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Keywords = Cs2PtI6

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18 pages, 2363 KiB  
Article
Mixed Pt-Ni Halide Perovskites for Photovoltaic Application
by Huilong Liu, Rubaiya Murshed and Shubhra Bansal
Materials 2024, 17(24), 6196; https://doi.org/10.3390/ma17246196 - 18 Dec 2024
Viewed by 490
Abstract
Cs2PtI6 is a promising photoabsorber with a direct bandgap of 1.4 eV and a high carrier lifetime; however, the cost of Pt inhibits its commercial viability. Here, we performed a cost analysis and experimentally explored the effect of replacing Pt [...] Read more.
Cs2PtI6 is a promising photoabsorber with a direct bandgap of 1.4 eV and a high carrier lifetime; however, the cost of Pt inhibits its commercial viability. Here, we performed a cost analysis and experimentally explored the effect of replacing Pt with earth-abundant Ni in solution-processed Cs(PtxNi1−x)(I,Cl)3 thin films on the properties and stability of the perovskite material. Films fabricated with CsI and PtI2 precursors result in a perovskite phase with a bandgap of 2.13 eV which transitions into stable Cs2PtI6 with a bandgap of 1.6 eV upon annealing. The complete substitution of PtI2 in films with CsI + NiCl2 precursors results in a wider bandgap of 2.35 eV and SEM shows two phases—a rod-like structure identified as CsNi(I,Cl)3 and residual white particles of CsI, also confirmed by XRD and Raman spectra. Upon extended thermal annealing, the bandgap reduces to 1.65 eV and transforms to CsNiCl3 with a peak shift to higher 2-theta. The partial substitution of PtI2 with NiCl2 in mixed 50-50 Pt-Ni-based films produces a bandgap of 1.9 eV, exhibiting a phase of Cs(Pt,Ni)(I,Cl)3 composition. A similar bandgap of 1.85 eV and the same diffraction pattern with improved crystallinity is observed after 100 h of annealing, confirming the formation of a stable mixed Pt-Ni phase. Full article
(This article belongs to the Special Issue Advanced Energy Materials for Perovskite Solar Cells)
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Figure 1

Figure 1
<p>Atmospheric synthesis of PtI<sub>2</sub>, mixed PtI<sub>2</sub>-NiCl<sub>2</sub>, and NiCl<sub>2</sub>-based films in 50:50 DMF: DMSO via solution processing.</p> Full article ">Figure 2
<p>USD/Watt (solute) of various Pb and Pb-free perovskite compositions calculated with respect to the PCE and thickness reported in the corresponding literature (blue) and the highest PCE of 25.6% and thickness of 2000 nm reported for the Pb-based FAPbI<sub>3</sub> perovskite (red). <a href="#app1-materials-17-06196" class="html-app">Figure S1</a> represents the USD/watt with the discrete effect of optimized PCE and absorber layer thickness.</p> Full article ">Figure 3
<p>USD/Watt (solute + encapsulant) of various Pb and Pb-free perovskite compounds calculated with respect to the highest PCE of 25.6% and thickness of 2000 nm reported for the Pb-based FAPbI<sub>3</sub> perovskite. E1, E2, E3, and E4 represent different encapsulants: Polyolefin, Teflon, PET, and EVA, respectively. <a href="#app1-materials-17-06196" class="html-app">Figure S2</a> represents the USD/Watt (solute + encapsulant) calculated with respect to the PCE and absorber layer thickness reported in the corresponding literature. <a href="#app1-materials-17-06196" class="html-app">Figure S3</a> represents the USD/watt (solute + encapsulant) with the discrete effect of optimized PCE reported for the Pb-based FAPbI<sub>3</sub> perovskite and the corresponding absorber layer thickness from the literature. <a href="#app1-materials-17-06196" class="html-app">Figure S4</a> represents the USD/watt (solute + encapsulant) with the discrete effect of the optimized absorber layer thickness reported for the Pb-based FAPbI<sub>3</sub> perovskite and PCE from the literature.</p> Full article ">Figure 4
<p>(<b>a</b>) Absorption spectrums of 2 h annealed (at −15 in Hg and 100 °C) PtI<sub>2</sub>, mixed PtI<sub>2</sub>-NiCl<sub>2</sub>, and NiCl<sub>2</sub>-based films; (<b>b</b>) Tauc plot showing the optical bandgap of the 2 h annealed (at −15 in Hg and 100 °C) PtI<sub>2</sub>, mixed PtI<sub>2</sub>-NiCl<sub>2</sub>, and NiCl<sub>2</sub>-based films; (<b>c</b>) XRD spectra of the 2 h annealed (at −15 in Hg and 100 °C) PtI<sub>2</sub>, mixed PtI<sub>2</sub>-NiCl<sub>2</sub>, and NiCl<sub>2</sub>-based films; SEM images of (<b>d</b>) PtI<sub>2</sub>, (<b>e</b>) mixed PtI<sub>2</sub>-NiCl<sub>2</sub>, and (<b>f</b>) NiCl<sub>2</sub>-based films; Raman spectra of (<b>g</b>) PtI<sub>2</sub>-based and (<b>h</b>) NiCl<sub>2</sub>-based films, respectively; (<b>i</b>) Goldschmidt and (<b>j</b>) Bartel tolerance factors for Cs(Pt,Ni)(Cl,I)<sub>3</sub>.</p> Full article ">Figure 5
<p>PtI<sub>2</sub>-based films before and after the dark thermal annealing test with t representing the annealing duration: (<b>a</b>) absorption coefficient; (<b>b</b>) Tauc plot; (<b>c</b>) XRD pattern; (<b>d</b>) cross-section SEM images before annealing; (<b>e</b>) cross-section SEM images after annealing; and (<b>f</b>) EDS analysis showing the atomic % of the elemental distribution.</p> Full article ">Figure 6
<p>Mixed PtI<sub>2</sub>-NiCl<sub>2</sub>-based films before and after the dark thermal annealing test with t representing the annealing duration: (<b>a</b>) absorption spectrum; (<b>b</b>) Tauc plot; (<b>c</b>) XRD pattern; (<b>d</b>) cross-section SEM image before annealing; (<b>e</b>) cross-section SEM image after annealing; and (<b>f</b>) EDS analysis showing the atomic % of the elemental distribution.</p> Full article ">Figure 7
<p>NiCl<sub>2</sub>-based films before and after the dark thermal annealing test with t representing the annealing duration: (<b>a</b>) absorption spectrum; (<b>b</b>) Tauc plot; (<b>c</b>) XRD pattern; (<b>d</b>) SEM morphology before annealing; (<b>e</b>) SEM morphology after annealing; and (<b>f</b>) EDS analysis showing the atomic % of the elemental distribution.</p> Full article ">
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