Growth mechanisms of co‐evaporated kesterite: a comparison of Cu‐rich and Zn‐rich composition paths

Earth abundant kesterite solar cells have achieved 7–10% cell efficiency mostly by processes that separate the film deposition and the annealing into two sequential steps. In contrast, co‐evaporation onto a high‐temperature substrate, demonstrating previous success in chalcopyrite (Cu(In,Ga)Se₂) solar cells, allows real‐time composition control. Chalcopyrite research widely supports the model that Cu‐rich growth conditions assist grain growth, and subsequently, the endpoint composition can be adjusted back to Cu‐poor via monitoring the surface emissivity of the film. On the basis of the same intentions, the recent development of co‐evaporated kesterite (Cu₂ZnSnSe₄) adapts the concept and achieves 9.2% efficiency. To understand the effect of growth strategies, this study examines the phase evolution, grain morphology, and device performance in Cu‐rich growth and other strategies (Zn‐rich and close‐to‐stoichiometric). By characterizing films obtained from interrupted depositions and also interpreting the variation in surface emission during growths, this study found a subtle hindrance in the reaction of Cu_xSe_y and ZnSe possibly caused by the volatile nature of SnSe_x. The hindrance explains why, distinctive from chalcopyrite, little difference in grain size is observed between kesterite films made by Cu‐rich versus Zn‐rich growth at these deposition rates. At last, a Zn‐rich growth 9.1% device, certified by the National Renewable Energy Laboratory, is presented, which equals the performance of the previously‐reported Cu‐rich growth device. At the present stage, we believe the Cu‐rich and Zn‐rich growth share equal promise for the optimization of kesterite solar cells. Copyright © 2013 John Wiley & Sons, Ltd.     

Enhancement of photo‐conversion efficiency in Cu2ZnSn(S,Se)4 thin‐film solar cells by control of ZnS precursor‐layer thickness

CZTSSe thin‐film absorbers were grown by stacked ZnS/SnS/Cu sputtering with compound targets, and the precursors were annealed in a furnace with a Se atmosphere. We controlled the thickness of the ZnS precursor layer for the CZTSSe thin films in order to reduce the secondary phases and to improve the performance of the devices. The optimal value of the ZnS precursor thickness was determined for the CZTSSe absorbers, and this configuration showed an efficiency of up to 9.1%. In this study, we investigated the depth profiles of the samples in order to determine the presence of secondary phases in the CZTSSe thin films by Raman spectroscopy and Kelvin probe force microscopy. Cu₂SnSe₃, ZnSe, and MoSe₂ secondary phases appeared near the back contact, and the work function distribution of the CZTSSe thin‐film surface and the secondary phase distribution were different depending on the depths of the absorber layer. This phase characterization allows us to describe the effects that changes in the thickness of the ZnS precursor can have on the performance of the CZTSSe thin‐film solar cells. Although it is important to identify the phases, the effects of secondary phases and point defects are not yet fully understood, even in optimal devices. Therefore, phase identification that is based on the work function and the results obtained from the Raman spectra in terms of the depth profile are instrumental to improve the surface and interface of CZTSSe thin‐film solar cells. Copyright © 2015 John Wiley & Sons, Ltd.     

Toward efficient Cu(In,Ga)Se2 solar cells prepared by reactive magnetron co‐sputtering from metallic targets in an Ar:H2Se atmosphere

In this paper, we show that a reactive co‐sputtering process using metallic CuGa and In targets; an Ar:H₂Se atmosphere is well suited for the deposition of photoactive Cu(In,Ga)Se₂ (CIGSe) absorber layers for thin‐film solar cells in a single process step. The achievement of single‐phase and well‐crystallized layers is thereby no major problem if a sufficiently high H₂Se content and substrate temperatures in the range of 400–500 °C are used. However, in order to achieve the desired Cu‐poor film stoichiometry, which is crucial for the device performance, it has to be considered already that, at moderate substrate temperatures in the range of 400–500 °C, indium has a strong tendency to re‐evaporate from the film surface if the film composition is Cu‐poor. If excess indium is supplied, this effect can lead to a self‐adjustment of the film composition. This allows a very wide process window in a one‐stage process concerning the supply ratio from the two targets of [Cu]/([In] + [Ga])_supply ≈ 0.35–0.8. However, the maximum efficiencies achievable with such a process are limited to 11.7% because an adequate Cu‐poor composition can only be achieved with significant Cu‐poor conditions, which allow only a low material quality. By using an improved process with an intermediate Cu‐rich composition and a final Cu‐poor stage, the absorber quality could be significantly improved; efficiencies of up to 14.3% have been achieved with CIGSe films prepared on Na‐doped Mo back contacts. Copyright © 2015 John Wiley & Sons, Ltd.     

