Correction to “Phase Matching, Strong Frequency Doubling, and Outstanding Laser-Induced Damage Threshold in the Biaxial, Quaternary Diamond-like Semiconductor Li4CdSn2S7”

At a Glance

Metadata	Details
Publication Date	2024-05-29
Journal	Chemistry of Materials
Authors	Katherine E. Colbaugh, Jian‐Han Zhang, Stanislav S. Stoyko, Andrew J. Craig, P. Grima
Institutions	Jingdong (China), Duquesne University
Analysis	Full AI Review Included

Technical Documentation & Analysis: High-Performance Diamond-Like Semiconductors for Nonlinear Optics

This analysis connects the findings regarding the high-performance nonlinear optical (NLO) material Li₄CdSn₂S₇ to the advanced MPCVD diamond solutions offered by 6CCVD.com, focusing on applications requiring high thermal management and optical purity.

Executive Summary

Core Material: The research confirms the strong polarization and resulting Second Harmonic Generation (SHG) response in the quaternary diamond-like semiconductor Li₄CdSn₂S₇.
Key Achievement: Corrected calculations validate a strong polarization of 265.18 x 10^-4 Debye/Å³, confirming its suitability for high-efficiency NLO applications.
Performance Metric: The material exhibits polarization 1.4x greater than LiInS₂ and 11.7x greater than LiGaS₂, positioning it as a superior mid-IR nonlinear crystal.
Structural Origin: The strong SHG response is primarily driven by significant distortions in the LiS₄ (3.52 D) and SnS₄ (2.88 D) tetrahedra.
Polarization Direction: The largest polarization is confirmed to be along the c-axis, specifically the [001] direction.
6CCVD Relevance: High-power NLO systems utilizing materials like Li₄CdSn₂S₇ require high-purity, low-loss CVD diamond for thermal management (heat sinks) and high-LIDT optical components (windows/lenses).

Technical Specifications

The following hard data points were extracted from the corrected dipole moment calculations for Li₄CdSn₂S₇ and comparative materials.

Parameter	Value	Unit	Context
Total Polarization (Li₄CdSn₂S₇)	265.18	x 10^-4 D/Å³	Total per volume (corrected value)
Total Dipole Moment (Li₄CdSn₂S₇)	3305.19	x 10^-2 D	Total per cell
Largest Polarization Direction	[001]	Direction	Confirmed along the c-axis
[001] Polarization Magnitude	-32.81	D	Largest polarization in the unit cell
Largest Tetrahedral Distortion	3.52	D	Observed in the Li(2)S₄ tetrahedron
Second Largest Distortion	2.88	D	Observed in the Sn(1)S₄ tetrahedron
Polarization Ratio (vs. LiInS₂)	1.4	Ratio	Li₄CdSn₂S₇ is 1.4x stronger
Polarization Ratio (vs. LiGaS₂)	11.7	Ratio	Li₄CdSn₂S₇ is 11.7x stronger

Key Methodologies

The research focused on correcting theoretical calculations to accurately model the material’s polarization, which dictates its NLO performance.

Calculation Method: Dipole moments were calculated using the established bond-valence method, consistent with prior publications.
Coordinate Correction: The primary error corrected was the use of fractional atomic coordinates; calculations were re-run using the required Cartesian coordinates.
Sign Correction: A critical sign error was corrected by including the positive bond valence (Sij) value as a negative value in the dipole moment calculations for the anions.
Structural Analysis: The corrected dipole moments were analyzed to confirm that the SHG response originates primarily from the large distortions observed in the LiS₄ and SnS₄ tetrahedra, validating the original structural proposition.
Directional Confirmation: Calculations confirmed that the largest polarization within the unit cell is found along the [001] direction (c-axis).

6CCVD Solutions & Capabilities

The development of high-performance mid-IR NLO crystals, such as Li₄CdSn₂S₇, necessitates robust thermal management and high-LIDT optical components to handle the high-power laser systems required for frequency doubling. 6CCVD specializes in providing the MPCVD diamond platforms essential for integrating and operating these advanced devices.

