15 Search Results

Antimony‐doping approaches for VaporTransport CdSeTe

Our team has achieved ~20% doping activation of CdSeTe with antimony (Sb), whose shallow acceptor level makes it a viable alternative to As.1,2 Arsenic (As)-doped graded CdSeTe photovoltaics have achieved record efficiencies of 22.3%. Remaining challenges include doping activation of only ~2% in polycrystalline films and radiative voltage losses of ~100 mV. Here we use (transient) terahertz and photoluminescence spectroscopy of CdTe:Sb and CdSeTe:Sb to show sufficiently long bulk lifetimes to enable high-efficiency devices. Early results also indicate dominant bandgap emission in CdSeTe:Sb and a lack of potential fluctuations with Sb-doping that have proven detrimental for As-doped films. While moremore » work is needed, these results show significant promise for Sb doping.« less

Pyrolyzer assisted Sb-doped CdTe deposition

A new method for in-situ Sb doping of CdTe that uses a modified vapor transport deposition system is described. This modification enables control of the Sb concentration with a pyrolysis stage to enhance the doping efficiency. CdTe:Sb films under different deposition conditions are characterized by SEM, XRD, and CV measurements for determining morphology, crystal structure, and hole concentration. Variations of the Sb dopant heater and pyrolyzer temperatures do not affect the CdTe morphology and crystal structure. However, CV measurements show that a higher dopant heater or pyrolyzer temperature leads to higher hole concentration. In this study, CdTe: Sb films achievemore » a hole concentration of 1016 cm-3 and 10% doping efficiency when the dopant heater is 600C and the pyrolyzer temperature is 1100C. This demonstrates a path to produce high hole concentration polycrystalline CdTe film with a low concentration of dopant-induced defect.« less

The reaction of metallic precursors has become the primary method of industrial manufacturing for Cu(In,Ga)Se2. Commonly used Cu3Ga sputter targets have thus far dictated that the relative Ga composition of these precursors is Ga/(In+Ga) ≈ 0.25. Cu-In-Ga precursors are prepared with varying DC sputtering conditions and Ga compositions ranging from 0 ≤ Ga/(In+Ga) ≤ 0.75. The phase evolution and morphology of these precursors is characterized using x-ray diffraction (XRD) and scanning electron microscopy, including in situ annealing of precursors during XRD measurements. It is observed that the Ga composition of as-deposited precursors affects phase evolution with annealing. Consistent morphology changesmore » were not observed with changing Ga, however, film morphology was controlled by adjusting In sputter conditions.« less

Understanding the nature of recombination and its dependence on defects and interfaces is essential for engineering materials and contacts for higher open circuit voltage (V_oc) and power conversion efficiency in photovoltaic (PV) devices. Time-resolved photoluminescence (TRPL) has conventionally been used to evaluate recombination, but carrier redistribution often dominates the response at short times. In this work, we report on the quantification of carrier dynamics and recombination mechanisms by complementary use of both time-resolved terahertz spectroscopy (TRTS) and TRPL combined with numerical modeling of the continuity equations and Poisson’s equation. We have demonstrated this approach using CdTe thin films. A thinmore » film stack with CdTe fabricated by vapor transport deposition and treated with CdCl₂ exhibited a bulk lifetime of 1.7 ± 0.1 ns, negligible CdTe/CdS interface recombination velocity, and back surface recombination velocity of 6.3 ± 1.3 x10⁴ cm/s. In contrast, a film stack without CdCl₂ treatment had a bulk lifetime of only 68 ± 12 ps and a higher interface recombination velocity of 4 ± 2 x10⁸ cm/s. By determining the locus and mechanisms of performance-limiting recombination, we can accelerate the development of thin-film PVs with higher V_oc and efficiency. While the method has been demonstrated here using CdTe, it is also applicable to perovskites, Cu(InGa)Se₂, Cu2ZnSn(S,Se)_4, and emerging technologies.« less

