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Wide-gap, high-Ga (Ag,Cu)(In,Ga)Se₂ thin-film solar cells with a wide range of Ag contents are fabricated and characterized before and after dark storage, dark annealing at 85 degrees C, and light soaking. A 1:4 ratio of Ag to Cu enhances initial device performance significantly, with excess Ag enhancing carrier collection at the expense of open-circuit voltage and fill factor for close-stoichiometric devices. For off-stoichiometric devices, increased open-circuit voltages are offset by losses in carrier collection. Efficiency degradation after treatments is typically increased with additional Ag alloying. A second observation is a behavior threshold identified slightly below an Ag to Cu ratio of 1:1. For compositions below the threshold, the doping response to light soaking and dark annealing is similar to that exhibited by low-Ga Cu(In,Ga)Se₂. Above the threshold, light soaking reduces net doping and that dark annealing can even increase net doping. Furthermore, devices above the threshold exhibit a far greater doping responsivity than those below and display a strong dependence of initial performance and stability on group-I/group-III stoichiometry. A third observation is that all devices lose approximate to 1-2% (absolute) in efficiency after a 3 h light soak, indicating that this loss originates from the high-Ga content (1:3 In:Ga), rather than the Ag alloying.

This study reports on the influence of air annealing and Na incorporation into the absorber on the performance of Cu2ZnSnS4 (CZTS) bifacial solar cells with FTO and W/FTO back contacts. Na was incorporated by depositing similar to 12 nm thick NaF on the CZTS precursors prior to the sulfurization process via thermal evaporation. After sulfurization, some of the samples were annealed in air at 300 degrees C for 90 s and subsequently at 200 degrees C for 600 s. Transmission electron microscopy confirmed sulfurization of the W interlayer to form WS2 which improves the FTO ohmicity. Na incorporation improved grain size of the absorber as revealed by scanning electron microscopy. Non-annealed samples had the unwanted SnS2 phase while the air annealed samples, particularly those with both W interlayer and Na incorporation, were exempt from SnS2 phase, as was confirmed through grazing incident X-ray diffraction and Raman spectroscopy. These results suggest that absorber air annealing and Na incorporation enhance absorber crystal growth which is advantageous in reducing bulk carrier recombination. As a result, the efficiency was significantly improved from 3.0% for solar cells fabricated directly on FTO to 5.2% for those whose absorbers were air annealed, incorporated with Na and made on W/FTO. The latter also exhibits the highest external quantum efficiency response and calculated short circuit current density for both sides illumination. This indicates that the air annealing, Na incorporation and W interlayer are enhancing the performance of bifacial CZTS solar cells with FTO back contact for both back side and front side illumination.

This licentiate thesis gives a summary of electrical characterisation techniques, detailing their use to investigate and understand stability and meta-stability in thin-film solar cells, with a focus on the chalcopyrite material system. Experimental data is used to illustrate the information that can be extracted with these measurements, highlighting the deeper insights that can be drawn from complementary measurements. For example, short-circuit current losses in (Ag,Cu)(In,Ga)Se₂ after prolonged storage and annealing are attributed to changes in the net doping, as are significant open-circuit voltage losses observed after lightsoaking. Characterisation is also shown to suggest that the amount of Ag in the alloy plays a significant role in its stability, with a similar significance indicated for Ga.

Thin film solar cells spanning a wide range of compositions within the (Ag,Cu)(In,Ga)Se2 system are fabricated and characterised using current-voltage, external quantum efficiency and capacitance-based measurements. The stability of the devices over time, after dry annealing and after lightsoaking is evaluated, and the role of Ag and Ga content is explored. Ag-free CuInSe2 and Cu(In,Ga)Se2 are observed to be stable, however high-Ag, high-Ga (Ag,Cu)(In,Ga)Se2 is observed to exhibit fluctuations in short-circuit current. High-Ag (Ag,Cu)InSe2 is instead observed to have stable current, but open-circuit voltage and fill-factor are strongly responsive. Thus, it is indicated that high fractions of Ag in the material lead to significant stability concerns, with high Ga fractions affecting the way in which degradation manifests. Discussion of probable causes and mechanisms follows.

The stability of thin-film solar cells spanning a wide range of compositions within the (Ag,Cu)(In,Ga)Se-2 material system is evaluated over time, after dry-heat annealing and after light soaking, and the role of Ag and Ga content is explored. Ag-free CuInSe2 is relatively stable to annealing and storage, while Cu(In,Ga)Se-2 suffers a degradation of fill factor and carrier collection. High-Ga (Ag,Cu)(In,Ga)Se-2 suffers degradation of carrier collection after prolonged annealing, reducing the short-circuit current by approximate to 12%. Ga-free (Ag,Cu)InSe2 loses up to a third of open-circuit voltage and a quarter of fill factor after all treatments are applied. All samples suffer voltage losses after light soaking, with the Ga-free devices losing up to 50 mV and those containing Ga losing up to 90 mV. Ag incorporation leads to a significant reduction in doping, and a significant increase in the response of doping to treatments, with the depletion width of (Ag,Cu)(In,Ga)Se-2 samples expanding from approximate to 0.1 mu m as-grown to beyond 1.0 mu m after all treatments, compared to the Cu(In,Ga)Se-2 sample variation of approximate to 0.1-0.3 mu m. Connections between Ag content, doping instability, and performance degradation are discussed.

In 2017, Cu(In,Ga)Se₂ (CIGS), Cu₂(Zn,Sn)S₄ (CZTS) and Cu₂(Zn,Sn)(S,Se)₄ (CZTSSe) thin film solar cells were irradiated by our group using 3 MeV protons to investigate the materials’ radiation hardness and subsequent recovery following dark storage. It was observed that the primary losses were in open-circuit voltage (V_OC), with the CZTS and CZTSSe being more resistant than the CIGS, also recovering to ∼ 95% of initial performance, compared to ∼ 70% for CIGS after two months dark storage. In 2021 the cells were investigated by external quantum efficiency and current-voltage measurements once again, to investigate further recovery. The CIGS cells had continued to recover, whilst the CZTSSe devices appear to have fully recovered from radiation induced damage, but now suffer from aging-related degradation and exhibit slight bandgap widening over time. The CZTS cells were observed to recover fully from the radiation induced damage, whilst also showing gains in V_OC.

(Ag,Cu)(In,Ga)Se₂ solar cells with bandgaps of ≈1.45 eV with a large spread in absorber stoichiometry are characterized with the intention of assessing the effect of composition on the stability of the devices. This material is observed to have a poor diffusion length, leading to very strong dependence upon the depletion region width for charge carrier collection. The depletion width is observed to depend strongly upon the stoichiometry value and shrinks significantly after an initial period of dark storage. It is also seen that the depletion width can be varied strongly through light-soaking and dry-heat treatments, with prolonged annealing leading to detrimental contraction and light soaking leading to expansion which increases current collection. The extent of depletion width variation in response to the treatments is also clearly linked to absorber stoichiometry. Consequently, the device performance, particularly the current output, exhibits a stoichiometry dependence and is considerably affected after each round of treatment. Possible causes of this behavior are discussed.

The effect of absorber stoichiometry in (Ag,Cu)(In,Ga)Se2(ACIGS) solar cells withbandgaps (Eg) > 1.40 eV is studied on a large sample set. It is conrmed thatmoving away in composition from ternary AgGaSe2by simultaneous reduction inGa and Ag content widens the chalcopyrite single-phase region and therebyreduces the amount of ordered vacancy compounds (OVCs). As a consequence, adistortion in currentvoltage characteristics, ascribed to OVCs at the back contact,can be successfully avoided. A clear anticorrelation between open-circuit voltage(VOC) and short-circuit current density (JSC) is detected with varying absorberstoichiometry, showing decreasingVOCand increasingJSCvalues for [I]/[III] > 0.9.Capacitance proling reveals that the absorber doping gradually decreases towardstoichiometric composition, eventually leading to complete depletion. It isobserved that only such fully depleted samples exhibit perfect carrier collection,evidencing a very low diffusion length in wide-gap ACIGS lms. The results indicatethat OVCs at the surface play a minor or passive role for device performance.Finally, a solar cell withVOC¼ 0.916 V atEg¼ 1.46 eV is measured, which is, to thebest of our knowledge, the highest value reported for this bandgap to date.