Efficient Optimization of the Performance of Mn2+‐Doped Kesterite Solar Cell: Machine Learning Aided Synthesis of High Efficient Cu2(Mn,Zn)Sn(S,Se)4 Solar Cells

Li, Xiuling; Hou, Zhufeng; Gao, Shoushuai; Zeng, Yu‐Jia; Ao, Jianping; Zhou, Zhiqiang; Da, Bo; Liu, Wei; Sun, Yun; Zhang, Yi

doi:10.1002/solr.201800198

Cited by 54 publications

(56 citation statements)

References 42 publications

(59 reference statements)

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“…The highest solar cell efficiency is achieved at 5.7% for 15% Mn in CMZTS [150], and 8.9% for 5% Mn in CMZTSSe [151]. The enhancement is attributed to the improved grain growth, better interface between absorber and buffer, and a change in majority defects from Cu Zn to V Cu defects for CMZTSSe [150,151]. As the amount of Mn substitution increases, the carrier concentration increased significantly ( figure 14), and the radiative recombination is quenched, resulting in poor photovoltaic performance for samples with high Mn content [140].…”

Section: Group Vii-b and Viii-bmentioning

confidence: 96%

“…In terms of partial substitution, Cu 2 Mn x Zn 1-x SnS 4 (CMZTS) and Cu 2 Mn x Zn 1-x Sn(S,Se) 4 (CMZTSSe) have been fabricated by different synthesis methods and shown improvement at low Mn substitution [150][151][152][153]. The highest solar cell efficiency is achieved at 5.7% for 15% Mn in CMZTS [150], and 8.9% for 5% Mn in CMZTSSe [151]. The enhancement is attributed to the improved grain growth, better interface between absorber and buffer, and a change in majority defects from Cu Zn to V Cu defects for CMZTSSe [150,151].…”

Section: Group Vii-b and Viii-bmentioning

confidence: 99%

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Doping and alloying of kesterites

et al. 2019

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Attempts to improve the efficiency of kesterite solar cells by changing the intrinsic stoichiometry have not helped to boost the device efficiency beyond the current record of 12.6%. In this light, the addition of extrinsic elements to the Cu 2 ZnSn(S,Se) 4 matrix in various quantities has emerged as a popular topic aiming to ameliorate electronic properties of the solar cell absorbers. This article reviews extrinsic doping and alloying concepts for kesterite absorbers with the focus on those that do not alter the parent zinc-blende derived kesterite structure. The latest state-of-the-art of possible extrinsic elements is presented in the order of groups of the periodic table. The highest reported solar cell efficiencies for each extrinsic dopant are tabulated at the end. Several dopants like alkali elements and substitutional alloying with Ag, Cd or Ge have been shown to improve the device performance of kesterite solar cells as compared to the nominally undoped references, although it is often difficult to differentiate between pure electronic effects and other possible influences such as changes in the crystallization path, deviations in matrix composition and presence of alkali dopants coming from the substrates. The review is concluded with a suggestion to intensify efforts for identifying intrinsic defects that negatively affect electronic properties of the kesterite absorbers, and, if identified, to test extrinsic strategies that may compensate these defects. Characterization techniques must be developed and widely used to reliably access semiconductor absorber metrics such as the quasi-Fermi level splitting, defect concentration and their energetic position, and carrier lifetime in order to assist in search for effective doping/alloying strategies.

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Section: Group Vii-b and Viii-bmentioning

confidence: 96%

Section: Group Vii-b and Viii-bmentioning

confidence: 99%

Doping and alloying of kesterites

et al. 2019

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“…In 2012, Chen et al reported a low formation energy for Cu Zn +Sn Zn and 2Cu Zn +Sn Zn in kesterites and also proposed their deleterious role of introducing deep defects and bandgap narrowing. [6,9,11,[20][21][22][23] Here, we study the role of the proposed performance-limiting defects Cu Zn +Zn Cu and 2Cu Zn +Sn Zn by systematically substituting cations in Cu 2 ZnSnS 4 as characterized by both experimental and theoretical methods. [19] Hence, based on theoretical calculations, the possible performance-limiting point defects in kesterites are proposed to be the Cu-Zn antisite Cu Zn +Zn Cu , and the deep-trap-level-inducing Sn-antisite 2Cu Zn +Sn Zn .…”

Section: Introductionmentioning

confidence: 99%

Suppressed Deep Traps and Bandgap Fluctuations in Cu₂CdSnS₄ Solar Cells with ≈8% Efficiency

