Journal of Solid State Chemistry最新文献

{"title":"Polar solvent-induced self-assembly of organic cocrystal helixes based on achiral molecules","authors":"Yuhao Ye ,&nbsp;Lei Yao ,&nbsp;Shulei Chen ,&nbsp;Guan Wang ,&nbsp;Yongyi Zhang ,&nbsp;Tao Jin ,&nbsp;Jing Zhang ,&nbsp;Jing Che","doi":"10.1016/j.jssc.2025.125602","DOIUrl":"10.1016/j.jssc.2025.125602","url":null,"abstract":"<div><div>Precise control over chirality in supramolecular structures has attracted significant attention in biology and optoelectronics. Herein, we report a novel helical cocrystal of organic donor−acceptor complex based on two achiral components. Depending on the solvent polarity, two red emissive cocrystals were self-assembled with different stacking manners. Notably, although the inversion symmetry of crystal lattice, strong solvent-solute interactions between polar crystal planes and acetonitrile governs the growth dynamics, to generate helical architectures. Furthermore, chiral additive tailoring was successfully established to regulate the supramolecular helix handedness which showed good circularly polarized luminescence performance, with an asymmetry factor (<em>g</em>_lum) of 0.005. This work demonstrates new pathway for chirality growth and tuning in circularly polarized optoelectronic devices and chiral recognition systems.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"352 ","pages":"Article 125602"},"PeriodicalIF":3.5,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144893438","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}

{"title":"One-step liquid metal interfacial engineering strategy to synthesize hierarchical porous carbon materials for the cycloaddition of CO2 with epoxides","authors":"Yang Zhao,&nbsp;Pengyu Tang,&nbsp;Wenting Zhang,&nbsp;Duihai Tang,&nbsp;Shigang Xin,&nbsp;Zhen Zhao","doi":"10.1016/j.jssc.2025.125600","DOIUrl":"10.1016/j.jssc.2025.125600","url":null,"abstract":"<div><div>This study develops a one-step liquid metal interfacial engineering strategy for synthesizing hierarchical porous carbon materials. Innovatively integrating porous structure construction and carbon-chlorine (C–Cl) bond introduction into a single process, this strategy overcomes the limitations of traditional methods that require separate template synthesis and post-functionalization. In this strategy, polystyrene (PS) nanospheres are introduced as pore-forming agents. Through the synergistic interaction between sodium-potassium (NaK) alloy (liquid metal) and carbon tetrachloride (CCl₄) at room temperature, hierarchical porous structures (mesopores and macropores) with abundant surface C–Cl bonds are successfully prepared. As active precursors for subsequent functionalization, C–Cl bonds can efficiently graft imidazole and bromoethyl groups. The resulting functionalized carbon materials exhibit excellent catalytic performance in the cycloaddition reaction of carbon dioxide (CO₂) with epoxides (e.g., 99.1 % conversion and 99.3 % selectivity for styrene oxide), demonstrating the practical value of this synthesis method. This one-step strategy features room-temperature operation, no need for complex equipment, and simultaneous realization of structural regulation and functional group introduction, providing a new approach for the design and preparation of high-performance functionalized carbon materials.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"352 ","pages":"Article 125600"},"PeriodicalIF":3.5,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144893434","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}

{"title":"Insights into the phase stability window, phase transformation behavior, and anisotropic thermal expansion of rhombohedral bismuth oxide","authors":"Mathias A. Kiefer ,&nbsp;Caren Billing ,&nbsp;Daniel Olds ,&nbsp;David G. Billing","doi":"10.1016/j.jssc.2025.125597","DOIUrl":"10.1016/j.jssc.2025.125597","url":null,"abstract":"<div><div>Rhombohedral bismuth oxide has emerged as a promising SOFC electrolyte material, particularly at low-to-intermediate temperatures. The stability window of this phase was explored using a co-doped system, using yttrium and lanthanum or aluminum, over 7.5–25 % total dopant content and 0.907–1.154 Å weighted average dopant cationic radius. The phase transformation behavior of rhombohedral-rich phase mixtures was also investigated <em>in situ</em> from 360 to 656 °C to assess the effects of minor impurity phases and thermal evolution pathways. Our results reveal that low-dopant, rhombohedral-rich compositions exhibit poor structural stability upon heating. Anisotropic thermal expansion behavior was observed over 450–656 °C, serving as a sensitive indicator of sequential phase changes, including the rhombohedral β₂-to-β₁ transition (∼450 °C), monoclinic phase formation, and delayed or incomplete formation of the cubic phase (∼ 550 °C). These multiple unfavorable phase transitions compromise the mechanical robustness required for SOFC operation. This study underscores the need for compositional tuning to balance ionic conductivity with thermal phase stability in rhombohedral Bi₂O₃-based systems.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"352 ","pages":"Article 125597"},"PeriodicalIF":3.5,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144911688","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}

