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Abstract
Article Growth of New, Optically Active, Semi-Organic Single Crystals Glycine-Copper Sulphate Doped by Silver Nanoparticles 1 2 2 2 Rasmiah Saad A. Almufarij , Alaa El-Deen Ali , Mohamed Elsayed Elba , Howida Eid Okab , 3 4 4 , Ollaa Moftah Mailoud , Hamida Abdel-Hamid and Howida Abouel Fetouh Elsayed * Chemistry Department, College of Science, Princess Nourah bint Abdulrahman University, P.O. Box 84428, Riyadh 11671, Saudi Arabia Chemistry Department, Faculty of Science, Damanhur University, Damanhour 22511, Egypt Physics Department, Faculty of Science, Benghazi University, Benghazi 21861, Libya Chemistry Department, Faculty of Science, Alexandria University, P.O. Box 426, Alexandria 21321, Egypt * Correspondence: howida_fetouh@alexu.edu.eg Abstract: The purpose of this study is to modify all physicochemical properties of glycine–copper sulphate single crystals, such as crystal habits, molar mass, thermal stability, optical activity, and electrical properties. The novelty of this study is growth of glycine–copper sulphate single crystals doped by a low concentration of silver nanoparticles (SNPs) that improved both crystal habits and physicochemical properties. The originality of this work is that trace amounts of SNPs largely increased the crystal size. Crystals have molar stoichiometric formula [glycine] , [CuSO 5H O] 0.95 4 2 0.05 in the absence and presence of silver nanoparticles (SNPs) in different concentrations: 10 ppm, 20 ppm, and 30 ppm. The crystals’ names and abbreviations are: glycine–copper sulphate (GCS), glycine– copper sulphate doped by 10 ppm SNPs (GCSN1), glycine–copper sulphate doped by 20 ppm SNPs (GCSN2), and glycine–copper sulphate doped by 30 ppm SNPs (GCSN3). Dopant silver nanoparticles increased: crystallinity reflecting purity, transparency to UV-Vis. electromagnetic radiation, thermal stability, and melting point of glycine–copper sulphate single crystal. GCSN3 is a super conductor. Citation: Almufarij, R.S.A.; Ali, 1 1 1 1 High thermal conductivity of crystals ranging from 1.1 Wmin K to 1.6 Wmin K enabled A.E.-D.; Elba, M.E.; Okab, H.E.; attenuation of electromagnetic radiation and rapid heat dissipation due to good dielectric and polar Mailoud, O.M.; Abdel-Hamid, H.; properties. On rising temperature, AC electrical conductivity and dielectric properties of perfect Fetouh Elsayed, H.A. Growth of New, crystal GCSN3 increased confirmed attenuation of thermal infrared radiation. Optically Active, Semi-Organic Single Crystals Glycine-Copper Keywords: glycine; copper sulphate; silver nanoparticle; single crystals; doping; optical activity Sulphate Doped by Silver Nanoparticles. Appl. Nano 2023, 4, 115–137. https://doi.org/10.3390/ applnano4020007 1. Introduction Academic Editors: Khaled Saoud, Good optical, dielectric, and thermal properties of semi-organic single crystals enable Sami Rtimi and Fadwa El-Mellouhi application in modern technologies for design components in photonic devices, optical com- Received: 15 February 2023 munication systems, optoelectronics, frequency convertors, and nonlinear optical (NLO) Revised: 15 March 2023 devices [1]. Single crystals of glycine amino acid containing copper sulphate (CuSO ) are Accepted: 11 April 2023 used in optical high-resolution band pass filters for spectral devices [2]. Such crystals Published: 18 April 2023 having a good optical quality are rarely reported. At room temperature, glycine amino acid in zwitterion form is crystalized to , , and polymorphs [3–5]. Glycine–copper sulphate single crystals possess NLO activity and thermal stability due to synergism of both organic and inorganic components [6,7]. Glycine has a chiral center that crystallizes in Copyright: © 2023 by the authors. non-centrosymmetric space groups [8]. Inorganic copper sulphate enhanced mechanical Licensee MDPI, Basel, Switzerland. and thermal stability of glycine crystals [9]. Crystals’ growth in the presence of doping This article is an open access article impurities modified crystal habit and properties [10,11]. No studies are reported dop- distributed under the terms and ing glycine–copper sulphate crystals by silver nanoparticles that is widely used in food, conditions of the Creative Commons medical, industrial, catalysis, and pharmaceutical applications [12,13]. This study aims to Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ grow new single crystals of glycine–copper sulphate in the absence and presence of silver 4.0/). nanoparticles to add new unique properties for these blue-colored glycine–copper sulphate Appl. Nano 2023, 4, 115–137. https://doi.org/10.3390/applnano4020007 https://www.mdpi.com/journal/applnano Appl. Nano 2023, 4 116 single crystals to improve absorption of weak infra-red photons reaching the earth from the sun causing global warming. 2. Experimental Procedure 2.1. Materials and Methods All chemicals in this study are highly pure, of analytical grade, and used as received without further purification: glycine (C H NO , Oxford Co.) purity 98.5%, CuSO 5H O 2 5 2 4 2 (Sigma Aldrich Co., St. Louis, MO, USA), purity 98%. SNPs with polyvinylpyrrolidone, purity 99.9%, was purchased from Sigma Aldrich Co. with these physical characteristics: spherical shape nanoparticles: average diameter 21.44 4.92 nm and UV: electronic absorption bands at maximum wavelength ( 430 nm) due to delocalized electronic max. surface plasmon. Slow solvent evaporation method is employed at 25 C for growth of GCS crystals doped by SNPs. The stoichiometric formula is (glycine) , [CuSO ] . Salts are dissolved 0.95 4 0.05 in double distilled water and agitated at 50 rpm using a magnetic stirrer for two h to obtain a homogeneous saturated solution. For SNP doping, a solution of glycine and CuSO are agitated at 50 rpm for two hours. Different concentrations of 10 ppm, 20 ppm, and 30 ppm SNPs are added to the filtrate that is further stirred for half an hour to complete homogeneity. The solution is covered by porous aluminum foil in a dust-free environment to allow slow solvent evaporation. High-quality, blue-color, pure crystals are harvested after one month, Figure 1. Figure 1. Visual inspection of crystals. GCS crystals increased in size and intensity of blue color as doping concentration of SNPs increased. 