Pub Date : 2025-02-12DOI: 10.1016/j.jssc.2025.125254
Alexander Stanislav Gzyl, Paul Kwesi Addo, Beatriz Molero Sanchez
The objective of this work was to develop a new radii scale to better geometrically describe perovskite oxides and aid in high-throughput discovery efforts. We hypothesized that by creating a scale dependent on anion and structure we can increase the performance of geometric descriptors for the perovskite oxide family. We partitioned the bond lengths into radii using radius ratio rules and extended the scale using a ridge regression model to increase its coverage to include more elements, coordination environments and oxidation states. As a proof of concept, we compared our scale to the more universal Shannon radii scale and its use in the Goldschmidt and Tau tolerance factors to classify ABO3 compositions as perovskite or not. Using the Goldschmidt tolerance factor with our scale we were able to classify (0.814 Matthews correlation coefficient, 0.914 wt F-Score, 0.910 Balanced Accuracy) an experimental dataset of 163 ABO3 compositions as perovskite or nonperovskites. Scores of 0.715, 0.867, 0.838 and 0.664, 0.838, 0.790 for Goldschmidt and Tau tolerance factor using the Shannon radii scale were obtained, respectively. The observed marked improvement encouraged us to use our scale to predict a list of feasible ABO3 perovskites. Our simple methodology is not constrained to perovskites only and can easily be used to create new radii scales for other ionic systems and provide better geometric descriptions.
{"title":"A new ionic radii scale derived from perovskite oxides","authors":"Alexander Stanislav Gzyl, Paul Kwesi Addo, Beatriz Molero Sanchez","doi":"10.1016/j.jssc.2025.125254","DOIUrl":"10.1016/j.jssc.2025.125254","url":null,"abstract":"<div><div>The objective of this work was to develop a new radii scale to better geometrically describe perovskite oxides and aid in high-throughput discovery efforts. We hypothesized that by creating a scale dependent on anion and structure we can increase the performance of geometric descriptors for the perovskite oxide family. We partitioned the bond lengths into radii using radius ratio rules and extended the scale using a ridge regression model to increase its coverage to include more elements, coordination environments and oxidation states. As a proof of concept, we compared our scale to the more universal Shannon radii scale and its use in the Goldschmidt and Tau tolerance factors to classify ABO<sub>3</sub> compositions as perovskite or not. Using the Goldschmidt tolerance factor with our scale we were able to classify (0.814 Matthews correlation coefficient, 0.914 wt F-Score, 0.910 Balanced Accuracy) an experimental dataset of 163 ABO<sub>3</sub> compositions as perovskite or nonperovskites. Scores of 0.715, 0.867, 0.838 and 0.664, 0.838, 0.790 for Goldschmidt and Tau tolerance factor using the Shannon radii scale were obtained, respectively. The observed marked improvement encouraged us to use our scale to predict a list of feasible ABO<sub>3</sub> perovskites. Our simple methodology is not constrained to perovskites only and can easily be used to create new radii scales for other ionic systems and provide better geometric descriptions.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"346 ","pages":"Article 125254"},"PeriodicalIF":3.2,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463385","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-12DOI: 10.1016/j.jssc.2025.125255
Radmehr Rahimi Moslehabadi, Farzaneh Rouhani
Converting metal-organic frameworks (MOFs) to quasi-MOFs is a thermally controlled manner for removing the ligands, generating structural defects, and increasing porosity. In the hydrolysis of NaBH4, unsaturated metal centers serve as catalysts to release hydrogen. The Response Surface Methodology (RSM) technique determined the optimal catalytic reaction conditions. The quasi-MOF-801 framework produced at 280 °C (Q801-280) demonstrates the highest turnover frequency in the series, measuring 10500 ml min⁻1 g⁻1 at room temperature in the absence of a base. It has an activation energy of 55.98 kJ mol⁻1. The exceptional catalytic performance of Q801-280 can be attributed to its unique structure, which includes micropores, mesopores, and unsaturated Lewis acid sites. It supports the Langmuir-Hinshelwood model, indicating that both reactants are adsorbed on the catalyst surface. The catalyst dosage and BH4− concentration also significantly influence the reaction.