Applicable Materials

To replicate or extend research involving high-power mid-IR NLO devices, 6CCVD recommends the following materials:

Optical Grade SCD (Single Crystal Diamond):
- Application: High-LIDT optical windows, lenses, and output couplers for the laser systems driving the SHG process. SCD offers superior transparency across the mid-IR spectrum and thermal conductivity (up to 2200 W/mK).
- Specifications: Thicknesses from 0.1 µm up to 500 µm, with ultra-low surface roughness (Ra < 1nm) for minimal scattering loss.
High Thermal Conductivity PCD (Polycrystalline Diamond):
- Application: Heat spreaders and submounts for the Li₄CdSn₂S₇ crystal and associated laser diodes/pump sources. PCD provides large area coverage and exceptional thermal dissipation.
- Specifications: Plates/wafers available up to 125mm diameter, with thicknesses up to 500 µm.

Customization Potential

6CCVD’s in-house fabrication capabilities are perfectly suited to meet the precise integration requirements of NLO devices:

Custom Dimensions and Shapes: We offer custom laser cutting and shaping of both SCD and PCD substrates to match the exact footprint of the NLO crystal or device package. Plates/wafers are available up to 125mm (PCD).
Advanced Metalization Services: For direct bonding of the Li₄CdSn₂S₇ crystal or for creating electrical contacts on Boron-Doped Diamond (BDD) platforms, 6CCVD provides custom metalization stacks, including Ti/Pt/Au, W, Cu, and Pd.
Precision Polishing: We guarantee surface finishes critical for high-power optics: Ra < 1nm for SCD and Ra < 5nm for inch-size PCD wafers.

Engineering Support

6CCVD’s in-house PhD team provides expert consultation to ensure optimal material selection and integration for complex photonics projects:

Thermal Modeling: Assistance with integrating NLO materials (like Li₄CdSn₂S₇) onto diamond heat sinks to manage waste heat generated during high-power frequency doubling.
Optical Design: Support for selecting the appropriate SCD grade and thickness for mid-IR optical components, maximizing transmission and minimizing absorption loss in high-power laser systems.
Material Specification: Guidance on selecting the correct doping (e.g., BDD for electrodes) or crystal orientation for similar Mid-IR Nonlinear Optical projects.

For custom specifications or material consultation, visit 6ccvd.com or contact our engineering team directly.

View Original Abstract

ADVERTISEMENT RETURN TO ARTICLES ASAPPREVAddition/CorrectionNEXTORIGINAL ARTICLEThis notice is a correctionCorrection to “Phase Matching, Strong Frequency Doubling, and Outstanding Laser-Induced Damage Threshold in the Biaxial, Quaternary Diamond-like Semiconductor Li4CdSn2S7”Katherine E. ColbaughKatherine E. ColbaughDepartment of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave., Mellon Hall 302a, Pittsburgh, Pennsylvania 15282, United StatesMore by Katherine E. Colbaugh, Jian-Han ZhangJian-Han ZhangSchool of Resources and Chemical Engineering, Sanming University, 25 Jingdong Rd., Sanming, Fujian 365004, P. R. ChinaMore by Jian-Han Zhanghttps://orcid.org/0000-0001-8248-5010, Stanislav S. StoykoStanislav S. StoykoDepartment of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave., Mellon Hall 302a, Pittsburgh, Pennsylvania 15282, United StatesMore by Stanislav S. Stoyko, Andrew J. CraigAndrew J. CraigDepartment of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave., Mellon Hall 302a, Pittsburgh, Pennsylvania 15282, United StatesMore by Andrew J. Craig, Pedro GrimaPedro GrimaDepartment of Physics, Sogang University, Seoul 04017, South KoreaCentro Nacional de Tecnologías Ópticas (CNTO), Mérida 5101, VenezuelaMore by Pedro Grima, Joshua W. KotcheyJoshua W. KotcheyDepartment of Chemistry and Biochemistry, Duquesne University, 600 Forbes Ave., Mellon Hall 302a, Pittsburgh, Pennsylvania 15282, United StatesMore by Joshua W. Kotchey, 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, 600 Forbes Ave., Mellon Hall 302a, 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 29, 2024Publication History Received1 April 2024Published online29 May 2024https://pubs.acs.org/doi/10.1021/acs.chemmater.4c00961https://doi.org/10.1021/acs.chemmater.4c00961correctionACS 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 (694 KB) Get e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts