Defect Control for 12.5% Efficiency Cu2ZnSnSe4 Kesterite Thin-Film Solar Cells by Engineering of Local Chemical Environment

Kesterite-based Cu₂ZnSn(S,Se)₄ semiconductors are emerging as promising materials for low-cost, environment-benign, and high-efficiency thin-film photovoltaics. However, the current state-of-the-art Cu₂ZnSn(S,Se)₄ devices suffer from cation-disordering defects and defect clusters, which generally result in severe potential fluctuation, low minority carrier lifetime, and ultimately unsatisfactory performance. Herein, critical growth conditions are reported for obtaining high-quality Cu₂ZnSnSe₄ absorber layers with the formation of detrimental intrinsic defects largely suppressed. By controlling the oxidation states of cations and modifying the local chemical composition, the local chemical environment is essentially modified during the synthesis of kesterite phase, thereby effectively suppressing detrimental intrinsic defects and activating desirable shallow acceptor Cu vacancies. Consequently, a confirmed 12.5% efficiency is demonstrated with a high V_OC of 491 mV, which is the new record efficiency of pure-selenide Cu₂ZnSnSe₄ cells with lowest V_OC deficit in the kesterite family by E_g/q-Voc. These encouraging results demonstrate an essential route to overcome the long-standing challenge of defect control in kesterite semiconductors, which may also be generally applicable to other multinary compound semiconductors.     

Earth‐Abundant Chalcogenide Photovoltaic Devices with over 5% Efficiency Based on a Cu2BaSn(S,Se)4 Absorber

In recent years, Cu₂ZnSn(S,Se)₄ (CZTSSe) materials have enabled important progress in associated thin‐film photovoltaic (PV) technology, while avoiding scarce and/or toxic metals; however, cationic disorder and associated band tailing fundamentally limit device performance. Cu₂BaSnS₄ (CBTS) has recently been proposed as a prospective alternative large bandgap (~2 eV), environmentally friendly PV material, with ~2% power conversion efficiency (PCE) already demonstrated in corresponding devices. In this study, a two‐step process (i.e., precursor sputter deposition followed by successive sulfurization/selenization) yields high‐quality nominally pinhole‐free films with large (>1 µm) grains of selenium‐incorporated (x = 3) Cu₂BaSnS_4?x Se_x (CBTSSe) for high‐efficiency PV devices. By incorporating Se in the sulfide film, absorber layers with 1.55 eV bandgap, ideal for single‐junction PV, have been achieved within the CBTSSe trigonal structural family. The abrupt transition in quantum efficiency data for wavelengths above the absorption edge, coupled with a strong sharp photoluminescence feature, confirms the relative absence of band tailing in CBTSSe compared to CZTSSe. For the first time, by combining bandgap tuning with an air‐annealing step, a CBTSSe‐based PV device with 5.2% PCE (total area 0.425 cm²) is reported, >2.5× better than the previous champion pure sulfide device. These results suggest substantial promise for the emerging Se‐rich Cu₂BaSnS_4–x Se_x family for high‐efficiency and earth‐abundant PV.     

Photoluminescence and Raman study of Cu2ZnSn(SexS1 − x)4 monograins for photovoltaic applications

The quaternary semiconductors Cu₂ZnSnSe₄ and Cu₂ZnSnS₄ have attracted a lot of attention as possible absorber materials for solar cells due to their direct bandgap and high absorption coefficient (> 10⁴ cm⁻¹). In this study we investigate the optical properties of Cu₂ZnSn(Se_xS_1 − x)₄ monograin powders that were synthesized from binary compounds in the liquid phase of potassium iodide (KI) flux materials in evacuated quartz ampoules. Radiative recombination processes in Cu₂ZnSn(Se_xS_1 − x)₄ monograins were studied by using low-temperature photoluminescence (PL) spectroscopy. A continuous shift from 1.3 eV to 0.95 eV of the PL emission peak position with increasing Se concentration was observed indicating the narrowing of the bandgap of the solid solutions. Recombination mechanisms responsible for the PL emission are discussed. Vibrational properties of Cu₂ZnSn(Se_xS_1 − x)₄ monograins were studied by using micro-Raman spectroscopy. The frequencies of the optical modes in the given materials were detected and the bimodal behaviour of the A₁ Raman modes of Cu₂ZnSnSe₄ and Cu₂ZnSnS₄ is established.     

