Study of the structural and optical properties of thin films of copper sulfide with different thicknesses prepared by pulsed laser deposition technique.

Study of the structural and optical properties of thin films of copper sulfide with different thicknesses prepared by pulsed laser deposition technique. | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Study of the structural and optical properties of thin films of copper sulfide with different thicknesses prepared by pulsed laser deposition technique. Majid K. Abdulhemza1, Asghar Esmaeili2, Saif M. Alshrefi3 This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6151714/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The unique properties of copper sulfide, particularly in the field of photovoltaic applications, have prompted an investigation. This practical research study of the compound includes structural and optical examinations. We prepared and deposited four thin films on glass slides using the pulsed laser deposition technique (PLD). The XRD data indicate that the films are polycrystalline and exhibit a hexagonal crystalline structure compared to the standard international diffraction cards. We conducted and analysed optical property tests over wavelengths ranging from (100–900) nm. The analysis results and graphs showed that the absorbance went up as the film thickness went up or as the number of laser pulses used to make the films went up. However, transmittance decreased as film thickness increased, unlike absorbance. The bandgap energy was calculated, and through mathematical calculations, it was found to be of the allowed direct type, with values ranging from 2.1eV to 2.4eV. Optical Materials and Devices Thin films (PLD) technique CuS X-ray diffraction Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 1. Introduction Transition metal chalcogenides have attracted considerable interest in recent years because of their advantageous physical and chemical properties, along with their potential applications in diverse fields. A variety of processes are available for thin film fabrication, “including pulsed laser deposition, electrodeposition, vacuum evaporation, chemical bath deposition, spray pyrolysis, sequential ionic layer adsorption and reaction (SILAR), and electron beam evaporation”. Recent studies have concentrated significantly on copper sulfide owing to its distinctive properties. It could be utilized in solar cells, medical gadgets, photocatalysis, sensors, and lithium rechargeable batteries. “It is a binary inorganic chemical compound that naturally exists as a dark indigo-blue mineral with the general formula CuxSy. It is present in synthetic compounds and minerals, including CuS (covellite) and Cu₂S (chalcocite)”. The properties and synthesis of copper sulfide nanostructures have become a significant area of research. CuS exhibits unique absorbance edges in both the ultraviolet and visible spectra [ 8 ]. Owing to the distinctive structural, electrical, and optical characteristics of CuS, thin films are widely employed as semiconductor and/or absorber materials in electronics, photovoltaic cells, and tubular solar collectors. CuS (covellite) thin films are noted for their metallic electrical conductivity and nearly optimal solar control properties [ 9 ]. Numerous disadvantages associated with these methods have been documented, impacting electrical and optical properties, including prolonged deposition times related to concentrations, difficulties in controlling film thickness and structure, utilization of hazardous chemical solutions, elevated temperatures and pressures, UV effects, protection costs, workforce requirements, and surfactant usage [ 10 , 11 , 12 , 13 , 14 ]. The optical characteristics of CuS are significantly influenced by copper vacancies [ 15 ]. PLD is an appropriate method for depositing thin films, offering advantages such as reduced deposition time, cost efficiency, and minimal manpower requirements. 2. Experimental Part The four thin films of copper sulfide compound were prepared using the pulsed laser deposition method in the laboratory, and the work steps include the following: 1. Place the powder inside a silicone container after cleaning it with distilled water and acetone using a mixing and grinding machine that does not react with the powder for 45 minutes. 2. The powder was pressed using a 10-ton hydraulic press, and the press was cleaned with ethyl alcohol before the pressing process, where the diameter of the prepared sample was 2cm centimetres and its thickness was mm. 3. The samples were prepared on glass substrates with a thickness of (1-1.2) mm and had good absorption for wavelengths within the ultraviolet region. 4. The glass slides were placed inside the deposition chamber of the system for half an hour to ensure they reached the ideal temperature of 250 degrees Celsius to increase material adhesion, under a vacuum pressure of 10 -3 millibar, using a Nd: YAG laser., with the slide situated 10 cm from the target. A Nd-YAG laser with a (λ) = 1064 nm was utilized at an incidence angle of 45 degrees. 3. Results &Discussion 3.1 XRD: The results of the XRD analysis of the membranes prepared using the pulsed laser deposition technique with different thicknesses showed the following: 1. The structure is polycrystalline and has a hexagonal system. 2. The preferred growth direction for the different membranes at the upper peaks was (103). 