Crystal Growth & Design最新文献

{"title":"Implementing κ-Ga2O3 Polymorphs Using Ga Predeposition","authors":"Sunjae Kim,&nbsp;Jae-Hyeong Lee,&nbsp;Hyeong-Yun Kim,&nbsp;Wan Sik Hwang,&nbsp;Ji-Hyeon Park* and Dae-Woo Jeon*,&nbsp;","doi":"10.1021/acs.cgd.4c0125910.1021/acs.cgd.4c01259","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01259https://doi.org/10.1021/acs.cgd.4c01259","url":null,"abstract":"<p >Single kappa-phase gallium oxide (κ-Ga₂O₃) has limited growth at low temperatures due to lattice constant mismatch with sapphire substrates. This study reports that gallium (Ga) predeposition effectively mitigates this mismatch, enabling the growth of κ-Ga₂O₃ epilayers at low temperatures rather than the more common α-Ga₂O₃ epilayers. High-resolution X-ray diffraction demonstrated that the Ga₂O₃ phase can be grown as pure α and κ-phases without the formation of mixed phases by controlling the gallium monochloride (GaCl) flow rate. Single κ-phase and mixed phases Ga₂O₃ samples for the structural and optical properties were analyzed. Furthermore, a deep ultraviolet photodetector device with a metal–semiconductor–metal structure was fabricated using κ-Ga₂O₃ thin films and lattice mismatch relaxation Ga predeposition layers grown at low temperatures. The device exhibited a sharp response with a maximum responsivity at 260 nm, indicating the potential of the grown κ-Ga₂O₃ as a highly selective ultraviolet C-band detector.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1364–1371 1364–1371"},"PeriodicalIF":3.2,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547150","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":"Mechanistic Understanding of Solid–Solid Phase Transition Based on In Situ Single-Crystal-to-Single-Crystal Transformations: A Case Study of AZD5462","authors":"Okky Dwichandra Putra*,&nbsp;Marika Lindhagen,&nbsp;Johanna Sjöström,&nbsp;Philip A. Corner,&nbsp;Eleanor M. Dodd,&nbsp;Emma S. E. Eriksson,&nbsp;Sten O. Nilsson Lill and James F. McCabe,&nbsp;","doi":"10.1021/acs.cgd.4c0164210.1021/acs.cgd.4c01642","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01642https://doi.org/10.1021/acs.cgd.4c01642","url":null,"abstract":"<p >Polymorphism in active pharmaceutical ingredients is a critical factor influencing their physicochemical properties and performance in pharmaceutical applications. This study investigates the polymorphic solid–solid phase transition of a single crystal of AZD5462, a novel oral agonist of relaxin family peptide receptor 1 (RXFP1), being developed for the treatment of cardiorenal diseases. Utilizing in situ single-crystal-to-single-crystal (SCSC) transformations, we investigated the structural changes occurring between polymorphs within an enantiotropic system. Various analytical techniques, including thermal analysis and X-ray diffraction, were also employed to characterize these transitions. The results revealed a reversible phase transition between AZD5462 Form A and Form G, driven by temperature-induced crystal and molecular conformational changes. This highlights the potential of SCSC transformations as a valuable tool in the study of polymorphic behavior in pharmaceutical compounds, offering a deeper mechanistic understanding that can facilitate the understanding of polymorphic transformation.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1565–1574 1565–1574"},"PeriodicalIF":3.2,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547436","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":"Balancing the Heterocycles···Pyromellitic Dianhydride Interactions to Achieve Tunable Emission in Charge-Transfer Cocrystals","authors":"Wanglong Hong,&nbsp;Yuxing Deng,&nbsp;Shengli Zhu,&nbsp;Zhenduo Cui,&nbsp;Zhaoyang Li,&nbsp;Shuilin Wu,&nbsp;Wence Xu,&nbsp;Zhonghui Gao,&nbsp;Te Ba,&nbsp;Yanqin Liang* and Hui Jiang*,&nbsp;","doi":"10.1021/acs.cgd.5c0003210.1021/acs.cgd.5c00032","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00032https://doi.org/10.1021/acs.cgd.5c00032","url":null,"abstract":"<p >Cocrystal engineering focuses on adjustable noncovalent interactions (NCIs) and packing motifs through different functional molecular blocks to modulate physicochemical properties. NCIs are vital driving forces in the construction of organic cocrystal materials, such as π–π interactions, arene–perfluoroarene interactions, hydrogen bonds, and halogen bonds. Herein, pyromellitic dianhydride (PMDA) serves as the electron acceptor, and three heterocycle–acene-fused electron-rich donors, including 5H-benzo[4,5]thieno[3,2-<i>c</i>]carbazole (BTCZ), 5H-benzofuro[3,2-<i>c</i>]carbazole (BFCZ), and 5,12-dihydroindolo[3,2-<i>a</i>]carbazole (ICZ), are selected to react with PMDA to fabricate cocrystals. Single crystals of BTCZ-PMDA, BFCZ-PMDA, and ICZ-PMDA were grown via slow cooling and solvent evaporation, and their crystal structures, quantified NCIs, and photoluminescent properties were investigated. The results indicate that two types of π–π interactions along the π–π stacking direction show imbalanced interaction energies for BTCZ-PMDA and BFCZ-PMDA, while two π–π interaction energies are well balanced within ICZ-PMDA. Moreover, the red shift of the photoluminescent peak from 1.83 eV (BTCZ-PMDA) to 1.53 eV (ICZ-PMDA) can be ascribed to the balanced heterocycles···PMDA interactions and the overall enhancement of π–π and hydrogen bond interactions (N–H···O and C–H···O). Therefore, balancing the solid-state NCIs can offer a promising strategy to modulate fluorescence within charge-transfer cocrystals.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1653–1666 1653–1666"},"PeriodicalIF":3.2,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547218","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":"Combined X-ray Crystallographic and Periodic DFT Study of Supramolecular Organization and Intermolecular Interactions in Crystalline Peroxosolvates of (Nitropyrazolyl)furazans","authors":"Alexander G. Medvedev,&nbsp;Petr V. Prikhodchenko,&nbsp;Igor L. Dalinger,&nbsp;Mikhail V. Vener and Andrei V. Churakov*,&nbsp;","doi":"10.1021/acs.cgd.4c0139610.1021/acs.cgd.4c01396","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01396https://doi.org/10.1021/acs.cgd.4c01396","url":null,"abstract":"<p >Hydrogen peroxide is a source of active oxygen, which can optimize the negative oxygen balance of energy compounds and improve their detonation properties due to the formation of crystalline peroxosolvates. This approach has been recently proposed but remains unexplored because the number of hydrogen peroxide adducts and energetic compounds is very limited. Due to its acidic nature, hydrogen peroxide usually forms stable peroxosolvates with basic or amphoteric coformers. Herein, peroxosolvates of amphoteric energetic compounds, (nitropyrazolyl)furazanes C₆H₅N₅O₃·H₂O₂ (<b>1</b>·H₂O₂), C₆H₄N₆O₅·H₂O₂ (<b>2</b>·H₂O₂), and 5(C₅H₂N₆O₅)·H₂O₂ (<b>3</b>·1/5H₂O₂), were obtained, and their crystal structures were determined. Crystal packings of <b>1</b>–<b>3</b> are based on the same supramolecular synthon formed by a peroxide molecule and three adjacent coformers. In this unit, H₂O₂ forms three hydrogen bonds: one with the furazan ring as the proton donor and two with pyrazolyl fragments as both a proton donor and a proton acceptor. Analysis of the metric parameters of H-bonds in previously published isostructural crystalline hydrates <b>1</b>·H₂O and <b>2</b>·H₂O indicates the predominant acidic nature of amphoteric coformers. Periodic density functional theory (DFT) calculations reveal that the total sum of hydrogen bonds as a proton donor of the hydrogen peroxide molecule is up to 10 kJ mol^–1 higher than the hydrogen bond energy as a proton acceptor, reflecting the acidic nature of H₂O₂. The contribution of hydrogen bonds of hydrogen peroxide molecules to the lattice energy of the resulting peroxosolvates is about 40–45%. <b>1</b>·H₂O₂ exhibits improved oxygen balance and estimated detonation parameters in comparison to unsolvated <b>1</b>, whose structure was also determined.