Emerging inorganic compound thin film photovoltaic materials: Progress,challenges and strategies

The efficient conversion of solar energy to electricity for human utilization heavily relies on the development of solar cells. Nowadays, a variety of high-performance solar cells are constantly emerging. Thin-film solar cells made from inorganic materials have constituted one of the major categories of solar cells showing potential in the fast growing photovoltaic (PV) market. In order to provide an overall grasp of and insight into the future direction of inorganic thin-film solar cell development, we review key emerging and representative inorganic photovoltaic materials including chalcopyrite Cu(In,Ga)Se₂ (CIGSe), kesterite Cu₂ZnSn(S,Se)₄ (CZTSSe), CdTe, Sb₂Se₃ and inorganic perovskite CsPb(I_1−xBr_x)₃ in this paper. Absorber materials, evolution of device development, and current challenges and key strategies for performance enhancement are detailed.     

Toward High Efficient Cu2ZnSn(Sx,Se1−x)4 Solar Cells: Break the Limitations of VOC and FF

Increasing the fill factor (FF) and the open-circuit voltage (V_OC) simultaneously together with non-decreased short-circuit current density (J_SC) are a challenge for highly efficient Cu₂ZnSn(S,Se)₄ (CZTSSe) solar cells. Aimed at such target in CZTSSe solar cells, a synergistic strategy to tailor the recombination in the bulk and at the heterojunction interface has been developed, consisting of atomic-layer deposited aluminum oxide (ALD-Al₂O₃) and (NH₄)₂S treatment. With this strategy, deep-level Cu_Zn defects are converted into shallower V_Cu defects and improved crystallinity, while the surface of the absorber is optimized by removing Zn- and Sn-related impurities and incorporating S. Consequently, the defects responsible for recombination in the bulk and at the heterojunction interface are effectively passivated, thereby prolonging the minority carrier lifetime and increasing the depletion region width, which promote carrier collection and reduce charge loss. As a consequence, the V_OC deficit decreases from 0.607 to 0.547 V, and the average FF increases from 64.2% to 69.7%, especially, J_SC does not decrease. Thus, the CZTSSe solar cell with the remarkable efficiency of 13.0% is fabricated. This study highlights the increased FF together with V_OC simultaneously to promote the efficiency of CZTSSe solar cells, which could also be applied to other photoelectronic devices.     

Classification of Lattice Defects in the Kesterite Cu2ZnSnS4 and Cu2ZnSnSe4 Earth‐Abundant Solar Cell Absorbers

The kesterite‐structured semiconductors Cu₂ZnSnS₄ and Cu₂ZnSnSe₄ are drawing considerable attention recently as the active layers in earth‐abundant low‐cost thin‐film solar cells. The additional number of elements in these quaternary compounds, relative to binary and ternary semiconductors, results in increased flexibility in the material properties. Conversely, a large variety of intrinsic lattice defects can also be formed, which have important influence on their optical and electrical properties, and hence their photovoltaic performance. Experimental identification of these defects is currently limited due to poor sample quality. Here recent theoretical research on defect formation and ionization in kesterite materials is reviewed based on new systematic calculations, and compared with the better studied chalcopyrite materials CuGaSe₂ and CuInSe₂. Four features are revealed and highlighted: (i) the strong phase‐competition between the kesterites and the coexisting secondary compounds; (ii) the intrinsic p‐type conductivity determined by the high population of acceptor Cu_Zn antisites and Cu vacancies, and their dependence on the Cu/(Zn+Sn) and Zn/Sn ratio; (iii) the role of charge‐compensated defect clusters such as [2Cu_Zn+Sn_Zn], [V_Cu+Zn_Cu] and [Zn_Sn+2Zn_Cu] and their contribution to non‐stoichiometry; (iv) the electron‐trapping effect of the abundant [2Cu_Zn+Sn_Zn] clusters, especially in Cu₂ZnSnS₄. The calculated properties explain the experimental observation that Cu poor and Zn rich conditions (Cu/(Zn+Sn) ≈ 0.8 and Zn/Sn ≈ 1.2) result in the highest solar cell efficiency, as well as suggesting an efficiency limitation in Cu₂ZnSn(S,Se)₄ cells when the S composition is high.     

