is primarily ascribed to the increase in exciton dissociation rates through the PCBDR/DNA interface and this process can be assisted by the interfacial dipole interaction.

A mechanistic study of the DNA interfacial layer that enhances the photoresponse in n-type field-effect transistors (FET) and lateral photoconductors using a solution-processed fullerene derivative embedded with disperse-red dye, namely PCBDR, is reported. Incorporation of the thin DNA layer simultaneously leads to increasing the electron injection from non-Ohmic contacts into the PCBDR active layer in dark and to increasing the photocurrent under irradiation. Such features lead to the observation of the enhancement of the photoresponsivity in PCBDR FETs up to 10³. Kelvin probe microscopy displays that in the presence of the DNA layer, the surface potential of PCBDR has a greater change in response to irradiation, which is rationalized by a larger number of photoinduced surface carriers. Transient absorption spectroscopy confirms that the increase in photoinduced carriers in PCBDR under irradiation is primarily ascribed to the increase in exciton dissociation rates through the PCBDR/DNA interface and this process can be assisted by the interfacial dipole interaction.

Substitution of the heteroatoms in the aromatic end-groups of three diketopyrrolopyrrole containing small molecules is investigated to evaluate how such substitutions affect various physical properties, charge transport, and the performance in bulk heterojunction solar cells. While the optical absorption and frontier orbital energy levels are insensitive to heteroatom substitution, the materials' solubility, thermal properties, film morphology, charge carrier mobility, and photovoltaic performance are altered significantly. Differences in material properties are found to arise from changes in intra- and intermolecular interactions in the solid state caused by heteroatom substitution, as revealed by the single crystal structures of three compounds. This study demonstrates a systematic investigation of structure–property relationships in conjugated small molecules.

Charge transport and nongeminate recombination are investigated in two solution-processed small molecule bulk heterojunction solar cells consisting of diketopyrrolopyrrole (DPP)-based donor molecules, mono-DPP and bis-DPP, blended with [6,6]-phenyl-C71-butyric acid methyl ester (PCBM). While the bis-DPP system exhibits a high fill factor (62%) the mono-DPP system suffers from pronounced voltage dependent losses, which limit both the fill factor (46%) and short circuit current. A method to determine the average charge carrier density, recombination current, and effective carrier lifetime in operating solar cells as a function of applied bias is demonstrated. These results and light intensity measurements of the current-voltage characteristics indicate that the mono-DPP system is severely limited by nongeminate recombination losses. Further analysis reveals that the most significant factor leading to the difference in fill factor is the comparatively poor hole transport properties in the mono-DPP system (2 × 10⁻⁵ cm² V⁻¹ s⁻¹ versus 34 × 10⁻⁵ cm² V⁻¹ s⁻¹). These results suggest that future design of donor molecules for organic photovoltaics should aim to increase charge carrier mobility thereby enabling faster sweep out of charge carriers before they are lost to nongeminate recombination.

Morphological control over the bulk heterojunction (BHJ) microstructure of a high-efficiency small molecule photovoltaic system is demonstrated using both thermal treatment and solvent additive processing. Single crystal X-ray diffraction is utilized to understand molecular interactions in the solid state and the BHJ morphology is examined using bright field, high-resolution, and cross-section transmission electron microscopy techniques. Controlling the domain size, while maintaining good molecular order within the semiconducting donor material, is found to be crucial in achieving high performance and over 90% internal quantum efficiency exhibited under the optimized conditions.

Ambipolar charge transport in a solution-processed small molecule 4,7-bis{2-[2,5-bis(2-ethylhexyl)-3-(5-hexyl-2,2′:5′,2″-terthiophene-5″-yl)-pyrrolo[3,4-c]pyrrolo-1,4-dione-6-yl]-thiophene-5-yl}-2,1,3-benzothiadiazole (BTDPP2) transistor has been investigated and shows a balanced field-effect mobility of electrons and holes of up to ∼10⁻² cm² V⁻¹ s⁻¹. Using low-work-function top electrodes such as Ba, the electron injection barrier is largely reduced. The observed ambipolar transport can be enhanced over one order of magnitude compared to devices using Al or Au electrodes. The field-effect mobility increases upon thermal annealing at 150 °C due to the formation of large crystalline domains, as shown by atomic force microscopy and X-ray diffraction. Organic inverter circuits based on BTDPP2 ambipolar transistors display a gain of over 25.

