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Vol. 8. Issue 2.
Pages 2326-2335 (April 2019)
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Vol. 8. Issue 2.
Pages 2326-2335 (April 2019)
Original Article
DOI: 10.1016/j.jmrt.2019.03.012
Open Access
Organic ligand capping of CuI for enhanced electrical and ionic conductivity
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Jositta Sherinea, Emayavaramban Indubalab,c, Revathy Rajagopald, Seshadri Harinipriyab,
Corresponding author
harinipriya.s@res.srmuniv.ac.in

Corresponding author at: Electrochemical Systems Laboratory, SRM Research Institute, SRM Institute of Science and Technology, Kattankulathur, Chennai, India.
a Department of Physics and Nanotechnology, SRM Institute of Science and Technology, Kattankulathur, Chennai, India
b Electrochemical Systems Lab, Research Institute, SRM Institute of Science and Technology, Kattankulathur, Chennai, India
c Department of Chemistry, SRM Research Institute, SRM Institute of Science and Technology, Kattankulathur, Chennai, India
d Department of Chemistry, Stella Mary's College for Women, Chennai, India
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Abstract

Green synthesis of copper iodide from Jamun seed extract (Syzygium cumini) is done and capped with 2-mercaptobenzothiazole (MBT). The structural, morphological, optical and electrochemical properties of capped and uncapped CuI were compared. Optical studies indicate 0.34eV decrease in the bandgap of CuI upon capping with MBT. Electrochemical Impedance Analysis (EIS) revealed four orders of magnitude increase in the electrical conductivity and two times increase in ionic conductivity upon capping by MBT. This lowering of band gap and higher electrical conductivity for CuI–MBT makes it a suitable material for optoelectronic devices and thin film solar cell applications in comparison with uncapped CuI.

Keywords:
CuI
CuI–MBT
Capping
Electrical conductivity
Ionic conductivity
Green synthesis
Full Text
1Introduction

Novel organic–inorganic hybrid materials such as coordination polymeric compounds involving metal ions and bridged ligand attract interest due to its versatile properties. In lieu of the adaptable coordination geometries of these coordination polymers with metal ions and its infinite structural and electronic states enable them to be utilized in magnetic [1–3], electrical [2–13], dielectric [14–16], sensor [17–19] and catalysis [20–23] applications. In addition, to the above listed properties CuX (X=F, Cl, Br, I) exhibits interesting luminescent [24–26] and non-linear optical properties [27,28]. In specific, CuX is capable of forming innumerous coordination geometries with organic or inorganic ligands [29]. Although, numerous studies on the hole concentration are reported for CuX, studies on coordination polymers [13,30–33] of CuX with organic and inorganic ligands remain unexplored. Specially CuI nanoparticles synthesized chemically has large band gap, unique dependence on temperature, abnormal diamagnetic property, better iconicity and new phase formation at high pressure [34,35]. The applications of CuI nanoparticles include superionic conductivity, solar cells [35] so on and so forth. Although CuI can be synthesized via simple chemical route, attaining purity is difficult [34,35]. To avoid such drawback and to synthesize CuI nanoparticles in an eco-friendly way, CuI is synthesized through green process employing plant or leaf extracts and nonhazardous chemicals. The biological synthetic route of nanoparticles using plants containing anthocyanins is very cost effective, as the plant extracts behave as reductant and ligands in nanoparticle synthesis [34]. The usage of natural products in the synthesis of CuI nanostructures involved green and rapid approach resulting in different morphologies at ambient temperature using sugar beet juice [36]. CuI nanostructures with cauliflower morphology is obtained via ampicillin-based clean, nonhazardous, environmentally benign process at room temperature [37]. The synthesis of CuI microstructures using pomegranate juice [38], involves pomegranate juice as reductant as well as ligand, that results in the self-assembly of trigonal nanostructures to form flower shaped CuI microstructures [38]. CuI is used for several applications such as organic solar cells, scintillators and bipolar diodes [39–41]. In addition to the above mentioned energy applications, CuI can be utilized in antimicrobial activity and other biological applications either uncapped or capped with organic ligands. The effect of metal complexes on the tumor cells relied on the kinetic behavior and redox stabilities, it is necessary to choose an appropriate ligand donor set (ca. S and N) to develop a highly stable and effective chemotherapeutic agent [42]. Recently, various thioamides [43–45] like 2-mercaptobenzothiazole (MBT), 5-ethoxy-2mercaptobenzimidazole (EtMBT), 2-mercapto-nicotinic acid(mnaH2), 2-mercapto-thiazolidine(mtzdH) and 5-chloro-2-mercapto-benzothiazole(ClMBT) have been used for the synthesis of Au(III) and Au(I) complexes using tetrachloroauric(III)acid(HAuCl4) and [Au (tpp)Cl] (tpp=triphenylphosphine(Ph3P)). The studies on anti-tumor activity of these complexes against leiomyosarcoma cells showed that ionic complex of Au(III)mercaptobenzothiazole {[AuCl4]·[bztH2]+} and Au(I)2-mercapto-thiazolidine [Au(tpp)(mtzd)] exhibited greater anti-tumor activity when compared to cisplatin [44,45]. Thus to the best of our knowledge, independently CuI and MBT had been studied for different applications but so far in the literature, CuI capped with 2-mercaptobenzothiazole had not been studied for their optoelectronic properties. Thus the major objectives of the present investigation are (i) green synthesis of CuI, (ii) capping of CuI by MBT via wet chemical process, (iii) morphological, structural, optical and electrochemical characterization of CuI–MBT employing SEM-EDS, XRD, UV–vis DRS, FTIR, Raman, cyclic voltammetry and EIS to understand its utility in thin film solar cells and optoelectronic devices.