Highly‐efficient Cd‐free CuInS2 thin‐film solar cells and mini‐modules with Zn(S,O) buffer layers prepared by an alternative chemical bath process

Recent progress in fabricating Cd‐ and Se‐free wide‐gap chalcopyrite thin‐film solar devices with Zn(S,O) buffer layers prepared by an alternative chemical bath process (CBD) using thiourea as complexing agent is discussed. Zn(S,O) has a larger band gap (E_g = 3·6–3·8 eV) than the conventional buffer material CdS (E_g = 2·4 eV) currently used in chalcopyrite‐based thin films solar cells. Thus, Zn(S,O) is a potential alternative buffer material, which already results in Cd‐free solar cell devices with increased spectral response in the blue wavelength region if low‐gap chalcopyrites are used. Suitable conditions for reproducible deposition of good‐quality Zn(S,O) thin films on wide‐gap CuInS₂ (‘CIS’) absorbers have been identified for an alternative, low‐temperature chemical route. The thickness of the different Zn(S,O) buffers and the coverage of the CIS absorber by those layers as well as their surface composition were controlled by scanning electron microscopy, X‐ray photoelectron spectroscopy, and X‐ray excited Auger electron spectroscopy. The minimum thickness required for a complete coverage of the rough CIS absorber by a Zn(S,O) layer deposited by this CBD process was estimated to ∼15 nm. The high transparency of this Zn(S,O) buffer layer in the short‐wavelength region leads to an increase of ∼1 mA/cm² in the short‐circuit current density of corresponding CIS‐based solar cells. Active area efficiencies exceeding 11·0% (total area: 10·4%) have been achieved for the first time, with an open circuit voltage of 700·4 mV, a fill factor of 65·8% and a short‐circuit current density of 24·5 mA/cm² (total area: 22·5 mA/cm²). These results are comparable to the performance of CdS buffered reference cells. First integrated series interconnected mini‐modules on 5 × 5 cm² substrates have been prepared and already reach an efficiency (active area: 17·2 cm²) of above 8%. Copyright © 2006 John Wiley & Sons, Ltd.     

Precursor Solution Annealing Forms Cubic‐Phase Perovskite and Improves Humidity Resistance of Solar Cells

Solar cells with light‐absorbing layers comprising organometal halide perovskites have recently exceeded 22% efficiency. Despite high power‐conversion efficiencies, the stability of these devices, particularly when exposed to humidity and oxygen, remains poor. In the current study, a pathway to increase the stability of methylammonium lead iodide (CH₃NH₃PbI₃) based solar cells towards humidity is demonstrated, while maintaining the simplicity and solution‐processability of the active layers. Thermal annealing of the precursor solution prior to deposition induces the formation of cubic‐phase perovskite films in the solid state at room temperature. The experiments demonstrate that this improved ambient stability is correlated with the presence of the cubic phase at device operating temperatures, with the cubic phase resisting the formation of perovskite monohydrate—a pathway of degradation in conventionally processed perovskite thin films—on exposure to humidity.     

One‐Step Solvent‐Free Synthesis and Characterization of Zn1−xMnxSe@C Nanorods and Nanowires

The carbon‐encapsulated, Mn‐doped ZnSe (Zn_1−xMn_xSe@C) nanowires, nanorods, and nanoparticles are synthesized by the solvent‐free, one‐step RAPET (reactions under autogenic pressure at elevated temperature) approach. The aspect ratio of the nanowires/nanorods is altered according to the Mn/Zn atomic ratio, with the maximum being observed for Mn/Zn = 1:20. A 10–20 nm amorphous carbon shell is evidenced from electron microscopy analysis. The replacement of Zn by Mn in the Zn_1−xMn_xSe lattice is confirmed by the hyperfine splitting values in the electron paramagnetic resonance (EPR) experiments. Raman experiments reveal that the Zn_1−xMn_xSe core is highly crystalline, while the shell consists of disordered graphitic carbon. Variable‐temperature cathodoluminescence measurements are performed for all samples and show distinct ZnSe near‐band‐edge and Mn‐related emissions. An intense and broad Mn‐related emission at the largest Mn alloy composition of 19.9% is further consistent with an efficient incorporation of Mn within the host ZnSe lattice. The formation of the core/shell nanowires and nanorods in the absence of any template or structure‐directing agent is controlled kinetically by the Zn_1−xMn_xSe nucleus formation and subsequent carbon encapsulation. Mn replaces Zn mainly in the (111) plane and catalyzes the nanowire growth in the [111] direction.     

High Performance PbS Colloidal Quantum Dot Solar Cells by Employing Solution‐Processed CdS Thin Films from a Single‐Source Precursor as the Electron Transport Layer

CdS thin films are a promising electron transport layer in PbS colloidal quantum dot (CQD) photovoltaic devices. Some traditional deposition techniques, such as chemical bath deposition and RF (radio frequency) magnetron sputtering, have been employed to fabricate CdS films and CdS/PbS CQD heterojunction photovoltaic devices. However, their power conversion efficiencies (PCEs) are moderate compared with ZnO/PbS and TiO₂/PbS heterojunction CQD solar cells. Here, efficiencies have been improved substantially by employing solution‐processed CdS thin films from a single‐source precursor. The CdS film is deposited by a straightforward spin‐coating and annealing process, which is a simple, low‐cost, and high‐material‐usage fabrication process compared to chemical bath deposition and RF magnetron sputtering. The best CdS/PbS CQD heterojunction solar cell is fabricated using an optimized deposition and air‐annealing process achieved over 8% PCE, demonstrating the great potential of CdS thin films fabricated by the single‐source precursor for PbS CQDs solar cells.     

Co‐optimization of SnS absorber and Zn(O,S) buffer materials for improved solar cells

Thin‐film solar cells consisting of earth‐abundant and non‐toxic materials were made from pulsed chemical vapor deposition (pulsed‐CVD) of SnS as the p‐type absorber layer and atomic layer deposition (ALD) of Zn(O,S) as the n‐type buffer layer. The effects of deposition temperature and annealing conditions of the SnS absorber layer were studied for solar cells with a structure of Mo/SnS/Zn(O,S)/ZnO/ITO. Solar cells were further optimized by varying the stoichiometry of Zn(O,S) and the annealing conditions of SnS. Post‐deposition annealing in pure hydrogen sulfide improved crystallinity and increased the carrier mobility by one order of magnitude, and a power conversion efficiency up to 2.9% was achieved. Copyright © 2014 John Wiley & Sons, Ltd.     

Improved performance of Ge‐alloyed CZTGeSSe thin‐film solar cells through control of elemental losses

Nanocrystal‐based Cu₂Zn(Sn_yGe_1‐y)(S_xSe_4‐x) (CZTGeSSe) thin‐film solar cell absorbers with tunable band gap have been prepared. Maximum solar‐conversion total area efficiencies of up to 9.4% are achieved with a Ge content of 30 at.%. Improved performance compared with similarly processed films of Cu₂ZnSn(S_xSe_4‐x) (CZTSSe, 8.4% efficiency) is achieved through controlling Ge loss from the bulk of the absorber film during the high‐temperature selenization treatment, although some Ge loss from the absorber surface is still observed following this step. Despite limitations imposed by elemental losses present at the absorber surface, we find that Ge alloying leads to enhanced performance due to increased minority charge carrier lifetimes as well as reduced voltage‐dependent charge carrier collection. Copyright © 2013 John Wiley & Sons, Ltd.     

Rapid annealing of reactively sputtered precursors for Cu2ZnSnS4 solar cells

Cu₂ZnSnS₄ (CZTS) is a promising thin‐film absorber material that presents some interesting challenges in fabrication when compared with Cu(In,Ga)Se₂. We introduce a two‐step process for fabrication of CZTS films, involving reactive sputtering of a Cu‐Zn‐Sn‐S precursor followed by rapid annealing. X‐ray diffraction and Raman measurements of the sputtered precursor suggest that it is in a disordered, metastable CZTS phase, similar to the high‐temperature cubic modification reported for CZTS. A few minutes of annealing at 550 °C are sufficient to produce crystalline CZTS films with grain sizes in the micrometer range. The first reported device using this approach has an AM1.5 efficiency of 4.6%, with J_sc and V_oc both appearing to be limited by interface recombination. Copyright © 2012 John Wiley & Sons, Ltd.     

