Crystal Growth & Design最新文献

{"title":"Mechanistic Elucidation of Solid-State Zeolite Crystallization of Dense-Phase Cancrinite Using Time-Elapsed Tracking","authors":"Debkrishna Dey,&nbsp; and ,&nbsp;Manjesh Kumar*,&nbsp;","doi":"10.1021/acs.cgd.5c0000310.1021/acs.cgd.5c00003","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00003https://doi.org/10.1021/acs.cgd.5c00003","url":null,"abstract":"<p >Designing a new class of functional materials is heavily dependent on the fundamental understanding of the crystallization mechanism and the effect of physicochemical parameters. The rational design of zeolite crystals is significantly understood via the extensive mechanistic study of hydrothermal routes; however, solid-state crystallization is still elusive and challenging to study. On this account, we have formulated a chemical composition to synthesize the pure cancrinite (CAN) phase through solid-state transformation and subsequently conducted a comprehensive time-lapsed study to decipher phase transformation and morphological evolution. Broadly, crystallization exhibits a trend of a slower rate of nucleation followed by a faster rate of phase formation similar to that of the hydrothermal pathway. However, crystals present a unique multipodal architecture. A detailed study on the role of seed crystals was made using CAN as an isomorphic seed and Faujasite (FAU) as the heteromorphic seed. CAN seed accelerates the crystallization kinetics to a greater extent while following the seed preservation pathway. Typical rod-shaped bulk particles with rough outer surfaces were formed. However, seeding using FAU crystals exerts a typical role as a kinetics accelerator while exerting the interzeolitic-transformation phenomenon in this relatively new synthesis route. Morphological evolution reveals an agglomeration-based nonclassical growth mechanism where nanoparticles with irregular shapes undergo particle-mediated attachment through the crystallographic plane to form nanodomains. These domains aggregate to furnish the final multipod-shaped bulk particles. The surface smoothing of the bulk particles was also observed with prolonged heat treatment. The study on the role of the FAU seed using Raman spectra suggests that the FAU phase supplements 4-MRs as the building units to the initial solid mixture that acts as the preformed precursors, facilitating the enhanced rate of phase kinetics. Overall, our study portrays a detailed blueprint of the phase and morphological evolution of a zeolite in solid-state crystallization, which lays the foundation needed for the rational design of efficient catalysts with finely tuned structural properties using this economically lucrative synthesis pathway.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"2947–2959 2947–2959"},"PeriodicalIF":3.2,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911268","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Iron-Based Trimetallic Metal–Organic Frameworks as Efficient Catalysts for Fixation of CO2 into Cyclic Carbonates","authors":"Jing Ye,&nbsp;Tianyu Chen,&nbsp;Ning Chai,&nbsp;Qiao Jiang,&nbsp;Qingqing Guo,&nbsp;Fei-Yan Yi and Xinghua Ma*,&nbsp;","doi":"10.1021/acs.cgd.4c0161610.1021/acs.cgd.4c01616","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01616https://doi.org/10.1021/acs.cgd.4c01616","url":null,"abstract":"<p >The fact that carbon dioxide (CO₂) is converted into high-value cyclic carbonates from the viewpoint of a dual carbon target has garnered wide attention. In this work, monometallic Fe₃-MOF and a series of bimetallic Fe_<i>x</i>Co_<i>y</i>-MOF (<i>x</i>:<i>y</i> = molar ratio of Fe to Co) materials are successfully obtained. They, as Lewis acid catalysts, realize highly effective cycloaddition reactions of CO₂ with epoxides under solvent-free reaction conditions and atmospheric pressure. Among them, bimetallic FeCo₂-MOF with an Fe/Co molar ratio of 1:2 exhibits the best catalytic performance toward CO₂ cycloaddition reaction and can reach conversions of up to 99% at optimal conditions (80 °C, 8 h, 0.1 MPa CO₂), which is far better than with monometallic Fe₃-MOF and previously reported related systems. As-designed contrast experiments fully demonstrate the synergistic effect of Fe/Co centers in target bimetallic Fe_<i>x</i>Co_<i>y</i>-MOF. The corresponding reaction mechanism is deeply analyzed and discussed. In summary, this work provides a simple and environmentally friendly synthetic strategy proposed by us to boost the catalytic performance of the CO₂ cycloaddition reaction.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"2903–2912 2903–2912"},"PeriodicalIF":3.2,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911266","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chocolate Tempering: A Perspective.","authors":"Jarvis A Stobbs, Saeed M Ghazani, Mary-Ellen Donnelly, Alejandro G Marangoni","doi":"10.1021/acs.cgd.5c00269","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00269","url":null,"abstract":"<p><p>Tempering is a critical step in chocolate production, ensuring desirable properties such as gloss, snap, and bloom resistance. Traditionally, tempering has been understood through the lens of cocoa butter polymorphism, with a predominant focus on achieving Form V crystals, due to their sharp melting profile and associated macroscopic physical properties. However, this Perspective challenges the notion that Form V alone guarantees high-quality, bloom-resistant chocolate. Recent research suggests that polymorphism is only one aspect of chocolate quality. Multiscale structural analyses-including small-angle X-ray scattering (SAXS), ultrasmall-angle X-ray scattering (USAXS), small-angle neutron scattering (SANS), and microcomputed tomography (μCT)-reveal that nanostructural to microstructural properties are key indicators of bloom susceptibility and can vary significantly, despite identical polymorphic phases. This Perspective proposes that tempering should be viewed as a hierarchical crystallization process, where nucleation rate, structural homogeneity, and microstructural organization play critical roles. A broader approach to tempering assessment-integrating microstructural probes alongside traditional solid-state characterization-may provide deeper insights into chocolate's mechanical stability and long-term bloom resistance. As supply chain fluctuations increasingly impact cocoa butter composition, this multiscale perspective could help manufacturers mitigate quality inconsistencies and adapt to cost-driven formulation changes that may otherwise compromise bloom resistance in tempered chocolate.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"2764-2783"},"PeriodicalIF":3.2,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12063059/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143955101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chocolate Tempering: A Perspective","authors":"Jarvis A. Stobbs,&nbsp;Saeed M. Ghazani,&nbsp;Mary-Ellen Donnelly and Alejandro G. Marangoni*,&nbsp;","doi":"10.1021/acs.cgd.5c0026910.1021/acs.cgd.5c00269","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00269https://doi.org/10.1021/acs.cgd.5c00269","url":null,"abstract":"<p >Tempering is a critical step in chocolate production, ensuring desirable properties such as gloss, snap, and bloom resistance. Traditionally, tempering has been understood through the lens of cocoa butter polymorphism, with a predominant focus on achieving Form V crystals, due to their sharp melting profile and associated macroscopic physical properties. However, this Perspective challenges the notion that Form V alone guarantees high-quality, bloom-resistant chocolate. Recent research suggests that polymorphism is only one aspect of chocolate quality. Multiscale structural analyses─including small-angle X-ray scattering (SAXS), ultrasmall-angle X-ray scattering (USAXS), small-angle neutron scattering (SANS), and microcomputed tomography (μCT)─reveal that nanostructural to microstructural properties are key indicators of bloom susceptibility and can vary significantly, despite identical polymorphic phases. This Perspective proposes that tempering should be viewed as a hierarchical crystallization process, where nucleation rate, structural homogeneity, and microstructural organization play critical roles. A broader approach to tempering assessment─integrating microstructural probes alongside traditional solid-state characterization─may provide deeper insights into chocolate’s mechanical stability and long-term bloom resistance. As supply chain fluctuations increasingly impact cocoa butter composition, this multiscale perspective could help manufacturers mitigate quality inconsistencies and adapt to cost-driven formulation changes that may otherwise compromise bloom resistance in tempered chocolate.</p><p >Chocolate tempering refers to the controlled crystallization of its structuring component, cocoa butter. Historically, tempering refers to achieving the formation of a triclinic, “Form V”, polymorph in the cocoa butter. This form has a melting point similar to that of a human mouth and its presence is correlated with a specific brittle hardness, surface gloss, and polymorphic stability. However, here, we present arguments that suggest that chocolate tempering is a multiscale phenomenon where the control of structure at multiple length scales needs to be considered in order to manufacture a high-quality chocolate.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"2764–2783 2764–2783"},"PeriodicalIF":3.2,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00269","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911209","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lanthanide(III) Cation Size Selective Formation of Two Different Metal–Organic Frameworks","authors":"Narhari Sapkota,&nbsp;Ermei Mäkilä,&nbsp;Ari Lehtonen and Anssi Peuronen*,&nbsp;","doi":"10.1021/acs.cgd.5c0015310.1021/acs.cgd.5c00153","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00153https://doi.org/10.1021/acs.cgd.5c00153","url":null,"abstract":"<p >The reaction between a 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin-FeCl linker (TCPP-Fe) and lanthanide ions (Ln³⁺) in excess of <span>l</span>-proline coligand provides a synthetic route to two structurally different metal–organic frameworks (TCPP-FeOH_0.5/H₂O_0.5)(<span>l</span>-proline)₂Ln₂(H₂O)(DMF)_0.5 (where Ln = La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, and Eu³⁺) and (TCPP-FeOH)(<span>l</span>-proline)Ln_1.5 (where Ln = Gd³⁺, Tb³⁺ Tm³⁺ and Yb³⁺). The selection between the two different structures is dependent on the lanthanide ion atomic number. From the different Ln³⁺ ions used in this study, early-to-mid lanthanides, La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, and Eu³⁺, give a structure consisting of discrete Ln₈ building units (<b>1-Ln</b>), while mid-to-late lanthanides, Gd³⁺, Tb³⁺, Tm³⁺, and Yb³⁺, give a framework built upon one-dimensional Ln³⁺ chains (<b>2-Ln</b>). Therefore, the size of the lanthanide ion seems to play a key role in the structure selection and stability, which contrast with the commonly accepted behavior of lanthanides. Activation and subsequent argon gas sorption analyses done using <b>1-Nd</b> and <b>2-Tb</b> showed that <b>1-Nd</b> is permanently porous with a determined surface area of 1223 ± 4 m²/g, while <b>2-Tb</b> undergoes a structural change significantly decreasing its surface area (236 m²/g) from its expected value (ca. 900 m²/g). Stability tests on the activated samples revealed that <b>1-Nd</b> lost its crystallinity after 1 month of exposure to atmospheric moisture, whereas <b>2-Tb</b> retained its crystallinity, underscoring the higher long-term stability of <b>2-Tb</b> compared to that of <b>1-Nd</b>.</p><p >Two new lanthanide-based MOFs were synthesized from Fe-porphyrin tetracarboxylate linkers and <span>l</span>-proline coligands under a single set of synthetic conditions by varying the lanthanide(III) species. The specific structure is determined by the size of the lanthanide(III) cation with the smaller radii late lanthanides preferring the structure with smaller coordination number, thus demonstrating the lanthanide contraction effect in the MOF assembly.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"3119–3127 3119–3127"},"PeriodicalIF":3.2,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00153","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911201","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Polymorph Transitions and Structure Evolutions in Rare Earth Sesquioxides","authors":"Chaoyang Lei,&nbsp;Mengyuan Xie,&nbsp;Quanhao Gao,&nbsp;Haiqiong Zhou,&nbsp;Hao Yin,&nbsp;Xiaodong Xu,&nbsp;Yinzhen Wang*,&nbsp;Zhen Li,&nbsp;Fengkai Ma* and Zhenqiang Chen,&nbsp;","doi":"10.1021/acs.cgd.4c0159710.1021/acs.cgd.4c01597","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01597https://doi.org/10.1021/acs.cgd.4c01597","url":null,"abstract":"<p >In this work, polymorph transformations in rare earth sesquioxides were studied. It reveals that the transitions among A-, B-, and C-type structures were caused by varied rare earth ionic radii-induced ionic movement, and pictures of the transformation processes were demonstrated. It was determined that the A to B transition is reversible and those of A to C and B to C are not completely reversible. Additionally, we examined the phases in binary sesquioxides, and they are intimately related with the concentrations and rare earth ionic radii. These results offer new insights into the structure evolutions of rare earth sesquioxides, providing a reference for exploiting advanced sesquioxide functional materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"2890–2902 2890–2902"},"PeriodicalIF":3.2,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nanoconfined Metal Halide Perovskite Crystallization within Removable Polymer Scaffolds","authors":"Mia Klopfenstein,&nbsp;Lance Emry,&nbsp;Pulkita Jain,&nbsp;Aida Alaei,&nbsp;Ben Schmelmer,&nbsp;Andrew Chou,&nbsp;Trinanjana Mandal,&nbsp;Min-Woo Kim,&nbsp;Eray S. Aydil,&nbsp;Tsengming Chou and Stephanie S. Lee*,&nbsp;","doi":"10.1021/acs.cgd.5c0007310.1021/acs.cgd.5c00073","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00073https://doi.org/10.1021/acs.cgd.5c00073","url":null,"abstract":"<p >Nanoconfining crystallization to access metastable polymorphs and prescribe crystal orientations typically involves filling inert nanoporous scaffolds with target compounds, resulting in isolated nanocrystals. Such crystal-scaffold composites are unsuitable for optoelectronic devices that require interconnected crystalline pathways for charge transport. Here, we reverse the order of fabricating crystal-scaffold composites by first electrospinning interconnected networks of amorphous methylammonium lead iodide (MAPbI₃) precursor nanofibers, then introducing a poly(methyl methacrylate) (PMMA) scaffold by spin coating from an antisolvent for MAPbI₃. PMMA suppresses MAPbI₃ crystal blooming from the fiber surface during thermal annealing, instead promoting the formation of densely packed polycrystalline networks of MAPbI₃ crystals at the fiber/PMMA interface. Near-IR photodetectors comprising densely packed MAPbI₃ nanocrystals grown within a PMMA scaffold in a coplanar electrode geometry exhibit photocurrents up to 60 times larger than those comprising fibers annealed without PMMA. These results indicate that MAPbI₃ crystals form a percolated network for charge carriers to flow through PMMA-confined fibers, resulting in significantly improved photodetector performance.</p><p >False-colored TEM images of electrospun MAPbI₃ fibers highlighting MAPbI₃ crystals that formed during thermal annealing in the absence and presence of a confining polymer scaffold. Large, isolated crystals bloomed from the surfaces of unconfined fibers, while confined fibers exhibited small, interconnected crystals at the fiber surface.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"3003–3012 3003–3012"},"PeriodicalIF":3.2,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00073","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nanoconfined Metal Halide Perovskite Crystallization within Removable Polymer Scaffolds.","authors":"Mia Klopfenstein, Lance Emry, Pulkita Jain, Aida Alaei, Ben Schmelmer, Andrew Chou, Trinanjana Mandal, Min-Woo Kim, Eray S Aydil, Tsengming Chou, Stephanie S Lee","doi":"10.1021/acs.cgd.5c00073","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00073","url":null,"abstract":"<p><p>Nanoconfining crystallization to access metastable polymorphs and prescribe crystal orientations typically involves filling inert nanoporous scaffolds with target compounds, resulting in isolated nanocrystals. Such crystal-scaffold composites are unsuitable for optoelectronic devices that require interconnected crystalline pathways for charge transport. Here, we reverse the order of fabricating crystal-scaffold composites by first electrospinning interconnected networks of amorphous methylammonium lead iodide (MAPbI₃) precursor nanofibers, then introducing a poly(methyl methacrylate) (PMMA) scaffold by spin coating from an antisolvent for MAPbI₃. PMMA suppresses MAPbI₃ crystal blooming from the fiber surface during thermal annealing, instead promoting the formation of densely packed polycrystalline networks of MAPbI₃ crystals at the fiber/PMMA interface. Near-IR photodetectors comprising densely packed MAPbI₃ nanocrystals grown within a PMMA scaffold in a coplanar electrode geometry exhibit photocurrents up to 60 times larger than those comprising fibers annealed without PMMA. These results indicate that MAPbI₃ crystals form a percolated network for charge carriers to flow through PMMA-confined fibers, resulting in significantly improved photodetector performance.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"3003-3012"},"PeriodicalIF":3.2,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12063054/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143955637","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of the Molecular Framework on the Photoconductivity Responses of Five Cu/Ni and Fe Heterometallic Materials Built with Cyanide and Ethylenediamine","authors":"Adetokunbo Temitope Famojuro*,&nbsp;Patrice Kenfack Tsobnang*,&nbsp;Loïc Landry Tchatchouang Tchouane,&nbsp;Gershon Amenuvor,&nbsp;James Darkwa and Omotayo A. Arotiba,&nbsp;","doi":"10.1021/acs.cgd.5c0013410.1021/acs.cgd.5c00134","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00134https://doi.org/10.1021/acs.cgd.5c00134","url":null,"abstract":"<p >The contribution of weak interactions in the photoconductive property of hybrid materials is clearly shown in this work with five materials having the same units but different connection modes: [Ni(en)₃]₃[Fe(CN)₆]₂ ·5H₂O (<b>1N</b>), {[Ni(en)₂]₃[Fe(CN)₆]₂}_n·3H₂O (<b>2N</b>), [Cu(en)₂(H₂O)_1.935]₂ [Fe(CN)₆]· 4H₂O (<b>3N</b>), {[Cu(en)₂][KFe(CN)₆]}_n (<b>4N</b>), and {[Cu(en)₂]₂[Fe(CN)₆]· 4.5H₂O}_n (<b>5N</b>); en = ethylenediamine (C₂H₈N₂); <b>1N</b> and <b>3N</b> are supramolecular compounds while <b>2N</b>, <b>4N</b>, and <b>5N</b> are coordination polymers. <b>1N</b> is a new material while <b>2N</b>, <b>3N</b>, <b>4N</b>, and <b>5N</b> were already reported with different synthesis methods. In the structure of <b>1N</b>, two [Fe(CN)₆]^3– anionic units over three crystallographic sites (noted <b>A</b>^<b>–</b>, <b>B</b>^–, and <b>C</b>^<b>–</b>) and three cationic [Ni(C₂H₈N₂)₃]²⁺ units (noted <b>A</b>^<b>+</b>, <b>B</b>⁺, and <b>C</b>^<b>+</b>) are involved. They build infinite chains with the packing of the <b>B</b>^<b>+</b><b>----A</b>^<b>–</b><b>--- A</b>^<b>+</b><b>----C</b>^<b>–</b><b>--- A</b>^<b>+</b><b>---- A</b>^<b>–</b><b>----B</b>⁺ units connected with the <b>C</b>^<b>+</b><b>---B</b>^<b>–</b><b>---C</b>^<b>+</b> short units. This packing results in zigzag 2D arrays running along the [010] direction and stacked along the [100] direction with the water molecules located between them. <b>4N</b> exhibits a one-electron quasi-reversible redox process while <b>1N</b>, <b>2N</b>, <b>3N</b>, and <b>5N</b> show multielectron processes in which the redox couples Cu²⁺/Cu³⁺ or Ni²⁺/Ni³⁺, Fe²⁺/Fe³⁺, and Fe³⁺/Fe⁴⁺ are involved. All these compounds are photoactive; <b>1N</b> and <b>3N</b>, which are built from hydrogen bonds, produced higher faradaic current with illumination than the materials <b>2N</b>, <b>4N</b>, and <b>5N</b>, which are built with coordinative bonds. The solid-state photoconductivity of <b>3N</b> shows a current increase as the voltage increases in the presence of light, while no real response was observed without light.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"3075–3086 3075–3086"},"PeriodicalIF":3.2,"publicationDate":"2025-04-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Suppression of Hillock Defects on (010) β-Ga2O3 Homoepitaxial Layer Growth via Halide Vapor Phase Epitaxy","authors":"Haohan Ye,&nbsp;Defan Wu*,&nbsp;Zhun Yang,&nbsp;Dacheng Xu,&nbsp;Yuchao Yan,&nbsp;Zhu Jin*,&nbsp;Ning Xia,&nbsp;Hui Zhang* and Deren Yang,&nbsp;","doi":"10.1021/acs.cgd.5c0007010.1021/acs.cgd.5c00070","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00070https://doi.org/10.1021/acs.cgd.5c00070","url":null,"abstract":"<p >Hillock, a type of surface defect with small mounds or protrusion morphologies, can significantly impair the flatness and uniformity of β phase gallium oxide (β-Ga₂O₃) epitaxy, particularly on the (010) plane. Herein, a high-quality, hillock-free (010) β-Ga₂O₃ homogeneous layer with a thickness of ∼10 μm was successfully grown by halide vapor phase epitaxy (HVPE). The growth mode and hillock structure were thoroughly investigated via optical microscopy (OM), confocal laser scanning microscopy (CLSM), X-ray rocking curve (XRC) analysis, and transmission electron microscopy (TEM). The results indicate that these hillocks are polycrystalline particles, which generate along the &lt;001&gt; direction with specific intersection planes of (610) and (61̅0). By adjusting the flow of O₂ while fixing the flow of HCl, a precise hillock hindrance method was implemented, resulting in a smoother (010) epitaxy surface at VI/III ratios below 18. This work offers a new perspective on the origin and suppression method of the hillock defect on HVPE (010) β-Ga₂O₃ layers, paving the path to fabricate high-performance power devices.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 9","pages":"2994–3002 2994–3002"},"PeriodicalIF":3.2,"publicationDate":"2025-04-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}