Ultra-Thin SnOx Buffer Layer Enables High-Efficiency Quantum Junction Photovoltaics.

Solution-processed solar cells are promising for the cost-effective, high-throughput production of photovoltaic devices. Colloidal quantum dots (CQDs) are attractive candidate materials for efficient, solution-processed solar cells, potentially realizing the broad-spectrum light utilization and multi-exciton generation effect for the future efficiency breakthrough of solar cells. The emerging quantum junction solar cells (QJSCs), constructed by n- and p-type CQDs only, open novel avenue for all-quantum-dot photovoltaics with a simplified device configuration and convenient processing technology. However, the development of high-efficiency QJSCs still faces the challenge of back carrier diffusion induced by the huge carrier density drop at the interface of CQDs and conductive glass substrate. Herein, an ultra-thin atomic layer deposited tin oxide (SnOx ) layer is employed to buffer this carrier density drop, significantly reducing the interfacial recombination and capacitance caused by the back carrier diffusion. The SnOx -modified QJSC achieves a record-high efficiency of 11.55% and a suppressed hysteresis factor of 0.04 in contrast with reference QJSC with an efficiency of 10.4% and hysteresis factor of 0.48. This work clarifies the critical effect of interfacial issues on the carrier recombination and hysteresis of QJSCs, and provides an effective pathway to design high-performance all-quantum-dot devices.

Emission Spectroscopy Investigation of the Enhancement of Carrier Collection Efficiency in AgBiS2-Nanocrystal/ZnO-Nanowire Heterojunction Solar Cells.

Eco-friendly solar cells were fabricated using interdigitated layers comprising ZnO nanowires (NWs) and infrared absorbing AgBiS2 nanocrystals (ITO/ZnO NWs/AgBiS2/P3HT/Au). The quality of ZnO NWs was studied using photoluminescence and Raman spectroscopy to identify the defects in ZnO NWs influencing solar cell performance. Oxygen vacancies and Zn interstitial sites, among various recombination sites, were observed to be the main sites for carrier recombination, which hinders the carrier collection in the solar cells. Accordingly, the power conversion efficiency of AgBiS2 solar cells exhibited a good correlation with the number of oxygen vacancies. The structural order and electron-phonon interaction in ZnO NWs were also investigated via Raman scattering spectroscopy. A lower concentration of oxygen vacancies and zinc interstitials (Zni) resulted in a higher structural order as well as a weaker electron-phonon interaction in ZnO NWs. When ZnO NWs were treated at 500 °C in oxygen with the lowest oxygen vacancy concentration, the solar cells (500-O2 solar cell (SC)) demonstrated an external quantum efficiency of approximately 70% in the visible region and a corresponding internal quantum efficiency of more than 80%. The 500-O2 SC exhibited a power conversion efficiency of 5.41% (JSC = 22.21 mA/cm2, VOC = 0.41 V, and FF = 60%) under quasi one-sun illumination. New methods that can efficiently reduce oxygen vacancies and Zni without affecting the structural order of ZnO NWs would further enhance the carrier collection efficiency. Moreover, since ZnO is a key electron transport material for constructing not only colloidal quantum dot solar cells but also other emerging solar cells, such as organic thin-film solar cells, the present findings provide significant information for improving their performance.

The effect of water on colloidal quantum dot solar cells.

Almost all surfaces sensitive to the ambient environment are covered by water, whereas the impacts of water on surface-dominated colloidal quantum dot (CQD) semiconductor electronics have rarely been explored. Here, strongly hydrogen-bonded water on hydroxylated lead sulfide (PbS) CQD is identified. The water could pilot the thermally induced evolution of surface chemical environment, which significantly influences the nanostructures, carrier dynamics, and trap behaviors in CQD solar cells. The aggravation of surface hydroxylation and water adsorption triggers epitaxial CQD fusion during device fabrication under humid ambient, giving rise to the inter-band traps and deficiency in solar cells. To address this problem, meniscus-guided-coating technique is introduced to achieve dense-packed CQD solids and extrude ambient water, improving device performance and thermal stability. Our works not only elucidate the water involved PbS CQD surface chemistry, but may also achieve a comprehensive understanding of the impact of ambient water on CQD based electronics.

Materials Design and Optimization for Next-Generation Solar Cell and Light-Emitting Technologies.