2Materials and methods2.1Green synthesis of CuI from Syzygium cumini extract

Jamun seeds were washed multiple times with water and rinsed with distilled water. The cleaned seeds were soaked in distilled water for a day. The soaked seeds were ground into a paste and diluted with distilled water. To attain homogeneity, the paste solution was stirred for 3h and centrifuged. The centrifuged extract was used for the synthesis of CuI nanoparticles [46].

2.2Synthesis of copper(I) iodide nanoparticles

Cu(NO3)2·3H2O and NaI were purchased from Qualigens and SDFCL respectively and used as it is. 30ml of navel extract was added drop wise into 2g of Cu(NO3)2·3H2O solution which was dissolved in 75ml of distilled water and stirred magnetically with dropwise addition of 1.2408g of NaI solution. The resultant dark brown precipitate was filtered, washed thoroughly with 50% ethanol and dried at 50°C [46].

2.3Synthesis of MBT capped CuI

2g of MBT was dispersed in 50ml of acetone by sonication. To the MBT solution, 0.2g of green synthesized CuI was added and sonicated until dry. The precipitated CuI–MBT yellow powder was collected and stored. The stoichiometry between CuI and MBT is maintained as 1:10 with excess MBT inorder to achieve complete capping of CuI. As CuI is in microflower structure upon centrifugation it breaks down into nanorods as the size of the particle reduces, more surface area is attained. Thus to cover higher surface area, MBT is added in excess [46].

2.4Materials characterization

The morphology and composition of green synthesized CuI and CuI–MBT were obtained by Carl-Zeiss-SEM with EDS from Oxford Instruments. XRD of the samples were recorded using Bruker D8 Advance Diffractometer with CuKα radiation at λ=1.5406Å. Surface morphology of the films made from the samples was analyzed employing metallurgical microscope (LEICA DM Model no. 1). FTIR analysis of green synthesized CuI and CuI–MBT was carried out using Bruker FTIR. Optical analysis of the samples was performed using UV–vis spectrophotometer (Specord 200 plus, Analytikjena, Germany) with diffuse reflectance spectral mode (DRS). Photoluminescence spectroscopic studies were carried out using Fluorolog Horiba spectrophotometer. Raman scattering investigations of the samples were observed by Perkin Elmer micro Raman spectrophotometer. Cyclic voltammetry (CV) analysis of green synthesized CuI and CuI–MBT was performed by Zahnner Zennium PP211 in three electrode mode. EIS analysis employing IVIUM Pocketstat electrochemical workstation in two electrode mode was done at the amplitude of 100mV and in the frequency range of 100Hz to 1MHz.

3Results and discussion

The morphological, structural, optical and electrochemical analysis of green synthesized CuI and CuI–MBT is discussed in detail in the following sections.