{"title":"The effective role of open metal sites in defective quasi-MOF-801 as hydrogen generation reactions catalyst","authors":"Radmehr Rahimi Moslehabadi, Farzaneh Rouhani","doi":"10.1016/j.jssc.2025.125255","DOIUrl":"10.1016/j.jssc.2025.125255","url":null,"abstract":"<div><div>Converting metal-organic frameworks (MOFs) to quasi-MOFs is a thermally controlled manner for removing the ligands, generating structural defects, and increasing porosity. In the hydrolysis of NaBH<sub>4</sub>, unsaturated metal centers serve as catalysts to release hydrogen. The Response Surface Methodology (RSM) technique determined the optimal catalytic reaction conditions. The quasi-MOF-801 framework produced at 280 °C (Q801-280) demonstrates the highest turnover frequency in the series, measuring 10500 ml min⁻<sup>1</sup> g⁻<sup>1</sup> at room temperature in the absence of a base. It has an activation energy of 55.98 kJ mol⁻<sup>1</sup>. The exceptional catalytic performance of Q801-280 can be attributed to its unique structure, which includes micropores, mesopores, and unsaturated Lewis acid sites. It supports the Langmuir-Hinshelwood model, indicating that both reactants are adsorbed on the catalyst surface. The catalyst dosage and BH<sub>4</sub><sup>−</sup> concentration also significantly influence the reaction.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"346 ","pages":"Article 125255"},"PeriodicalIF":3.2,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143420846","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-11DOI: 10.1016/j.jssc.2025.125249
Yihang Song , Fan Li , Guang-Hui Chen , Jiao Wu , Xiaofeng Yi , Jian Zhang
Indium-oxo clusters (InOCs) represent a relatively underexplored class within metal-oxo cluster chemistry, with limited research on their core structures, functional modifications, and performance characteristics. In this study, we introduce eight distinct aliphatic and aromatic carboxylate ligands into bixbyite-like In₁₂-oxo clusters (InOC-7 to InOC-14), utilizing the labile substitution sites on the robust In₁₂ skeleton. This ligand incorporation enhances electronic delocalization, narrows the bandgap, and promotes extensive intermolecular π-π interactions. Building upon these structural features and heavy metal effects, the optical limiting (OL) properties of these clusters were systematically investigated. The clusters exhibit characteristic reverse saturable absorption (RSA) behavior, with InOC-8 and InOC-12 demonstrating particularly outstanding OL performance. The excellent optical limiting properties of these crystalline InOCs make them highly relevant to the Journal of Solid State Chemistry, which focuses on the properties and applications of solid materials. This study highlights the scientific value of functionalizing InOCs through labile sites, enriching their structural chemistry, fine-tuning their optical limiting properties, and opening new avenues for potential applications.
{"title":"Design and functionalization of bixbyite-like In12-Oxo clusters for enhanced optical limiting","authors":"Yihang Song , Fan Li , Guang-Hui Chen , Jiao Wu , Xiaofeng Yi , Jian Zhang","doi":"10.1016/j.jssc.2025.125249","DOIUrl":"10.1016/j.jssc.2025.125249","url":null,"abstract":"<div><div>Indium-oxo clusters (InOCs) represent a relatively underexplored class within metal-oxo cluster chemistry, with limited research on their core structures, functional modifications, and performance characteristics. In this study, we introduce eight distinct aliphatic and aromatic carboxylate ligands into bixbyite-like In₁₂-oxo clusters (<strong>InOC-7</strong> to <strong>InOC-14</strong>), utilizing the labile substitution sites on the robust In₁₂ skeleton. This ligand incorporation enhances electronic delocalization, narrows the bandgap, and promotes extensive intermolecular π-π interactions. Building upon these structural features and heavy metal effects, the optical limiting (OL) properties of these clusters were systematically investigated. The clusters exhibit characteristic reverse saturable absorption (RSA) behavior, with <strong>InOC-8</strong> and <strong>InOC-12</strong> demonstrating particularly outstanding OL performance. The excellent optical limiting properties of these crystalline InOCs make them highly relevant to the <em>Journal of Solid State Chemistry</em>, which focuses on the properties and applications of solid materials. This study highlights the scientific value of functionalizing InOCs through labile sites, enriching their structural chemistry, fine-tuning their optical limiting properties, and opening new avenues for potential applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"346 ","pages":"Article 125249"},"PeriodicalIF":3.2,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143421009","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-10DOI: 10.1016/j.jssc.2025.125251
Jiafeng Fan , Zhilong Song , Baoting Tan , Haibo Wang , Zhigang Chen , Hui Xu , Jia Yan
Photocatalytic water splitting for hydrogen production is a promising solution to address the global energy crisis, but its development is hampered by low catalyst efficiency. This study introduces an approach to improve the photocatalytic performance of BaTiO3 (BTO) by engineering its crystalline phase through simple thermal annealing. The optimized BaTiO3 composition, with a 43 % cubic (C-BTO) and 57 % tetragonal (T-BTO) phase ratio, achieved a remarkable hydrogen evolution rate of 2245.1 μmol g⁻1 h⁻1 with long-term stability over 25 h, representing a ten-fold enhancement over pristine BTO. Experimental results indicate that this crystal phase engineering enhances photogenerated electron-hole separation and migration, significantly improving photocatalytic efficiency. This work offers an effective strategy for enhancing single photocatalyst performance, paving the way for more efficient hydrogen production.