3. The peak locations clearly correspond with the reflections at the specified angles. 4 . By comparing Figure ) 3 ( with the practical results in Table ) 1 ( and the "ICDD numbered (06-0464)" (X'Pert HighScore software Plus) The results were found to be nearly equivalent, with observations indicating that the peaks on the produced membranes are distinctly enhanced by an increase in the thickness. The thickness of the produced films demonstrates that the degree of crystallization increases with greater film thickness. This outcome aligns with the published research [5]. Table1:phases of different thickness CuS thinfilms CuS-sample 2ϴ (Deg.) hkl Phase Card no. 100 pulses 26.7800 (101) Orthorhobic 00-042-1278 200 pulses 27.2902 (102) Hexgonal 00-006-0464 300 pulses 24.3119 (101) Orthorhombic 00-042-1278 400 pulses 33.1233 (103) Hexagonal 00-006-0464 An increase in the frequency of laser pulses during Pulsed Laser Deposition (PLD) results in a greater deposition of material, yielding thicker films. This directly influences the XRD peak intensities for various reasons: 1. Enhanced Crystallinity: An increase in pulse frequency results in greater material deposition, hence improving crystallization. This improves the intensity of diffraction peaks. 2. Increase in Film Thickness: Thicker films augment the amount of diffracted X-rays, hence enhancing peak intensity. Thin films frequently exhibit diminished peaks owing to restricted material interaction with X-rays. 3. Improved Grain Growth: A higher number of pulses can improve grain growth and minimize flaws, leading to stronger diffraction signals. 4. Preferred Orientation: As the film thickness increases, some crystal planes may align preferentially, resulting in enhanced intensity of specific peaks. 5. Decreased Amorphous Content: At reduced pulse counts, the film may exhibit a greater degree of disorder or be partially amorphous. Augmenting the pulse count facilitates improved atomic organization, enhancing peak intensity. For the production of a high-efficiency solar cell, it is preferable to select a thin film exhibiting optimal crystallization and minimal crystalline flaws, as these factors influence electrical conductivity and electron transmission inside the material. The XRD curves in the image reveal the following observations. An augmentation in the quantity of pulses results in an enhancement of peak intensity, signifying superior crystallization. However, it is essential to consider the dimensions of the crystal grains and their orientation, as certain crystallographic directions may facilitate electron transport more effectively than others. The presence of an optimal thickness for the thin film is crucial. An excessively thick coating may lead to heightened recombination, diminishing the cell's efficiency. What is the optimal number of pulses? A poorly crystalline layer from 100 pulses may be unsuitable because of its high electrical resistance. Utilizing 400 pulses may yield high crystallinity, but if the layer gets excessively thick, it could increase light absorption without enhancing energy conversion efficiency. The best number of pulses may be between 200 and 300, which helps find a balance between crystallization, layer thickness, and crystal orientation. 3.2 Absorbance: The “absorption spectrum” was measured as a function of wavelength. By analyzing the “Absorbance spectrum”, one can determine several optical constants. Measurements were performed over the (λ) range of 100 to 900 nm for all CuS thin films. The UV-VIS measurement results are presented in Fig. 4, showing the fluctuation of the absorbance spectrum relative to wavelength. The data demonstrated that absorbance escalates with the number of pulses, leading to increased thickness. The photons can energize the electron, enabling its passage from the V.band to the C.band, as the ( Energy incident photon )surpasses the semiconductor's energy gap.. Consequently, absorbance rises with increasing wavelength, consistent with prior studies [8] [9]. Fig.4 shows the “Absorption Spectrum” of thin films of (CuS) in the (λ) range of 300-1000 nanometers. The curve shows the change in absorbance according to the variation in the number of pulses and energy during the preparation of the films using the (PLD) technique: The green curve (1200mj-100p): shows the lowest absorbance among all the curves, indicating that the layer prepared under these conditions is less dense or thinner. The black curve (200p) demonstrates a distinct rise in absorbance, signifying that an escalation in the number of pulses results in enhanced density and thickness of the film, therefore augmenting absorption. The blue curve (A 3-300p) and the red curve (A 4-400p): They show an additional increase in absorbance with the increase in the no. of pulses, where the absorbance reaches its highest value at the red curve (400p), indicating the formation of a thicker film or improved nanostructures. We notice that the absorption edge moves gradually with changes in the number of pulses and energy, which is an indicator of changes in the crystal size or the electronic structure of the film. The edge shift towards longer wavelengths (Redshift) may be due to an increase in crystal size or the formation of different phases of CuS. On the other hand, if a shift towards shorter wavelengths (Blueshift) occurs, it may indicate a reduction in the size of nanoparticles and quantum effects. 