3.1Mechanism of CuI formation

As there are no peaks observed at 499 and 623nm for the CuI dissolved in acetonitrile, it clearly indicates the absence of other organic impurities such as chlorophylls and pelargonidin-3-5-diglycosides constituting the jamun extract. Thus eventhough the synthesis procedure does not involve extracting the reducing agent separately, interference of other constituents are either minimal or negligible (cf. Scheme 1).

Scheme 1.

Mechanism of reduction of Cu(NO3)2 to CuI by Jamun extract.

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3.2Morphological analysis

SEM analysis revealed the morphology of green synthesized CuI as nanoflowers. In the present case, naval extract acts as reducing as well as capping agent thereby self-assembling the CuI in the form of microflowers [46] (cf. Fig. 1(a and b)). CuI–MBT as seen from Fig. 1(c and d) appears as nanosticks. The rationale behind the change in morphology upon capping CuI with MBT is as follows: ultrasonication of CuI microflowers with diameter of 1.981μm breaks it into pieces of nanosticks with length of 3.352μm, breadth of 2.011μm and thickness of 0.355μm. Capping with MBT uniformly covers the surface of nanosticks. The EDS pattern, Fig. 2(a) shows peaks for Cu and I. Absence of additional peaks due to C, N and S indicates that impurities such as anthocyanins are not interfering with the precipitate of CuI during its green synthesis. From Fig. 2(b), it can be observed that additional peaks corresponding to S, N and C confirming the existence of MBT in CuI–MBT nanosticks.

Fig. 1.

FESEM of (a and b) CuI nanoflowers extracted from naval seeds and (c and d) CuI–MBT nanosticks uniformly.

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Fig. 2.

EDS patterns of (a) green synthesized CuI and (b) CuI–MBT.

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3.3Structural analysis

The powder XRD patterns of green synthesized CuI and CuI–MBT are provided in Fig. 3. The crystallite size of green synthesized CuI and CuI–MBT was calculated as 30nm and 134nm respectively using Scherrer equation. The diffraction peaks of CuI could be indexed to the face centered cubic symmetry with cell parameters of a=b=c=6.146Å (JCPDS file no. D60246). The 2θ values of 25°, 29°, 41°, 49°, 61°, 67°, 77° could be attributed to the crystal planes (111), (200), (220), (311), (222), (400), (331) and (420) respectively. High intense peak at 24° and 28° was attributed to MBT [47] that depicts the complete coverage of CuI by MBT. All the observed peaks agree well with the reported JCPDS data of commercial CuI and MBT. The comparison of the same is provided in Fig. 3. As the stoichiometry of CuI and MBT is in the ratio 1:10, all the nanosticks formed from the microflowers of CuI are completely covered by MBT. The crystallite size is increased from 30nm to 134nm upon capping CuI with MBT. This increment in crystallite size along with high intense MBT peak indicates, thick coating of MBT on CuI surface. The suppression of CuI peak intensity in Fig. 3 for CuI–MBT justifies the complete coverage of CuI by MBT (Fig. 4).

Fig. 3.

XRD of green synthesized CuI and CuI–MBT.

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Fig. 4.

FTIR of spectra of (a) CuI and (b) CuI–MBT.

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3.4Optical analysis

The optical analysis of green synthesized CuI and CuI–MBT had been investigated employing vibrational, electronic, photoluminescence, Raman spectroscopy and optical microscopy.

3.4.1Vibrational spectra analysis

The band from 2000 to 3846cm−1 is ascribed to CuI [48] and the CN stretching mode is identified by strong peak around 2347cm−1. Peaks at 1027, 1530cm−1 contributes to CO and CO stretching vibrations respectively [49]. From 3100 to 3417cm−1 represents intermolecular hydrogen bonding [48] is reflected via a broad peak. The peak at 672cm−1 is the characteristic peak of CuI [48,49]. The broad peak from 2000 to 3800cm−1 of CuI is suppressed due to capping by MBT in CuI–MBT. At 1232, 1317 and 1487cm−1 bending mode of NH and stretching vibrations of CN associated with CNH bonds of MBT are noticed. The intense bands near 742 and 1416cm−1 attribute to wagging vibrations of NH and CH bonds. The weak bands at 8,531,124 and 1587cm−1 contribute to CH wagging and CC stretching vibrations. Peaks at lower wave numbers such as 573 and 656cm−1 correspond to CS stretching. Due to the coordination bonding between Cu+ and SC of MBT peak at 672cm−1 in CuI shifts to 656cm−1 in CuI–MBT. The small peak in the proximity of 1074cm−1 is contributed by stretching mode of CS in SCS bond of MBT [48–51]. The blue shift in the CuI peaks is due to the capping of CuI by MBT via coordination bonds between Cu and S [52] (cf. Fig. 4 and Scheme 2).