Although the fabrication procedures for bulk heterojunction (BHJ) solar cells are routinely optimized to accommodate new organic materials, the influence of solvent properties and cohesive forces on the film-forming process and the self-assembly of donor and acceptor molecules on the nanoscale are poorly understood. In this study, we measure the solubility of a variety of organic semiconductors in a range of solvents and calculate cohesive forces including dispersion forces, dipole interactions, and hydrogen bonding via Hansen Solubility Parameters (HSPs). HSPs were calculated by measuring the solubilities of various organic semiconductors in 27 solvents and the influence of solvent identity on film morphology of different BHJ mixtures was explored via atomic force microscopy (AFM). The possibility of correlations between HSPs and film morphology was considered; however, it is apparent that the HSP values alone do not play a critical role in determining the morphology of the films of conjugated polymers and molecules. This collection of solubility data constitutes the first of its type for organic semiconducting materials, and may act as a useful reference for the organic semiconductor community to aid in the understanding and selection of solvents for donor–acceptor BHJ mixtures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012

The solubilities of 3,6-bis(5-(benzofuran-2-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4-dione (DPP(TBFu)₂) and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) in a series of solvents are measured, and this data is used to calculate the Hansen solubility parameters of the two materials. The dispersion, polar, and H-bonding parameters of DPP(TBFu)₂ and PC₇₁BM were found to be (19.3, 4.8, 6.3) and (20.2, 5.4, 4.5) MPa^1/2, respectively, with an error of ± 0.8 MPa^1/2. Based on the solubility properties of the two materials, three new solvents (thiophene, trichloroethylene and carbon disulfide) were utilized for the DPP(TBFu)₂:PC₇₁BM system which, after device optimization, led to power conversion efficiencies up to 4.3%.

Solution-processed organic BHJ solar cells based on 3,6-bis[5-(benzofuran-2-yl)thiophen-2-yl]-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4-dione (DPP(TBFu)₂) or poly(3-hexylthiophene) blended with [6,6]-phenyl-C₆₀₍₇₀₎ -butyric acid methyl ester (PC₆₀₍₇₀₎ BM) behave differently under various irradiation intensities. Small molecule-based DPP(TBFu)₂:PC₆₀ BM solar cells show up to 5.2% power conversion efficiency and a high fill factor at low light intensity. At 100 mW cm⁻² illumination, the efficiency and fill factor decrease, resulting in stronger power losses. Impedance spectroscopy at various light intensities reveals that high charge recombination is the cause of the low fill factor in DPP(TBFu)₂:PC₆₀ BM.

Photoconductive atomic force microscopy is employed to study the nano­scale morphology and optoelectronic properties of bulk heterojunction solar cells based on small molecules containing a benzofuran substituted diketopyrrolopyrrole (DPP) core (3,6-bis(5-(benzofuran-2-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4-dione, DPP(TBFu)₂, and [6,6]–phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), which were recently reported to have power conversion efficiencies of 4.4%. Electron and hole collection networks are visualized for blends with different donor:acceptor ratios. Formation of nanostructures in the blends leads to a higher interfacial area for charge dissociation, while maintaining bicontinuous collection networks; conditions that lead to the high efficiency observed in the devices. An excellent agreement between nanoscale and bulk open-circuit voltage measurements is achieved by surface modification of the indium tin oxide (ITO) substrate by using aminopropyltrimethoxysilane. The local open-circuit voltage is linearly dependent on the cathode work function. These results demonstrate that photoconductive atomic force microscopy coupled with surface modification of ITO substrate can be used to study nanoscale optoelectronic phenomena of organic solar cells.

Photoconductive atomic force microscopy is employed to study the nano­scale morphology and optoelectronic properties of bulk heterojunction solar cells based on small molecules containing a benzofuran substituted diketopyrrolopyrrole (DPP) core (3,6-bis(5-(benzofuran-2-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4-dione, DPP(TBFu)₂, and [6,6]–phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), which were recently reported to have power conversion efficiencies of 4.4%. Electron and hole collection networks are visualized for blends with different donor:acceptor ratios. Formation of nanostructures in the blends leads to a higher interfacial area for charge dissociation, while maintaining bicontinuous collection networks; conditions that lead to the high efficiency observed in the devices. An excellent agreement between nanoscale and bulk open-circuit voltage measurements is achieved by surface modification of the indium tin oxide (ITO) substrate by using aminopropyltrimethoxysilane. The local open-circuit voltage is linearly dependent on the cathode work function. These results demonstrate that photoconductive atomic force microscopy coupled with surface modification of ITO substrate can be used to study nanoscale optoelectronic phenomena of organic solar cells.

Research relating to organic solar cells based on solution-processed, bulk heterojunction (BHJ) films has been dominated by polymeric donor materials, as they typically have better film-forming characteristics and film morphology than their small-molecule counterparts. Despite these morphological advantages, semiconducting polymers suffer from synthetic reproducibility and difficult purification procedures, which hinder their commercial viability. Here, a non-polymeric, diketopyrrolopyrrole-based donor material that can be solution processed with a fullerene acceptor to produce good quality films is reported. Thermal annealing leads to suitable phase separation and material distribution so that highly effective BHJ morphologies are obtained. The frontier orbitals of the material are well aligned with those of the fullerene acceptor, allowing efficient electron transfer and suitable open-circuit voltages, leading to power conversion efficiencies of 4.4 ± 0.4% under AM1.5G illumination (100 mW cm⁻²). Small molecules can therefore be solution processed to form high-quality BHJ films, which may be used for low-cost, flexible organic solar cells.