Tim F. Schulze

Improving the light-harvesting of amorphous silicon solar cells with photochemical upconversion

Single-threshold solar cells are fundamentally limited by their ability to harvest only those photons above a certain energy. Harvesting below-threshold photons and re-radiating this energy at a shorter wavelength would thus boost the efficiency of such devices. We report an increase in light harvesting efficiency of a hydrogenated amorphous silicon (a-Si:H) thin-film solar cell due to a rear upconvertor based on sensitized triplet–triplet-annihilation in organic molecules. Low energy light in the range 600–750 nm is converted to 550–600 nm light due to the incoherent photochemical process. A peak efficiency enhancement of (1.0 ± 0.2)% at 720 nm is measured under irradiation equivalent to (48 ± 3) suns (AM1.5). We discuss the pathways to be explored in adapting photochemical UC for application in various single threshold devices.

Photochemical upconversion: present status and prospects for its application to solar energy conversion

All photovoltaic solar cells transmit photons with energies below the absorption threshold (bandgap) of the absorber material, which are therefore usually lost for the purpose of solar energy conversion. Upconversion (UC) devices can harvest this unused sub-threshold light behind the solar cell, and create one higher energy photon out of (at least) two transmitted photons. This higher energy photon is radiated back towards the solar cell, thus expanding the utilization of the solar spectrum. Key requirements for UC units are a broad absorption and high UC quantum yield under low-intensity incoherent illumination, as relevant to solar energy conversion devices, as well as long term photostability. Upconversion by triplet–triplet annihilation (TTA) in organic chromophores has proven to fulfil the first two basic requirements, and first proof-of-concept applications in photovoltaic conversion as well as photo(electro)chemical energy storage have been demonstrated. Here we review the basic concept of TTA-UC and its application in the field of solar energy harvesting, and assess the challenges and prospects for its large-scale application, including the long term photostability of TTA upconversion materials.

Dye-Sensitized Solar Cell with Integrated Triplet-Triplet Annihilation Upconversion System.

Photon upconversion (UC) by triplet-triplet annihilation (TTA-UC) is employed in order to enhance the response of solar cells to sub-bandgap light. Here, we present the first report of an integrated photovoltaic device, combining a dye-sensitized solar cell (DSC) and TTA-UC system. The integrated device displays enhanced current under sub-bandgap illumination, resulting in a figure of merit (FoM) under low concentration (3 suns), which is competitive with the best values recorded to date for nonintegrated systems. Thus, we demonstrate both the compatibility of DSC and TTA-UC and a viable method for device integration.

Interplay of amorphous silicon disorder and hydrogen content with interface defects in amorphous/crystalline silicon heterojunctions

We analyze the dependence of the interface defect density Dit in amorphous/crystalline silicon (a-Si:H/c-Si) heterojunctions on the microscopic properties of ultrathin (10 nm) undoped a-Si:H passivation layers. It is shown that the hydrogen bonding and network disorder, probed by infrared- and photoelectron spectroscopy, govern the initial Dit and its behavior upon a short thermal treatment at 200 °C. While the initial Dit is determined by the local and nonequilibrated interface structure, the annealed Dit is defined by the bulk a-Si:H network strain. Thus it appears that the equilibrated a-Si:H/c-Si interface does not possess unique electronic properties but is governed by the a-Si:H bulk defects.

Hydrogen plasma treatments for passivation of amorphous-crystalline silicon-heterojunctions on surfaces promoting epitaxy

The impact of post-deposition hydrogen plasma treatment (HPT) on passivation in amorphous/crystalline silicon (a-Si:H/c-Si) interfaces is investigated. Combining low temperature a-Si:H deposition and successive HPT, a high minority carrier lifetime >8 ms is achieved on c-Si 〈100〉, which is otherwise prone to epitaxial growth and thus inferior passivation. It is shown that the passivation improvement stems from diffusion of hydrogen atoms to the heterointerface and subsequent dangling bond passivation. Concomitantly, the a-Si:H hydrogen density increases, leading to band gap widening and void formation, while the film disorder is not increased. Thus, HPT allows for a-Si:H band gap and a-Si:H/c-Si band offset engineering.The impact of post-deposition hydrogen plasma treatment (HPT) on passivation in amorphous/crystalline silicon (a-Si:H/c-Si) interfaces is investigated. Combining low temperature a-Si:H deposition and successive HPT, a high minority carrier lifetime >8 ms is achieved on c-Si 〈100〉, which is otherwise prone to epitaxial growth and thus inferior passivation. It is shown that the passivation improvement stems from diffusion of hydrogen atoms to the heterointerface and subsequent dangling bond passivation. Concomitantly, the a-Si:H hydrogen density increases, leading to band gap widening and void formation, while the film disorder is not increased. Thus, HPT allows for a-Si:H band gap and a-Si:H/c-Si band offset engineering.

Electrical transport mechanisms in a-Si:H/c-Si heterojunction solar cells

We present temperature-dependent measurements of I-V curves in the dark and under illumination in order to elucidate the dominant transport mechanisms in amorphous silicon-crystalline silicon (a-Si:H/c-Si) heterojunction solar cells. ZnO:Al/(p)a-Si:H/(n)c-Si/(n+)a-Si:H cells are compared with inversely doped structures and the impact of thin undoped a-Si:H buffer layers on charge carrier transport is explored. The solar cell I-V curves are analyzed employing a generalized two-diode model which allows fitting of the experimental data for a broad range of samples. The results obtained from the fitting are discussed using prevalent transport models under consideration of auxiliary data from constant-final-state-yield photoelectron spectroscopy, surface photovoltage, and minority carrier lifetime measurements. Thus, an in-depth understanding of the device characteristics is developed in terms of the electronic properties of the interfaces and thin films forming the heterojunction. It is shown that dark I-V cu...

Photochemical Upconversion Enhanced Solar Cells: Effect of a Back Reflector

Photochemical upconversion is applied to a hydrogenated amorphous silicon solar cell in the presence of a back-scattering layer. A custom-synthesized porphyrin was utilized as the sensitizer species, with rubrene as the emitter. Under a bias of 24 suns, a peak external quantum efficiency (EQE) enhancement of ~2 % was observed at a wavelength of 720 nm. Without the scattering layer, the EQE enhancement was half this value, indicating that the effect of the back-scatterer is to double the efficacy of the upconverting device. The results represent an upconversion figure of merit of 3.5 × 10–4 mA cm–2 sun–2, which is the highest reported to date.

Discerning passivation mechanisms at a-Si:H/c-Si interfaces by means of photoconductance measurements

The photoconductance decay (PCD) measurement is a fast and simple method to characterize amorphous/crystalline (a-Si:H/c-Si) silicon interfaces for high-efficiency solar cells. However, PCD only yields information concerning the overall recombination rate in the structure. To overcome this limitation, we have developed and validated a computer-aided PCD (CA-PCD) analysis method to determine the defect density of recombination-active dangling bonds at the interface and the potential drop in the crystalline absorber adjacent to the interface. As a practical example, we investigate a-Si:H(p)/a-Si:H(i)/c-Si(n) layer stacks and show that the CA-PCD method is capable of discerning the influence of field-effect and defect passivation.

Accelerated interface defect removal in amorphous/crystalline silicon heterostructures using pulsed annealing and microwave heating

We present postdeposition annealing experiments on undoped amorphous-/n-type crystalline silicon [(i)a-Si:H/(n)c-Si/(i)a-Si:H] heterostructures used as precursors for a-Si:H/c-Si high-efficiency solar cells. Comparing conventional hotplate-heating with pulsed microwave-heating we obtain excellent interface passivation and demonstrate that microwave annealing proceeds significantly faster. The effect is ascribed to the details of microwave absorption, which selectively affects Si–H bonds and thus facilitates hydrogen bond reconfiguration needed for interface passivation. Infrared absorption spectroscopy shows that the main contribution to passivation is not stemming from bulk hydrogen reconfiguration. This suggests a hydrogen-rich interface layer, whose occurrence depends on a-Si:H deposition conditions, to be responsible for the fast annealing.

Valence band offset in heterojunctions between crystalline silicon and amorphous silicon (sub)oxides (a-SiOx:H, 0 < x < 2)

The heterojunction between amorphous silicon (sub)oxides (a-SiOx:H, 0  4 eV for the a-SiO2/c-Si interface, while the electronic quality of the heterointerface deteriorates. High-bandgap a-SiOx:H is therefore unsuitable for the hole contact in heterojunction solar cells, due to electronic transport hindrance resulting from the large ΔEV. Our method is readily applicable to other heterojunctions.