Journal of Physics D: Applied Physics

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Field effect transistor based on proton conductive metal organic

framework (CuBTC)
To cite this article before publication: Gajanan A Bodkhe et al 2019 J. Phys. D: Appl. Phys. in press https://doi.org/10.1088/1361-6463/ab1987

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Page 1 of 19 AUTHOR SUBMITTED MANUSCRIPT - JPhysD-119157.R1

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Field Effect Transistor based on Proton Conductive Metal Organic

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5 Framework (CuBTC)
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7 Gajanan A. Bodkhe1, Megha A. Deshmukh1, Harshada K. Patil1, Sumedh M. Shirsat2, Velaga
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9 Srihari3, Krishan K. Pandey3, Gyanendra Panchal4, Devdatta M. Phase4, Ashok Mulchandani5,

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10 Mahendra D. Shirsat1*
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13 RUSA Center for Advanced Sensor Technology, Department of Physics, Dr. Babasaheb
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Ambedkar Marathwada University, Aurangabad (MS) - 431 004, India
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Department of Electronics & Telecommunication Engineering, Jawaharlal Nehru Engineering

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18 College, Aurangabad (MS) – 431 001
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20 High Pressure & Synchrotron Radiation Physics Division, Bhabha Atomic Research Centre,
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UGC-DAE Consortium for Scientific Research, University Campus, Khandwa Road, Indore
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Department of Chemical and Environmental Engineering, University of California, Riverside, CA
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92521, USA.
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30 *Corresponding Author email: mdshirsat.phy@bamu.ac.in
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34 Abstract:
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Metal organic frameworks (MOFs) are crystalline materials having ultrahigh porosity, tunable
38 physico-chemical properties. But most of the MOFs are electrical insulators which restricts MOFs
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40 in electronic devices. In the present study Field Effect Transistor (FET) based on proton conductive
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42 Metal Organic Framework was investigated. Imidazole was used as a proton conductor to increase
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conductivity of copper benzene tricarboxylate (CuBTC) MOF and further it was used to develop
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45 field effect transistor (FET). The CuBTC was synthesized by traditional solvothermal method.
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47 Proton conductive MOF was synthesized by post modification of CuBTC via Pore filling method
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49 by imidazole molecules and achieved proton conductivity ~ 1.04 x 10-4 S cm-1 at 70 oC (anhydrous
50 conditions). The proton conductive MOF was characterized by various techniques such as
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52 spectroscopic viz. Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron
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54 Spectroscopy (XPS), X-ray Absorption spectroscopy (XAS), Energy dispersive spectroscopy
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(EDS), alternating current (a.c.) impedance spectroscopy; thermal using thermogravimetric
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3 analysis (TGDTA); structural using powder X –ray diffraction (PXRD); morphological using Field
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5 Emission Scanning Electron Microscopy (FE-SEM); electrical by Field Effect Transistors (FETs).
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29 Fig. Graphical Abstract
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33 Keywords: Proton conductive MOF, Field effect transistor (FET), Imidazole, Copper benzene
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35 tricarboxylate (CuBTC), solvothermal method.
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40 1. Introduction:
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42 Metal Organic Frameworks (MOFs) has attained great attention of researchers around the
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44 globe due to their unique physico-chemical properties such as tunable pore size, large surface area1,
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46 diverse structure topology, good thermostability2, and permanent nanoscale porosity. MOFs has
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various applications viz. catalysis3, gas storage4, sensing5, drug delivery6, adsorption7 and
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49 separation7, etc. However, very few studies have been carried out on MOFs as electronic devices8,
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51 because most of the MOFs are electrically insulator, due to insulating nature of organic linker
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molecules and poor overlap between central metal ion π orbitals and d orbitals9. Takaishi et al.
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54 reported (Cu[Cu(pdt)2] (pdt = 2,3-pyrazinedithilate), first electrically conductive MOFs in 2009
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56 having electrical conductivity of 6 x 10-4 S cm-1 at 300 K, but crystal structure collapses upon
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Page 3 of 19 AUTHOR SUBMITTED MANUSCRIPT - JPhysD-119157.R1