3.3 Transmittance: The transmission measurement was conducted across the wavelength is 200 to 900 nm for all CuS thin films. UV-VIS studies demonstrated that the transmission spectrum displays markedly distinct behaviour compared to the " Absorbance Spectrum " , as illustrated in Fig. (5). The transmission of the thin film diminished with increasing (λ); furthermore, these results indicated that the thin films exhibit high transmission in the visible and IR spectra, especially between (500 – 760) nm. This range of wavelengths is referred to as the fundamental absorption edge, depicted as a curve, indicating that the film structure is Polycrystalline. The Absorption and transmission are influenced by various factors, including material composition, thickness, light wavelength, surface characteristics, and crystalline structure. The transmission variance of thin films is contingent upon the preparation methodology and conditions, as indicated in [10]. The thickness of the films produced by the (PLD) technology significantly influences optical transmission, and this effect can be stated as follows: Augmenting the thickness results in a reduction in permeability. As the number of pulses rises (from 100 to 400), the thickness of the films formed on the substrate also increases.. The increase in thickness leads to more absorption and scattering of light, which reduces light transmittance. Thin films often exhibit nonlinear behavior; that is, the effect may not be perfectly proportional to the number of pulses. Changes in crystal structure and roughness: Increasing the number of pulses can improve crystallization, which may indirectly affect permeability. A rougher surface may lead to light scattering, which also reduces permeability. The wavelength of the light used in the measurement is important: Usually, permeability is higher at longer wavelengths (near-infrared) and decreases in the ultraviolet range. When the thickness increases, the optical absorption edge may shift to different wavelengths due to changes in the band gap. 3.4 Bandgap: The band gap of thin films prepared by (PLD) method is significantly influenced by the number of laser pulses (100–400 pulses) due to several key factors: 1. Effect of Film Thickness on Band Gap Increasing the number of pulses from 100 to 400 leads to thicker films, which can reduce the band gap due to: Quantum confinement effects: Thin films deposited with fewer pulses (e.g., 100 pulses) tend to exhibit a wider band gap due to size confinement of the nanostructures. Reduced defects and improved crystallinity: More pulses typically enhance crystallinity, reducing localized states and narrowing the band gap. 2. Structural and Morphological Influence Low pulse numbers (100–200 pulses): May result in nanostructured films with small grains and increased quantum confinement, leading to a higher band gap (~2.1 eV or more). High pulse numbers (300–400 pulses): Produce thicker films with better crystallinity, reducing the band gap to values closer to bulk CuS (~1.8–2.0 eV) due to reduced confinement effects. 3. Oxygen and Sulfur Deficiency Effects PLD films can exhibit stoichiometry variations, particularly sulfur vacancies, which may introduce defect states and slightly shift the band gap. 4. Optical Absorption Analysis Measured using UV-Vis spectroscopy, the band gap can be estimated via Tauc plots where Eg (band gap) depends on film thickness and deposition parameters. “(αhν) n =A(hν−Eg)”, where: “α = Absorption coeff., hν is photon Energy”, n = material-dependent constant, n depends on the nature of the transition (for CuS, it is typically n = 2 for a direct band gap) Table 2: Values bandgaps,no. of pulses, gap effect. 4. Conclusion Copper sulfide (CuS) films formed on glass substrates via pulsed laser evaporation with varying pulse parameters exhibited diverse hexagonal crystalline structures, as evidenced by XRD data. The optical tests indicated that the thin films exhibited direct allowed transitions, and the energy gap diminished as the no. of pulses increased. The energy gap diminishes with increasing thickness, with values from)2.1to 2.4 ( eV. References Mustafa Amer Hassan, “The effect of annealing processes on some physical properties of the Cu2S film prepared by thermal decomposition method”, Master Thesis, University of Technology, Department of Applied Sciences (2006). M. T. S. Nair and P. K. Nair, "Chemical Bath Deposition of CuS Thin Films and their Prospective Large Area Applications", Semicond. Sci. Technol., Vol. 4, pp. (191- 199), (1989). Dr. Mohamed Ezz El-Din, "Mineralogy", Cairo The Anglo-Egyptian Library, (1994). R.F.Bunshah " Hand Book of Deposition technologies for films and Coatings" Book ,2th ,(1994),William Andrew publishing 13Eston Avenue ,Norwich,NY13815. W. Daranfed, M. S. Aido, A. Hafdallah and H. Lekiket, "Substrate Temperature Influence on ZnS Thin Films Prepared by Ultrasonic Spray", Thin Solid Films, Vol. 518, pp. (1082-1084), (2009). M. Caglar, S. Ilcan and Y. Caglar, "Influence of Substrate Temperature on Structural and Electrical Properties of ZnO Films", J. Sci, Vol.7 No.2, pp. (153-159), (2006). A. Wei, J. Liu, M. Zhuan and Y. Zhao, "Preparation and Characterization of ZnS thin films prepared by chemical bath deposition", Mater. Sci. Semicond. Proc, Vol. 16, pp. (1478-1484), (2013). Shamraiz, U.; Azadar, R.; Badshah, A. Fabrication and applications of copper sulfide (CuS) nanostructure. J. Solid State Chem. 2016, 238, 25–40. [Google Scholar] [CrossRef]. L. A. Isac and A. Duta, “The growth of CuS thin films by Spray Pyrolysis” , journal of physics: Conference Series 61 (2007) 477–481 , 2007. M.A. Sangamesha, K. Pushpalatha, G.L. Shekar, S. Shamsundar, Preparation and characterization of nanocrystalline CuS thin films for dye-sensitized solar cells, ISRN Nanomater. 