Correction to “α-Li2ZnGeS4 - A Wide-Bandgap Diamond-like Semiconductor with Excellent Balance between Laser-Induced Damage Threshold and Second Harmonic Generation Response”
At a Glance
Section titled “At a Glance”| Metadata | Details |
|---|---|
| Publication Date | 2024-05-29 |
| Journal | Chemistry of Materials |
| Authors | Katherine E. Colbaugh, Jian‐Han Zhang, Daniel J. Clark, Jacilynn A. Brant, Kimberly A. Rosmus |
| Institutions | Binghamton University, Sogang University |
| Citations | 1 |
| Analysis | Full AI Review Included |
Executive Summary
Section titled “Executive Summary”This document provides a technical correction to the calculated dipole moments for the nonlinear optical (NLO) material $\alpha$-Li2ZnGeS4, confirming its superior performance characteristics.
- Validation of Core Conclusion: The revised calculations confirm the original finding that $\alpha$-Li2ZnGeS4 possesses a dipole moment density (0.0150 D/A3) that is greater than 3x that of the $\beta$-phase (0.00443 D/A3).
- Performance Correlation: This significantly stronger dipole moment in the $\alpha$-phase is the primary factor explaining its superior macroscopic Second Harmonic Generation (SHG) response.
- Calculation Errors Rectified: Two critical errors in the original methodology were corrected: switching from fractional atomic coordinates to required Cartesian coordinates, and incorporating anion bond valence ($S_{ij}$) as a negative value.
- Polarization Alignment: The analysis confirms that the polarization derived from the constituent tetrahedra amasses most significantly along the crystallographic c-axis (z-direction), yielding a net polarization of -9.55 D.
- Tetrahedral Distortion: The LiS4 tetrahedra exhibit greater distortion (2.07 D and 1.59 D) compared to the ZnS4 and GeS4 tetrahedra (1.00 D and 1.23 D, respectively), driving the overall NLO activity.
Technical Specifications
Section titled “Technical Specifications”| Parameter | Value | Unit | Context |
|---|---|---|---|
| Revised Dipole Moment ($\alpha$-Li2ZnGeS4) | 0.0150 | D/A3 | Net dipole moment density (corrected value). |
| Redetermined Dipole Moment ($\beta$-Li2ZnGeS4) | 0.00443 | D/A3 | Net dipole moment density (corrected value). |
| Dipole Moment Ratio ($\alpha$ / $\beta$) | > 3 | Ratio | Explains superior macroscopic SHG response. |
| Net Polarization (z-direction, $\alpha$-phase) | -9.55 | D | Polarization along the c-axis; x- and y-directions are 0.00 D. |
| Total Moment Li(1)S4 ($\alpha$-phase) | 2.07 x 4 | D | Distortion per tetrahedron (multiplicity included). |
| Total Moment Li(2)S4 ($\alpha$-phase) | 1.59 x 4 | D | Distortion per tetrahedron (multiplicity included). |
| Total Moment Zn(1)S4 ($\alpha$-phase) | 1.00 x 4 | D | Distortion per tetrahedron (multiplicity included). |
| Total Moment Ge(1)S4 ($\alpha$-phase) | 1.23 x 4 | D | Distortion per tetrahedron (multiplicity included). |
| Cell Volume ($\alpha$-Li2ZnGeS4) | 636.76 | A3 | Unit cell volume used for density calculation. |
| Cell Volume ($\beta$-Li2ZnGeS4) | 317.4 | A3 | Unit cell volume used for density calculation. |
Key Methodologies
Section titled “Key Methodologies”The correction focused entirely on refining the computational methodology for calculating dipole moments based on crystallographic data, ensuring consistency with established bond-valence approaches.
- Coordinate System Correction: The calculation was revised to utilize Cartesian coordinates for all atomic positions, replacing the previously used fractional atomic coordinates, which are unsuitable for accurate dipole moment determination.
- Anion Bond Valence Adjustment: The bond valence ($S_{ij}$) for the anions was incorporated into the dipole moment calculation as a negative number. This step is necessary to correctly account for the charge contribution of the anions.