Scheme 2.

Coordination complex formation of mercaptobenzothiazole with CuI.

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3.4.2Electronic spectroscopy analysis

The absorption coefficient, α of CuI–MBT is calculated employing Frenel's equation:

where α, d, R and Tf denotes absorption coeffecient, film thickness in μm, reflectance and transmittance of the film respectively. The Tauc's plot [46] is between vs (αhν)2 with an x-intercept of 2.48eV for CuI–MBT. Thus the band gap of CuI–MBT is 2.48eV(c.f. Fig. 5a). The optical band gap of CuI synthesized from naval extract is found to be 2.82eV (c.f. Fig. 5b) [46]. Hence, when capped with MBT the band gap of CuI is reduced by 0.34eV. The rationale behind this decrease in band gap is due to the fact that MBT is a highly conjugated molecule and is expected to coordinate with Cu+ via double bonded exo sulfur atom (CS). Through this coordination bond between Cu+ and S, electronic percolation occurs from MBT to CuI. Due to this electronic percolation, HOMO and LUMO of the valence and conduction bands of CuI overlap leading to reduction in the band gap. Thus by forming coordination polymer (cf. Scheme 2) of the type (MBT)4Cu2I2, the energy band gap of CuI–MBT is expected to decrease (cf. Scheme 3). As anticipated, band gap of CuI–MBT decreases to 2.48 from 2.82eV of CuI, due to the formation of coordination polymer.

Fig. 5.

Tauc's plot of (a) CuI and (b) CuI–MBT.

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Scheme 3.

Band structure.

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3.4.3Photoluminescence studies (PL)

Fig. 6 shows PL spectra of green synthesized CuI and CuI–MBT recorded in powder phase using Fluorolog-2000 fluorescence spectrophotometer. The samples were excited at wavelength of 320nm. In the literature, CuI synthesized by annealing Cu in the presence of I2 vapor resulted in transparent and brown crystal [53] with a band gap of 2.915eV [53]. The red shift from normal bulk value of 3.1eV is attributed toward the defects in the CuI crystal which are filled by elemental I2[53]. In the present case, CuI synthesized from naval extract shows significant peak at 417nm and 680nm. CuI–MBT showed peak at 603nm with a red shift in the visible region. The intensity of the peak of CuI–MBT is very high due to its fluorescent nature [52]. The broadness of this peak is due to the coordination polymer formation of Cu(I) with MBT [52] (cf. Scheme 2). Thus XRD, FTIR, UV–VIS DRS and PL analysis supports the formation of coordination polymer between CuI and MBT as depicted in Scheme 2.

Fig. 6.

Photoluminescence spectra of green synthesized CuI and CuI–MBT.

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3.4.4Raman analysis

The lower wave number peaks in Raman spectra (Fig. 7) at 168 and 297cm−1 are characteristic of CuI [51]. Around 393cm−1 bending vibrations due to SCS is noticed. The high intensity peak at 1248cm−1 indicates the interaction of bending mode of NH and CN stretching vibration in CNH group. Other peaks seen near 1428, 1466cm−1 are due to CNH group. The band mixing of CC stretching and CH bending is observed at 1491cm−1, CC stretching mode is shown at 1581cm−1. Peaks at 1592, 1567, 1939, 2208 and 2240cm−1 were overtone and combinational bands of fundamental frequencies of MBT [50]. The tautomers of MBT involve (i) thione form with NH group and (ii) thiol form with SH group. Thus lone pair of electrons and aromatic π electrons coordinate to the metal surface [54] via conjugation. Thus structural, morphological and optical characterization confirms the capping of CuI by MBT via coordination polymer formation as depicted in Scheme 2.

Fig. 7.

Raman spectra of CuI–MBT; insets show Raman spectra of CuI and MBT from Refs. [50,51] respectively.