We review some of the most potent directions in the design of materials for next-generation solar cell and light-emitting technologies that go beyond traditional solid-state inorganic semiconductor-based devices, from both the experimental and computational standpoints. We focus on selected recent conceptual advances in tackling issues which are expected to significantly impact applied literature in the coming years. Specifically, we consider solution processability, design of dopant-free charge transport materials, two-dimensional conjugated polymeric semiconductors, and colloidal quantum dot assemblies in the fields of experimental synthesis, characterization, and device fabrication. Key modeling issues that we consider are calculations of optical properties and of effects of aggregation, including recent advances in methods beyond linear-response time-dependent density functional theory and recent insights into the effects of correlation when going beyond the single-particle ansatz as well as in the context of modeling of thermally activated fluorescence.

Eco-Friendly AgBiS2 Nanocrystal/ZnO Nanowire Heterojunction Solar Cells with Enhanced Carrier Collection Efficiency.

AgBiS2 nanocrystals (NCs) are nontoxic, lead-free, and near-infrared absorbing materials. Eco-friendly solar cells were constructed using interdigitated layers of ZnO nanowires (NWs) and AgBiS2 NCs, with the aim of elongating the otherwise short carrier diffusion length of the AgBiS2 NC assembly. AgBiS2 NCs were uniformly infiltrated into the ZnO NW layers using a low-cost and easily scalable dip coating method. The resulting ZnO NW/AgBiS2 NC interdigitated structures provided efficient carrier pathways in constructed nanowire solar cells (NWSCs), composed of a transparent electrode/ZnO NW/AgBiS2 NC interdigitated layer/P3HT hole transport layer/Au. The photocurrent external quantum efficiency (EQE) in the visible to near-infrared regions was enhanced compared to those of the control solar cells made with ZnO/AgBiS2 tandem layered structures. The maximum EQE for the NWSCs reached 82% in the visible region, which is higher than the EQE values previously reported for solar cells fabricated with ZnO/AgBiS2 NCs. Air stability tests on unsealed NWSCs demonstrated that 90% or more of the initial power conversion efficiency was maintained even after 6 months.

Material challenges for solar cells in the twenty-first century: directions in emerging technologies.

Photovoltaic generation has stepped up within the last decade from outsider status to one of the important contributors of the ongoing energy transition, with about 1.7% of world electricity provided by solar cells. Progress in materials and production processes has played an important part in this development. Yet, there are many challenges before photovoltaics could provide clean, abundant, and cheap energy. Here, we review this research direction, with a focus on the results obtained within a Japan-French cooperation program, NextPV, working on promising solar cell technologies. The cooperation was focused on efficient photovoltaic devices, such as multijunction, ultrathin, intermediate band, and hot-carrier solar cells, and on printable solar cell materials such as colloidal quantum dots.

Determination of unique power conversion efficiency of solar cell showing hysteresis in the I-V curve under various light intensities.

Energy harvesting at low light intensities has recently attracted a great deal of attention of perovskite solar cells (PSCs) which are regarded as promising candidate for indoor application. Anomalous hysteresis of the PSCs a complex issue for reliable evaluation of the cell performance. In order to address these challenges, we constructed two new evaluation methods to determinate the power conversion efficiencies (PCEs) of PSCs. The first setup is a solar simulator based on light emitting diodes (LEDs) allowing evaluation of the solar cells at wider range of light intensities, ranging from 102 to 10-3 mW·cm-2. As the overestimate error, we found that the PCEs of dye sensitized solar cell (DSC) and PSCs increase dramatically at low light intensities conditions. Due to the internal capacitance at the interfaces on hybrid solar cells, the measurement of current below 10-2 mW·cm-2 shows constant value given high PCE, which is related to the capacitive current and origin of the hysteresis. The second setup is a photovoltaic power analyzing system, designed for tracking the maximum power (P max) with time. The paper suggests the combination of the LED solar simulator and P max tracking technique as a standard to evaluate the PCE of capacitive solar cells.

Hysteresis-free perovskite solar cells made of potassium-doped organometal halide perovskite.