2.2. Characterization of Single Crystals The grown crystals are characterized by: Mass spectra (MS) by electron ionization technique at 70 eV using Thermo GCMS- ISQLT mass spectrometer; elemental analysis by energy dispersive X-ray analysis (EDX), and scanning electron microscope (SEM) using JSM-IT200 SEM. Powder X-ray diffraction pXRD patterns at 25 C and diffraction, reflection angle (2-theta) ranges from 5 to 70 at 0.02 step and scan rate 1 min using Cu-K radiation of wavelength 1.5418 Å and acceleration voltage 40 kV using Bruker D8 advance diffrac- tometer. Intensity of reflected X-rays in arbitrary units is plotted versus incidence and reflection angles 2 , FTIR vibrational spectra at the frequency range 400–4000 cm using IR Prestige-21, Borken, Germany. Appl. Nano 2023, 4 117 Appl. Nano 2023, 4, FOR PEER REVIEW 3 UV-Vis. electronic absorption spectra using Helios alpha Unicom UV-Spectrophotometer at wavelength range 190–1200 nm; differential scanning calorimetry (DSC), thermal gravi- Powder X-ray diffraction pXRD patterns at 25 °C and diffraction, reflection angle (2- metric analysis (TGA), and differential thermal gravimetric (DTG) analysis at temperature −1 theta) ranges from 5° to 70° at 0.02° step and scan rate 1° min. using Cu-Kα radiation of range: 25–800 C using SDT Q600 V20.9 Build 20 instrument, 20 Cmin heating rate in wavelength 1.5418 Å and acceleration voltage 40 kV using Bruker D8 advance diffractom- de-aerated alumina cell to avoid sample oxidation by atmospheric oxygen; X-band electron eter. Intensity of reflected X-rays in arbitrary units is plotted versus incidence an d reflec- spin resonance spectra ESR at room temperature, 9.43 GHz using reflection JES-RE1X ESR −1 tion angles 2θ°, FTIR vibrational spectra at the frequency range 400–4000 cm using IR spectrometer in cylindrical resonance cavity with 100 kHz modulation, 5 mW power where Prestige-21, Borken, Germany. applied magnetic field is controlled with LMR Gauss meter; electrical conductivity and UV-Vis. electronic absorption spectra using Helios alpha Unicom UV-Spectropho- dielectric characteristics of GCSN3 sample is measured using four probes Agilent 4294 A impedance tometer at w bridge avelen with gth ra sinusoidal nge 190–120 voltage 0 nm; signal differen 10timV al scamplitude. anning calor The imesample try (DSC is),com- ther- 2 5 2 mal gravimetric analysis (TGA), and differential thermal gravimetric (DTG) analysis at pressed as a pellet: 0.5 cm radius, 0.23 10 m thickness, and 7.854 10 m geometrical −1 temperature range: 25–800 °C using SDT Q600 V20.9 Build 20 instrument, 20 °C.min area, coated on two opposite surfaces by silver paste for Ohmic contact with copper elec- tr he odes ating and ratannealed e in de-aerat ate 120 d alu C; mithermal na cell toconductivity avoid sample is omeasur xidation ed by a at t rm oom osptemperatur heric oxygee n; using X-ban hot d el disk ectro TP n s2500 pin res [14 o]. nance spectra ESR at room temperature, 9.43 GHz using reflec- tion JES-RE1X ESR spectrometer in cylindrical resonance cavity with 100 kHz modulation, 3. Results and Discussion 5 mW power where applied magnetic field is controlled with LMR Gauss meter; electrical cond MS uctis ivin ity a Supplementary nd dielectric c Information haracterist(SI); ics oFigur f GCe SN S13showed samplethe is m relative easure abundance d using fo of ur mass(m) probes Agilent 4294 A impedance bridge with sinusoidal voltage signal 10 mV amplitude. the fragmented molecular ion versus ratio peaked at m/z 73.37, 75.2, 73.32, and charge(z) −2 The sample is compressed as a pellet: 0.5 cm radius, 0.23 × 10 m thickness, and 7.854 × 70.29, corresponding to molecular weight (M.wt) 75.07 g mol of glycine. The last peaks −5 2 10 m geometrical area, coated on two opposite surfaces b 1 y silver paste for Ohmic contact correspond to M.w. 614.32, 662.38, 758.57, 834.65 g mol for glycine–copper sulphate with copper electrodes and annealed at 120 °C; thermal conductivity is measured at room (GCS), glycine–copper sulphate doped 10 ppm SNPs (GCSN1), glycine–copper sulphate temperature using hot disk TP 2500 [14]. doped 20 ppm SNPs (GCSN2), and glycine–copper sulphate doped 30 ppm SNPs (GCSN3) crystals, respectively. An increasing concentration of SNPs increased chelation of glycine 3. Results and Discussion organic ligand to Cu(II) ion in CuSO . MS is in Supplementary Information (SI); Figure S1 showed the relative abundance EDX spectra and SEM micrographs: Figure 2a–d show SEM-EDX analysis of GCS, 𝑚𝑚𝑚𝑚 (𝑚𝑚 ) GCSN1, GCSN2, and GCSN3 crystals, respectively. These spectra were produced as of the fragmented molecular ion versus ratio peaked at m/z 73.37, 75.2, 73.32, 𝑐𝑐 ℎ𝑚𝑚 𝑎𝑎 (𝑧𝑧 ) a focused electron beam on the sample ejected electrons from the inner-most electron −1 and 70.29, corresponding to molecular weight (M.wt) 75.07 g mol of glycine. The last atoms in the crystal leaving holes filled by ejected electrons from higher level emissions of −1 peaks correspond to M.w. 614.32, 662.38, 758.57, 834.65 g mol for glycine–copper sul- X-ray [14,15]. phate (GCS), glycine–copper sulphate doped 10 ppm SNPs (GCSN1), glycine–copper sul- EDX spectra confirmed that SNPs improved self-assembly of GCS from Figure 2a–d. phate doped 20 ppm SNPs (GCSN2), and glycine–copper sulphate doped 30 ppm SNPs Perfect crystallization is attained in Figure 2d. (GCSN3) crystals, respectively. An increasing concentration of SNPs increased chelation The data in Table 1 indicated that oxygen, carbon, and nitrogen have maximum weight of glycine organic ligand to Cu(II) ion in CuSO4. %, confirming that glycine is the base matrix of these single crystals. EDX spectrums of the EDX spectra and SEM micrographs: Figure 2a–d show SEM-EDX analysis of GCS, doped crystals confirm the entry of both Cu(II) ion and Ag(I) ions into glycine crystal lattice. GCSN1, GCSN2, and GCSN3 crystals, respectively. These spectra were produced as a fo- The crystals have molar stoichiometric formula [CH NH COOH] , [CuSO 5H O] 2 2 0.95 4 2 0.05 cused electron beam on the sample ejected electrons from the inner-most electron atoms in the absence and presence of SNPs. in the crystal leaving holes filled by ejected electrons from higher level emissions of X-ray The vibrational band in FTIR spectra, as shown in Figure S2, is assigned to the function [14,15]. groups in the crystals, Table 2. (a) Figure 2. Cont. 𝑎𝑎𝑎𝑎 𝑚𝑚𝑚𝑚 Appl. Nano 2023, 4, FOR PEER REVIEW 4 Appl. Nano 2023, 4 118 (b) (c) (d) Figure 2. (a–d): EDX spectra and SEM micrographs of GCS, GCSN1, GCSN2, and GCSN3, respec- Figure 2. (a–d): EDX spectra and SEM micrographs of GCS, GCSN1, GCSN2, and GCSN3, respectively. tively. Table 1. Weight percentage elements in crystals. EDX spectra confirmed that SNPs improved self-assembly of GCS from Figure 2a–d. Weight % Perfect crystallization is attained in Figure 2 d. Crystal C N O Cu S Ag The data in Table 1 indicated that oxygen, carbon, and nitrogen have maximum weigh GCS t %, confirm 25.71 ing that glyc 24.00 ine is the b 50.09 ase matrix o0.15 f these single0.5 crystals. EDX - spec- trums of the doped crystals confirm the entry of both Cu(II) ion and Ag(I) ions into glycine GCSN1 26.01 22.86 50.37 0.29 0.40 0.08 crystal lattice. GCSN2 27.59 23.43 48.34 0.54 - 0.10 GCSN3 30.75 24.72 45.95 1.13 - 0.42 Table 1. Weight percentage elements in crystals. Weight % IR spectra of the GCS crystal showed a strong vibrational band at 509.21 cm due Crystal C N O Cu 1 S Ag to Cu–N stretching [16], NH stretching band at 3811.34 cm , And medium peak at 1 1 GCS 25.71 24.00 50.09 0.15 0.5 - 1111.00 cm for CH rocking [17]. There is a strong peak at 1334.79 cm due to CH 2 2 GCSN1 26.01 22.86 50.37 0.29 0.40 0.08 wagging. Intense peak C=O asymmetric stretching occurs at 1604.77 cm [18], sym- – 1 – metric stretching COO at 1411.68 cm , intense band asymmetric stretching COO at GCSN2 27.59 23.43 48.34 0.54 - 0.10 Appl. Nano 2023, 4 119 1 1 1519.91 cm [19], and medium peak at 1033.85 cm for CCN asymmetric stretching deformation [20]. There is strong band SO stretching at 894.97 cm , an intense band 1 1 due to bending COO at 694.37 cm , medium peak wagging COO at 609.51 cm [13], and NH asymmetric stretching at 2823.79 cm [21]. FTIR spectra of the samples GCSN1, GCSN2, and GCSN3 have small shift compared to that of GCS observed, which suggests the incorporation of SNPs into the crystals lattice. Table 2. Assigned FTIR vibrational bands. Wave Number (cm ) Vibration Mode Glycine [15] GCS GCSN1 GCNN2 GCSN3 Cu-N stretching - 509.21 509.21 509.21 509.21 COO wagging 606.30 609.51 609.51 609.51 609.51 COO bending 696.9 694.37 694.37 694.37 694.37 CCN asymmetric stretching 1031.93 1033.85 1033.85 1033.85 1033.85 CH rocking 1112.44 1111.00 1111.00 1126.43 1118.71 SO stretching - 894.97 894.97 894.97 902.51 COO symmetric stretching 1492.39 1411.68 1411.89 1411.89 1404.18 CH wagging 1311.89 1334.79 1334.74 1334.74 1319.31 COO asymmetric stretching 1554.25 1519.91 1519.91 1504.48 1512.19 C=O asymmetric stretching 1643.53 1604.77 1604.77 1604.77 1604.77 NH asymmetric stretching 2924.04 2823.79 2831.50 2831.50 2831.50 NH stretching 3921.39 3811.34 3996.21 3895.48 3903.92 Figure 3a–d showed indexed pXRD profile versus Rietveld refined PXRD patterns for GCS, GCSN1, GCSN2, and GCSN3 crystals. All pXRD patterns showed a prominent sharp diffraction peak at 30 . SNPs increased the peaks’ intensity and modified crystal structure and lattice planes [22–24]. The crystals’ structure and geometry agreed with Crystallography Opened Database, COD files. GCS and GCSN1 have monoclinic unit cell alpha glycine. Triclinic GCSN2 and GCSN3 have gamma glycine. pXRD patterns are refined using Full prof Suit software using CIF files containing crystal information. Peak patterns are refined following pseudo-Voigt profile analytical function [25]. Background and peak shapes are modeled with linear fitting by applying least-squares cycles and six background (polynomial 6th grade parameters) at the wavelength of Cu-detector and neglecting instrument contribution [26]. The crystallinity followed the trend: GCSN3 > GCSN2 > GCSN1 > GCS Doping GCS with SNPs improved crystallinity, hence purity and crystal engineering. During refinement, the number and order of crystalline planes and diffraction peaks increased in the same order. Many iteration cycles and all noise data are neglected; too long iteration time is consumed for GCSN2 and GCSN3 due to extra high crystallinity, long cartesian coordinates, and different angles in the triclinic unit cell. Intense peaks shifted to lower 2-theta, indicating a pillared crystal structure. Small peak absence and no polycrystallinity regions are observed in the perfect GCSN3 crystal, which confirmed good surface. There is good fitting of pXRD spectra (calculated intensity of the diffraction peaks are close to each other, resulting in a very negligible difference between the observed and calculated intensities (Yobs.-Ycal.)) with less than zero in arbitrary unit. Both observed and calculated profiles are closely coincided to each other in a nonlinearly fit. Sharp intense pXRD patterns with a dominating diffraction peak in crystals confirmed good crystallinity. Intensity changes and a slight shift in peak positions of GCS by SNPs (-3 1 3) (-2 5 1) (3 0 1) (-2 1 3) (-1 1 4) (-2 0 2) (-1 3 2) (1 3 1) (1 3 0) (1 1 2) (1 1 1) Appl. Nano 2023, 4, FOR PEER REVIEW 6 Appl. Nano 2023, 4 120 shifted to lower 2-theta, indicating a pillared crystal structure. Small peak absence and no reflected modified crystalline planes [23]. Diffraction peaks at 44.4 and 64.7 in GCSN2 polycrystallinity regions are observed in the perfect GCSN3 crystal, which confirmed and GCSN3 confirmed doping impurities [24]. good surface. There is good fitting of pXRD spectra (calculated intensity of the diffraction Miller indices h k ` of the crystal planes, full width at half maximum (FWHM) of peaks are close to each other, resulting in a very negligible difference between the ob- XRD patterns, peak position, and inter planar distance (d .), are collected in Table S1. The cal sercrystallinity ved and calc and ulageometry ted intensit of ie single s (Yocrystals bs.-Ycaar l.)e ) wi deduced th less t from hanpXRD zero in by amatching rbitrary u these nit. diffraction patterns to pdf cards of similar crystals in Crystallography Opened Database Both observed and calculated profiles are closely coincided to each other in a nonlin- using FWHM that characterized different material properties and surface integrity fea- early fit. tures [25,26]. The unit cell parameters are collected in Table 3. 1100 GCS 0 10 20 30 40 50 60 70 2 theta° (a) Figure 3. Cont. Intensity (2 5 3) ( -2 5 1) ( 3 0 1) (-2 1 3) ( -1 1 4) (-2 3 1) (-2 0 2) (-1 3 2) (1 3 0) (1 1 2) (1 1 1 ) Appl. Nano 2023, 4, FOR PEER REVIEW 7 Appl. Nano 2023, 4 121 GCSN1 0 10 20 30 40 50 60 70 2 theta° (b) Figure 3. Cont. Intensity (6 5 3) (-5 -3 3) (- 4 0 3) (2 2 5) (4 -1 0) (2 3 2) (1 -3 2) (0 -3 1) (2 -1 2) (1 0 2) Appl. Nano 2023, 4, FOR PEER REVIEW 8 Appl. Nano 2023, 4 122 GCSN2 0 10 20 30 40 50 60 70 2 theta° (c) Figure 3. Cont. Intensity (6 5 3) (-5 -3 3 ) (- 4 0 3) (2 2 5) (4 -1 0) (-3 2 1) (2 3 2) (1 -3 2) (0 -3 1) (-2 1 1) (1 0 2) Appl. Nano 2023, 4, FOR PEER REVIEW 9 Appl. Nano 2023, 4 123 GCSN3 0 10 20 30 40 50 60 70 2 theta° (d) Figure 3. Observed and refined pXRD patterns of crystals respectively: (a) GCS, (b) GCSN1, (c): Figure 3. Observed and refined pXRD patterns of crystals respectively: (a): GCS, (b): GCSN1, GCSN2 and (d): GCSN3. (c): GCSN2 and (d): GCSN3. UV-Vis. absorbance spectrum of crystals at wavelength range 190–1100 nm are shown Sharp intense pXRD patterns with a dominating diffraction peak in crystals con- in Figure 4. UV-Vis. absorbance curve showed cut-off of wavelength is lower than cut off firmed good crystallinity. Intensity changes and a slight shift in peak positions of GCS by that of glycine [27]. SNPs reflected modified crystalline planes [23]. Diffraction peaks at 44.4° and 64.7° in GCSN2 and GCSN3 confirmed doping impurities [24]. Miller indices h k ℓ of the crystal planes, full width at half maximum (FWHM) of XRD patterns , peak position, and inter planar distance (dcal.), are collected in Table S1. The crystallinity and geometry of single crystals are deduced from pXRD by matching these diffraction pattern s to pdf cards of similar crystals in Crystallography Opened Database using FWHM that characterized different material properties and surface integrity fea- tures [25,26]. The unit cell parameters are collected in Table 3. Intensity Appl. Nano 2023, 4, FOR PEER REVIEW 10 Table 3. Crystal parameters. Appl. Nano 2023, 4 124 Crystal GCS GCSN1 GCSN2 GCSN3 Identifier ID 1,505,763 1,505,763 4,342,413 4,342,413 Crystal System Monoclinic Triclinic Table 3. Crystal parameters. Polymorph α ɣ Space Group P 21 P −1 Crystal GCS GCSN1 GCSN2 GCSN3 a = 7.890 Å, b = 15.94Å, c = 13.063Å a = 10.8222Å, b = 11.0221Å, c = 12.8735Å, Identifier ID 1,505,763 1,505,763 4,342,413 4,342,413 Lattice Parameter ° ° ° ° Crystal System α = 𝛾𝛾 = 90 Monoclinic , β = 94.58 α = 88.85 , β = Triclinic 77.52 , 𝛾𝛾 = 84.55 Polymorph Volume (Å ) 1638.14 1492.54 Space Group P 2 P 1 a = 7.890 Å, b = 15.94 Å, c = 13.063 Å a = 10.8222 Å, b = 11.0221 Å, c = 12.8735 Å, UV-Vis. absorbance spectrum of crystals at wavelength range 190–1100 nm are Lattice Parameter = g = 90 , = 94.58 = 88.85 , = 77.52 , g = 84.55 shown in Figure 4. UV-Vis. absorbance curve showed cut-off of wavelength λcut off is lower Volume (Å ) 1638.14 1492.54 than that of glycine [27]. GCS GCSN1 GCSN2 GCSN3 2.0 2.2 2.0 GCS 1.8 GCSN1 1.6 GCSN2 1.5 GCSN3 1.4 1.2 1.0 0.8 0.6 1.0 λcut 0.4 λcut λcut λcut 0.2 0.0 200 210 220 230 240 250 260 270 280 290 300 310 0.5 λ(nm) 0.0 200 400 600 800 1000 λ(nm) Figure 4. UV-Vis. absorbance curve. Figure 4. UV-Vis. absorbance curve. Doping Doping by by S SNPs NPs d decr ec eased rease d λcut off , i.e., , i.e.incr , inc eased reased b band angas d ga for s fUV or U –electr V–elec onic trotransition. nic transi- cut off SNPs tion. S enhanced NPs enha transpar nced tra ency nspaof renc crystals y of cr to yst UV als t radiation-enabled o UV radiation-edeposition nabled depas osit thin ionfilm as th on in glass film o for n g pr laotection ss for pro against tectionUV agaradiation inst UV ra [28 dia ,29 tio ]:n [28,29]: 2.3042 ×𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝐴𝐴 2.3042 absorbance A Ab Absorption sorption ffraction ractiona 𝛼𝛼 = = (1) (1) sample thickness t sample thickness 𝑡𝑡 Band gap-controlled UV absorption coefficient depends on the energy of the incident Band gap-controlled UV absorption coefficient depends on the energy of the incident photon and is estimated using Equation (2) [30,31]. photon and is estimated using Equation (2) [30,31]. 𝑎𝑎 ( r ) (2) 𝛼𝛼ℎ𝜈𝜈 = 𝐴𝐴 ℎ𝜐𝜐− Eg ahn = A(hu Eg) (2) where ν frequency of the incident radiation is inversely proportional to the wavelength of where frequency of the incident radiation is inversely proportional to the wavelength absorbance (λ), A is constant, and the exponent r depends on the nature of electronic tran- of absorbance (), A is constant, and the exponent r depends on the nature of electronic sition. r = 2 for indirect transition, and r = ½ for allowed direct transition, r = ½. Since all 1 1 transition. r = 2 for indirect transition, and r = for allowed direct transition, r = . Since 2 2 all crystals are blue colored, allowed direct transition is considered [15,30]. The optical gaps, Eg, are calculated from plots ( h) as a function of photon energy (h), as shown Absorbance (a.u.) Absorbance (a.u.) Appl. Nano 2023, 4, FOR PEER REVIEW 11 Appl. Nano 2023, 4 125 crystals are blue colored, allowed direct transition is considered [15,30]. The optical gaps, Eg, are calculated from plots (αhν) as a function of photon energy (hν), as shown in Fig- u in re 5 Figur , and t e 5h , e o and bsthe erved v observed alues Eg values are gEg ivear n i engiven Table in 4 aT lo able ng w 4it along h the v with alueth s of e values all repo of rted all glycine single crystals. reported glycine single crystals. 1000 1000 GCSN1 GCS 800 800 600 600 200 200 Eg=4.58(e.V) Eg=4.61(e.V) 0 0 0 2 4 6 0 2 4 6 1000 1000 hν(e.V) hν(e.V) GCSN2 GCSN3 800 800 600 600 400 400 200 200 Eg=4.65(e.V) Eg=4.67(e.V) 0 0 0 2 4 6 0 2 4 6 hν(e.V) hν(e.V) Figure 5. Tauc’s plots for calculation of band gap. Figure 5. Tauc’s plots for calculation of band gap. Table 4. Comparison between reported and present study: optical band gap (E ) and . cut off Table 4. Comparison between reported and present study: optical band gap (Eg) and λcut off. Band Gap (nm) cut off Band Gap λcut off (nm) Single Crystal Single Crystal Value Ref. Value Ref. Value Ref Value Ref. Glycine 3.13 [15] 346 [15] Glycine 3.13 [15] 346 [15] GCS 4.58 287 GCS 4.58 287 GCSN1 4.61 283 GCSN1 4.61 283 Present study Present study Present study Present study GCSN2 4.65 276 GCSN2 4.65 276 GCSN3 4.67 280 GCSN3 4.67 280 GCS 3.8 [23] 250 [23] GCS 3.8 [23] 250 [23] GCN 5.77 [15] 231 [15] GCN 5.77 [15] 231 [15] GLS 5.428 [32] 330 [32] GLS 5.428 [32] 330 [32] GZS 6.2 [33] 200 [33] GZS 6.2 [33] 200 [33] λcut off 287 nm for GCS decreased to 283, 276, and 280 nm for GCSN1, GCSN2, and GCSN3, respectively, which indicated an increasing band gap. Blue shift of λcutoff to lower 287 nm for GCS decreased to 283, 276, and 280 nm for GCSN1, GCSN2, and cut off values indicated SNPs’ improved polarizability of electron density on the single crystals. GCSN3, respectively, which indicated an increasing band gap. Blue shift of to lower cut off This finding suggested the suitability of GCS-doped SNPs single crystals for applications values indicated SNPs’ improved polarizability of electron density on the single crystals. in optoelectronic devices such as frequency multiplier, sum-, difference-, and blue laser This finding suggested the suitability of GCS-doped SNPs single crystals for applications frequency generators, etc. [34]. Optical band gaps’ eV are 4.58, 4.61, 4.65, and 4.67 for GCS, in optoelectronic devices such as frequency multiplier, sum-, difference-, and blue laser GCSN1, GCSN2, and GCSN3 crystals, respectively. SNPs increased Eg and enhanced op- frequency generators, etc. [34]. Optical band gaps’ eV are 4.58, 4.61, 4.65, and 4.67 for tical properties of GCS. High Eg indicated the decrease in the localized energy states on GCS, GCSN1, GCSN2, and GCSN3 crystals, respectively. SNPs increased Eg and enhanced doping by SNPs due to extrinsic defects or disorders in GCS caused by interstitial doped optical properties of GCS. High Eg indicated the decrease in the localized energy states on SNPs [35]. doping by SNPs due to extrinsic defects or disorders in GCS caused by interstitial doped SNPs [35]. 