2013 (2013) 1–8. A. K. Sahoo, P. Mohanta, A.S. Bhattacharyya, Structural and optical properties of CuS thin films deposited by thermal co-evaporation, IOP Conf. Ser. Mater. Sci. Eng. 73(1) (2015). X.-S. Hu, Y. Shen, L.-H. Xu, L.-M. Wang, Y.-J. Xing, Preparation of flower-like CuS by solvothermal method and its photodegradation and UV protection, J. Alloys Compd. 674 (2016) 289–294. T. Mahalingam, C. Sanjeeviraja, Characterization of electrodeposited zinc sulphide thin films, Phys. Status Solidi 129 (2) (1992) K89–K92. M. Saranya, C. Santhosh, R. Ramachandran, A. Nirmala Grace, Growth of CuS nanostructures by hydrothermal route and its optical properties, J. Nanotechnol. 2014 (2014) 1–8. A. Singh, R. Manivannan, S. Noyel Victoria, Simple one-pot sonochemical synthesis of copper sulphide nanoparticles for solar cell applications, Arab. J. Chem. 12 (8) (2019) 2439–2447. Additional Declarations The authors declare no competing interests. Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6151714","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":430048613,"identity":"9baf1c98-b68d-4376-8f1d-488013853a08","order_by":0,"name":"Majid K. 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Alshrefi3","email":"","orcid":"","institution":"Department of Laser Physics, College of Science for Women, University of Babylon, Iraq","correspondingAuthor":false,"prefix":"","firstName":"Saif","middleName":"M.","lastName":"Alshrefi3","suffix":""}],"badges":[],"createdAt":"2025-03-04 07:11:44","currentVersionCode":1,"declarations":{"humanSubjects":false,"vertebrateSubjects":false,"conflictsOfInterestStatement":false,"humanSubjectEthicalGuidelines":false,"humanSubjectConsent":false,"humanSubjectClinicalTrial":false,"humanSubjectCaseReport":false,"vertebrateSubjectEthicalGuidelines":false},"doi":"10.21203/rs.3.rs-6151714/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6151714/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":78730619,"identity":"05c32363-9811-4a81-8e7e-2b1e57dfcf1b","added_by":"auto","created_at":"2025-03-18 07:30:52","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":249095,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eCrystal structure of the copper sulfide [1].\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-6151714/v1/0be9672f0f5e6a5ec5d130c7.png"},{"id":78730013,"identity":"45c55942-b47d-46d3-aaf5-e981b0f241c8","added_by":"auto","created_at":"2025-03-18 07:22:52","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":71740,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(PLD) system.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6151714/v1/1cd26af58bb260df7c2dd00e.jpeg"},{"id":78730014,"identity":"50d2ffe3-ef56-434e-acc0-8fab2167f0a0","added_by":"auto","created_at":"2025-03-18 07:22:52","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":77447,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ethe (XRD) of the (CuS) prepared films.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-6151714/v1/a9c23245c10e481a635e2a0b.png"},{"id":78730622,"identity":"02cb5bf0-bf20-4e41-b510-d372f40df179","added_by":"auto","created_at":"2025-03-18 07:30:52","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":162439,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ethe Absorbance of CuS thin films for different thickness\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-6151714/v1/21f94d495ef68bef5ff48cb1.png"},{"id":78731394,"identity":"c4c8d48d-e1e5-4024-87eb-264c9e28ccf4","added_by":"auto","created_at":"2025-03-18 07:38:52","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":81109,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eFig.(4): Transmittance of CuS thin films for different thickness.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-6151714/v1/e0f8cfba19efffd3da4d4fca.png"},{"id":78730028,"identity":"bb74fe4d-5c09-4212-93c8-f1265efa798f","added_by":"auto","created_at":"2025-03-18 07:22:52","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":216955,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eFig.(5): Bandgaps of CuS thin films for different thickness.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-6151714/v1/e3b3e57d7045a7f4cc07f44f.png"},{"id":78732399,"identity":"06f73ae6-e879-4024-9003-098d820ffe8b","added_by":"auto","created_at":"2025-03-18 07:46:52","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1432451,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6151714/v1/acfc5716-78fd-43a8-8bf6-2c4aa7803da5.pdf"}],"financialInterests":"The authors declare no competing interests.","formattedTitle":"\u003cp\u003eStudy of the structural and optical properties of thin films of copper sulfide with different thicknesses prepared by pulsed laser deposition technique.