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1394–1405 1394–1405"},"PeriodicalIF":3.2,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547296","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":"Halogen Engineering Enables Tunable Dielectric Response and Dimensional Regulation in Organic–Inorganic Hybrid Halides","authors":"Lei Pan,&nbsp;Gele Teri,&nbsp;Cha-Hui Du,&nbsp;Zeng-Jie Xiao,&nbsp;Ji Liu,&nbsp;Pengcheng Zhuge,&nbsp;Pei-Guo Liu,&nbsp;Qiang-Qiang Jia,&nbsp;Zhi-Xu Zhang*,&nbsp;Da-Wei Fu* and Yi Zhang*,&nbsp;","doi":"10.1021/acs.cgd.4c0169310.1021/acs.cgd.4c01693","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01693https://doi.org/10.1021/acs.cgd.4c01693","url":null,"abstract":"<p >Organic–inorganic metal halides (OIMHs) have attracted great interest in the design of various functional materials due to their advantages of easy processability, rich structural diversity, and assembly flexibility. However, rational control of structural stacking patterns of the OIMHs for functional regulation has been a long-standing challenge. Particularly, little is known about the intrinsic relationship between structural dimensions and the dielectric response at the molecular scale. Here, we have investigated the modulation effect of cationic halogen engineering of (<i>N</i>,<i>N</i>-dimethylethanolamine)PbBr₃ on structural stacking, as well as its impact on thermal, electrical, and optical physical properties. Halogen regulation brings about varied structural stacking from a one-dimensional (1D) hexagonal perovskite structure and two-dimensional (2D) layered structure to an interlocking 1D chain structure. These varied attributes have been demonstrated to be closely related to molecular interactions in the crystal lattice, leading to variation in the sequential increase in phase transition temperature and differences in dielectric response, with the similar optical bandgaps that are mainly determined by inorganic frameworks. This study offers new insights into the structural stacking regulation and performance optimization of organic–inorganic hybrids.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1597–1604 1597–1604"},"PeriodicalIF":3.2,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547451","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":"Phosphonate Lanthanide Carbonate Cages: Remarkably Aggregated Lanthanide-Oxo Cores with Removable Cation Templates","authors":"Chaolun Wei,&nbsp;Xiaojuan Li,&nbsp;Yi Liu,&nbsp;Hai-Ye Li*,&nbsp;Houting Liu* and Haiquan Tian*,&nbsp;","doi":"10.1021/acs.cgd.5c0008210.1021/acs.cgd.5c00082","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00082https://doi.org/10.1021/acs.cgd.5c00082","url":null,"abstract":"<p >Phosphonate lanthanide carbonate cages represent a fascinating class of clusters capable of supplying carbonate ions to the center of the cages; furthermore, the phosphonate ligands enclose the exterior. By removing sodium templating cations and regulating the release of carbonate templating anions, two significantly aggregated lanthanide shell–core–shell topologies have now been synthesized through the reaction of lanthanide naphthalene-functionalized phosphonates and two differently terminated C₂-symmetric double hydrazones. The resulting two new phosphonate dysprosium carbonate cages [Dy₁₂Na₂₆(μ₃-O₃PC₁₁H₉)(μ₄-O₃PC₁₁H₉)(μ₆-O₃PC₁₁H₉)₉(μ₈-CO₃)₇(μ₉-CO₃)₃(L¹)₅(μ₃-O)₆(μ₂-O)₁₀(DMF)₆(H₂O)₉]·5DMF·4MeCN·4H₂O (<b>1</b>) and [Dy₂₂(μ₃-O₃PC₁₀H₇)₄(μ₅-O₃PC₁₀H₇)₄(μ₆-O₃PC₁₀H₇)₆(μ₅-CO₃)₂(μ₆-CO₃)₄(L²)₄(μ₂-COO)₄(μ₃-O)₄(μ₂-O)₂(H₂O)₁₁]·95MeOH·78H₂O (<b>2</b>) were obtained. Two types of hydrazones function as tridecadentate and enneadentate intercepted coligands, coordinating the periphery of phosphonate dysprosium carbonate cages. The mixed hexacosaple sodium and decaple carbonate ions act as templating cations and anions for constructing heterobimetallic <b>1</b> by filling the void, showcasing the ability to effectively control dysprosium cage aggregation in homometallic <b>2</b> through the removal of the cation and anion templates. Additionally, it was noted that the aggregation of the dysprosium shell–core–shell cages significantly influences the magnetic relaxation behavior, shifting from a field-induced two-step process in <b>1</b> to a zero-field one-step process in <b>2</b>.