2 2 (αhν) (αhν) (αhν) (αhν) Appl. Nano 2023, 4 126 Appl. Nano 2023, 4, FOR PEER REVIEW 12 Good optical properties of the GCS crystals doped by SNPs are confirmed by extinction Good optical properties of the GCS crystals doped by SNPs are confirmed by extinc- coefficient K calculated using Equation (3); and refractive index (n) reflect dissipated tion coefficient K calculated using Equation (3); α and refractive index (n) reflect dissi- incident radiation by absorption and scattering [36,37]. pated incident radiation by absorption and scattering [36,37]. la K = (3) (3) 𝐾𝐾 = 4p 4𝜋𝜋 Re Reflectance flectance R R and and K K depend dependon on p photon hoton e ener ne gy rg ,y Figu , Figu re r S3: e S3 The : Th reflectance e reflectanis ce calculated is calcu- la using ted uEquation sing Equa(4): tion ( [36 4] ): [36] ( ) ( ) � 11 − exp ex(p − t)α+ t exp + e ( xp t) αt (4) R = 1 (4) R = 1 ± 1 + exp( t) 1 + exp(−αt) where t is the sample thickness. where t is the sample thickness. R Refractive efractive iindex ndex ((n) n) dep depends ends o on n w wavelength, avelength, aand nd p photon hoton eener nerg gy y is is ccalculated alculated u using sing m mathematical athematical E Equation quation ((5): 5): [3 [36 6– –38] 38], , Figu Figur re e 6. 6. (R + 1) ± 3 2R + 10R-3 (R + 1) 3R + 10R 3 (5) n = − n = (5) 2(R-1) 2 R 1 ( ) Positive refractive index (n) 1.6–1.8 indicated dispersion of incident radiation on the Positive refractive index (n) 1.6–1.8 indicated dispersion of incident radiation on the crystals is inversely proportional to the photon energy. Refractive index (n) is decreased crystals is inversely proportional to the photon energy. Refractive index (n) is decreased by increasing photon energy and concentration of SNPs. High photon energy enables by increasing photon energy and concentration of SNPs. High photon energy enables passing through the crystal lattice with low dispersion. SNPs decreased dispersion of in- passing through the crystal lattice with low dispersion. SNPs decreased dispersion of cident radiation by improving transparency to UV radiation. High transmission and low incident radiation by improving transparency to UV radiation. High transmission and low absorbance of UV radiation and low refractive index suggest the single crystals are suita- absorbance of UV radiation and low refractive index suggest the single crystals are suitable ble for antireflection coating in solar thermal devices and NLO applications [38]. for antireflection coating in solar thermal devices and NLO applications [38]. 1.8 GCS 1.8 GCSN1 GCSN2 1.6 1.6 GCSN3 GCS GCSN1 1.4 1.4 GCSN2 GCSN3 1.2 1.2 1.0 1.0 0.8 0.8 0.6 0.6 0.4 0.4 200 300 400 500 600 700 800 900 2 3 4 5 6 λ(nm) hν(e.V) Figure 6. Refractive index with wavelength and photon energy. Figure 6. Refractive index with wavelength and photon energy. Figure 7 shows the nonlinear variation of the electrical susceptibility ( ) with the photon Figu ener re 7gy sh . ows the nonlinear variation of the electrical susceptibility (χ) with the pho- ton ene GSC rgycrystals . showed large noise scattering in electrical susceptibility. This scattering disappeared on doping by SNPs that elevated electrical susceptibility ( ) at high photon energy following the order: GCSN2 > GCSN3 > GCSN1>>> GCS GCSN3 showed lower than GCSN2 due to extra high crystallinity; GCSN3 decreased the mean free path for electron charge transfer. Reflactive index(n) Refractive index(n) 𝜆𝜆𝜆𝜆 Appl. Appl. N Nano ano 2023 2023,, 4 4, FOR PEER REVIEW 127 13 0.30 GCS GCSN1 GCSN2 0.25 GCSN3 0.20 0.15 0.10 0.05 0.00 2 3 4 5 6 hν(e.V) Figure 7. χ -photon energy plot. Figure 7. -photon energy plot. GSC crystals showed large noise scattering in electrical susceptibility. This scattering The calculated electric susceptibility is plotted with photon energy; Figure 7 shows electric disappe susceptibility ared on dopin ( g b ) is y about SNPs t 0.25 hat e for lev all ate crystals d electrat ica low l suphoton sceptibilit ener y (gy χ). at high photon energ Melting y follow point, ing the o cryst rder: allization, phase transition, enthalpy, and entropy changes are clarified using DSC thermograms [39], Figure 8a–d. A sharp endothermic peak at decompo- GCSN2 > GCSN3 > GCSN1>>> GCS sition temperature reflects good crystallinity. A weak broad peak at 195.80 and 206.29 C in GCSN2 GCand SN3GCSN3 showed characterized lower χ thaphase n GCSchange N2 due fr t om o eg xt -glycine ra high c tory s -glycine tallinity;[ 40 G]. CS Melting N3 de- point (m.p.) is 253.83, 262.37, 265.64, 268.25 C for GCS, GCSN1, GCSN2, and GCSN3, creased the mean free path for electron charge transfer. respectively. Increased m.p. on doping by SNPs is attributed to high thermal stability. The calculated electric susceptibility is plotted with photon energy; Figure 7 shows Heat capacity “Cp” is the ratio between heat flow to heating rate and depends on electric susceptibility (χ) is about 0.25 for all crystals at low photon energy. temperature: [41–44]. Melting point, crystallization, phase transition, enthalpy, and entropy changes are clarified using DSC thermograms [39], Figure 8a–d. A sharp endothermic peak at decom- C = a T + b, = T + (6) position temperature reflects good crystallinity. A weak broad peak at 195.80 and 206.29 ℃ where parameters a and b are calculated from intercept (a) and slope b of straight-line in GCSN2 and GCSN3 characterized phase change from 𝛾𝛾 - glycine to α-glycine [40]. Melt- Cp-T plot. Cp of all prepared single crystals showed nonlinear variation with the absolute ing point (m.p.) is 253.83, 262.37, 265.64, 268.25 °C for GCS, GCSN1, GCSN2, and GCSN3, temperature, Figures S4–S7. respectively. Increased m.p. on doping by SNPs is attributed to high thermal stability. Thermal lattice coefficient and electronic heat capacities are obtained from linear Heat capacity “Cp” is the ratio between heat flow to heating rate and depends on 2 2 temperature: [41–44]. versus T plot, (coefficient, R above 0.99) Figures S4a,b and S7a,b. Table 5 shows linear fits parameters of DCS. (6) C = aT + b, = αT + γ Heat capacity at constant pressur p e, Cp, is the heat required to raise the temperature of the crystal sample by 1 C and represents the variation of the heat content of the where parameters a and b are calculated from intercept (a) and slope b of straight-line Cp- crystal sample on heating. The variation of , coefficients approved Cp variation with T plot. Cp of all prepared single crystals showed nonlinear variation with the absolute temperature. This finding indicated that the Cp amount of thermal heat absorbed by the temperature, Figures S4–S7. crystals increases on heating, enabling the application of a heat shielding coating on thin Thermal lattice coefficient α and electronic heat capacities γ are obtained from linear film glasses. 