Low‐temperature flexible Ti/TiO2 photoanode for dye‐sensitized solar cells with binder‐free TiO2 paste

An energy‐economical dye‐sensitized solar cell (DSSC) with highly flexible Ti/TiO₂ photoanode was developed through a low‐temperature process, using a binder‐free TiO₂ paste. Ti foils, coated with the binder‐free TiO₂ films were annealed at various temperature. Scanning electron microscopic (SEM) images of the films show uniform, mesoporous and crack‐free surface morphologies as well as interpenetrated TiO₂ network. DSSCs with binder‐free TiO₂ films annealed at 450, 350, 250 and 120°C show solar‐to‐electricity conversion efficiencies (η) of 4.33, 4.34, 3.72 and 3.40%, respectively, which are comparable to the efficiency of 4.56% obtained by using a paste with binder and annealing it at 450°C; this observation demonstrates the benefits of a binder‐free TiO₂ paste for the fabrication of energy‐fugal DSSCs. On the other hand, when organic binder was used in the TiO₂ paste for film preparation, a drastic deterioration in the cell performance with decreasing annealing temperature is noticed. Laser‐induced photo‐voltage transient technique is used to estimate the electron lifetime in various Ti/TiO₂ films. Electrochemical impedance spectroscopic (EIS) analysis shows that the lower the annealing temperature of the TiO₂ coated Ti foil, the larger the charge transfer resistance at the TiO₂/dye/electrolyte interface (R_ct2). Copyright © 2011 John Wiley & Sons, Ltd.     

Epitaxial Growth of Large‐Scale Orthorhombic CsPbBr3 Perovskite Thin Films with Anisotropic Photoresponse Property

Inorganic cesium lead halide perovskite (CsPbX₃, X = Cl, Br, I) is a promising material for developing novel electronic and optoelectronic devices. Despite the substantial progress that has been made in the development of large perovskite single crystals, the fabrication of high‐quality 2D perovskite single‐crystal films, especially perovskite with a low symmetry, still remains a challenge. Herein, large‐scale orthorhombic CsPbBr₃ single‐crystal thin films on zinc‐blende ZnSe crystals are synthesized via vapor‐phase epitaxy. Structural characterizations reveal a “CsPbBr₃(110)//ZnSe(100), CsPbBr₃[?110]//ZnSe[001] and CsPbBr₃[001]//ZnSe[010]” heteroepitaxial relationship between the covering CsPbBr₃ layer and the ZnSe growth substrate. It is exciting that the epitaxial film presents an in‐plane anisotropic absorption property from 350 to 535 nm and polarization‐dependent photoluminescence. Photodetectors based on the epitaxial film exhibit a high photoresponsivity of 200 A W^?1, a large on/off current ratio exceeding 10⁴, a fast photoresponse time of about 20 ms, and good repeatability at room temperature. Importantly, a strong polarization‐dependent photoresponse is also found on the device fabricated using the epitaxial CsPbBr₃ film, making the orthorhombic perovskite promising building blocks for optoelectronic devices featured with anisotropy.     

ZnSe–Si Bi‐coaxial Nanowire Heterostructures

We report on the fabrication, structural characterization, and luminescence properties of ZnSe/Si bi‐coaxial nanowire heterostructures. Uniform ZnSe/Si bi‐coaxial nanowire heterostructures are grown on silicon substrates by the simple one‐step thermal evaporation of ZnSe powder in the presence of hydrogen. Both ZnSe and silicon are single‐crystalline in the bi‐coaxial nanowire heterostructures, and there is a sharp interface along the nanowire axial direction. Furthermore, secondary nanostructures of either ZnSe nanobrushes or a SiO_x sheath are also grown on the primary bi‐coaxial nanowires, depending on the ratio of the source materials. The experimental evidence strongly suggests that bi‐coaxial nanowires are formed via a co‐growth mechanism, that is, ZnSe terminates specific surfaces of silicon and leads to anisotropic, one‐dimensional silicon growth, which simultaneously serves as preferential nucleation sites for ZnSe, resulting in the bi‐coaxial nanowire heterostructures. In addition, the optical properties of ZnSe/Si nanowires are investigated using low‐temperature photoluminescence spectroscopy.     

Difluorobenzothiadiazole‐Based Small‐Molecule Organic Solar Cells with 8.7% Efficiency by Tuning of π‐Conjugated Spacers and Solvent Vapor Annealing

The synthesis of a series of tetrafluorine‐substituted, wide‐bandgap, small molecules consisting of various π‐conjugated spacers (furan, thiophene, selenophene) between indacenodithiophene as the electron‐donating core and the electron‐deficient difluorobenzothiadiazole unit is reported and the effect of the π‐conjugated spacers on the photovoltaic properties is investigated. The alteration of the π‐conjugated spacer enables fine‐tuning of the photophysical properties and energy levels of the small molecules, and allows the adjustment of the charge‐transport properties, the morphology of the photoactive films, as well as their photovoltaic properties. Moreover, most of these devices exhibit superior device performances after CH₂Cl₂ solvent annealing than without annealing, with a high fill factor (0.70–0.75 for all cases). Notably, the devices based on the new molecule BIT4FTh (with thiophene as the spacer) show an outstanding PCE of 8.7% (with an impressive FF of 0.75), considering its wide‐bandgap (1.81 eV), which is among the highest efficiencies reported so far for small‐molecules‐based solar cells. The morphologies of the photoactive layers with/without CH₂Cl₂ solvent annealing are characterized by atomic force microscopy, transmission electron microscopy and two‐dimensional grazing incidence X‐ray diffraction analysis. The results reported here clearly indicate that highly efficient small‐molecules‐based solar cells can be achieved through rational design of their molecular structure and optimization of the phase‐separated morphology via an adapted solvent–vapor annealing process.     

All‐Solution‐Processed Cu2ZnSnS4 Solar Cells with Self‐Depleted Na2S Back Contact Modification Layer

The thin‐film photovoltaic material Cu₂ZnSnS₄ (CZTS) has drawn worldwide attention in recent years due to its earth‐abundant, nontoxic element constitution, and remarkable photovoltaic performance. Although state‐of‐the‐art power conversion efficiency is achieved by hydrazine‐based methods, effort to fabricate such devices in a high throughput, environmental‐friendly way is still highlydesired. Here a hydrazine‐free all‐solution‐processed CZTS solar cell with Na₂S self‐depleted back contact modification layer for the first time is demonstrated, using a ball‐milled CZTS as light absorber, low‐temperature solution‐processed ZnO electron‐transport layer as well as silver‐nanowire transparent electrode. The inserting of Na₂S self‐depleted layer is proven to effectively stabilize the CZTS/Mo interface by eliminating a detrimental phase segregation reaction between CZTS and Mo‐coated soda lime glass, thus leading to a better crystallinity of CZTS light absorbing layer, enhanced carrier transportation at CZTS/Mo interface as well as a smaller series resistance. Furthermore, the self‐depletion feature of the Na₂S modification layer also averts hole‐transportation barrier within the devices. The results show the vital importance of interfacial engineering for these CZST devices and the Na₂S interface layer can be extended to other optoelectronic devices using Mo contact.     

Effect of sputter deposited Zn precursor film thickness and annealing time on the properties of Cu2ZnSnS4 thin films deposited by sequential reactive sputtering of metal targets

Cu₂ZnSnS₄ (CZTS) is made of earth abundant elements and also have suitable optical properties for solar cell applications. But, in phase diagram, CZTS exists in a narrow range of temperature and composition. Therefore, optimizing the elemental composition and annealing time is very important for obtaining phase pure CZTS. In this study, the effects of elemental composition and short annealing time on the structural and optical properties of reactively sputtered CZTS thin films are reported. Thin films were deposited by reactive sputtering of Cu: Sn (60:40 wt%), Sn and Zn targets sequentially in the presence of H₂S at room temperature. Amount of Zn precursor was varied by changing the sputter time for Zn. The films were rapidly annealed in inert atmosphere for varying time. The band gap of sample changed with change in the composition as well as annealing time. Sample with higher Zn content showed better crystallinity. With increase in the annealing time the crystallinity of samples improved. Sample annealed for 12 min at 550 °C was phase pure. Obtaining good quality film even for very short anneal time is the novelty of reactive sputtering method as all the elements are already mixed and short annealing is required only for crystal growth. Through detailed experiments, the optimum composition and annealing time required for the growth of phase pure CZTS has been established.     

Room‐Temperature Partial Conversion of α‐FAPbI3 Perovskite Phase via PbI2 Solvation Enables High‐Performance Solar Cells