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3.4.5Optical microscopic analysis

The optical images (Fig. 8) show the CuI–MBT film surface was smooth and were continuous which adheres well to the surface of the substrate and did not peel off. Thus it is suitable for the fabrication of smooth and uniformed surfaced optoelectronics devices with extended life.

Fig. 8.

Optical microscopy image of (a) CuI and (b) CuI–MBT.

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3.5Electrochemical analysis

The electrochemical analysis of CuI and CuI–MBT is done employing 3-electrode in the case of CV and 2-electrode thin film for EIS and discussed in the following sections.

3.5.1CV analysis

From Fig. 9 we can infer that redox reactions occur for CuI whereas the redox reactions are suppressed in the case of CuI–MBT. The forward scan of green synthesized CuI shows bimodal peak at 0.33 and 0.55V. These peaks correspond to

Cu++eCuE0=0.33V
Cu2++eCu+E0=0.55V

Fig. 9.

Cyclic voltammogram of green synthesized CuI and CuI–MBT.

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Hence the forward scan peaks account for the redox reactions involved in the formation of cupric and metallic copper on the platinum surface, due to the degradation of CuI into Cu+ and Cu. Both the reactions involve single electron transfer, wherein the first step, reduction of CuI to metallic copper occurs and in the second stage oxidation of CuI into Cu2+ happens. In the reverse scan, two peaks at 0.23 and −0.39V appeared and are attributed to the reaction of CuI leading to anionic species and metallic copper. The reactions are represented as follows:

CuI(s)+eCu(s)+IE0=−0.39V

The observed peaks for CuI are in agreement with the literature [55]. The CV of CuI–MBT shows redox peaks with shift and low intensity. The shift in peak potential and decrease in peak intensity is attributed to the complete capping of CuI by MBT.

3.5.2Electrode kinetics from CV analysis

The heterogeneous rate constant khet, for the redox behavior of CuI and CuI–MBT is obtained from Butler–Volmer equation as follows [56]:

where i0, n, F represents the exchange current density (A/cm2), number of electrons taking part in the reaction (n=1) and Faraday's constant(96,500C/mol). Under steady state conditions, i0 is approximated as the peak current from CV. The average khet values for CuI and CuI–MBT are calculated as 2.98×10−9 and 5.6×10−11mol/cm2/s respectively. The two orders of magnitude decrease in khet for CuI upon capping by MBT indicates that the capping reduces the reduction of CuI into Cu and I2 via formation of coordination polymer (cf. Scheme 2). This reduction in the redox behavior indicates non-availability of free Cu+ and I ions in the coordination polymer for formation of metallic copper and evolution of iodine gas. The average free energy of activation ΔG for the redox behavior of CuI and CuI–MBT can be obtained via Arrhenius kinetics as
108.86 and 131.96kJ/mol respectively. Increase in the ΔG upon capping CuI with MBT indicates that the complex is already electron rich due to coordination polymer formation and hence cannot accept more electrons to get reduced to Cu and I2. Thus from CV analysis, we can infer that CuI is completely capped by MBT and forms coordination polymer with high stability. The values khet and ΔG for CuI and CuI–MBT of is provided in Supporting Information S1.

3.5.3EIS analysis

The x-intercept of 35Ω is observed in the Nyquist plot (cf. Fig. 10) for both CuI and CuI–MBT. This could be attributed to the series resistance Rs developed at the interface of Ag/CuI and Ag/CuI–MBT. The Nyquist plot is fitted with the equivalent circuit R1C1Q1 by Zman Software. In case of CuI, C1 represented as charge transfer capacitance with value of 232.907F. C2 was a constant phase element since the value is 0.07835μF. Qy1 and Qy2 are of negligible values of 0.0031 and 0.21847Ω which represent warburg component. In case of CuI–MBT, C1 and C2 are identical (17.22F) representing the charge transfer capacitance. Qy1 and Qy2 are very low of the order 410 and 366,600μF indicating warburg component. This is caused by the charge accumulation at FTO/CuI and CuI/Ag interfaces. Constant phase elements were absent due to MBT capping in CuI–MBT and the voids are reduced.

Fig. 10.

EIS of green synthesized CuI and CuI–MBT; where Rint–Pt/CuI/pores/electrolyte interface and Rint1–Pt/CuI or Pt/CuI–MBT.