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 6","pages":"1912–1922 1912–1922"},"PeriodicalIF":3.2,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143641587","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":"Long-Range Ferroelectric Order Regulated by Cl–Cl Halogen Bonding in a 1D Ru-Based Hybrid Double Perovskite","authors":"Ze-Jiang Xu,&nbsp;Hua-Kai Li,&nbsp;Mei-Ling Ren,&nbsp;Liang-Han Shen,&nbsp;Xiang Zhang,&nbsp;Zi-Ao Qiu,&nbsp;Chao Shi,&nbsp;Li-De Yu*,&nbsp;Na Wang*,&nbsp;Heng-Yun Ye* and Le-Ping Miao*,&nbsp;","doi":"10.1021/acs.cgd.5c0006010.1021/acs.cgd.5c00060","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00060https://doi.org/10.1021/acs.cgd.5c00060","url":null,"abstract":"<p >Long-range order of electric dipoles means important physical properties such as ferroelectricity or antiferroelectricity, making materials have broad applications in information storage, sensors, switches, and optical electric devices. However, the orientation control of electric dipoles remains a great challenge on a molecular/ion level. Herein, we report the realization of ferroelectric order via Cl–Cl halogen-bond interactions in hybrid double perovskite [CH₂ClN(CH₃)₃]₂NaRuCl₆ (TCNRC) derived from [(CH₃)₄N]₂NaRuCl₆ (TNRC) for the first time. TCNRC shows spontaneous polarization (<i>P</i>_s = 2.67 μC cm^–2) and piezoelectricity (<i>d</i>₃₃ = 4 pC N^1–) with a Curie temperature (<i>T</i>_c) of 320 K. This study reveals the important role of halogen-bonding interactions to form ferroelectric orders and provides new insights into the molecular level regulatory polarity in molecular ferroelectric systems.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1682–1687 1682–1687"},"PeriodicalIF":3.2,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547625","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":"Precisely Designed Synthesis of Hollow Zn2SiO4 Particles from ZnO/SiO2 Core/Shell Particles with Varied Silica Thicknesses","authors":"Siraphat Jan Cheepborisutikul,&nbsp;Tanika Kessaratikoon,&nbsp;Valerio D’Elia and Makoto Ogawa*,&nbsp;","doi":"10.1021/acs.cgd.4c0132010.1021/acs.cgd.4c01320","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01320https://doi.org/10.1021/acs.cgd.4c01320","url":null,"abstract":"<p >ZnO/SiO₂ core/shell particles were prepared by the hydrolysis and condensation of tetraethyl orthosilicate on ZnO nanoparticles (particle size of ca. 50–200 nm) and ZnO nanorods (diameter of 124 nm and length of 400–950 nm). The silica shell thickness was varied (28 to 40 nm) to adjust the composition (Si/Zn ratio) by reiterating the coating procedure. Heat treatment of ZnO nanoparticle/SiO₂ core/shell particles with suitable stoichiometry (Si/Zn ratio of 0.5) at 1000 °C resulted in the formation of single-phase Zn₂SiO₄ as hollow particles. The use of ZnO with different morphologies (ZnO nanorods) (leading to ZnO nanorods/SiO₂ core/shell particles) with a Si/Zn ratio of 0.616 confirmed the generality of the synthetic method by the formation of hollow Zn₂SiO₄ nanorods as the main product despite the presence of minor amounts of ZnO. This study demonstrates a systematic structural design to obtain ZnO/SiO₂ core/shell particles with precisely tuned composition and its application to the formation of hollow Zn₂SiO₄ particles of different morphologies.