- Dipole Moment Recalculation: The total dipole moment for each constituent tetrahedron (LiS4, ZnS4, GeS4) was recalculated using the corrected coordinates and valence parameters, including the appropriate multiplicity factor.
- Net Polarization Determination: The net polarizations along the x-, y-, and z-directions were calculated. For $\alpha$-Li2ZnGeS4, the net polarization was found to be concentrated along the z-direction (-9.55 D), confirming the structural origin of the macroscopic polarization.
- Density Calculation: The total dipole moment per unit cell was divided by the cell volume (636.76 A3 for the $\alpha$-phase) to yield the final, corrected dipole moment density (0.0150 D/A3).
Commercial Applications
Section titled “Commercial Applications”The material $\alpha$-Li2ZnGeS4 is a wide-bandgap, diamond-like infrared nonlinear optical material characterized by an excellent balance between a high laser damage threshold (LDT) and a strong Second Harmonic Generation (SHG) response.
- High-Power Infrared (IR) Lasers: Used as a frequency conversion element (e.g., frequency doubler) in high-energy laser systems where resistance to laser-induced damage is paramount.
- Optical Parametric Oscillators (OPOs): Essential component for generating widely tunable mid-infrared light sources, critical for chemical sensing and atmospheric monitoring.
- Defense and Aerospace Systems: Applications requiring robust, wide-bandgap NLO crystals for laser countermeasures, targeting, or remote sensing in harsh environments.
- Spectroscopy and Scientific Instrumentation: Manufacturing of frequency conversion optics for generating specific wavelengths necessary for advanced research and analytical techniques.
- Telecommunications: Potential use in high-speed optical switches or modulators, leveraging the material’s strong nonlinear response.
View Original Abstract
ADVERTISEMENT RETURN TO ARTICLES ASAPPREVAddition/CorrectionNEXTORIGINAL ARTICLEThis notice is a correctionCorrection to “α-Li2ZnGeS4: A Wide-Bandgap Diamond-like Semiconductor with Excellent Balance between Laser-Induced Damage Threshold and Second Harmonic Generation Response”Katherine E. ColbaughKatherine E. ColbaughDepartment of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282, United StatesMore by Katherine E. Colbaugh, Jian-Han ZhangJian-Han ZhangSchool of Resources and Chemical Engineering, Sanming University, Sanming 365004, P. R. ChinaMore by Jian-Han Zhanghttps://orcid.org/0000-0001-8248-5010, Daniel J. ClarkDaniel J. ClarkDepartment of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902, United StatesMore by Daniel J. Clark, Jacilynn A. BrantJacilynn A. BrantDepartment of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282, United StatesMore by Jacilynn A. Brant, Kimberly A. RosmusKimberly A. RosmusDepartment of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282, United StatesMore by Kimberly A. Rosmus, Pedro GrimaPedro GrimaCentro de Estudios de Semiconductores, Departamento de Física, Facultad de Ciencias, Universidad de Los Andes, Mérida 5101, VenezuelaCentro Nacional de Tecnologías Ópticas (CNTO), Mérida 5101, VenezeulaMore by Pedro Grima, Jonathan W. LekseJonathan W. LekseDepartment of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282, United StatesMore by Jonathan W. Lekse, Joon I. JangJoon I. JangDepartment of Physics, Sogang University, Seoul 04017, South KoreaMore by Joon I. Janghttps://orcid.org/0000-0002-1608-8321, and Jennifer A. AitkenJennifer A. AitkenDepartment of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282, United StatesMore by Jennifer A. Aitkenhttps://orcid.org/0000-0001-8281-5091Cite this: Chem. Mater. 2024, XXXX, XXX, XXX-XXXPublication Date (Web):May 28, 2024Publication History Received27 February 2024Published online28 May 2024https://pubs.acs.org/doi/10.1021/acs.chemmater.4c00551https://doi.org/10.1021/acs.chemmater.4c00551correctionACS Publications© 2024 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions This publication is free to access through this site. Learn MoreArticle Views-Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (710 KB) Get e-Alertsclose Get e-Alerts
Tech Support
Section titled “Tech Support”Original Source
Section titled “Original Source”References
Section titled “References”- 1929 - Polar Molecules