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From charge transfer resistance (Rct), the electrical conductivity for CuI and CuI–MBT is calculated as 3.64×10−7 and 1.022×10−3S/cm respectively. Thus by capping CuI with MBT, due to the formation of coordination polymer (cf. Scheme 2), the electrical conductivity increases by four orders of magnitude. The free energy of activation for electronic percolation is calculated to be −25kJ/mol employing Arrhenius model as follows [57]:

where R, T, σ and σ0 denote gas constant (8.314J/K/mol), temperature (298K), electrical conductivity of CuI–MBT and electrical conductivity of CuI in S/cm. The electrical conductivities of CuI and CuI–MBT were calculated from Rct as σ0=l/(Rct0×A); σ=l/(Rct×A) where Rct0 and Rct represent charge transfer resistance for CuI and CuI–MBT obtained in ohms from the equivalent circuit fitting of Nyquist plots, l and A denote the length and area of the CuI (as well as CuI–MBT) coating on FTO coated glass. The negative ΔG for electrical conductivity indicates facile electronic percolation in CuI upon capping with MBT. As MBT contains ample positive inductive effect (+I), the electrons are conjugated to CuI via resonance and coordination bonds. This increases the electronic mobility in the polymer and four orders of magnitude increase in the electrical conductivity. Analogously, the ionic (or hole) conductivity of CuI and CuI–MBT is calculated from the diffusion resistance as 0.0052 and 0.0102S/cm respectively. Thus from the above mentioned Arrhenius model, the free energy of activation for ionic conductivity is calculated as 20kJ/mol. The higher ΔG (positive) for ionic conductivity in comparison to electrical conductivity indicates that upon capping by MBT, CuI experiences more electron mobility than hole conduction. But the ionic conductivity of CuI–MBT is twice that of CuI, this clearly implies that with electronic percolation, there is also increased hole conductivity in the opposite direction. From the coordination polymer structure in Scheme 2, it can be clearly understood that as electron flow toward CuI via coordination bonds, hole conduction happens on the exo sulfur atoms of MBT which is bonded to hetero-sulfur and nitrogen atoms and in conjugation with the aromatic ring. Thus when electron flows through coordination bond toward CuI from MBT, hole mobility occurs through CuI via coordination bonds to MBT. Thus EIS analysis in conjunction with CV and spectroscopic studies supports the increase in electrical and ionic conductivity of CuI upon capping by MBT.

4Conclusion

In the present study, green synthesized CuI is capped with MBT by wet chemical method. In order to investigate the electronic behavior of as synthesized CuI–MBT, optical, vibrational, electronic, photoluminescence and Raman spectroscopy studies were carried out and the results indicated formation of coordination polymer formation between CuI and MBT as shown in Scheme 2. The energy band gap of CuI–MBT decreases from 2.82 (band gap of CuI) to 2.48eV due to the formation of coordination polymer (cf. Scheme 3). From CV analysis, average khet values for CuI and CuI–MBT are observed to be two orders of magnitude less upon capping by MBT. EIS studies indicated the electrical conductivity for CuI and CuI–MBT increasing by four orders of magnitude. The free energy of activation (ΔG) for electronic percolation calculated employing Arrhenius model is for electrical conductivity indicating facile electronic percolation in CuI upon capping with MBT. The free energy of activation (ΔG) for ionic conductivity showed higher value for ionic conductivity in comparison to electrical conductivity indicating more electron mobility than hole conduction in CuI upon capping by MBT. But the ionic conductivity of CuI–MBT is twice that of CuI, this clearly implies that with electronic percolation, there is also increased hole conductivity in the opposite direction. Thus, EIS in conjunction with CV and spectroscopic studies supports the increase in electrical and hole conductivity of CuI upon capping by MBT. Hence, the lower band gap and higher conductivity make CuI–MBT a feasible material for optoelectronic devices and solar cell applications.

Conflicts of interest

The authors declare no conflicts of interest.

Acknowledgements

The authors acknowledge the experimental facilities provided by Department of Science and Technology – FIST, Government of India in Department of Physics and Nanotechnology and Department of Chemistry at SRM IST. The authors acknowledge SRMIST for photoluminescence experiments.

Appendix A
Supplementary data

The following are the supplementary data to this article:

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Journal of Materials Research and Technology

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