The two‐step conversion process consisting of metal halide deposition followed by conversion to hybrid perovskite has been successfully applied toward producing high‐quality solar cells of the archetypal MAPbI₃ hybrid perovskite, but the conversion of other halide perovskites, such as the lower bandgap FAPbI₃, is more challenging and tends to be hampered by the formation of hexagonal nonperovskite polymorph of FAPbI₃, requiring Cs addition and/or extensive thermal annealing. Here, an efficient room‐temperature conversion route of PbI₂ into the α‐FAPbI₃ perovskite phase without the use of cesium is demonstrated. Using in situ grazing incidence wide‐angle X‐ray scattering (GIWAXS) and quartz crystal microbalance with dissipation (QCM‐D), the conversion behaviors of the PbI₂ precursor from its different states are compared. α‐FAPbI₃ forms spontaneously and efficiently at room temperature from P₂ (ordered solvated polymorphs with DMF) without hexagonal phase formation and leads to complete conversion after thermal annealing. The average power conversion efficiency (PCE) of the fabricated solar cells is greatly improved from 16.0(±0.32)% (conversion from annealed PbI₂) to 17.23(±0.28)% (from solvated PbI₂) with a champion device PCE > 18% due to reduction of carrier recombination rate. This work provides new design rules toward the room‐temperature phase transformation and processing of hybrid perovskite films based on FA⁺ cation without the need for Cs⁺ or mixed halide formulation.     

Growth of Cu(In,Ga)Se2 thin films by a novel single‐stage route based on pulsed electron deposition

We report a novel route for growing Cu(In,Ga)Se₂ (CIGS) thin films, based upon the Pulsed Electron Deposition (PED) technique. Unlike other well‐known deposition techniques, PED process allows the stoichiometric deposition of CIGS layers in a single stage, without requiring any further treatments for Cu/(In + Ga) ratio adjustment nor selenization. The structural properties of polycrystalline CIGS films strongly depend on the growth temperature, whereas post‐deposition annealing enhances the grain size and the <112> out‐of‐plane preferred orientation of the chalcopyrite structure, without affecting the film composition. Preliminary measurements of the performances of solar cells based on these films confirm the great potentiality of PED‐grown CIGS as absorber layers. Copyright © 2011 John Wiley & Sons, Ltd.     

Effects of Na and MoS2 on Cu2ZnSnS4 thin‐film solar cell

Cu₂ZnSnS₄ (CZTS)‐based materials have a useful band gap and a high absorption coefficient; however, their power conversion efficiency is low compared with that of CdTe and Cu(In,Ga)Se₂‐based solar cells. Two of the factors that strongly affect CZTS solar cell characteristics are the MoS₂ layer and the presence of defects. In this study, Mo back‐contact layers were annealed to control MoS₂ layer formation and the Na content in the Mo layer before the absorber precursor layer was deposited. The increase in oxygen content in the Mo layer suppressed MoS₂ layer formation. In addition, the increase in Na diffusion during the initial stage of the absorber precursor deposition decreased the defect density in the absorber layer and in the absorber–buffer interface. These results were verified through measurements of the external quantum efficiency, the temperature dependence of the open‐circuit voltage (V_OC), and admittance spectra. The current densities (J_SC) and V_OC, as well as the power conversion efficiencies, improved as the annealing temperature of the Mo layer increased, which suggests that CZTS solar cell characteristics can be improved by suppressing MoS₂ layer formation and increasing Na content in the Mo layer before deposition of the absorber precursor layer. Copyright © 2014 John Wiley & Sons, Ltd.     

Nanoscale Morphology of Conjugated Polymer/Fullerene‐Based Bulk‐ Heterojunction Solar Cells

The relation between the nanoscale morphology and associated device properties in conjugated polymer/fullerene bulk‐heterojunction “plastic solar cells” is investigated. We perform complementary measurements on solid‐state blends of poly[2‐methoxy‐5‐(3,7‐dimethyloctyloxy)]‐1,4‐phenylenevinylene (MDMO‐PPV) and the soluble fullerene C₆₀ derivative 1‐(3‐methoxycarbonyl) propyl‐1‐phenyl [6,6]C₆₁ (PCBM), spin‐cast from either toluene or chlorobenzene solutions. The characterization of the nanomorphology is carried out via scanning electron microscopy (SEM) and atomic force microscopy (AFM), while solar‐cell devices were characterized by means of current–voltage (I–V) and spectral photocurrent measurements. In addition, the morphology is manipulated via annealing, to increase the extent of phase separation in the thin‐film blends and to identify the distribution of materials. Photoluminescence measurements confirm the demixing of the materials under thermal treatment. Furthermore the photoluminescence of PCBM clusters with sizes of up to a few hundred nanometers indicates a photocurrent loss in films of the coarser phase‐separated blends cast from toluene. For toluene‐cast films the scale of phase separation depends strongly on the ratio of MDMO‐PPV to PCBM, as well as on the total concentration of the casting solution. Finally we observe small beads of 20–30 nm diameter, attributed to MDMO‐PPV, in blend films cast from both toluene and chlorobenzene.