Conformal fabrication of colloidal quantum dot solids for optically enhanced photovoltaics.

Colloidal quantum dots (CQD) are an attractive thin-film material for photovoltaic applications due to low material costs, ease of fabrication, and size-tunable band gap. Unfortunately, today they suffer from a compromise between light absorption and photocarrier extraction, a fact that currently prevents the complete harvest of incoming above-band-gap solar photons. We have investigated the use of structured substrates and/or electrodes to increase the effective light path through the active material and found that these designs require highly conformal application of the light-absorbing films to achieve the greatest enhancement. This conformality requirement derives from the need for maximal absorption enhancement combined with shortest-distance charge transport. Here we report on a means of processing highly conformal layer-by-layer deposited CQD absorber films onto microstructured, light-recycling electrodes. Specifically, we engineer surface hydrophilicity to achieve conformal deposition of upper layers atop underlying ones. We show that only with the application of conformal coating can we achieve optimal quantum efficiency and enhanced power conversion efficiency in structured-electrode CQD cells.

Photojunction field-effect transistor based on a colloidal quantum dot absorber channel layer.

The performance of photodetectors is judged via high responsivity, fast speed of response, and low background current. Many previously reported photodetectors based on size-tuned colloidal quantum dots (CQDs) have relied either on photodiodes, which, since they are primary photocarrier devices, lack gain; or photoconductors, which provide gain but at the expense of slow response (due to delayed charge carrier escape from sensitizing centers) and an inherent dark current vs responsivity trade-off. Here we report a photojunction field-effect transistor (photoJFET), which provides gain while breaking prior photoconductors' response/speed/dark current trade-off. This is achieved by ensuring that, in the dark, the channel is fully depleted due to a rectifying junction between a deep-work-function transparent conductive top contact (MoO3) and a moderately n-type CQD film (iodine treated PbS CQDs). We characterize the rectifying behavior of the junction and the linearity of the channel characteristics under illumination, and we observe a 10 µs rise time, a record for a gain-providing, low-dark-current CQD photodetector. We prove, using an analytical model validated using experimental measurements, that for a given response time the device provides a two-orders-of-magnitude improvement in photocurrent-to-dark-current ratio compared to photoconductors. The photoJFET, which relies on a junction gate-effect, enriches the growing family of CQD photosensitive transistors.

Colloidal quantum dot solar cells exploiting hierarchical structuring.

Extremely thin-absorber solar cells offer low materials utilization and simplified manufacture but require improved means to enhance photon absorption in the active layer. Here, we report enhanced-absorption colloidal quantum dot (CQD) solar cells that feature transfer-stamped solution-processed pyramid-shaped electrodes employed in a hierarchically structured device. The pyramids increase, by up to a factor of 2, the external quantum efficiency of the device at absorption-limited wavelengths near the absorber band edge. We show that absorption enhancement can be optimized with increased pyramid angle with an appreciable net improvement in power conversion efficiency, that is, with the gain in current associated with improved absorption and extraction overcoming the smaller fractional decrease in open-circuit voltage associated with increased junction area. We show that the hierarchical combination of micron-scale structured electrodes with nanoscale films provides for an optimized enhancement at absorption-limited wavelengths. We fabricate 54.7° pyramid-patterned electrodes, conformally apply the quantum dot films, and report pyramid CQD solar cells that exhibit a 24% improvement in overall short-circuit current density with champion devices providing a power conversion efficiency of 9.2%.

Broadband solar absorption enhancement via periodic nanostructuring of electrodes.

Solution processed colloidal quantum dot (CQD) solar cells have great potential for large area low-cost photovoltaics. However, light utilization remains low mainly due to the tradeoff between small carrier transport lengths and longer infrared photon absorption lengths. Here, we demonstrate a bottom-illuminated periodic nanostructured CQD solar cell that enhances broadband absorption without compromising charge extraction efficiency of the device. We use finite difference time domain (FDTD) simulations to study the nanostructure for implementation in a realistic device and then build proof-of-concept nanostructured solar cells, which exhibit a broadband absorption enhancement over the wavelength range of λ = 600 to 1,100 nm, leading to a 31% improvement in overall short-circuit current density compared to a planar device containing an approximately equal volume of active material. Remarkably, the improved current density is achieved using a light-absorber volume less than half that typically used in the best planar devices.

Folded-light-path colloidal quantum dot solar cells.

Colloidal quantum dot photovoltaics combine low-cost solution processing with quantum size-effect tuning to match absorption to the solar spectrum. Rapid advances have led to certified solar power conversion efficiencies of over 7%. Nevertheless, these devices remain held back by a compromise in the choice of quantum dot film thickness, balancing on the one hand the need to maximize photon absorption, mandating a thicker film, and, on the other, the need for efficient carrier extraction, a consideration that limits film thickness. Here we report an architecture that breaks this compromise by folding the path of light propagating in the colloidal quantum dot solid. Using this method, we achieve a substantial increase in short-circuit current, ultimately leading to improved power conversion efficiency.

The donor-supply electrode enhances performance in colloidal quantum dot solar cells.

Colloidal quantum dot (CQD) solar cells combine solution-processability with quantum-size-effect tunability for low-cost harvesting of the sun's broad visible and infrared spectrum. The highest-performing colloidal quantum dot solar cells have, to date, relied on a depleted-heterojunction architecture in which an n-type transparent metal oxide such as TiO2 induces a depletion region in the p-type CQD solid. These devices have, until now, been limited by a modest depletion region depth produced in the CQD solid owing to limitations in the doping available in TiO2. Herein we report a new device geometry-one based on a donor-supply electrode (DSE)-that leads to record-performing CQD photovoltaic devices. Only by employing this new charge-extracting approach do we deepen the depletion region in the CQD solid and thereby extract notably more photocarriers, the key element in achieving record photocurrent and device performance. With the use of optoelectronic modeling corroborated by experiment, we develop the guidelines for building a superior CQD solar cell based on the DSE concept. We confirm that using a shallow-work-function terminal electrode is essential to producing improved charge extraction and enhanced performance.