Hadke

Levcenko

Gautam

et al. 2019

Advanced Energy Materials

119

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postdeposition alkali treatment to improve heterojunction diode quality in Cu(In,Ga) Se 2 (CIGS) solar cells and chloride treatment to passivate grain boundaries in CdTe solar cells. [1] These solar-cell technologies are already commercialized, with lab-scale photovoltaic efficiencies exceeding 22%. [2] However, kesterite-based solar cells, such as Cu 2 ZnSn(S,Se) 4 , which share many of the same characteristics of CIGS and CdTe, significantly lag behind, with a record power conversion efficiency (PCE) of 12.6%. [3] Although the dominant limiting factors for this low performance are a matter of considerable discussion, [4] the following observations are consistent among kesterite absorbers: i) a low photoluminescence quantum yield (PLQY) and a short chargecarrier lifetime, [5] ii) a high value of Urbach band tail energy (larger than 30 meV for S-rich kesterites) and lack of a steep absorption onset, [6,7] and iii) the presence of secondary phases. [4,6,8,9] The extent to which these factors individually affect the photovoltaic performance is debated, but their ubiquity among kesterite absorbers indicates the presence of a large density of point defects. [10][11][12] Specifically, i) the low PLQY arises from the presence of nonradiative mid-gap The identification of performance-limiting factors is a crucial step in the development of solar cell technologies. Cu 2 ZnSn(S,Se) 4 -based solar cells have shown promising power conversion efficiencies in recent years, but their performance remains inferior compared to other thin-film solar cells. Moreover, the fundamental material characteristics that contribute to this inferior performance are unclear. In this paper, the performance-limiting role of deep-trap-level-inducing 2Cu Zn +Sn Zn defect clusters is revealed by comparing the defect formation energies and optoelectronic characteristics of Cu 2 ZnSnS 4 and Cu 2 CdSnS 4 . It is shown that these deleterious defect clusters can be suppressed by substituting Zn withCd in a Cu-poor compositional region. The substitution of Zn with Cd also significantly reduces the bandgap fluctuations, despite the similarity in the formation energy of the Cu Zn +Zn Cu and Cu Cd +Cd Cu antisites. Detailed investigation of the Cu 2 CdSnS 4 series with varying Cu/[Cd+Sn] ratios highlights the importance of Cu-poor composition, presumably via the presence of V Cu , in improving the optoelectronic properties of the cation-substituted absorber. Finally, a 7.96% efficient Cu 2 CdSnS 4 solar cell is demonstrated, which shows the highest efficiency among fully cation-substituted absorbers based on Cu 2 ZnSnS 4 .

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“…So far, solar cells based on Cu 2 MnSnS 4 absorber with conversion efficiencies of up to PCE = 1.8% have been demonstrated . It crystallizes in a tetragonal crystal structure similar to kesterite and has a direct band gap at 1.61 eV and high absorption coefficient .…”

Section: Introductionmentioning

confidence: 99%

Structural and Electronic Properties of Cu₂MnSnS₄ from Experiment and First‐Principles Calculations

Rudisch

Espinosa-García

Osório-Guillén

et al. 2019

Physica Status Solidi (b)

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Cu 2 MnSnS 4 shares several promising properties with the widely investigated Cu 2 ZnSnS 4 for photovoltaic applications such as containing only earth abundant and non-toxic elements, and suitable absorption characteristics for absorber materials. Thin film Cu 2 MnSnS 4 samples with various cation compositions are co-sputtered reactively followed by a high temperature anneal. Formation of Cu 2 MnSnS 4 and co-existence of several secondary phases is verified by XRD and Raman. Our investigation of the crystal structure based on first-principles DFT confirms that stannite crystal structure is preferred over kesterite, although, further verification considering cation disorder is needed. The direct band gap of Cu 2 MnSnS 4 is calculated as 1.52 eV (1.62 eV) for stannite (kesterite), which coincides with the range of the measured band gaps from spectrophotometry of 1.42-1.59 eV. After further annealing treatments below 240 C, the absorption shows reversible changes: the band gap blue-shifts and the Urbach tail energy is reduced. It is concluded that, just like Cu 2 ZnSnS 4 , disorder also occurs in Cu 2 MnSnS 4 . The implications of our findings are discussed and related to the current understanding of cation disorder in Cu 2 ZnSnS 4 and related compounds. Furthermore, for the first time first-principles DFT investigations are presented for the thiospinel Cu 2 MnSn 3 S 8 which is observed experimentally as a secondary phase in Sn-rich Cu 2 MnSnS 4 thin films.

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Efficient Optimization of the Performance of Mn²⁺‐Doped Kesterite Solar Cell: Machine Learning Aided Synthesis of High Efficient Cu₂(Mn,Zn)Sn(S,Se)₄ Solar Cells

Cited by 54 publications

References 42 publications

Doping and alloying of kesterites

Doping and alloying of kesterites

Suppressed Deep Traps and Bandgap Fluctuations in Cu₂CdSnS₄ Solar Cells with ≈8% Efficiency

Structural and Electronic Properties of Cu₂MnSnS₄ from Experiment and First‐Principles Calculations

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Efficient Optimization of the Performance of Mn2+‐Doped Kesterite Solar Cell: Machine Learning Aided Synthesis of High Efficient Cu2(Mn,Zn)Sn(S,Se)4 Solar Cells

Cited by 54 publications

References 42 publications

Doping and alloying of kesterites

Doping and alloying of kesterites

Suppressed Deep Traps and Bandgap Fluctuations in Cu2CdSnS4 Solar Cells with ≈8% Efficiency

Structural and Electronic Properties of Cu2MnSnS4 from Experiment and First‐Principles Calculations

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Efficient Optimization of the Performance of Mn²⁺‐Doped Kesterite Solar Cell: Machine Learning Aided Synthesis of High Efficient Cu₂(Mn,Zn)Sn(S,Se)₄ Solar Cells

Suppressed Deep Traps and Bandgap Fluctuations in Cu₂CdSnS₄ Solar Cells with ≈8% Efficiency

Structural and Electronic Properties of Cu₂MnSnS₄ from Experiment and First‐Principles Calculations