{"title":"Two novel photochromic complexes based on viologen for amine sensing","authors":"Xinxin Liu,&nbsp;Shoujia Shi,&nbsp;Boyu Shan,&nbsp;Jia Yu,&nbsp;Jinghan Zhang,&nbsp;Shuqi Zhang,&nbsp;Baili Zhu,&nbsp;Changbin Shao,&nbsp;Minghui Zuo,&nbsp;Shuxin Cui","doi":"10.1016/j.jssc.2025.125581","DOIUrl":"10.1016/j.jssc.2025.125581","url":null,"abstract":"<div><div>Multifunctional viologen-based complexes with photochromic and photoluminescent properties have always been an actively studied subject owing to their remarkable characteristics. Based on 1,2,4,5-benzenetetracarboxylic acid (H₄BTEC), ZnSO₄·7H₂O or 3CdSO₄·8H₂O, and a novel viologen ligand, 1,1'-[1,4-phenylenebis(methylene)]-bis(4,4′-bipyridyl) dichloride (pbpy·2Cl), we have synthesized two viologen-based complexes, named {[Zn(pbpy)_0.5(BTEC)_0.75]·2H₂O}_n (<strong>1</strong>) and {[Cd₃(pbpy)(BTEC)₂(H₂O)₂]·H₂O}_n (<strong>2</strong>), under solvothermal conditions. Complexes <strong>1</strong> and <strong>2</strong> not only show reversible photochromic properties, but also possess photo-controlled luminescence properties. The discoloration mechanism of complexes <strong>1</strong> and <strong>2</strong> was investigated via Time-Dependent Density Functional Theory (TDDFT). Notably, because of the electron-deficient capability of pbpy, complex <strong>1</strong> shows significant visual color change after being exposed to NH₃·H₂O, Aniline and <em>o</em>-Toluidine. At the same time, complex <strong>2</strong> exhibits a distinct color change when exposed to ammonia vapor. Both complexes <strong>1</strong> and <strong>2</strong> exhibited low limits of detection (LOD) for NH₃·H₂O, 8.52 × 10⁻⁶ M⁻¹ and 15.56 × 10⁻⁶ M⁻¹, respectively. The binuclear zinc clusters are bridged through ligands to construct a 2D honeycomb structure in complex <strong>1</strong>, while the trinuclear cadmium clusters are connected to form a 3D network structure in complex <strong>2</strong>. Complex <strong>1</strong> has a faster discoloration rate and a lower detection limit concentration for NH₃·H₂O.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"352 ","pages":"Article 125581"},"PeriodicalIF":3.5,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144893436","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}

{"title":"Optimizing ferroelectric, dielectric, magnetic and strong magnetoelectric coupling through strain engineering in (0–3) types multiferroic composites","authors":"M. Arshad ,&nbsp;Pravin Varade ,&nbsp;Kharanshu Bhojak ,&nbsp;Wasi khan ,&nbsp;Ajit R. Kulkarni","doi":"10.1016/j.jssc.2025.125590","DOIUrl":"10.1016/j.jssc.2025.125590","url":null,"abstract":"<div><div>In the present study, the eco-friendly magnetoelectric multiferroic (1-x) BaTiO₃-(x) CoFe₂O₄ (0–3) type composites (x = 0.0, 0.2, 0.4, 0.5, 0.6, 0.8, and 1.0) were synthesized using the solid-state reaction method. The average crystallite size and strain induced in the synthesized composites samples were calculated using the Williamson-Hall approach. The Rietveld refinement analysis confirms both phases retain their parent structure. BaTiO₃ phase crystallizes into the tetragonal with P4mm space group, while the CoFe₂O₄ phase exists in cubic with Fd-3m space group. The heterogeneous valence state of Ti³⁺/Ti⁴⁺, Fe²⁺/Fe³⁺ ions, and enhancement in oxygen vacancies stoichiometry ratio were confirmed through the X-ray photoelectron spectroscopy. The distribution of closely packed CoFe₂O₄ grains in the BaTiO₃ matrix was amply demonstrated by the microstructural results. The ferroelectricity of composites drops down due to fluctuations in the state of Fe²⁺/Fe³⁺ ions that enhance the leakage current of the composite sample. The observed dielectric relaxation phenomena in the composites are explained by the electron hopping mechanism, which also accounts for the higher dielectric constant (ε′). With an increase in the CoFe₂O₄ weight percentage, the magnetic moment is found to be 8 emu/g for 80 % of CFO based composites. For 50 and 60 mol % CFO, the highest observed values of α_ME are 22.63 mV/cm. Oe and 17.56. mV/cm. Oe respectively. These composites may be investigated for magnetic sensor and ME memory device applications due to the strong ME interaction and significant value of self-biased α_ME.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"352 ","pages":"Article 125590"},"PeriodicalIF":3.5,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144885855","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}