Jointly tuned plasmonic-excitonic photovoltaics using nanoshells.

Recent advances in spectrally tuned, solution-processed plasmonic nanoparticles have provided unprecedented control over light's propagation and absorption via engineering at the nanoscale. Simultaneous parallel progress in colloidal quantum dot photovoltaics offers the potential for low-cost, large-area solar power; however, these devices suffer from poor quantum efficiency in the more weakly absorbed infrared portion of the sun's spectrum. Here, we report a plasmonic-excitonic solar cell that combines two classes of solution-processed infrared materials that we tune jointly. We show through experiment and theory that a plasmonic-excitonic design using gold nanoshells with optimized single particle scattering-to-absorption cross-section ratios leads to a strong enhancement in near-field absorption and a resultant 35% enhancement in photocurrent in the performance-limiting near-infrared spectral region.

Self-assembled, nanowire network electrodes for depleted bulk heterojunction solar cells.

Herein, a solution-processed, bottom-up-fabricated, nanowire network electrode is developed. This electrode features a ZnO template which is converted into locally connected, infiltratable, TiO2 nanowires. This new electrode is used to build a depleted bulk heterojunction solar cell employing hybrid-passivated colloidal quantum dots. The new electrode allows the application of a thicker, and thus more light-absorbing, colloidal quantum dot active layer, from which charge extraction of an efficiency comparable to that obtained from a thinner, planar device could be obtained.

Hybrid passivated colloidal quantum dot solids.

Colloidal quantum dot (CQD) films allow large-area solution processing and bandgap tuning through the quantum size effect. However, the high ratio of surface area to volume makes CQD films prone to high trap state densities if surfaces are imperfectly passivated, promoting recombination of charge carriers that is detrimental to device performance. Recent advances have replaced the long insulating ligands that enable colloidal stability following synthesis with shorter organic linkers or halide anions, leading to improved passivation and higher packing densities. Although this substitution has been performed using solid-state ligand exchange, a solution-based approach is preferable because it enables increased control over the balance of charges on the surface of the quantum dot, which is essential for eliminating midgap trap states. Furthermore, the solution-based approach leverages recent progress in metal:chalcogen chemistry in the liquid phase. Here, we quantify the density of midgap trap states in CQD solids and show that the performance of CQD-based photovoltaics is now limited by electron-hole recombination due to these states. Next, using density functional theory and optoelectronic device modelling, we show that to improve this performance it is essential to bind a suitable ligand to each potential trap site on the surface of the quantum dot. We then develop a robust hybrid passivation scheme that involves introducing halide anions during the end stages of the synthesis process, which can passivate trap sites that are inaccessible to much larger organic ligands. An organic crosslinking strategy is then used to form the film. Finally, we use our hybrid passivated CQD solid to fabricate a solar cell with a certified efficiency of 7.0%, which is a record for a CQD photovoltaic device.

Colloidal quantum dot photovoltaics: the effect of polydispersity.

The size-effect tunability of colloidal quantum dots enables facile engineering of the bandgap at the time of nanoparticle synthesis. The dependence of effective bandgap on nanoparticle size also presents a challenge if the size dispersion, hence bandgap variability, is not well-controlled within a given quantum dot solid. The impact of this polydispersity is well-studied in luminescent devices as well as in unipolar electronic transport; however, the requirements on monodispersity have yet to be quantified in photovoltaics. Here we carry out a series of combined experimental and model-based studies aimed at clarifying, and quantifying, the importance of quantum dot monodispersity in photovoltaics. We successfully predict, using a simple model, the dependence of both open-circuit voltage and photoluminescence behavior on the density of small-bandgap (large-diameter) quantum dot inclusions. The model requires inclusion of trap states to explain the experimental data quantitatively. We then explore using this same experimentally tested model the implications of a broadened quantum dot population on device performance. We report that present-day colloidal quantum dot photovoltaic devices with typical inhomogeneous linewidths of 100-150 meV are dominated by surface traps, and it is for this reason that they see marginal benefit from reduction in polydispersity. Upon eliminating surface traps, achieving inhomogeneous broadening of 50 meV or less will lead to device performance that sees very little deleterious impact from polydispersity.

A donor-supply electrode (DSE) for colloidal quantum dot photovoltaics.

The highest-performing colloidal quantum dot (CQD) photovoltaics (PV) reported to date have relied on high-temperature (>500°C) annealing of electron-accepting TiO2. Room-temperature processing reduces energy payback time and manufacturing cost, enables flexible substrates, and permits tandem solar cells that integrate a small-bandgap back cell atop a low-thermal-budget larger-bandgap front cell. Here we report an electrode strategy that enables a depleted-heterojunction CQD PV device to be fabricated entirely at room temperature. We find that simply replacing the high-temperature-processed TiO2 with a sputtered version of the same material leads to poor performance due to the low mobility of the sputtered oxide. We develop instead a two-layer donor-supply electrode (DSE) in which a highly doped, shallow work function layer supplies a high density of free electrons to an ultrathin TiO2 layer via charge-transfer doping. Using the DSE we build all-room-temperature-processed small-bandgap (1 eV) colloidal quantum dot solar cells having 4% solar power conversion efficiency and high fill factor. These 1 eV bandgap cells are suitable for use as the back junction in tandem solar cells. The DSE concept, combined with control over TiO2 stoichiometry in sputtering, provides a much-needed tunable electrode to pair with quantum-size-effect CQD films.