Colloidal Wurtzite Cu<sub>2</sub>SnS<sub>3</sub> (CTS) Nanocrystals and Their Applications in Solar Cells

Ghorpade, Uma V.; Suryawanshi, Mahesh P.; Shin, Seung Wook; Kim, In-Young; Ahn, Seung Kyu; Yun, Jae Ho; Jeong, Chaehwan; Kolekar, Sanjay S.

doi:10.1021/acs.chemmater.6b00176

Cited by 76 publications

(54 citation statements)

References 55 publications

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“… 42 , 49 As the optical absorption plays a crucial role in determining the suitability of a material for photovoltaic and PEC application, we have recorded the optical absorption of CTS in the wavelength range of 300–1200 nm as shown in Figure 1 c and it is consistent with a recent report. 50 The optical band gap of the CTS NPs was calculated using the Tauc relation α hυ = B ( hυ – E g ) n , where B is the Tauc constant, h is Plank’s constant, υ is the photon frequency, and E g is the band gap of the material. In the Tauc plot shown in Figure 1 d, the band gap of CTS NPs is estimated at 1.1 eV, indicating that it can be effectively used as an absorber layer in a photoelectrochemical cell.…”

Section: Resultsmentioning

confidence: 99%

Ternary Cu₂SnS₃: Synthesis, Structure, Photoelectrochemical Activity, and Heterojunction Band Offset and Alignment

et al. 2021

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Ternary Cu 2 SnS 3 (CTS) is an attractive nontoxic and earth-abundant absorber material with suitable optoelectronic properties for cost-effective photoelectrochemical applications. Herein, we report the synthesis of high-quality CTS nanoparticles (NPs) using a low-cost facile hot injection route, which is a very simple and nontoxic synthesis method. The structural, morphological, optoelectronic, and photoelectrochemical (PEC) properties and heterojunction band alignment of the as-synthesized CTS NPs have been systematically characterized using various state-of-the-art experimental techniques and atomistic first-principles density functional theory (DFT) calculations. The phase-pure CTS NPs confirmed by X-ray diffraction (XRD) and Raman spectroscopy analyses have an optical band gap of 1.1 eV and exhibit a random distribution of uniform spherical particles with size of approximately 15–25 nm as determined from high-resolution transmission electron microscopy (HR-TEM) images. The CTS photocathode exhibits excellent photoelectrochemical properties with PCE of 0.55% (fill factor (FF) = 0.26 and open circuit voltage (Voc) = 0.54 V) and photocurrent density of −3.95 mA/cm 2 under AM 1.5 illumination (100 mW/cm 2 ). Additionally, the PEC activities of CdS and ZnS NPs are investigated as possible photoanodes to create a heterojunction with CTS to enhance the PEC activity. CdS is demonstrated to exhibit a higher current density than ZnS, indicating that it is a better photoanode material to form a heterojunction with CTS. Consistently, we predict a staggered type-II band alignment at the CTS/CdS interface with a small conduction band offset (CBO) of 0.08 eV compared to a straddling type-I band alignment at the CTS/ZnS interface with a CBO of 0.29 eV. The observed small CBO at the type-II band aligned CTS/CdS interface points to efficient charge carrier separation and transport across the interface, which are necessary to achieve enhanced PEC activity. The facile CTS synthesis, PEC measurements, and heterojunction band alignment results provide a promising approach for fabricating next-generation Cu-based light-absorbing materials for efficient photoelectrochemical applications.

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Section: Resultsmentioning

confidence: 99%

Ternary Cu₂SnS₃: Synthesis, Structure, Photoelectrochemical Activity, and Heterojunction Band Offset and Alignment

et al. 2021

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“…A detailed fabrication process of a full-device structure can be found in our previous reports. 37,38…”

Section: Methodsmentioning

confidence: 99%

Aqueous-Solution-Processed Cu₂ZnSn(S,Se)₄ Thin-Film Solar Cells via an Improved Successive Ion-Layer-Adsorption–Reaction Sequence

et al. 2017

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A facile improved successive ionic-layer adsorption and reaction (SILAR) sequence is described for the fabrication of Cu 2 ZnSn(S,Se) 4 (CZTSSe) thin-film solar cells (TFSCs) via the selenization of a precursor film. The precursor films were fabricated using a modified SILAR sequence to overcome compositional inhomogeneity due to different adsorptivities of the cations (Cu + , Sn 4+ , and Zn 2+ ) in a single cationic bath. Rapid thermal annealing of the precursor films under S and Se vapor atmospheres led to the formation of carbon-free Cu 2 ZnSnS 4 (CZTS) and CZTSSe absorber layers, respectively, with single large-grained layers. The best devices based on CZTS and CZTSSe absorber layers showed total area (∼0.30 cm 2 ) power conversion efficiencies (PCEs) of 1.96 and 3.74%, respectively, which are notably the first-demonstrated efficiencies using a modified SILAR sequence. Detailed diode analyses of these solar cells revealed that a high shunt conductance ( G sh ), reverse saturation current density ( J o ), and ideality factor ( n d ) significantly affected the PCE, open-circuit voltage ( V oc ), and fill factor (FF), whereas the short-circuit current density ( J sc ) was dominated by the series resistance ( R s ) and G sh . However, the diode analyses combined with the compositional and interface microstructural analyses shed light on further improvements to the device efficiency. The facile layer-by-layer growth of the kesterite CZTS-based thin films in aqueous solution provides a great promise as an environmentally benign pathway to fabricate a variety of multielement-component compounds with high compositional homogeneities.