{"title":"Electrical properties and high-temperature stability of high-entropy pyrochlore ceramics (La0.2Nd0.2Sm0.2Gd0.2M0.2)2Sn2O7 (M = Eu, Dy, Ho, or Yb) for negative temperature coefficient thermistor applications","authors":"Xiaohui Li ,&nbsp;Pengjun Zhao ,&nbsp;Wenwen Kong ,&nbsp;Aimin Chang ,&nbsp;Bo Gao","doi":"10.1016/j.jssc.2025.125582","DOIUrl":"10.1016/j.jssc.2025.125582","url":null,"abstract":"<div><div>Understanding electrical transport mechanisms and key thermal stability factors in high-temperature thermosensitive ceramics is essential for developing highly stable temperature sensors under extreme thermal conditions. This study develops the high-entropy pyrochlore stannates (La_0.2Nd_0.2Sm_0.2Gd_0.2M_0.2)₂Sn₂O₇ (M = Eu, Dy, Ho, or Yb) via solid-state synthesis, demonstrating exceptional negative temperature coefficient (NTC) behavior across 300–1400 °C. Hall measurements and X-ray photoelectron spectroscopy (XPS) analyses reveal a dual redox mechanism for these ceramics: partial reduction of Sn⁴⁺ to Sn²⁺ at B-sites and rare-earth ions (Sm/Eu/Yb) to RE²⁺ at A-sites, generating hole-dominated p-type conductivity. The materials exhibit outstanding thermal stability, with resistance drift below 1.96 % after 500 h at 1400 °C, attributed to the entropy-stabilized structure that effectively suppresses lattice disorder transformation. Aging studies further demonstrate that high oxygen vacancy concentrations lead to resistance drifts, as oxygen filling at elevated temperatures oxidizes RE²⁺ to RE³⁺, reducing charge carriers and ultimately increasing resistivity. This study elucidates for the first time the hole-dominated conduction mechanism arising from dual-site cation valence changes (Sn/RE) and the regulation effect of oxygen vacancies on high-temperature stability, which provides an important theoretical basis and material design strategy for the development of the next-generation high-temperature NTC sensors with excellent stability.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"352 ","pages":"Article 125582"},"PeriodicalIF":3.5,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144893435","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}

{"title":"Tunable luminescent color and anti-thermal quenching of Dy3+ or/and Eu3+ doping in Sc2(WO4)3 phosphors for white light-emitting diode applications","authors":"Jiating Li ,&nbsp;Yiqi Yu ,&nbsp;Jia Liao ,&nbsp;Liming Zhang ,&nbsp;Xian Xiao ,&nbsp;Honghui Xiao ,&nbsp;Jinsheng Liao","doi":"10.1016/j.jssc.2025.125599","DOIUrl":"10.1016/j.jssc.2025.125599","url":null,"abstract":"<div><div>To address issues such as poor thermal stability and tunable luminescent colors of conventional phosphors for solid-state lighting applications, a series of Sc₂(WO₄)₃: Ln³⁺ (Ln = Dy or/and Eu) phosphors were synthesized via a high-temperature solid-state method, and their luminescent behaviors were investigated in detail. Under 350 nm excitation, the Sc₂(WO₄)₃:xDy³⁺ phosphor exhibits blue (487 nm), yellow (576 nm) and red (666 nm) emission peaks, and the optimal doping concentration of Dy³⁺ is 4 %. In the Sc₂(WO₄)₃:4 %Dy³⁺/yEu³⁺ phosphor, energy transfer is revealed through the analysis of the spectral overlap of Dy³⁺ and Eu³⁺, thereby achieving tunable luminescence from orange to red. Combined with the results of FT-IR and TG analyses, the Sc₂(WO₄)₃:4 %Dy³⁺/2 %Eu³⁺ phosphor exhibits non-hygroscopic properties. Furthermore, the Sc₂(WO₄)₃:4 %Dy³⁺ and Sc₂(WO₄)₃:4 %Dy³⁺/2 %Eu³⁺ phosphors exhibit excellent thermal stability (At 423 K, the intensity of the orange (576 nm) and red (612 nm) light both exceed 95 % of that of room temperature). In addition, the anti-thermal quenching mechanism is systematically investigated through temperature-dependent PL dynamics. This is attributed to combined action for the stabilized energy transfer process from Dy³⁺ to Eu³⁺ and the suppression of non-radiative transitions with the increase of temperature. These findings demonstrate that Sc₂(WO₄)₃:Dy³⁺/Eu³⁺ phosphors with excellent thermal stability and tunable luminescence can be used as potential applications in WLED fields.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"352 ","pages":"Article 125599"},"PeriodicalIF":3.5,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144893437","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}