{"title":"Enhanced hydrogen production via piezo-photocatalytic water splitting using BaTiO3 crystal phase engineering","authors":"Jiafeng Fan , Zhilong Song , Baoting Tan , Haibo Wang , Zhigang Chen , Hui Xu , Jia Yan","doi":"10.1016/j.jssc.2025.125251","DOIUrl":"10.1016/j.jssc.2025.125251","url":null,"abstract":"<div><div>Photocatalytic water splitting for hydrogen production is a promising solution to address the global energy crisis, but its development is hampered by low catalyst efficiency. This study introduces an approach to improve the photocatalytic performance of BaTiO<sub>3</sub> (BTO) by engineering its crystalline phase through simple thermal annealing. The optimized BaTiO<sub>3</sub> composition, with a 43 % cubic (C-BTO) and 57 % tetragonal (T-BTO) phase ratio, achieved a remarkable hydrogen evolution rate of 2245.1 μmol g⁻<sup>1</sup> h⁻<sup>1</sup> with long-term stability over 25 h, representing a ten-fold enhancement over pristine BTO. Experimental results indicate that this crystal phase engineering enhances photogenerated electron-hole separation and migration, significantly improving photocatalytic efficiency. This work offers an effective strategy for enhancing single photocatalyst performance, paving the way for more efficient hydrogen production.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125251"},"PeriodicalIF":3.2,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143388457","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-10DOI: 10.1016/j.jssc.2025.125250
Muhammad Saqib , Muhammad Sagir , Sairah , Mudassir Hussain Tahir , Hosam O. Elansary , Muqadas Javed
Conventional computational methods have long history in designing the organic compounds, however, these approaches generally require significantly higher computational cost. To overcome these challenges, machine learning is applied as a powerful approach to screen and design high performance materials in a rapid and computationally cost-effective manner. Reorganization energy (Re) is predicted using machine learning. Mordred software is used to calculate molecular descriptors. Different algorithms such as random forest regressor, gradient boosting regressor, K-neighbors regressor, and extra tree regressor models are used to train the machine learning models. Random forest regressor model reveals higher predictive capability (R2 = 0.73). Automatic method is used to design new compounds. 30 potential candidates are identified and their synthetic ability score are predicted. Clustering is used for similarity analysis. Interestingly, synthetic accessibility score reveals that these compounds can be synthesize with ease. The proposed approach holds immense potential for screening and designing high performance hole transport materials for perovskite solar cells in a cost-effective and rapid manner.