2 2 versus T plot, (coefficient, R above 0.99) Figures S4a,b and S7a,b. Table 5 shows linear Thermograms are shown in Figure 8a–d. DTG showed one peak confirmed one ther- mal decomposition step. GCS showed weight loss (wt. loss) 74.3 wt. % at temperature range fits parameters of DCS. 200.65–787.67 C, DTG peak at 249.7 C. Glycine decomposed into CO , NH [45] leaving 2 3 25.7% Table 5. residue, Linear fi 72.31%. ts param GCSN1 eters of D decomposed SC curves. at 208.27–788.29 C and 27.69% residue. DTG peak was at 257.88 C. In addition, 72.93 wt. % of GCSN2 decomposed at 217.41–788.84 C, Cp = a T + b Cp/T = α T + γ 27.07 wt. % residue, DTG peaked at 262.28 C. Additionally, 72.86 wt. % of GCSN3 de- Crystal Temperature Range ( C) −6 a b α × 10 γ composed at 221.54–787.96 C, gave 27.14 wt. % residue, and peak at 264.07 C. SNPs 22–206 0.003 −0.441 0.0070.7 0.001 decreased wt. loss on thermal decomposition of the crystals. Higher residue left after 206–254 −0.379 185.6 −0.7 0.181 thermal decomposition confirmed improved crystallinity on doping GCS by SNPs. GCS 253.8–321 0.231 −134.9 0.5 −0.166 321–788 −0.031 21.91 −0.02 0.007 GCSN1 23.8–86 0.0429 −10.95 −0.15 0.006 Electric Susceptiblity Appl. Nano 2023, 4, FOR PEER REVIEW 15 Appl. Nano 2023, 4 128 (a) (b) Figure 8. Cont. Appl. Nano 2023, 4, FOR PEER REVIEW 16 Appl. Nano 2023, 4 129 (c) (d) Figure 8. (a–d): Thermograms: a. TGA, b. DTG, and c. DSC of GCS, GCSN1, GCSN2, and GCSN3. Appl. Nano 2023, 4 130 Table 5. Linear fits parameters of DSC curves. C = a T + b C /T = T + p p Temperature Crystal Range ( C) 6 a b 10 22–206 0.003 0.441 0.00707 0.001 206–254 0.379 185.6 0.7 0.181 GCS 253.8–321 0.231 134.9 0.5 0.166 321–788 0.031 21.91 0.02 0.007 23.8–86 0.0429 10.95 0.15 0.006 86–223 0.007 1.851 0.01 0.139 223–262 1.266 657.3 2.10 0.575 GCSN1 262–325 0.410 233.6 0.89 0.284 325–788 0.031 29.75 0.023 0.0212 28.8–227 0.002 2.029 0.016 0.005 226.8–265 0.986 510.2 1.4 0.378 GCSN2 265–331 0.393 231.7 0.62 0.213 331–788 0.021 14.65 0.014 0.006 30–87 0.045 15.04 0.2 0.024 87–228 1.34 0.0077 0.004 1.29 10 GCSN3 228–268 0.981 509.01 1.9 0.535 268–334 0.349 206.01 0.59 0.208 334–787 0.011 10.78 0.009 0.008 Crystals contain no water of crystallization as wt. loss at 100 C is absent [46]. TGA thermograms confirmed thermal stability up to 200.65, 208.27, 217.41, and 221.54 C for GCS, GCSN1, GCSN2, and GCSN3, which enabled laser applications [47]. Peak temperature Tm increased from 249.71 to 257.88, 262.28, 264.07 C on increasing SNPs’ concentration. ESR spectra of powder sample crystals are shown in Figure 9. Anisotropy g-factor for crystals confirmed low symmetry. Spin Hamiltonian parameters g and A tensors revealed rhombic symmetry crystal field around Cu(II) ion split ground state. Degeneracy of ground state energy level is lifted giving static Jahn–Teller distortion [48,49]. Value g and unpaired electronic state R are given by Equations (7) and (8): [50,51]. g = g + g /2 (7) ? x y R = (g g )/(g g ) (8) x y z x Table 6 includes g factor, hyper fine constants A, and R for the crystals. Values A and g factor have no axial symmetry in the crystal lattice (no dynamic Jahn–Teller) [52]. R = 0.1805, 0.1224, 0.1673, 0.1418 for GCS, GCSN1, GCSN2, and GCSN3, 2 2 respectively; less than unity indicated d ground state for unpaired electron [53]. x y A , A equals A are lower than A g-parallel is greater than perpendicular g and x y z; k ? 2 2 confirmed d ground state [52]. g value is less than 2.3, indicating strong covalent x y copper–glycine bond [54]. bond coefficient or covalence parameter for unpaired electron density on Cu(II) ion is estimated using Equation (9) [54,55], Table 7. = A /0.036 + g 2.0023 + 3/7 g 2.0023 + 0.04 (9) ( ) k ? where A =A , A = A + A /2 (10) Z ? x y The parameter is less than unity, indicating covalent bonding between Cu(II) and glycine ligand [56]. SNPs decreased covalence parameter ( ) of glycine-Cu(II) bond, except that GCSN2 showed abnormally high , which confirmed its highest electrical susceptibility. Appl. Nano 2023, 4, FOR PEER REVIEW 17 Figure 8. (a–d): Thermograms: (a) TGA, (b) DTG, and (c) DSC of GCS, GCSN1, GCSN2, and Appl. Nano 2023, 4 131 GCSN3. GCS GCSN1 1000 600 -300 -500 -600 -1000 -900 -1500 2600 2800 3000 3200 3400 3600 3800 2600 2800 3000 3200 3400 3600 3800 Magnetic field(Gauss) Magnetic field(Gauss) GCSN3 GCSN2 -300 -300 -600 -600 -900 -900 -1200 2600 2800 3000 3200 3400 3600 3800 2600 2800 3000 3200 3400 3600 3800 Magnetic field(Gauss) Magnetic field (gauss) Figure 9. Powder ESR spectra of Cu(II) ions in crystals. Figure 9. Powder ESR spectra of Cu(II) ions in crystals. Table 6. g values and A (mT) matrices for Cu(II) ion in crystals. Table 6. g values and A (mT) matrices for Cu(II) ion in crystals. Crystal g g g A A A g g R x y z x y z k ? GCS 2.0859 2.0531 2.2676 13.309 10.872 18.183 2.2676 g 2.0691 g 0.1805 Crystal gx gy gz Ax Ay Az R GCSN1 GCS 2.0921 2.0859 2.0705 2.0531 2. 2.2685 2676 13. 12.548 309 10. 13.949 872 14.229 18.183 2.2685 2.2676 2.0813 2.0691 0. 0.1224 1805 GCSN1 2.0921 2.0705 2.2685 12.548 13.949 14.229 2.2685 2.0813 0.1224 GCSN2 2.0883 2.0551 2.2868 11.154 16.183 17.871 2.2868 2.0717 0.1673 GCSN2 2.0883 2.0551 2.2868 11.154 16.183 17.871 2.2868 2.0717 0.1673 GCSN3 2.0887 2.0637 2.265 13.27 12.465 15.965 2.265 2.0762 0.1418 GCSN3 2.0887 2.0637 2.265 13.27 12.465 15.965 2.265 2.0762 0.1418 Table 7. EPR parameters. Values A and g factor have no axial symmetry in the crystal lattice (no dynamic Jahn– 2 2 Teller ) [52]. R = 0.1805, 0.1224, 0.1673, 0.1418 for GCS, GCSN1, GCSN2, and GCSN3, re- Crystals A (G) A (G) Crystals A (G) A (G) ? ? k k 2 2 spectively; less than unity indicated dx –y ground state for unpaired electron [53]. GCS 120.908 181.831 0.8392 GCSN2 136.685 178.707 0.8507 Ax, Ay equals A are lower than Az; g-parallel is greater than perpendicular g and GCSN1 132.491 142.299 0.7353 GCSN3 128.719 159.649 0.7778 2 2 confirmed dx –y ground state [52]. g value is less than 2.3, indicating strong covalent cop- per–glycine bond [54]. Figure 10 showed UV of thin film coating of GCSN3 on the aluminum (Al) foil sample. An aqueous solution of GCSN3 was evaporated under ultra-high vacuum conditions onto the Al foil where carboxylate COOH of glycine zwitterion amino acid is chemically adsorbed on the aluminum surface. Absorption at long 900–1100 nm for this crystal near Intensity Intensity Intensity Intensity Appl. Nano 2023, 4, FOR PEER REVIEW 18 σ bond coefficient or covalence parameter α for unpaired electron density on Cu(II) ion is estimated using Equation (9) [54,55], Table7. α = A /0.036 + (g −2.0023) +3/7(g −2.0023) + 0.04 (9) ∥ ⊥ where (10) A = A , A = (A + A )/2 Z x y ∥ ⊥ Table 7. EPR parameters. 