Chemical liquid deposition of CuInSe2 and CuIn(S,Se)2 films for solar cells

Several non-vacuum based approaches have been employed to deposit the Cu(In,Ga)Se₂ layer in photovoltaic devices, but most of them use processing temperatures in the vicinity of 500 °C. Here, we present the results on a facile solution-based deposition technique for CuInSe₂ (CISe) and CuIn(S,Se)₂ (CISSe) thin films with deposition temperatures of 300 °C. Cu_xSe (1.5 ≤ x ≤ 2) or Cu_yS (1 ≤ y ≤ 2) precursor films deposited on a substrate were reacted with InCl₃ and Se reactants in oleylamine to form CISe or CISSe thin films of the desired thickness, composition and crystal structure. Solar cells processed from these films on Mo-coated glass substrates demonstrated an efficiency of 2% under AM 1.5 illumination. We also present external quantum efficiency and capacitance-voltage measurements from these devices providing insights into the device performance.     

Cu2ZnSnS4 solar cell prepared entirely by non-vacuum processes

Cu₂ZnSnS₄ (CZTS) solar cell with superstrate structure of fluorine-doped tin oxide glass/TiO₂/In₂S₃/CZTS/Carbon was prepared entirely by non-vacuum processes. The compact TiO₂ window and In₂S₃ buffer layers, CZTS absorber layer and Carbon electrode layer were prepared by spray pyrolysis method, ball milling and screen printing combination processes and screen printing process, respectively. The short-circuit current density, open-circuit voltage, fill factor and conversion efficiency of the best fabricated solar cell are 8.76 mA/cm², 250 mV, 0.27 and 0.6%, respectively. The fabrication process for the CZTS solar cell did not employ any vacuum conditions or high-toxic materials (such as CdS, H₂Se, H₂S or Se).     

The influence of gallium on phase transitions during the crystallisation of thin film absorber materials Cu(In,Ga)(S,Se)2 investigated by in-situ X-ray diffraction

Chalcopyrite based photovoltaic materials Cu(In_xGa_1 − x)(S_ySe_1 − y)₂ (CIGSSe) are substituted in the cation and anion lattice to adopt the semiconductor bandgap to the terrestrial solar spectrum. In-situ X-ray diffraction (XRD) investigations on the crystallisation of thin film absorber materials Cu(In,Ga)(S,Se)₂ while annealing stacked elemental layers (SEL) show phase transitions proceeding during the chalcopyrite synthesis.Thin layers of metals with elemental ratio Cu:In:Ga = 3:2:1 are deposited onto Mo-coated polyimide foil by DC-magnetron sputtering. The metal precursor is covered with S and subsequently Se by thermal evaporation of the elements in chalcogen excess (S + Se) / (Cu + In + Ga) = 2.3. Investigated chalcogen ratios reach from pure Se to pure S. Crystalline phases formed during the annealing of SEL are qualitatively determined. The results are compared to conclusions drawn from previous experiments on Ga-free CuIn(S,Se)₂ absorbers. The presence of Ga and S influences significantly the time-scale and the temperatures of phase transitions, i.e. the sulfoselenisation of precursor phases Cu₁₆(In,Ga)₉ and Cu₉(Ga,In)₄ proceeds faster with increasing S and is shifted to higher temperatures as compared to Ga-free Cu₁₁In₉/Cu₁₆In₉.     