{"title":"Data-assisted approach for optimal designing of small molecules for perovskite solar cells","authors":"Muhammad Saqib , Muhammad Sagir , Sairah , Mudassir Hussain Tahir , Hosam O. Elansary , Muqadas Javed","doi":"10.1016/j.jssc.2025.125250","DOIUrl":"10.1016/j.jssc.2025.125250","url":null,"abstract":"<div><div>Conventional computational methods have long history in designing the organic compounds, however, these approaches generally require significantly higher computational cost. To overcome these challenges, machine learning is applied as a powerful approach to screen and design high performance materials in a rapid and computationally cost-effective manner. Reorganization energy (Re) is predicted using machine learning. Mordred software is used to calculate molecular descriptors. Different algorithms such as random forest regressor, gradient boosting regressor, K-neighbors regressor, and extra tree regressor models are used to train the machine learning models. Random forest regressor model reveals higher predictive capability (R<sup>2</sup> = 0.73). Automatic method is used to design new compounds. 30 potential candidates are identified and their synthetic ability score are predicted. Clustering is used for similarity analysis. Interestingly, synthetic accessibility score reveals that these compounds can be synthesize with ease. The proposed approach holds immense potential for screening and designing high performance hole transport materials for perovskite solar cells in a cost-effective and rapid manner.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125250"},"PeriodicalIF":3.2,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143403026","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-08DOI: 10.1016/j.jssc.2025.125247
Qiusheng Shi , Miaomiao Wang
The electronic, optical and mechanical properties of doping with O, S, Se and point defects in p-BCN are investigated. The results show that X@N and VB have the smallest Ef, indicating that N and B site are the most stable doping and defect site. O@B, O@N, S@B, S@N, Se@B, Se@N, VB, and VN produce magnetism. VB transforms from semiconductor to semimetal. The light absorption performance of X@N, VN and VB enhance in the infrared and visible light regions. Mechanical properties show that O@N and VN are mechanically anisotropic, and the Young's modulus and Poisson's ratio of O@N decrease compared to p-BCN, indicating that O@N is less hard and has a strong resistance to shear. The stress-strain curves show that the ideal strengths of the doping and defective systems are all 22 %, and the maximum stresses that can be withstood by O@N are 21.32 Gpa, and VN are 20.70 Gpa.
{"title":"Doping and point defects regulating the photoelectric and mechanical properties of pentagonal-BCN","authors":"Qiusheng Shi , Miaomiao Wang","doi":"10.1016/j.jssc.2025.125247","DOIUrl":"10.1016/j.jssc.2025.125247","url":null,"abstract":"<div><div>The electronic, optical and mechanical properties of doping with O, S, Se and point defects in p-BCN are investigated. The results show that X@N and V<sub>B</sub> have the smallest <em>E</em><sub><em>f</em></sub>, indicating that N and B site are the most stable doping and defect site. O@B, O@N, S@B, S@N, Se@B, Se@N, V<sub>B</sub>, and V<sub>N</sub> produce magnetism. V<sub>B</sub> transforms from semiconductor to semimetal. The light absorption performance of X@N, V<sub>N</sub> and V<sub>B</sub> enhance in the infrared and visible light regions. Mechanical properties show that O@N and V<sub>N</sub> are mechanically anisotropic, and the Young's modulus and Poisson's ratio of O@N decrease compared to p-BCN, indicating that O@N is less hard and has a strong resistance to shear. The stress-strain curves show that the ideal strengths of the doping and defective systems are all 22 %, and the maximum stresses that can be withstood by O@N are 21.32 Gpa, and V<sub>N</sub> are 20.70 Gpa.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125247"},"PeriodicalIF":3.2,"publicationDate":"2025-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143388459","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-07DOI: 10.1016/j.jssc.2025.125245
Dmitry Vrublevskiy, Loïc Robert, Balaranjan Selvaratnam, Arthur Mar
The first-order Ruddlesden-Popper (RP) phases A2BX4 adopt three structure types that differ in coordination geometry around the B site: T-type (octahedral) and T′-type (square planar), which are most common, and T∗-type (square pyramidal), which is rare. Especially for RP cuprates A2CuO4–δ, it is not intuitively obvious which structure is preferred depending on the combination of cations occupying the A site. Machine learning models were developed that can separate the T- and T′-type structures among these cuprates with an accuracy of >90 %, provided that the T∗-type does not form and the phases can be synthesized. Based on these models, structures were predicted for solid solutions (A′, A″, A‴)2CuO4–δ containing a complex mixture of A cations (A′, A″, A‴ = Sr, La, Gd, Ho, In, Bi). The predictions were tested by targeting various members of these solid solutions through high-temperature reactions followed by slow cooling. Three samples contained pure RP phases which were confirmed to adopt the predicted structures: T-type for Sr0.4La1.5Ho0.1CuO3.8, and T′-type for Gd1.7Ho0.2Bi0.1CuO4 and La0.4Gd1.2Ho0.4CuO4. Five other samples were mixtures that contained RP phases whose structures (when not T∗-type) were correctly identified by a slightly better performing model based on extra randomized trees classifier.