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“…But in the NIR region the collection efficiency is reduced, which indicates that the electronic properties (space charge region, carrier lifetime, and diffusion length) can be improved. [ 43–45 ] When the Se content increases in the absorber layer composition, the spectral range is increased from 900 (pure CZTS) to 1250 nm (pure CZTSe), remaining inside of this range those samples with partial S/Se substitution. It is also observed that the carrier collection is improved when the Cu content is increased.…”

Section: Resultsmentioning

confidence: 99%

High Vapor Transport Deposition: A Novel Process to Develop Cu₂ZnSn(S_xSe_1–x)₄ Thin Film Solar Cells

Delgado-Sánchez

Lillo-Bravo

2021

Solar RRL

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Materials such as cadmium telluride (CdTe), copper indium gallium selenide (CIGSe), and copper zinc tin selenide (CZTSe) with higher absorption coefficient are trying to make headway in the competitive photovoltaic market covered mainly by silicon materials. [1] The most important key factors of those emerging semiconductors are the cost-effective mass production, together with high photovoltaic conversion factor (PCE) and long-term stability. Despite CdTe and CIGSe are already industrialized, and their PCE is reaching the commercial silicon ones, the kesterite (CZTSe) is still an emerging technology with high absorption and low raw material cost. But one of its main bottlenecks is its hidden capability to be manufactured at large scale with reasonably good quality. [2] The CZTSe has the properties desired for photovoltaic materials to be selected as potential p-type semiconductors: direct bandgap, high absorption coefficient (10 4 cm À1 in the visible light range), and optical bandgap energy of the range 1.4-1.5 eV, close to the optimum singlejunction value predicted by Shockley-Queisser model. Today, CZTSe is considered a good competitor for CIGSbased solar cells. CZTSe is described by the structural model of two natural minerals: stannite (space group I-42 m) and kesterite (space group I-4). [3][4][5] These structures are very similar: in both structures the cations are located on tetrahedral sites, but their distributions on planes perpendicular to the x-axis are not the same. Additionally, the position of the chalcogen atom is slightly different in both structures. Design and manufacturing of high efficiency CZTSe solar cells need high accuracy in the composition of the absorber material: slight modifications in composition, structural electronic, and defect properties of the alloys have a high impact in the bandgap energy. [6] CZTSe solar cells have achieved the highest efficiency of 12.6%, [7] which is still far from the offered by CIGS-based solar cells: 23.35%. [8] It has known that this limitation is mainly related with the short minority carrier lifetime and the high series resistance imposed by the contact barrier due to the formation of the MoSe 2 at the CZTSe/Mo interface. The presence of secondary phases and defect states in the absorber also increases the recombination rate. [9,10] The influence of the deposition method on the structure, morphology, optical, and electrical properties of CZTSe has been investigated by other researchers: sputtering, thermal evaporation, spray pyrolysis, electrodeposition, dip coating, SILAR method, spin coating, sol-gel, solvothermal method, and chemical bath deposition (CBD). [1] In all of these techniques, the control of the presence of secondary phases is the major critical issue, so the final performance of the device is dependent on the manufacturing route selected: the highest conversion efficiency of CZTS achieved using vacuum techniques such as

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Colloidal Wurtzite Cu₂SnS₃ (CTS) Nanocrystals and Their Applications in Solar Cells

Cited by 76 publications

References 55 publications

Ternary Cu₂SnS₃: Synthesis, Structure, Photoelectrochemical Activity, and Heterojunction Band Offset and Alignment

Ternary Cu₂SnS₃: Synthesis, Structure, Photoelectrochemical Activity, and Heterojunction Band Offset and Alignment

Aqueous-Solution-Processed Cu₂ZnSn(S,Se)₄ Thin-Film Solar Cells via an Improved Successive Ion-Layer-Adsorption–Reaction Sequence

High Vapor Transport Deposition: A Novel Process to Develop Cu₂ZnSn(S_xSe_1–x)₄ Thin Film Solar Cells

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Colloidal Wurtzite Cu2SnS3 (CTS) Nanocrystals and Their Applications in Solar Cells

Cited by 76 publications

References 55 publications

Ternary Cu2SnS3: Synthesis, Structure, Photoelectrochemical Activity, and Heterojunction Band Offset and Alignment

Ternary Cu2SnS3: Synthesis, Structure, Photoelectrochemical Activity, and Heterojunction Band Offset and Alignment

Aqueous-Solution-Processed Cu2ZnSn(S,Se)4 Thin-Film Solar Cells via an Improved Successive Ion-Layer-Adsorption–Reaction Sequence

High Vapor Transport Deposition: A Novel Process to Develop Cu2ZnSn(SxSe1–x)4 Thin Film Solar Cells

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Colloidal Wurtzite Cu₂SnS₃ (CTS) Nanocrystals and Their Applications in Solar Cells

Ternary Cu₂SnS₃: Synthesis, Structure, Photoelectrochemical Activity, and Heterojunction Band Offset and Alignment

Ternary Cu₂SnS₃: Synthesis, Structure, Photoelectrochemical Activity, and Heterojunction Band Offset and Alignment

Aqueous-Solution-Processed Cu₂ZnSn(S,Se)₄ Thin-Film Solar Cells via an Improved Successive Ion-Layer-Adsorption–Reaction Sequence

High Vapor Transport Deposition: A Novel Process to Develop Cu₂ZnSn(S_xSe_1–x)₄ Thin Film Solar Cells