\u003c/p\u003e","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eTransition metal chalcogenides have attracted considerable interest in recent years because of their advantageous physical and chemical properties, along with their potential applications in diverse fields. A variety of processes are available for thin film fabrication, \u0026ldquo;including pulsed laser deposition, electrodeposition, vacuum evaporation, chemical bath deposition, spray pyrolysis, sequential ionic layer adsorption and reaction (SILAR), and electron beam evaporation\u0026rdquo;. Recent studies have concentrated significantly on copper sulfide owing to its distinctive properties. It could be utilized in solar cells, medical gadgets, photocatalysis, sensors, and lithium rechargeable batteries. \u0026ldquo;It is a binary inorganic chemical compound that naturally exists as a dark indigo-blue mineral with the general formula CuxSy. It is present in synthetic compounds and minerals, including CuS (covellite) and Cu₂S (chalcocite)\u0026rdquo;. The properties and synthesis of copper sulfide nanostructures have become a significant area of research. CuS exhibits unique absorbance edges in both the ultraviolet and visible spectra [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]. Owing to the distinctive structural, electrical, and optical characteristics of CuS, thin films are widely employed as semiconductor and/or absorber materials in electronics, photovoltaic cells, and tubular solar collectors. CuS (covellite) thin films are noted for their metallic electrical conductivity and nearly optimal solar control properties [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. Numerous disadvantages associated with these methods have been documented, impacting electrical and optical properties, including prolonged deposition times related to concentrations, difficulties in controlling film thickness and structure, utilization of hazardous chemical solutions, elevated temperatures and pressures, UV effects, protection costs, workforce requirements, and surfactant usage [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]. The optical characteristics of CuS are significantly influenced by copper vacancies [\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. PLD is an appropriate method for depositing thin films, offering advantages such as reduced deposition time, cost efficiency, and minimal manpower requirements.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"2. Experimental Part","content":"\u003cp\u003eThe four thin films of copper sulfide compound were prepared using the pulsed laser deposition method in the laboratory, and the work steps include the following:\u003c/p\u003e\n\u003cp\u003e1. Place the powder inside a silicone container after cleaning it with distilled water and acetone using a mixing and grinding machine that does not react with the powder for 45 minutes.\u003c/p\u003e\n\u003cp\u003e2. The powder was pressed using a 10-ton hydraulic press, and the press was cleaned with ethyl alcohol before the pressing process, where the diameter of the prepared sample was 2cm centimetres and its thickness was mm.\u003c/p\u003e\n\u003cp\u003e3. The samples were prepared on glass substrates with a thickness of (1-1.2) mm and had good absorption for wavelengths within the ultraviolet region.\u003c/p\u003e\n\u003cp\u003e4. The glass slides were placed inside the deposition chamber of the system for half an hour to ensure they reached the ideal temperature of 250 degrees Celsius to increase material adhesion, under a vacuum pressure of 10\u003csup\u003e-3\u003c/sup\u003e millibar, using a Nd: YAG laser., with the slide situated 10 cm from the target. \u0026nbsp;A Nd-YAG laser with a (\u0026lambda;) = 1064 nm was utilized at an incidence angle of 45 degrees.\u003c/p\u003e"},{"header":"3. Results \u0026Discussion ","content":"\u003cp\u003e\u003cstrong\u003e3.1 XRD:\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe results of the XRD analysis of the membranes prepared using the pulsed laser deposition technique with different thicknesses showed the following:\u003c/p\u003e\n\u003cp\u003e1. The structure is polycrystalline and has a hexagonal system.\u003c/p\u003e\n\u003cp\u003e2. The preferred growth direction for the different membranes at the upper peaks was (103).\u003c/p\u003e\n\u003cp\u003e3. The peak locations clearly correspond with the reflections at the specified angles.\u003c/p\u003e\n\u003cp\u003e\u003cspan dir=\"RTL\"\u003e4\u003c/span\u003e. By comparing Figure \u003cspan dir=\"RTL\"\u003e)\u003c/span\u003e3\u003cspan dir=\"RTL\"\u003e(\u003c/span\u003e with the practical results in Table \u003cspan dir=\"RTL\"\u003e)\u003c/span\u003e1\u003cspan dir=\"RTL\"\u003e(\u003c/span\u003e and the \u0026quot;ICDD numbered (06-0464)\u0026quot; (X\u0026apos;Pert HighScore software Plus) The results were found to be nearly equivalent, with observations indicating that the peaks on the produced membranes are distinctly enhanced by an increase in the thickness. The thickness of the produced films demonstrates that the degree of crystallization increases with greater film thickness. This outcome aligns with the published research [5].\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e\u0026nbsp;Table1:phases of different thickness CuS thinfilms\u003c/strong\u003e\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u003cstrong\u003eCuS-sample\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e2ϴ (Deg.)