Potassium-doped organometal halide perovskite solar cells (PSCs) of more than 20% power conversion efficiency (PCE) without I-V hysteresis were constructed. The crystal lattice of the organometal halide perovskite was expanded with increasing of the potassium ratio, where both absorption and photoluminescence spectra shifted to the longer wavelength, suggesting that the optical band gap decreased. In the case of the perovskite with the 5% K+, the conduction band minimum (CBM) became similar to the CBM level of the TiO2-Li. In this situation, the electron transfer barrier at the interface between TiO2-Li and the perovskite was minimised. In fact, the transient current rise at the maximum power voltages of PSCs with 5% K+ was faster than that without K+. It is concluded that stagnation-less carrier transportation could minimise the I-V hysteresis of PSCs.

Spectral splitting photovoltaics using perovskite and wideband dye-sensitized solar cells.

The extension of the light absorption of photovoltaics into the near-infrared region is important to increase the energy conversion efficiency. Although the progress of the lead halide perovskite solar cells is remarkable, and high conversion efficiency of >20% has been reached, their absorption limit on the long-wavelength side is ∼800 nm. To further enhance the conversion efficiency of perovskite-based photovoltaics, a hybridized system with near-infrared photovoltaics is a useful approach. Here we report a panchromatic sensitizer, coded DX3, that exhibits a broad response into the near-infrared, up to ∼1100 nm, and a photocurrent density exceeding 30 mA cm(-2) in simulated air mass 1.5 standard solar radiation. Using the DX3-based dye-sensitized solar cell in conjunction with a perovskite cell that harvests visible light, the hybridized mesoscopic photovoltaics achieved a conversion efficiency of 21.5% using a system of spectral splitting.

Efficiency Enhancement of PbS Quantum Dot/ZnO Nanowire Bulk-Heterojunction Solar Cells by Plasmonic Silver Nanocubes.

For improvement of solar cell performance, it is important to make efficient use of near-infrared light, which accounts for ∼40% of sunlight energy. Here we introduce plasmonic Ag nanocubes (NCs) to colloidal PbS quantum dot/ZnO nanowire (PbS QD/ZnO NW) bulk-heterojunction solar cells, which are characterized by high photocurrents, for further improvement in the photocurrent and power conversion efficiency (PCE) in the visible and near-infrared regions. The Ag NCs exhibit strong far field scattering and intense optical near field in the wavelength region where light absorption of PbS QDs is relatively weak. Photocurrents of the solar cells are enhanced by the Ag NCs particularly in the range 700-1200 nm because of plasmonic enhancement of light absorption and possible facilitation of exciton dissociation. As a result of the optimization of the position and amount of Ag NCs, the PCE of PbS QD/ZnO NW bulk-heterojunction solar cells is improved from 4.45% to 6.03% by 1.36 times.

Dye-sensitized solar cells using ethynyl-linked porphyrin trimers.

Toward the extension of the light-harvesting region of sensitizers in dye-sensitized solar cells (DSSCs), two ethynyl-linked porphyrin trimers were synthesized and investigated. The zinc­freebase­zinc trimer (Zn­FbA­Zn) showed an absorption maximum at a longer wavelength than the all-zinc trimer (Zn­ZnA­Zn), although the energy level of Zn­FbA­Zn was lower than that of Zn­ZnA­Zn. The DSSCs using these trimers showed spectral sensitivities up to 900 nm. Reflecting the energy levels of these trimers, the DSSC using Zn­ZnA­Zn showed better performance than that using Zn­FbA­Zn. After the optimization of cell fabrication conditions, the photoelectric conversion efficiency η of the DSSC using Zn­ZnA­Zn reached 3.17%. The larger TiO2 nanoparticles (ca. 37 nm) than the conventional cases (ca. 13 nm) were found to be preferable in this case, due to high molar extinction coefficients of the porphyrin trimers.

Investigation of plasmonic gold-silica core-shell nanoparticle stability in dye-sensitized solar cell applications.