{"title":"How to separate two Ts in a pod: Classifying T- and T′-type Ruddlesden-Popper cuprates by machine learning","authors":"Dmitry Vrublevskiy, Loïc Robert, Balaranjan Selvaratnam, Arthur Mar","doi":"10.1016/j.jssc.2025.125245","DOIUrl":"10.1016/j.jssc.2025.125245","url":null,"abstract":"<div><div>The first-order Ruddlesden-Popper (RP) phases <em>A</em><sub>2</sub><em>BX</em><sub>4</sub> adopt three structure types that differ in coordination geometry around the <em>B</em> site: T-type (octahedral) and T′-type (square planar), which are most common, and T∗-type (square pyramidal), which is rare. Especially for RP cuprates <em>A</em><sub>2</sub>CuO<sub>4–δ</sub>, it is not intuitively obvious which structure is preferred depending on the combination of cations occupying the <em>A</em> site. Machine learning models were developed that can separate the T- and T′-type structures among these cuprates with an accuracy of >90 %, provided that the T∗-type does not form and the phases can be synthesized. Based on these models, structures were predicted for solid solutions (<em>A</em>′, <em>A</em>″, <em>A</em>‴)<sub>2</sub>CuO<sub>4–δ</sub> containing a complex mixture of <em>A</em> cations (<em>A</em>′, <em>A</em>″, <em>A</em>‴ = Sr, La, Gd, Ho, In, Bi). The predictions were tested by targeting various members of these solid solutions through high-temperature reactions followed by slow cooling. Three samples contained pure RP phases which were confirmed to adopt the predicted structures: T-type for Sr<sub>0.4</sub>La<sub>1.5</sub>Ho<sub>0.1</sub>CuO<sub>3.8</sub>, and T′-type for Gd<sub>1.7</sub>Ho<sub>0.2</sub>Bi<sub>0.1</sub>CuO<sub>4</sub> and La<sub>0.4</sub>Gd<sub>1.2</sub>Ho<sub>0.4</sub>CuO<sub>4</sub>. Five other samples were mixtures that contained RP phases whose structures (when not T∗-type) were correctly identified by a slightly better performing model based on extra randomized trees classifier.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125245"},"PeriodicalIF":3.2,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143377095","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The defect properties of NaF-deposited Cu2Sn1–xGexS3 (CTGS) thin films, which are expected to improve the conversion efficiency of CTGS solar cells, were investigated by photoluminescence (PL). The PL spectra from a 0 mg of NaF deposited CTGS thin film were observed to have four peaks: three of donor-acceptor pair (DAP) recombination luminescence and one of the excitons (EX) or near the band edge (NBE) luminescence. On the other hand, 10 mg of NaF-deposited CTGS thin film exhibited PL spectra with three peaks, including two from DAP recombination luminescence and one from EX or NBE luminescence. One peak in the Na-undoped CTGS thin film exhibited an activation energy of 39.5 ± 21.2 meV, indicating deeper level defects compared to the energy levels of approximately 26 meV at room temperature (RT), which serves as a capture center for minority carriers at RT. In contrast, the Na-doped CTGS thin film exhibited shallower defect levels of 8.2 ± 3.9 meV lower than the energy levels at RT. These results suggest that Na doping generated new defects that served as carrier sources. Consequently, this study suggests that Na element incorporation holds promise for improving the electrical properties of CTGS solar cells. Based on the above findings, we believe that Na-doped CTGS solar cells represent a promising alternative to existing solar cell materials and have, the potential to enhance low conversion efficiency.
{"title":"Investigation of intrinsic and extrinsic defects in Na-doped Cu2Sn1-xGexS3 thin films by photoluminescence","authors":"Ryodai Ichihara , Takeshi Tasaki , Ayaka Kanai , Hideaki Araki , Kunihiko Tanaka","doi":"10.1016/j.jssc.2025.125244","DOIUrl":"10.1016/j.jssc.2025.125244","url":null,"abstract":"<div><div>The defect properties of NaF-deposited Cu<sub>2</sub>Sn<sub>1–<em>x</em></sub>Ge<sub><em>x</em></sub>S<sub>3</sub> (CTGS) thin films, which are expected to improve the conversion efficiency of CTGS solar cells, were investigated by photoluminescence (PL). The PL spectra from a 0 mg of NaF deposited CTGS thin film were observed to have four peaks: three of donor-acceptor pair (DAP) recombination luminescence and one of the excitons (EX) or near the band edge (NBE) luminescence. On the other hand, 10 mg of NaF-deposited CTGS thin film exhibited PL spectra with three peaks, including two from DAP recombination luminescence and one from EX or NBE luminescence. One peak in the Na-undoped CTGS thin film exhibited an activation energy of 39.5 ± 21.2 meV, indicating deeper level defects compared to the energy levels of approximately 26 meV at room temperature (RT), which serves as a capture center for minority carriers at RT. In contrast, the Na-doped CTGS thin film exhibited shallower defect levels of 8.2 ± 3.9 meV lower than the energy levels at RT. These results suggest that Na doping generated new defects that served as carrier sources. Consequently, this study suggests that Na element incorporation holds promise for improving the electrical properties of CTGS solar cells. Based on the above findings, we believe that Na-doped CTGS solar cells represent a promising alternative to existing solar cell materials and have, the potential to enhance low conversion efficiency.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125244"},"PeriodicalIF":3.2,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143388458","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-07DOI: 10.1016/j.jssc.2025.125248
Chang Xu , Qiang Li , Pengju Dong , Haibin Xu , Dezhi Zhang , Kangzhen Xu
Silver acetylide-silver nitrate (SASN) is a promising light-initiated explosive for the synchronized short-pulse loading which can simulate the blow-off impulse loading of intense pulsed X-ray, but high electrostatic discharge (ESD) and mechanical sensitivities limit its broad application. To address this issue, novel SASN/g-C3N4 composites were synthesized using a facile self-assembly method, in which graphitic carbon nitride (g-C3N4) nanosheets were uniformly adsorbed on the surface of SASN by strong electrostatic interaction, and the content of g-C3N4 was precisely controlled form 0.5 wt% to 1.5 wt%. The thermal decomposition peak temperature (223.1 °C), impact sensitivity (1.86 J) and friction sensitivity (108 N) of SASN/(1 %)g-C3N4 composite were all improved greatly, compared to that of pure SASN, and the ESD threshold energy of SASN/g-C3N4 composite increased from 0.36 to 0.56 mJ. Importantly, the small addition of g-C3N4 does not affect the photosensitivity and detonation performances of SASN. This work offers a viable approach to improve the safety of SASN explosives while maintaining its inherent performances.
{"title":"Design and fabrication of high-energy SASN/g-C3N4 composites for enhanced electrostatic safety and thermal stability","authors":"Chang Xu , Qiang Li , Pengju Dong , Haibin Xu , Dezhi Zhang , Kangzhen Xu","doi":"10.1016/j.jssc.2025.125248","DOIUrl":"10.1016/j.jssc.2025.125248","url":null,"abstract":"<div><div>Silver acetylide-silver nitrate (SASN) is a promising light-initiated explosive for the synchronized short-pulse loading which can simulate the blow-off impulse loading of intense pulsed X-ray, but high electrostatic discharge (ESD) and mechanical sensitivities limit its broad application. To address this issue, novel SASN/g-C<sub>3</sub>N<sub>4</sub> composites were synthesized using a facile self-assembly method, in which graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) nanosheets were uniformly adsorbed on the surface of SASN by strong electrostatic interaction, and the content of g-C<sub>3</sub>N<sub>4</sub> was precisely controlled form 0.5 wt% to 1.5 wt%. The thermal decomposition peak temperature (223.1 °C), impact sensitivity (1.86 J) and friction sensitivity (108 <em>N</em>) of SASN/(1 %)g-C<sub>3</sub>N<sub>4</sub> composite were all improved greatly, compared to that of pure SASN, and the ESD threshold energy of SASN/g-C<sub>3</sub>N<sub>4</sub> composite increased from 0.36 to 0.56 mJ. Importantly, the small addition of g-C<sub>3</sub>N<sub>4</sub> does not affect the photosensitivity and detonation performances of SASN. This work offers a viable approach to improve the safety of SASN explosives while maintaining its inherent performances.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125248"},"PeriodicalIF":3.2,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143377723","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-07DOI: 10.1016/j.jssc.2025.125246
Muhammad Tariq Aziz , Waqas Amber Gill , Muhammad Kaleem Khosa , Saba Jamil , Songnan Li , Saad M. Alshehri , Muhammad Ramzan Saeed Ashraf Janjua
In this study, we investigate the quadrupole moment of ammonia (NH3) using the coupled cluster method with single, double, and perturbative triple excitations [CCSD(T)] and the quadruple-zeta valence plus polarization (QZVPP) basis set. The calculated values for the quadrupole moment, polarizability, and entropy of NH3 (−2.44 a.u, 2.113 Å3, 192.69 JK−1mol−1) are in excellent agreement with the corresponding experimental values (−2.45 a.u, 2.109 Å3, 192.77 JK−1mol−1) respectively. The vibrational mode of frequencies of ammonia is close to calculated values. Additionally, we explore the application of ILJP parameters (ILJPP) to determine the SVC B of NH3. By employing the ILJP limitations, we obtain calculated values of B that exhibit a remarkable agreement with the experimental values. This result highlights the accurateness and reliability of the ILJP in describing the intermolecular interactions of NH3 dimer. Our findings demonstrate the capability of the CCSD(T)/QZVPP method to accurately determine the quadrupole moment of NH3, validating its agreement with experimental values. Furthermore, the successful implementation of ILJPP to calculate the SVC emphasizes the effectiveness of this approach in capturing the thermodynamic properties of NH3. This research contributes to a deeper understanding of NH3's molecular properties and facilitates its application in various scientific and technological domains. In gas-phase chemistry, knowledge of ammonia-ammonia interactions is essential for predicting reaction rates, exploring molecular dynamics, and understanding gas-phase equilibria involving ammonia. Furthermore, in atmospheric science, studying NH3–NH3 interactions can contribute to our understanding of ammonia's role in air pollution, aerosol formation, and acid deposition.
{"title":"Exploring NH3–NH3 interactions: A comparative study of force field and CCSD(T)/QZVPP calculations for thermodynamic analysis and second virial coefficient in gas-phase chemistry and atmospheric science","authors":"Muhammad Tariq Aziz , Waqas Amber Gill , Muhammad Kaleem Khosa , Saba Jamil , Songnan Li , Saad M. Alshehri , Muhammad Ramzan Saeed Ashraf Janjua","doi":"10.1016/j.jssc.2025.125246","DOIUrl":"10.1016/j.jssc.2025.125246","url":null,"abstract":"<div><div>In this study, we investigate the quadrupole moment of ammonia (NH<sub>3</sub>) using the coupled cluster method with single, double, and perturbative triple excitations [CCSD(T)] and the quadruple-zeta valence plus polarization (QZVPP) basis set. The calculated values for the quadrupole moment, polarizability, and entropy of NH<sub>3</sub> (−2.44 a.u, 2.113 Å<sup>3</sup>, 192.69 JK<sup>−1</sup>mol<sup>−1</sup>) are in excellent agreement with the corresponding experimental values (−2.45 a.u, 2.109 Å<sup>3</sup>, 192.77 JK<sup>−1</sup>mol<sup>−1</sup>) respectively. The vibrational mode of frequencies of ammonia is close to calculated values. Additionally, we explore the application of ILJP parameters (ILJPP) to determine the SVC B of NH<sub>3</sub>. By employing the ILJP limitations, we obtain calculated values of B that exhibit a remarkable agreement with the experimental values. This result highlights the accurateness and reliability of the ILJP in describing the intermolecular interactions of NH<sub>3</sub> dimer. Our findings demonstrate the capability of the CCSD(T)/QZVPP method to accurately determine the quadrupole moment of NH<sub>3</sub>, validating its agreement with experimental values. Furthermore, the successful implementation of ILJPP to calculate the SVC emphasizes the effectiveness of this approach in capturing the thermodynamic properties of NH<sub>3</sub>. This research contributes to a deeper understanding of NH<sub>3</sub>'s molecular properties and facilitates its application in various scientific and technological domains. In gas-phase chemistry, knowledge of ammonia-ammonia interactions is essential for predicting reaction rates, exploring molecular dynamics, and understanding gas-phase equilibria involving ammonia. Furthermore, in atmospheric science, studying NH<sub>3</sub>–NH<sub>3</sub> interactions can contribute to our understanding of ammonia's role in air pollution, aerosol formation, and acid deposition.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"345 ","pages":"Article 125246"},"PeriodicalIF":3.2,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143388391","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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