\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;hkl\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e\u0026nbsp; \u0026nbsp; Phase\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp;Card no.\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e\u0026nbsp; 100 pulses\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u0026nbsp; 26.7800\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u0026nbsp; \u0026nbsp; (101)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u0026nbsp;Orthorhobic\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u0026nbsp; 00-042-1278\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e200 pulses\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e27.2902\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u0026nbsp; (102)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003eHexgonal\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e00-006-0464\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e300 pulses\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e24.3119\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp;(101)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003eOrthorhombic\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e00-042-1278\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u003cstrong\u003e400 pulses\u003c/strong\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e33.1233\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e\u0026nbsp; (103)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003eHexagonal\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 128px;\"\u003e\n \u003cp\u003e00-006-0464\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003eAn increase in the frequency of laser pulses during Pulsed Laser Deposition (PLD) results in a greater deposition of material, yielding thicker films. This directly influences the XRD peak intensities for various reasons: 1. Enhanced Crystallinity: An increase in pulse frequency results in greater material deposition, hence improving crystallization. This improves the intensity of diffraction peaks. 2. Increase in Film Thickness: Thicker films augment the amount of diffracted X-rays, hence enhancing peak intensity. Thin films frequently exhibit diminished peaks owing to restricted material interaction with X-rays. 3. Improved Grain Growth: A higher number of pulses can improve grain growth and minimize flaws, leading to stronger diffraction signals. 4. Preferred Orientation: As the film thickness increases, some crystal planes may align preferentially, resulting in enhanced intensity of specific peaks. 5. Decreased Amorphous Content: At reduced pulse counts, the film may exhibit a greater degree of disorder or be partially amorphous. Augmenting the pulse count facilitates improved atomic organization, enhancing peak intensity. For the production of a high-efficiency solar cell, it is preferable to select a thin film exhibiting optimal crystallization and minimal crystalline flaws, as these factors influence electrical conductivity and electron transmission inside the material. The XRD curves in the image reveal the following observations. An augmentation in the quantity of pulses results in an enhancement of peak intensity, signifying superior crystallization. However, it is essential to consider the dimensions of the crystal grains and their orientation, as certain crystallographic directions may facilitate electron transport more effectively than others. The presence of an optimal thickness for the thin film is crucial. An excessively thick coating may lead to heightened recombination, diminishing the cell\u0026apos;s efficiency. What is the optimal number of pulses? A poorly crystalline layer from 100 pulses may be unsuitable because of its high electrical resistance. Utilizing 400 pulses may yield high crystallinity, but if the layer gets excessively thick, it could increase light absorption without enhancing energy conversion efficiency. The best number of pulses may be between 200 and 300, which helps find a balance between crystallization, layer thickness, and crystal orientation.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.2 Absorbance:\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe \u0026ldquo;absorption spectrum\u0026rdquo; was measured as a function of wavelength. By analyzing the \u0026ldquo;Absorbance spectrum\u0026rdquo;, one can determine several optical constants. Measurements were performed over the (\u0026lambda;) range of 100 to 900 nm for all CuS thin films. The UV-VIS measurement results are presented in Fig. 4, showing the fluctuation of the absorbance spectrum relative to wavelength. The data demonstrated that absorbance escalates with the number of pulses, leading to increased thickness. The photons can energize the electron, enabling its passage from the V.band to the C.band, as the (\u003cstrong\u003eEnergy \u003csup\u003eincident photon\u003c/sup\u003e\u003c/strong\u003e )surpasses the semiconductor\u0026apos;s energy gap.. Consequently, absorbance rises with increasing wavelength, consistent with prior studies [8] [9]. Fig.4 shows the \u0026ldquo;Absorption Spectrum\u0026rdquo; of thin films of (CuS) in the (\u0026lambda;) range of 300-1000 nanometers. The curve shows the change in absorbance according to the variation in the number of pulses and energy during the preparation of the films using the (PLD) technique: The green curve (1200mj-100p): shows the lowest absorbance