XPS study of CZTSSe monograin powders

The surface and bulk composition of Cu₂ZnSn(Se_xS_1-x)₄ (CZTSSe) monograin powders were investigated by X-ray photoelectron spectroscopy (XPS). The concentration depth profiling of CZTSSe monograin powders was obtained by Ar⁺ ion etching.According to the XPS spectra of CZTSSe monograin powder, the binding energies of Zn 2p_3/2, Cu 2p_3/2, Sn 3d_5/2, S 2p_3/2 and Se 3d_5/2 core levels after surface cleaning are located at 1021.6 eV, 932.4 eV, 486.1 eV, 161.5 eV, 53.9 eV, respectively. From XPS depth profile analysis, Cu deficiency and the excess of chalcogenides on the powder crystals surface were observed.     

Are Cu2Te‐Based Compounds Excellent Thermoelectric Materials?

Most of the state‐of‐the‐art thermoelectric (TE) materials exhibit high crystal symmetry, multiple valleys near the Fermi level, heavy constituent elements with small electronegativity differences, or complex crystal structure. Typically, such general features have been well observed in those well‐known TE materials such as Bi₂X₃‐, SnX‐, and PbX‐based compounds (X = S, Se, and Te). The performance is usually high in the materials with heavy constituent elements such as Te and Se, but it is low for light constituent elements such as S. However, there is a great abnormality in Cu₂X‐based compounds in which Cu₂Te has much lower TE figure of merit (zT) than Cu₂S and Cu₂Se. It is demonstrated that the Cu₂Te‐based compounds are also excellent TE materials if Cu deficiency is sufficiently suppressed. By introducing Ag₂Te into Cu₂Te, the carrier concentration is substantially reduced to significantly improve the zT with a record‐high value of 1.8, 323% improvement over Cu₂Te and outperforms any other Cu₂Te‐based materials. The single parabolic band model is used to further prove that all Cu₂X‐based compounds are excellent TE materials. Such finding makes Cu₂X‐based compounds the only type of material composed of three sequent main group elements that all possess very high zT s above 1.5.     

Pre-annealing induced oxide barrier to suppress the over-selenization of Mo contact

Molybdenum (Mo) is commonly used as the back contact material complying well with the formation of an ohmic contact for chalcogenide thin film solar cells. However, the easy formation of an over-thick MoSe₂ layer between the Cu₂ZnSn(S,Se)₄ absorber and Mo back contact significantly deteriorates the device performance. To overcome the degradation, the effects of thermal treatment on Mo layers have been investigated in this paper. It was found that pre-annealing Mo back contacts is effective to control the growth of interfacial MoSe₂ layer during selenization. Moreover, the thickness of MoSe₂ layer could be conveniently tailored by simply varying the pre-annealing temperature. The work provides direct proof that the appearance of a thin MoO₂ layer on the top of annealed Mo film indeed acts as a temporary barrier to block the over-selenization of Mo back contact.     

Promising and Eco-Friendly Cu2X-Based Thermoelectric Materials: Progress and Applications

Due to the nature of their liquid-like behavior and high dimensionless figure of merit, Cu₂X (X = Te, Se, and S)-based thermoelectric materials have attracted extensive attention. The superionicity and Cu disorder at the high temperature can dramatically affect the electronic structure of Cu₂X and in turn result in temperature-dependent carrier-transport properties. Here, the effective strategies in enhancing the thermoelectric performance of Cu₂X-based thermoelectric materials are summarized, in which the proper optimization of carrier concentration and minimization of the lattice thermal conductivity are the main focus. Then, the stabilities, mechanical properties, and module assembly of Cu₂X-based thermoelectric materials are investigated. Finally, the future directions for further improving the energy conversion efficiency of Cu₂X-based thermoelectric materials are highlighted.     