2 2 Crystals A (G) A (G) α Crystals A (G) A (G) α ⊥ ∥ ⊥ ∥ GCS 120.908 181.831 0.8392 GCSN2 136.685 178.707 0.8507 GCSN1 132.491 142.299 0.7353 GCSN3 128.719 159.649 0.7778 The parameter α is less than unity, indicating covalent bonding between Cu(II) and glycine ligand [56]. SNPs decreased covalence parameter (α ) of glycine-Cu(II) bond, ex- cept that GCSN2 showed abnormally high α , which confirmed its highest electrical sus- ceptibility. Figure 10 showed UV of thin film coating of GCSN3 on the aluminum (Al) foil sam- ple. An aqueous solution of GCSN3 was evaporated under ultra-high vacuum conditions Appl. Nano 2023, 4 132 onto the Al foil where carboxylate COOH of glycine zwitterion amino acid is c hemically adsorbed on the aluminum surface. Absorption at long λ 900–1100 nm for this crystal near IR region indicates absorption of thermal energy of IR radiation. Phonon bands at 900 nm IR region indicates absorption of thermal energy of IR radiation. Phonon bands at 900 nm originate from vibrational modes of harmonic and unharmonic oscillators in the crystal originate from vibrational modes of harmonic and unharmonic oscillators in the crystal lattice. Absorbed IR radiation causes thermal vibrations of atoms or molecules and creates lattice. Absorbed IR radiation causes thermal vibrations of atoms or molecules and creates thermal phonon waves that propagate in the crystal lattice , dissipating thermal IR energy. thermal phonon waves that propagate in the crystal lattice, dissipating thermal IR energy. F Figure igure 1 10. 0. UV UV-V -V is. is. a absorbance bsorbance spectra spectra of oGCSN3 f GCSNthin 3 thi film n filcoated m coate on d o Al n foil. Al foil. Absorptivity of GCSN3 near the IR region of electromagnetic radiation indicated Absorptivity of GCSN3 near the IR region of electromagnetic radiation indicated that that crystals can shield thermal heat of IR radiation on the coating as dispersed thin film crystals can shield thermal heat of IR radiation on the coating as dispersed thin film on on alumetal. alumetal. The sun provides thousands Wm energy on the earth’s surface daily. Total solar −2 The sun provides thousands W.m energy on the earth’s surface daily. Total solar energy in the upper atmosphere contains 50% IR radiation, 40% Vis. Light, and 10% UV energy in the upper atmosphere contains 50% IR radiation, 40% Vis. Light, and 10% UV radiation. IR radiation causes vibrations that heats earth’s surface [57]. Attenuation of radiation. IR radiation causes vibrations that heats earth’s surface [57]. Attenuation of thermal energy can be achieved by painting glass windows with these blue color crystals thermal energy can be achieved by painting glass windows with these blue color crystals transparent to UV radiation, filtering, and that dissipates IR radiation. 1 1 transparent to UV radiation, filtering, and that dissipates IR radiation. High thermal conductivity of crystals equals: 1.10, 1.21, 1.54, and 1.6 Wm K for GCS, GCSN1, GCSN2, and GCSN3 confirmed rapid attenuation of many incident EM waves by dielectric components and rapidly dissipated as heat. Figure 11 showed electrical conductivity of GCSN3 increased on heating as a typical semiconductor behavior due to thermally activated charge carriers’ mobility [58]. Impedance plots confirmed super conductivity. A plateau region at low 0.1Hz fre- quency region represents total conductivity of grain boundary. A high-frequency region at 100 kHz represents the contribution of grains to total conductivity. An intermediate fre- quency region at 1 kHz is due to charges trapped between grain boundaries and grains [15]. AC conductivity confirmed the dielectric nature of a single crystal can dissipate heat rapidly. The high-frequency dielectric constant is 4.49. Dielectric study of GCSN3 crystal response of charges to applied electric field showed dielectric constants at 100 Hz, 1 kHz, 10 kHz, and 100 kHz and a temperature range of 200–550 K. Dielectric constant was calculated using equation [59]: Cd " = (11) " A where " is free space permittivity, C and d are capacitance and thickness of pellet, and A is electrode area. Appl. Nano 2023, 4, FOR PEER REVIEW 19 −1 −1 High thermal conductivity of crystals equals: 1.10, 1.21, 1.54, and 1.6 W.m K for GCS, GCSN1, GCSN2, and GCSN3 confirmed rapid attenuation of many incident EM Appl. Nano 2023, 4, FOR PEER REVIEW 19 waves by dielectric components and rapidly dissipated as heat. Figure 11 showed electrical conductivity of GCSN3 increased on heating as a typical semiconductor behavior due to thermally activated charge carriers’ mobility [58]. −1 −1 High thermal conductivity of crystals equals: 1.10, 1.21, 1.54, and 1.6 W.m K for GCS, GCSN1, GCSN2, and GCSN3 confirmed rapid attenuation of many incident EM waves by dielectric components and rapidly dissipated as heat. Appl. Nano 2023, 4 133 Figure 11 showed electrical conductivity of GCSN3 increased on heating as a typical semiconductor behavior due to thermally activated charge carriers’ mobility [58]. Figure 11. Variation of electrical conductivity of GCSN3 on heating. Figure 11. Variation of electrical conductivity of GCSN3 on heating. Figure 11. Variation of electrical conductivity of GCSN3 on heating. Figure 12 showed variation of impedance of GCSN3 with applied frequency. Figure 12 showed variation of impedance of GCSN3 with applied frequency. Figure 12 showed variation of impedance of GCSN3 with applied frequency. Figure 12. Charge transfer resistance of GCSN3 as a function of applied frequency and absolute temperature (K): (a) 200, (b) 300, (c) 350, (d) 400, (e) 450, (f) 500, (g) 550. Figure 12. Charge transfer resistance of GCSN3 as a function of applied frequency and absolute Figure 12. Charge transfer resistance of GCSN3 as a function of applied frequency and absolute Impedance plots confirmed super conductivity. A plateau region at low 0.1Hz fre- temperature (K): (a) 200, (b) 300, (c) 350, (d) 400, (e) 450, (f) 500, (g) 550. temperature (K): (a) 200, (b) 300, (c) 350, (d) 400, (e) 450, (f) 500, (g) 550. quency region represents total conductivity of grain boundary. A high-frequency region Real " and imaginary "” components of " represented equals [60]: at 100 kHz represents the contribution of grains to total conductivity. An intermediate Impedance plots confirmed super conductivity. A plateau region at low 0.1Hz fre- frequency region at 1 kHz is due to charges trapped between grain boundaries and grains " =|"|cos, "”=|"|sin (12) [15]. AC condq uu cte iv nic ty y r con egi firo me n r de tp he r e di se eln ec ts tr t ico n ta atl c ure o n of d a u sin ctiv gle it c y ryst of gr al ca ain n d b iso sip un ad tea h re y. at A high-frequency region rapidly. The high- Figur frequ e e 13 nc showed y dielec"trvaried ic const with ant temperatur is 4.49. e at a different frequency and decreased at 100 kHz represents the contribution of grains to total conductivity. An intermediate with increasing frequency, indicating an ability to dissipate incident IR radiation. " de- Dielectric study of GCSN3 crystal response of charges to applied electric field showed frequency region at 1 kHz is due to charges trapped between grain boundaries and grains creased until it reached glass transition Tg at 380 K, then became limited up to 470 K. Peak dielectric constants at 100 Hz, 1 kHz, 10 kHz, and 100 kHz and a temperature range of 200– [15]. AC conductivity confirmed the dielectric nature of a single crystal can dissipate heat at Curie TC represented phase transition from ferroelectric to paraelectric behavior. 