{"title":"The Gd3+ doping induced improvement of broadband NIR emission of NaScGe2O6:Cr3+ nanophosphors for contrast imaging lighting","authors":"Baolu Lin ,&nbsp;Jian Yang ,&nbsp;Yangyang Zhao ,&nbsp;Xiaoyu Dong ,&nbsp;Wanqin Yang ,&nbsp;Xingwang Zhou ,&nbsp;Hancheng Zhu ,&nbsp;Duanting Yan ,&nbsp;Changshan Xu ,&nbsp;Yuxue Liu","doi":"10.1016/j.jssc.2025.125598","DOIUrl":"10.1016/j.jssc.2025.125598","url":null,"abstract":"<div><div>Herein, nano-sized NaScGe₂O₆:Cr³⁺ phosphors (NSGO:Cr³⁺, 16–35 nm) were successfully synthesized via the sol-gel method. Cr³⁺ ions preferentially substitute for the Sc³⁺ sites by occupying octahedral sites with a weak crystal field strength (Dq/B = 2.00). A broadband emission was observed within the first Near-infrared biological transparency window (NIR-I), located at 893 nm, which can be assigned to ⁴T₂→⁴A₂ transition of Cr³⁺ in NSGO:Cr³⁺. The full width at half maximum of the emission peak is approximately 150 nm. When doping concentration of Cr³⁺ reached 0.003, its NIR emission intensity became the strongest. The corresponding Huang-Rhys factor (0.44) is less than 1, indicating relatively weak phonon-electron coupling. Subsequently, the luminescence intensity of NSGO:Cr³⁺ was increased ∼20 % via incorporating Gd³⁺ into NSGO:Cr³⁺(NSGO:Cr³⁺,Gd³⁺) phosphors. Their phonon energy decreased from 0.131 eV to 0.125 eV. Meanwhile, the thermal stability of the luminescence in NSGO:Cr³⁺,Gd³⁺ was enhanced, resulting in an increase in thermal activation energy from 0.255 eV to 0.275 eV. The emission intensity of NSGO:Cr³⁺,Gd³⁺ at 150 °C retained 26.3 % of that at 20 °C. By combining blue LED chip with NSGO:Cr³⁺,Gd³⁺ phosphors, a NIR-I phosphor conversion light-emitting diode (NIR-I pc-LED) was fabricated and utilized as a backlighting source for contrast imaging. Both NIR contrast imaging photos of plant and animal tissues were successfully acquired using a NIR camera and the NIR-I pc-LED.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"352 ","pages":"Article 125598"},"PeriodicalIF":3.5,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144885857","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}