Influence of the nature and density of defects on the thermodynamic and electrical properties of semiconductor materials

This paper examines the use of coulometric titration in studies of the nonstoichiometry, defect structure, and thermodynamic properties of semiconductor materials and also for doping of a number of chalcogenides with lead, copper, and germanium. A direct relationship is established between the thermodynamic and electrical properties of the binary compound semiconductors Pb_{1 ± δ}X (X = S, Se, Te), Cu_{2 ± δ}Se, and Cd_{2 ± δ}Se and the ternary spinel semiconductors Cd_{1 ? δ}Cr₂Se₄ and Cu_{1 ± δ}Cr₂S₄ within their homogeneity ranges. The width and symmetry of the homogeneity range of these semiconductor materials are determined using coulometric titration in combination with emf and electrical conductivity measurements. Electrochemically doped nonstoichiometric copper selenide samples are shown to have compositions in the range Cu_1.27Se–Cu_2.73Se.     

Low-Cost Antimony Selenosulfide with Tunable Bandgap for Highly Efficient Solar Cells

About 10% efficient antimony selenosulfide (Sb₂(S,Se)₃) solar cell is realized by using selenourea as a hydrothermal raw material to prepare absorber layers. However, tailoring the bandgap of hydrothermal-based Sb₂(S,Se)₃ film to the ideal bandgap (1.3–1.4 eV) using the selenourea for optimal efficiency is still a challenge. Moreover, the expensive selenourea dramatically increases the fabricating cost. Here, a straightforward one-step hydrothermal method is developed to prepare high-quality Sb₂(S,Se)₃ films using a novel precursor sodium selenosulfate as the selenium source. By tuning the Se/(Se+S) ratio in the hydrothermal precursor solution, a series of high-quality Sb₂(S,Se)₃ films with reduced density of deep defect states and tunable bandgap from 1.31 to 1.71 eV is successfully prepared. Consequently, the best efficiency of 10.05% with a high current density of 26.01 mA cm⁻² is achieved in 1.35 eV Sb₂(S,Se)₃ solar cells. Compared with the traditional method using selenourea, the production cost for the Sb₂(S,Se)₃ devices is reduced by over 80%. In addition, the device exhibits outstanding stability, maintaining more than 93% of the initial power conversion efficiency after 30 days of exposure in the atmosphere without encapsulation. The present work definitely paves a facile and effective way to develop low-cost and high-efficiency chalcogenide-based photovoltaic devices.     

Thin film solar cells based on the ternary compound Cu2SnS3

Alongside with Cu₂ZnSnS₄ and SnS, the p-type semiconductor Cu₂SnS₃ also consists of only Earth abundant and low-cost elements and shows comparable opto-electronic properties, with respect to Cu₂ZnSnS₄ and SnS, making it a promising candidate for photovoltaic applications of the future. In this work, the ternary compound has been produced via the annealing of an electrodeposited precursor in a sulfur and tin sulfide environment. The obtained absorber layer has been structurally investigated by X-ray diffraction and results indicate the crystal structure to be monoclinic. Its optical properties have been measured via photoluminescence, where an asymmetric peak at 0.95 eV has been found. The evaluation of the photoluminescence spectrum indicates a band gap of 0.93 eV which agrees well with the results from the external quantum efficiency. Furthermore, this semiconductor layer has been processed into a photovoltaic device with a power conversion efficiency of 0.54%, a short circuit current of 17.1 mA/cm², an open circuit voltage of 104 mV hampered by a small shunt resistance, a fill factor of 30.4%, and a maximal external quantum efficiency of just less than 60%. In addition, the potential of this Cu₂SnS₃ absorber layer for photovoltaic applications is discussed.     

Predicted formation reactions for the solid-state syntheses of the semiconductor materials Cu2SnX3 and Cu2ZnSnX4 (X = S, Se) starting from binary chalcogenides

The compounds Cu₂ZnSnX₄ and Cu₂SnX₃ (X = S or Se) are promising semiconductor materials for thin film photovoltaic applications. Based on a crystallographic growth model we derive the solid-state reactions for these four compounds starting from the binary sulphides and selenides of copper, zinc and tin. Exploiting these predicted solid-state reactions which are promoted by epitaxial relations between the educts will result in fast formation reactions as preferred in technical processes. The direct formation of Cu₂ZnSnX₄ is concurring with a two-step process in which Cu₂SnX₃ occurs as an intermediate product.     