among all the curves, indicating that the layer prepared under these conditions is less dense or thinner. The black curve (200p) demonstrates a distinct rise in absorbance, signifying that an escalation in the number of pulses results in enhanced density and thickness of the film, therefore augmenting absorption. The blue curve (A 3-300p) and the red curve (A 4-400p): They show an additional increase in absorbance with the increase in the no. of pulses, where the absorbance reaches its highest value at the red curve (400p), indicating the formation of a thicker film or improved nanostructures. We notice that the absorption edge moves gradually with changes in the number of pulses and energy, which is an indicator of changes in the crystal size or the electronic structure of the film. The edge shift towards longer wavelengths (Redshift) may be due to an increase in crystal size or the formation of different phases of CuS. On the other hand, if a shift towards shorter wavelengths (Blueshift) occurs, it may indicate a reduction in the size of nanoparticles and quantum effects.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.3 Transmittance:\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe transmission measurement was conducted across the wavelength is 200 to 900 nm for all CuS thin films. UV-VIS studies demonstrated that the transmission spectrum displays markedly distinct behaviour compared to the \u003cspan dir=\"RTL\"\u003e\u0026quot;\u003c/span\u003eAbsorbance Spectrum\u003cspan dir=\"RTL\"\u003e\u0026quot;\u003c/span\u003e, as illustrated in Fig. (5). The transmission of the thin film diminished with increasing (\u0026lambda;); furthermore, these results indicated that the thin films exhibit high transmission in the visible and IR spectra, especially between (500 \u0026ndash; 760) nm. This range of wavelengths is referred to as the fundamental absorption edge, depicted as a curve, indicating that the film structure is Polycrystalline. The Absorption and transmission are influenced by various factors, including material composition, thickness, light wavelength, surface characteristics, and crystalline structure. The transmission variance of thin films is contingent upon the preparation methodology and conditions, as indicated in [10]. The thickness of the films produced by the (PLD) technology significantly influences optical transmission, and this effect can be stated as follows: Augmenting the thickness results in a reduction in permeability. As the number of pulses rises (from 100 to 400), the thickness of the films formed on the substrate also increases.. The increase in thickness leads to more absorption and scattering of light, which reduces light transmittance. Thin films often exhibit nonlinear behavior; that is, the effect may not be perfectly proportional to the number of pulses. Changes in crystal structure and roughness: Increasing the number of pulses can improve crystallization, which may indirectly affect permeability. A rougher surface may lead to light scattering, which also reduces permeability. The wavelength of the light used in the measurement is important: Usually, permeability is higher at longer wavelengths (near-infrared) and decreases in the ultraviolet range. When the thickness increases, the optical absorption edge may shift to different wavelengths due to changes in the band gap.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e3.4 Bandgap:\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe band gap of thin films prepared by (PLD) method \u0026nbsp;is significantly influenced by the number of laser pulses (100\u0026ndash;400 pulses) due to several key factors:\u003c/p\u003e\n\u003cp\u003e1. \u003cstrong\u003eEffect of Film Thickness on Band Gap\u003c/strong\u003e\u003c/p\u003e\n\u003cul type=\"disc\"\u003e\n \u003cli\u003eIncreasing the number of pulses from 100 to 400 leads to thicker films, which can reduce the band gap due to:\u003cul type=\"circle\"\u003e\n \u003cli\u003eQuantum confinement effects: Thin films deposited with fewer pulses (e.g., 100 pulses) tend to exhibit a wider band gap due to size confinement of the nanostructures.\u003c/li\u003e\n \u003cli\u003eReduced defects and improved crystallinity: More pulses typically enhance crystallinity, reducing localized states and narrowing the band gap.\u003c/li\u003e\n \u003c/ul\u003e\n \u003c/li\u003e\n\u003c/ul\u003e\n\u003cp\u003e2. \u003cstrong\u003eStructural and Morphological Influence\u003c/strong\u003e\u003c/p\u003e\n\u003cul type=\"disc\"\u003e\n \u003cli\u003eLow pulse numbers (100\u0026ndash;200 pulses):\u003cul type=\"circle\"\u003e\n \u003cli\u003eMay result in nanostructured films with small grains and increased quantum confinement, leading to a higher band gap (~2.1 eV or more).\u003c/li\u003e\n \u003c/ul\u003e\n \u003c/li\u003e\n \u003cli\u003eHigh pulse numbers (300\u0026ndash;400 pulses):\u003cul type=\"circle\"\u003e\n \u003cli\u003eProduce thicker films with better crystallinity, reducing the band gap to values closer to bulk CuS (~1.8\u0026ndash;2.0 eV) due to reduced confinement effects.\u003c/li\u003e\n \u003c/ul\u003e\n \u003c/li\u003e\n\u003c/ul\u003e\n\u003cp\u003e3. \u003cstrong\u003eOxygen and Sulfur Deficiency Effects\u003c/strong\u003e\u003c/p\u003e\n\u003cul type=\"disc\"\u003e\n \u003cli\u003ePLD films can exhibit stoichiometry variations, particularly sulfur vacancies, which may introduce defect states and slightly shift the band gap.