Plasmonic core-shell Au@SiO2 nanoparticles have previously been shown to enhance the performance of dye-sensitized solar cells (DSSCs). A thin silica coating can provide a better stability during thermal processing and chemical stability to survive the corrosive electrolyte used in DSSCs. However, the thickness and completeness of the silica shell has proven crucial for the performance of the plasmonic particles and is largely controlled by the linking chemistry between the gold core and silica shell. We have evaluated four different silica coating procedures of ∼15 nm gold nanoparticles for usage in DSSCs. The chemical stability of these core-shell nanoparticles was assessed by dispersing the particles in iodide/triiodide electrolyte solution and the thermal stability by heating the particles up to 500°C. In order to maintain stable gold cores a complete silica coating was required, which was best obtained by using a mercaptosilane as a linker. In situ TEM characterization indicated that the heating process only had minor effects on the core-shell particles. The final step was to evaluate how the stable Au@SiO2 nanoparticles were influencing a real DSSC device when mixed into the TiO2 photoanode. The plasmon-incorporated DSSCs showed a ∼10% increase in efficiency compared to devices without core-shell nanoparticles.

A donor-acceptor type organic dye connected with a quinoidal thiophene for dye-sensitized solar cells.

A donor-acceptor type organic dye connected with a quinoidal thiophene as a π-conjugated chain, cyano-[5'-(4''-(N,N-dimethylamino)benzylidene)-5H-thiophen-2'-ylidene]acetic acid, was synthesized and applied to dye-sensitized solar cells (DSSCs). The absorption band of this quinoidal thiophene dye appeared at longer wavelengths than those of dyes with similar π-conjugation length, indicating the effective π-conjugation through the quinoidal structure. Although the excited state of the quinoidal thiophene dye is deactivated within several picoseconds even in solution, the DSSCs using the quinoidal thiophene dye showed incident photon to current conversion efficiency (IPCE) values of more than 90%, demonstrating the fast and efficient electron injection from the excited dye to TiO(2). By optimizing the fabrication conditions, the DSSC using this dye afforded a photoelectric conversion efficiency of 5.2%, without enlarging the molecular size.

Ethynyl-linked push-pull porphyrin hetero-dimers for near-IR dye-sensitized solar cells: photovoltaic performances versus excited-state dynamics.

Ethynyl-linked porphyrin hetero-dimers substituted by a series of electron donors, namely, bis(4-methoxyphenyl)amino (BMPA), bis(4-tert-butylphenyl)amino (BTBPA) and 3,6-di-tert-butylcarbazol-9-yl (DTBC) as well as a reference dimer with a non-donor moiety (3,5-di-tert-butylphenyl, DTBP) have been synthesized to systematically investigate the influence of donor introduction on the photovoltaic performances of near-IR dye-sensitized solar cells (DSCs) with these sensitizers incorporated. Despite the expected bathochromic shift and intensification of long-wavelength absorption bands as well as elevated LUMO levels and thus increased electron injection driving forces, the substitution of diphenylamino groups (BMPA and BTBPA) with stronger electron-donating abilities gave rise to surprising mediocrity in the short-circuit photocurrent densities (J(sc)), leading to overall energy conversion efficiencies in the order BMPA (3.94%) < DTBP (4.57%) < BTBPA (4.83%) < DTBC (5.21%). A study of the in situ fluorescent behavior of these sensitizers revealed that for all the sensitizers, excited-state lifetimes were significantly shortened in the simulated DSC environment compared to those in a free solution. BMPA showed the shortest intrinsic in situ lifetime while DTBC showed the longest one. These results were correlated with the photovoltaic performances, which is required for a better understanding and further design of porphyrin array sensitizers.

Enhancement of Near-IR Photoelectric Conversion in Dye-Sensitized Solar Cells Using an Osmium Sensitizer with Strong Spin-Forbidden Transition.

A new osmium (Os) complex of the [Os(tcterpy)-(4,4'-bis(p-butoxystyryl)-2,2'-bipyridine)Cl]PF6 (Os-stbpy) has been synthesized and characterized for dye-sensitized solar cells (DSSCs). The Os-stbpy dye shows enhanced spin-forbidden absorptions around 900 nm. The DSSCs with Os-stbpy show a wide-band spectral response up to 1100 nm with high overall conversion efficiency of 6.1% under standard solar illumination.

N-fused carbazole-zinc porphyrin-free-base porphyrin triad for efficient near-IR dye-sensitized solar cells.

N-fused carbazole-zinc porphyrin-free-base porphyrin triad featuring an ethynyl-linkage was synthesized; efficient sensitization as long as 900 nm was demonstrated and an overall light-to-electricity conversion efficiency of 5.21% was achieved under AM 1.5 G one sun illumination.