Reaction pathway for synthesis of Cu<Subscript>2</Subscript>ZnSn(S/Se)<Subscript>4</Subscript> via mechano-chemical route and annealing studies

Reaction pathway for the formation of kesterite Cu₂ZnSn(S/Se)₄ (CZTS/Se) from elemental precursors (Cu, Zn, Sn, S/Se) has been investigated experimentally and is being reported in the current paper. To identify the various stages of reaction pathway and to identify the formation and consumption of secondary phases, X-ray diffraction and Raman spectroscopy tools were employed. A series of experiments for different ballmilling durations (5, 10, 15, 20, 25 and 30 h) were performed and the presence of different phases was recorded for each experiment. In addition to XRD and Raman studies, phase formation has also been confirmed using detailed XPS, TEM and SEM–EDS analysis. In addition, the effect of annealing temperature on composition and band gap of the CZTS/Se material has been discussed. Optical band gap of various samples of CZTS was observed in the range of 1.40–1.60 eV and that of CZTSe was observed in the range of 1.08–1.18 eV. The relatively simple, low cost, easily scalable mechanical alloying process along with understanding of reaction pathway will provide a future scope for bulk production of CZTS/Se absorber material for thin film solar cells.     

Novel Mg- and Ga-doped ZnO/Li-Doped Graphene Oxide Transparent Electrode/Electron-Transporting Layer Combinations for High-Performance Thin-Film Solar Cells (Small 22/2023)

Herein, a novel combination of Mg- and Ga-co-doped ZnO (MGZO)/Li-doped graphene oxide (LGO) transparent electrode (TE)/electron-transporting layer (ETL) has been applied for the first time in Cu₂ZnSn(S,Se)₄ (CZTSSe) thin-film solar cells (TFSCs). MGZO has a wide optical spectrum with high transmittance compared to that with conventional Al-doped ZnO (AZO), enabling additional photon harvesting, and has a low electrical resistance that increases electron collection rate. These excellent optoelectronic properties significantly improved the short-circuit current density and fill factor of the TFSCs. Additionally, the solution-processable alternative LGO ETL prevented plasma-induced damage to chemical bath deposited cadmium sulfide (CdS) buffer, thereby enabling the maintenance of high-quality junctions using a thin CdS buffer layer (≈30 nm). Interfacial engineering with LGO improved the V_oc of the CZTSSe TFSCs from 466 to 502 mV. Furthermore, the tunable work function obtained through Li doping generated a more favorable band offset in CdS/LGO/MGZO interfaces, thereby, improving the electron collection. The MGZO/LGO TE/ETL combination achieved a power conversion efficiency of 10.67%, which is considerably higher than that of conventional AZO/intrinsic ZnO (8.33%).     

Interfacial chemistry control in thin film solar cells based on electrodeposited CuIn(S,Se)2

In this work, we present a study on CuIn(S,Se)₂ absorbers prepared by electrodeposition followed by rapid thermal annealing promising to lower manufacturing cost. However the annealed material contains copper sulpho-selenide of Cu(S_y,Se_1 − y) type which is harmful for the electrical properties of photovoltaic devices. These phases are removed by a cyanide etching. Because of an intrinsic variability of absorber fabrication process, the presented survey is based on statistic approach. We highlighted the influence of a cyanide treatment on surface and bulk compositions. The surface composition follows a distribution according to a Cu(S,Se)-CuIn(S,Se)₂ system and the bulk composition agrees with Cu(S,Se)₂-CuIn₃(S,Se)₅ system. Moreover, surface composition can be modified by adjusting the cyanide concentrations of etching solution without any changes in the bulk one. It ensues that Cu(S,Se) is not only present on the surface but also in the bulk of samples.