This project “Improved Performance of Cu(InGa)(SeS)₂ PV Modules using the Reaction of Metal Precursors” was a partnership led by the Institute of Energy Conversion (IEC) at the University of Delaware with Columbia University and the Molecular Foundry at the Lawrence Berkeley National Laboratory. The aim was to develop pathways to improve Cu(InGa)(SeS)₂ (CIGSS) thin film photovoltaic modules using processes compatible with low manufacturing cost. The CIGSS approach investigated was a two-step process including deposition of metal precursor films following by reaction in hydride gases utilizing IEC’s novel reactor. The process was similar to that under commercial development by the project’smore » industry partner Stion. When Stion went out of business mid-project the focus changed to a rapid thermal process considered more commercially viable. Approaches to improve the performance of solar cells using the reacted films focused on two material innovations. First, the overall Ga content was increased to increase the operating voltage, which is desirable for scale-up to commercial modules. Second, the processing and performance advantages arising from Ag alloying were investigated. Advanced characterization guided process and material development including control of relative composition gradients. Research on the formation of Cu-Ga-In metal precursors utilized sputtering deposition which is normally used in commercial applications. The work resulted in processes for deposition of precursor stacks with increased relative Ga content and effects of deposition parameters on morphology and phase composition were established. It was shown that the metal precursor films have comparable phase composition and morphology so subsequent reaction follows from the same starting point. The addition of Ag to the metal precursors gave more uniform morphology and improved adhesion of reacted films which enable higher reaction temperature for faster processing. A novel outcome was the discovery of a previously undocumented material phase in sputter-deposited and evaporated Ag-Cu-In-Ga thin films. Hydride gas reaction processes including time-temperature-concentration profiles were developed for different precursor compositions. This enables control of composition profiles to engineer through-film gradients for solar cell optimization with characterization and simulations used to correlate measured film composition profiles to measurements of devices. In particular, the gradient of sulfur at the front of the CIGSS film was found to be critical. The simulations guided process development leading to improved reproducibility of devices improved performance with higher Ga content and higher voltage. With Ag-alloyed precursors, the reaction pathways leading were determined. A significant finding was that Ag-alloying increases the reaction rate to completely convert precursor films to the final chalcopyrite which could enable reduced reaction time to benefit manufacturability. To maintain potential commercial viability, the process under investigation was refocused to a rapid thermal process that could potentially be incorporated into an in-line process for manufacturing. Precursors with different composition were capped with an extra selenium layer and reacted in hydrogen sulfide 5-15 minutes, compared to typically 2 hours in the previous multi-step batch process. Critical RTP parameters were identified to control the reaction. Further optimization would be needed for high efficiency solar cells but pathways to high quality devices with further optimization and improved heating uniformity were developed. The project also developed new optoelectronic characterization approaches with a focus on development and application of spatial- and time-resolved photoluminescence and a custom mapping photoluminescence microscope built. It was shown how critical electronic transport properties strongly depend on the chemical composition of the material and that a wide range of samples show inhomogeneity on a length scale larger than the grains in the films. Additionally, two-photon excitation capability was developed to distinguish bulk vs surface losses. The project advances the state-of-the -art for precursor reaction processes in several ways that could impact manufacturing. This includes validation of approaches to increase voltage and establishment of model-guided control to form optimal composition profiles. The application of process control approaches with knowledge of phase formation and reaction pathways can be critically valuable in designing a large-scale process.« less

The precursor reaction process for the fabrication of Cu(In,Ga)Se₂ solar cells potentially allows for low-cost fabrication and scalable processing for manufacturing. Additionally, this process has yielded record efficiencies in lab-scale experiments. Thus far, research on the precursor reaction method has been restricted to relatively low Ga compositions with Ga/(In+Ga) ≈ 25%. By increasing the ratio of Ga, it is possible to increase the bandgap, and thus, increase the open-circuit voltage. This work develops and characterizes the precursor reaction process for use with Ga/(In+Ga) ≈ 50%, with the goal of improving the open-circuit voltage and efficiency. It is shown that withmore » an increased Ga ratio, increased V_∞ is achieved, but the rate of conversion from the precursor to absorber phases is decreased. Additionally, increased Ga improves the film adhesion at increased selenization temperatures as well as improving the film morphology.« less

Vapor deposition processes have shown promise for high-quality perovskite solar cells with potential pathways for scale-up to large area manufacturing. Here, we present a sequential close space vapor transport process to deposit CH₃NH₃PbI₃ (MAPI) perovskite thin films by depositing a layer of PbI₂ then reacting it with CH₃NH₃I (MAI) vapor. We find that, at T = 100 °C and pressure = 9 torr, a ~225 nm-thick PbI₂ film requires ≥125 minutes in MAI vapor to form a fully-reacted MAPI film. Raising the temperature to 160 °C increases the rate of reaction, such that MAPI forms within 15 minutes, but withmore » reduced surface coverage. The reaction kinetics can be approximated as roughly first-order with respect to PbI₂, though there is evidence for a more complicated functional relation. Perovskite films reacted at 100 °C for 150 minutes were fabricated into solar cells with an SLG/ITO/CdS/MAPI/Spiro-OMeTAD/Au structure, and a device efficiency of 12.1% was achieved. These results validate the close space vapor transport process and serve as an advance toward scaled-up, vapor-phase perovskite manufacturing through continuous vapor transport deposition.« less

The addition of Ag to Cu-Ga-In precursors for synthesizing (Ag,Cu)(In,Ga)Se ₂ (ACIGS) thin films has shown benefits including improved adhesion, greater process tolerance, and potential for improved device performance. In this study, reaction pathways to form Cu(In,Ga)Se ₂ (CIGS) and ACIGS were studied by time-progressive reactions at 450 °C in a 5% Ar/H ₂ Se atmosphere followed by ex situ characterization. Results indicated that the addition of 25% Ag/(Ag+Cu) to the CIGS film reduces the reaction time by 50%. X-ray diffraction (XRD) analysis of CIGS films showed that the CuInSe ₂ phase initially formed after 3.5 min. The slow reactionmore » of the stable γ-Cu ₉ (In,Ga) ₄ phase, however, required more than 20 min to complete. Importantly, the addition of Ag to the CIGS film accelerated the reaction. Energy-dispersive X-ray spectroscopy shows that Ga/(Ga+In) grading occurs in the first 10 min of the reaction. XRD analysis showed that the chalcopyrite phase fully forms after 10 min and no significant changes were observed in samples selenized from 10-45 min. Reaction pathways of Ag-alloyed films were further characterized using in situ high temperature XRD analysis. The onset temperature of Se reaction was detected at 230 °C and a AgIn ₂ phase transformation to (Ag,Cu)In ₂ occurred during the early stage of the reaction.« less