550 K. Dielectric constant was calculated using equation [59]: rapidly. The high-frequency dielectric constant is 4.49. Dielectric study of GCSN3 crystal response of charges to applied electric field showed dielectric constants at 100 Hz, 1 kHz, 10 kHz, and 100 kHz and a temperature range of 200– 550 K. Dielectric constant was calculated using equation [59]: Appl. Nano 2023, 4, FOR PEER REVIEW 20 C𝑑𝑑 ε = (11) ε 𝐴𝐴 𝑜𝑜 where ε is free space permittivity, C and d are capacitance and thickness of pellet, and 𝑜𝑜 A is electrode area. Real ε′ and imaginary ε″ components of ε represented equals [60]: (12) ε′=|ε|cosθ, ε″=|ε|sinθ Figure 13 showed ε′ varied with temperature at a different frequency and decreased with increasing frequency, indicating an ability to dissipate incident IR radiation. ε′ de- Appl. Nano 2023, 4 134 creased until it reached glass transition Tg at 380 K, then became limited up to 470 K. Peak at Curie TC represented phase transition from ferroelectric to paraelectric behavior. Figure 13. Temperature dependent of the dielectric constant for (GCSN3) single crystal. Figure 13. Temperature dependent of the dielectric constant for (GCSN3) single crystal. 4. Conclusions 4. Conclusions SNPs dopant increased thermal stability of gamma and alpha glycine single crystals. SNPs dopant increased thermal stability of gamma and alpha glycine single crystals. Optical absorption studies revealed that cut-off wavelengths are 287, 283, 276, and 280 nm Optical absorption studies revealed that cut-off wavelengths are 287, 283, 276, and 280 nm and optical band gap energy 4.58, 4.61, 4.65, and 4.67 eV for GCS, GCSN1, GCSN2, and and optical band gap energy 4.58, 4.61, 4.65, and 4.67 eV for GCS, GCSN1, GCSN2, and GCSN3 single crystals, respectively. SNPs increased band gaps of crystals, hence trans- GCSN3 single crystals, respectively. SNPs increased band gaps of crystals, hence trans- parency to UV radiation. AC electrical conductivity of the thin film sample of perfect parency to UV radiation. AC electrical conductivity of the thin film sample of perfect crys- 1 1 crystal increased to 0.03 Siemens/cm. High thermal conductivity, Wm K in range −1 −1 tal increased to 0.03 Siemens/cm. High thermal conductivity, W.m K in range 1.10–1.6, 1.10–1.6, confirmed efficient radiation attenuation by rapid heat dissipation due to dielectric confirmed efficient radiation attenuation by rapid heat dissipation due to dielectric prop- properties of single crystals. Single crystals could be used to shield and dissipate thermal erties of single crystals. Single crystals could be used to shield and dissipate thermal heat heat of IR radiation. AC confirmed the dielectric component and increased on heating due of IR radiation. AC confirmed the dielectric component and increased on heating due to to thermal activation of charge carriers. thermal activation of charge carriers. Supplementary Materials: The following supporting information can be downloaded at: https:// Supplementary Materials: The following supporting information can be downloaded at: www.mdpi.com/article/10.3390/applnano4020007/s1, Figure S1. Mass spectra of the single crystals www.mdpi.com/xxx/s1, Figure S1: Mass spectra of the single crystals (a) GCS, (b) GCSN1, (c) (a) GCS, (b) GCSN1, (c) GCSN2 and (d) GCSN3; Figure S2. FTIR spectra of the single crystals GCS, GCSN2 and (d) GCSN3.; Figure S2. FTIR spectra of the single crystals GCS, GCSN1, GCSN2 and GCSN1, GCSN2 and GCSN3; Figure S3. Plot extinction coefficient (k) (a) and reflectance versus (b) GCSN3; Figure S3. Plot extinction coefficient (k) a) and reflectance versus b) photon energy (eV) of photon energy (eV) of GCS, GCSN1, GCSN2, and GCSN3; Figure S4. DSC curves for GCS crystals: GCS, GCSN1, GCSN2, and GCSN3; Figure S4. DSC curves for GCS crystals:a. specific heat capacity a. specific heat capacity versus 2 T, b. C /T versus T ; Figure S5. DSC curves for GCSN1 crystal: versus T, b. Cp/T versus T ; Figure S5. DSC curves for GCSN1 crystal: a. specific heat capacity versus a. specific heat capacity versus T, b. C /T versus T ; Figure S6. DSC curves for GCSN2 crystal: T, b. Cp/T versus T ; Figure S6. DSC curves for GCSN2 crystal: a. specific heat capacity versus T, b. a. specific heat capacity versus T, b. C /T versus T ; Figure S7. DSC curves for GCSN3 crystal: a. Cp/T versus T ; Figure S7. DSC curves f por GCSN3 crystal: a. Specific heat capacity versus T, b. C p/T Specific heat capacity versus T, b. C /T versus T ; Table S1. Indexed PXRD patterns of GCS, GCSN1, versus T ; Table S1. Indexed PXRD p p atterns of GCS, GCSN1, GCSN2 and GCSN3 single crystals. GCSN2 and GCSN3 single crystals. Author Contributions: Conceptualization, H.A.F.E.; methodology, H.A.F.E., H.E.O., O.M.M.; soft- Author Contributions: Conceptualization, H.A.F.E.; methodology, H.A.F.E., H.E.O. and O.M.M.; soft- ware, H.E.O., O.M.M., H.A.F.E.; validation, A.E.-D.A., M.E.E., H.A.-H., H.A.F.E. and R.S.A.A.; for- war mal a e, H.E.O., nalysis, O.M.M. H.E.O., and O.M. H.A.F M., R .E.; .S.A validation, .A. and H A.E.-D.A., .A.F.E.; inM.E.E., vestigatH.A.-H., ion, H.AH.A.F .F.E., .E. R.Sand .A.A R.S.A.A.; .; resourc for es,- mal analysis, H.E.O., O.M.M., R.S.A.A. and H.A.F.E.; investigation, H.A.F.E. and R.S.A.A.; resources, H.A.F.E. and H.A.-H.; data curation, H.E.O., O.M.M. and H.A.F.E.; writing—original draft prepa- ration, O.M.M., H.E.O. and H.A.F.E.; writing—review and editing, H.A.F.E., H.E.O. and R.S.A.A.; visualization, A.E.-D.A., M.E.E. and H.A.-H.; supervision, A.E.-D.A., M.E.E. and H.A.-H., project administration, H.A.F.E.; funding acquisition, R.S.A.A. All authors have read and agreed to the published version of the manuscript. Funding: Princess Nourah bint Abdulrahman University Researchers Supporting Project number (PNURSP2023R316), Princess Nourah bint Abdulrahman University, Riyadh, Saudi Arabia. Institutional Review Board Statement: Not applicable. Informed Consent Statement: Authors approved consent on publication. Appl. 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Journal
Applied Nano – Multidisciplinary Digital Publishing Institute
Published: Apr 18, 2023
Keywords: glycine; copper sulphate; silver nanoparticle; single crystals; doping; optical activity