\u003c/li\u003e\n\u003c/ul\u003e\n\u003cp\u003e4. \u003cstrong\u003eOptical Absorption Analysis\u003c/strong\u003e\u003c/p\u003e\n\u003cul type=\"disc\"\u003e\n \u003cli\u003eMeasured using UV-Vis spectroscopy, the band gap can be estimated via Tauc plots\u003c/li\u003e\n\u003c/ul\u003e\n\u003cp\u003ewhere \u003cstrong\u003eEg (band gap)\u003c/strong\u003e depends on film thickness and deposition parameters.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u0026nbsp; \u0026nbsp; \u0026nbsp; \u0026nbsp;\u0026ldquo;(\u0026alpha;h\u0026nu;)\u003csup\u003en\u003c/sup\u003e=A(h\u0026nu;\u0026minus;Eg)\u0026rdquo;, where:\u003c/p\u003e\n\u003cul\u003e\n \u003cli\u003e\u0026ldquo;\u0026alpha; = Absorption coeff., h\u0026nu; is photon Energy\u0026rdquo;, n = material-dependent constant,\u003c/li\u003e\n \u003cli\u003en depends on the nature of the transition (for CuS, it is typically \u003cstrong\u003en = 2\u003c/strong\u003e for a direct band gap)\u003c/li\u003e\n\u003c/ul\u003e\n\u003cp\u003e\u003cstrong\u003eTable 2: Values bandgaps,no. of pulses, gap effect.\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cimg 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\" width=\"948\" height=\"237\"\u003e\u003cbr\u003e\u003c/p\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eCopper sulfide (CuS) films formed on glass substrates via pulsed laser evaporation with varying pulse parameters exhibited diverse hexagonal crystalline structures, as evidenced by XRD data. The optical tests indicated that the thin films exhibited direct allowed transitions, and the energy gap diminished as the no. of pulses increased. The energy gap diminishes with increasing thickness, with values from)2.1to 2.4\u003cspan dir=\"RTL\"\u003e(\u003c/span\u003eeV.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eMustafa Amer Hassan, \u0026ldquo;The effect of annealing processes on some physical properties of the Cu2S film prepared by thermal decomposition method\u0026rdquo;, Master Thesis, University of Technology, Department of Applied Sciences (2006).\u003c/li\u003e\n\u003cli\u003eM. T. S. Nair and P. K. 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Bhattacharyya, Structural and optical properties of CuS thin films deposited by thermal co-evaporation, IOP Conf. Ser. Mater. Sci. Eng. 73(1) (2015).\u003c/li\u003e\n\u003cli\u003eX.-S. Hu, Y. Shen, L.-H. Xu, L.-M. Wang, Y.-J. Xing, Preparation of flower-like CuS by solvothermal method and its photodegradation and UV protection, J. Alloys Compd. 674 (2016) 289\u0026ndash;294.\u003c/li\u003e\n\u003cli\u003eT. Mahalingam, C. Sanjeeviraja, Characterization of electrodeposited zinc sulphide thin films, Phys. Status Solidi 129 (2) (1992) K89\u0026ndash;K92.\u003c/li\u003e\n\u003cli\u003eM. Saranya, C. Santhosh, R. Ramachandran, A. Nirmala Grace, Growth of CuS nanostructures by hydrothermal route and its optical properties, J. Nanotechnol. 2014 (2014) 1\u0026ndash;8.\u003c/li\u003e\n\u003cli\u003eA. Singh, R. Manivannan, S. Noyel Victoria, Simple one-pot sonochemical synthesis of copper sulphide nanoparticles for solar cell applications, Arab. J. Chem. 12 (8) (2019) 2439\u0026ndash;2447. \u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"university of urmia","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Thin films, (PLD) technique, CuS, X-ray diffraction","lastPublishedDoi":"10.21203/rs.3.rs-6151714/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6151714/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe unique properties of copper sulfide, particularly in the field of photovoltaic applications, have prompted an investigation. This practical research study of the compound includes structural and optical examinations. We prepared and deposited four thin films on glass slides using the pulsed laser deposition technique (PLD). The XRD data indicate that the films are polycrystalline and exhibit a hexagonal crystalline structure compared to the standard international diffraction cards. We conducted and analysed optical property tests over wavelengths ranging from (100\u0026ndash;900) nm. The analysis results and graphs showed that the absorbance went up as the film thickness went up or as the number of laser pulses used to make the films went up. However, transmittance decreased as film thickness increased, unlike absorbance. The bandgap energy was calculated, and through mathematical calculations, it was found to be of the allowed direct type, with values ranging from 2.1eV to 2.4eV.\u003c/p\u003e","manuscriptTitle":"Study of the structural and optical properties of thin films of copper sulfide with different thicknesses prepared by pulsed laser deposition technique.","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-03-18 07:22:47","doi":"10.21203/rs.3.rs-6151714/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"10aed031-8d2b-489c-8aeb-5b51a38346b4","owner":[],"postedDate":"March 18th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":45801970,"name":"Optical Materials and Devices"}],"tags":[],"updatedAt":"2025-03-18T07:22:47+00:00","versionOfRecord":[],"versionCreatedAt":"2025-03-18 07:22:47","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6151714","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6151714","identity":"rs-6151714","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}