{"title":"Syntheses, structural characterization, and nonlinear optical properties of mixed alkaline/alkaline earth metal borophosphates","authors":"Yang Pan ,&nbsp;Jian Deng ,&nbsp;Yucheng Hao ,&nbsp;Xi Zhao ,&nbsp;Yuanyuan Bao ,&nbsp;Zixuan Fang ,&nbsp;Chonghai Deng ,&nbsp;Kunhong Hu ,&nbsp;Wei Cheng ,&nbsp;Yuan Lin","doi":"10.1016/j.jssc.2025.125575","DOIUrl":"10.1016/j.jssc.2025.125575","url":null,"abstract":"<div><div>Borophosphates have attracted significant attention due to their unique structural characteristics and exceptional properties. The incorporation of monovalent alkaline metals and divalent alkaline earth metals into the borophosphate system has significantly diversified the crystal structures. A new borophosphate, KMg [B(PO₄)₂](H₂O)₂, along with two previously reported nonlinear optical (NLO) materials, NaMg(H₂O)₂(BP₂O₈) (H₂O) and LiMg(H₂O)₂(BP₂O₈) (H₂O), were synthesized using low-temperature hydrothermal methods. These compounds crystallized in the same polar space group of <em>P</em>6₁22. The fundamental building units of KMg [B(PO₄)₂](H₂O)₂, NaMg(H₂O)₂(BP₂O₈) (H₂O) and LiMg(H₂O)₂(BP₂O₈) (H₂O) consist of BO₄ tetrahedra, PO₄ tetrahedra and MgO₆ octahedra. In these structures, two BO₄ tetrahedra and two PO₄ tetrahedra form helical chains, while the MgO₆ octahedra connect to four PO₄ tetrahedra through shared oxygen atoms, linking adjacent helical chains to form a three-dimensional (3D) framework. Alkaline metals (K, Na, Li) are situated within the voids of these frameworks. KMg[B(PO₄)₂](H₂O)₂, NaMg(H₂O)₂(BP₂O₈) (H₂O) and LiMg(H₂O)₂(BP₂O₈) (H₂O) exhibit moderate second harmonic generation (SHG) responses in the ultraviolet region, with of ∼0.13 × KDP, ∼0.10 × KDP and ∼0.17 × KDP, respectively. The syntheses and topological structures, elemental analyses, thermal stability, infrared spectroscopy, Raman spectroscopy, UV–Vis diffuse reflectance spectroscopy and NLO properties are discussed.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"352 ","pages":"Article 125575"},"PeriodicalIF":3.5,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144879004","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}

{"title":"Investigating the role of base chemistry in doping efficiency and crystallinity of F-doped SnO2 nanoparticles","authors":"Pattama Apichai ,&nbsp;Watcharapong Pudkon ,&nbsp;Thanawat Kanlayapattamapong ,&nbsp;Araya Ruengsuk ,&nbsp;Duangmanee Wongratanaphisan ,&nbsp;Atcharawon Gardchareon ,&nbsp;Pipat Ruankham","doi":"10.1016/j.jssc.2025.125570","DOIUrl":"10.1016/j.jssc.2025.125570","url":null,"abstract":"<div><div>Fluorine-doped tin oxide (FTO) is a widely used transparent conductive oxide, yet its synthesis through hydrothermal methods remains challenging due to low dopant efficiency. The pH of the reaction medium, adjusted by acids or bases, plays a crucial role in determining doping efficiency by influencing the hydrolysis rate of Sn precursors and the solubility of fluorine sources. This study systematically investigated the effect of pH on doping efficiency and crystallinity in F-doped SnO₂ nanoparticles synthesised hydrothermally using two base adjusters: ammonium hydroxide (NH₄OH) and tetramethylammonium hydroxide (TMAH). The results showed that pH directly affected both crystallite size and fluorine incorporation. Fine crystalline SnO₂ nanoparticles with a tetragonal rutile phase were successfully obtained, with average crystallite sizes decreasing from 4.51 nm (pH ∼0.6, unadjusted) to 3.65 nm (NH₄OH, pH 7) and 3.45 nm (TMAH, pH 7), driven by enhanced hydrolysis and nucleation at higher pH. While decreasing proton concentration (at pH &gt; 3) promotes Sn–F interaction, excessive OH⁻ and base-derived cations can hinder fluorine diffusion. The optimal F/Sn ratios of 0.61 (NH₄OH, pH 3) and 0.36 (TMAH, pH 2) were achieved under conditions that balance hydrolysis kinetics and cation interference. Elemental and spectroscopic analysis further confirmed that fluorine was successfully incorporated into the SnO₂ lattice <em>via</em> O-to-F substitution. These findings emphasise the importance of precise pH control in tailoring the structural and chemical properties of F-doped SnO₂, reinforcing its potential for future optoelectronic applications.</div></div>","PeriodicalId":378,"journal":{"name":"Journal of Solid State Chemistry","volume":"352 ","pages":"Article 125570"},"PeriodicalIF":3.5,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144885856","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}