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1386–1393 1386–1393"},"PeriodicalIF":3.2,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547212","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":"Hybrid[4]arene-Based Supramolecular Tessellations Driven by Exo-Wall Interaction","authors":"Minghao Liang,&nbsp;Jingyu Chen,&nbsp;Jiawang Hou,&nbsp;Sha Wu,&nbsp;Yuhao Wang,&nbsp;Qian Dong and Jiong Zhou*,&nbsp;","doi":"10.1021/acs.cgd.4c0154710.1021/acs.cgd.4c01547","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01547https://doi.org/10.1021/acs.cgd.4c01547","url":null,"abstract":"<p >As an emerging field in supramolecular chemistry, supramolecular tessellations have attracted more and more attention because of their potential application prospects. Herein, we construct novel supramolecular tessellation systems by the exowall complexation of an electron-rich macrocycle hybrid[4]arene (<b>H</b>) with electron-deficient guests tetrafluoroterephthalonitrile (DCTFB), 1,2,4,5-tetracyanobenzene (TCNB), 7,7,8,8-tetracyanoquinodimethane (TCNQ), and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F₄TCNQ). By analyzing their crystal structures, it is found that <b>H</b> can form highly ordered two-dimensional tiled planar structures with electron-deficient guests driven by charge-transfer interactions. The structure of <b>H</b> is deformed when complexed with various electron-deficient guests. According to their independent gradient model, we find that the reason for this phenomenon is the change in noncovalent interactions between <b>H</b> and these guests. This study not only opens up the potential of hybrid[<i>n</i>]arenes-based macrocyclic building blocks but also provides valuable insights into the construction of diverse two-dimensional organic structures.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 7","pages":"2020–2030 2020–2030"},"PeriodicalIF":3.2,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745917","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":"Halide Vapor Phase Epitaxy of Ge from an Elemental Source","authors":"Edgard Winter da Costa*,&nbsp;Megan Goh,&nbsp;Kevin L. Schulte,&nbsp;Matthew R. Young,&nbsp;John Simon and Aaron J. Ptak,&nbsp;","doi":"10.1021/acs.cgd.4c0161510.1021/acs.cgd.4c01615","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01615https://doi.org/10.1021/acs.cgd.4c01615","url":null,"abstract":"<p >Halide vapor phase epitaxy shows promise for low-cost photovoltaic device manufacturing because of its high growth rates and lower cost elemental precursors but previously has not been used to deposit epitaxial Ge. Here, we demonstrate Ge deposition by generating GeCl₂ in situ from solid Ge and HCl in a N₂ ambient. To achieve Ge growth, we inject AsH₃ and PH₃ as sources of active hydrogen to the growth surface to create a driving force for growth. We do not observe Ge growth unless a supply of hydrogen is added, consistent with thermodynamic calculations. Furthermore, we show the hydrogen source must crack readily on the substrate surface to enable growth; relatively stable sources such as H₂ do not cause growth. Unintentional group V doping is one drawback of using AsH₃ and PH₃ to drive the Ge reaction. We observed As or P concentrations in the Ge films ranging from 4 × 10¹⁷ to 1 × 10¹⁸ atoms/cm³, concentrations that can drastically influence device characteristics. However, we note there are numerous other “helper molecule” options that can provide active hydrogen without doping or etching the material. This work provides a path forward for Ge deposition for optoelectronic devices from an elemental source.</p><p >In this work we were able to deposit Ge from an elemental source for the first time on a Halide Vapor Phase Epitaxy reactor. We achieve growth by injecting a source of hydride like arsine to create a driving force for growth. We showed computational and experimental data that support the growth results and, also the high crystalline quality achieved.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1526–1532 1526–1532"},"PeriodicalIF":3.2,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01615","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547214","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}