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3 desolvation10. Till date various possibilities (viz. doping of redox active species like I23b, pore
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5 filling with guest molecules like tetracyanoquinodimethane (TCNQ)11, substitution of metal ions
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7 and ligands12, etc.) have been explored to increase the electrical conductivity in MOFs. However,
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these studies are limited to specific MOFs only, therefore other MOFs need to be explored. This

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10 will help to explore the utility of this porous extraordinary material in other technologies viz.
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12 chemiresistive and ChemFET sensors, fuel cells, supercapacitors, thermoelectric, etc.
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14 In addition to above mentioned approaches, proton conductivity is one of the more effective
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approach to increase the conductivity of MOFs13. To increase proton conductivity in MOFs mainly
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17 three approaches have been widely used viz. i) Functionalization of the framework or modulation
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19 of Brønsted acidity14; ii) tuning of phase transition, defects and amorphization of MOFs14; and
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21 iii) physical introduction of proton donors and or carriers15 (such as imidazole, triazole, ammonium
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salts, etc.) into the pores of the already synthesized MOFs. In the present study we adopted third
approach to increase the conductivity of CuBTC MOFs i.e. filling of pores with proton conducting
guest molecules. For this study we have selected copper benzene tricarboxylate (CuBTC) an
insulating MOF, also known as HKUST-1, first reported in 1999 by Stephen S.-Y. Chui et al.16
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29 and also it is the most studied MOF too. CuBTC MOF contains Cu(II) as a metal center and
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31 benzene tri-carboxylic acid (BTC) acting as ligand. We have selected imidazole as guest proton
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33 conducing molecule species due to its widespread use in MOFs17, polymers and porous materials
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to increase proton conductivity. This synthesized proton conducting compound (we called this as
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36 Im@CuBTC) has achieved proton conductivity better than nafion (conductivity ~ 1.04 X 10-4 S
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38 cm-1 at the anhydrous conditions at 70 oC).
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40 Field effect transistor is a three terminal voltage controlled device having source, drain and
41 gate terminals. Source-drain current can be controlled on gate voltage. FETs play crucial role in
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43 electronic applications. Recently, FETs have been explored for memory devices18, 18b, sensors19,
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45 flat panel devices20, etc. Researchers have explored materials like conducting polymers, graphene,
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carbon nanotubes for FETs, but only few studies carried out on MOF FETs. Guodong Wu et al.
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48 reported microporous FET device on semiconductive MOF (Ni3(HITP)2 as active channel21.
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50 Huang et al. reported Pd3(BHT)2 a 2D MOF based FET device22. Till date very few studies carried
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52 out on development of FET devices based on conducting/semiconducting MOFs FETs21. To the
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53 best of our knowledge, this is the first attempt to develop field effect transistor (FET) based on
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55 proton conducting MOFs.
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3 The fabricated proton conducting MOFs FET shows both holes and electrons as charge
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5 carriers i.e. ambipolar, which is a quit interesting. Ambipolar FETs would be next generation
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7 alternative to CMOS circuits23. Moreover, ambipolar devices can also be useful organic light
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emitting device . The synthesized CuBTC and proton conducting Im@CuBTC MOF were

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10 systematically characterized by structural using PXRD; morphological using FE-SEM; elemental
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12 using EDS; spectroscopic using FTIR, XPS, XAS; thermal using TGDTA ; surface area and pore
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14 size using BET/BJT and electrical using FET and a.c. impedance spectroscopy. The comparative
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analysis based of the characterization of CuBTC and proton conducting Im@CuBTC MOF is
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21 Experimental
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2.1. Materials and chemicals

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All reagents and solvents were analytical grade and used without purification. Copper
nitrate trihydrate (Cu(NO3)2,3H2O), benzene-1,3,5-tricarboxylic acid (BTC) and N, N dimethyl
formamide (DMF) purchased from Sigma Aldrich. Imidazole and ethanol purchased from
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30 Molychem, India.
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32 1.2. Synthesis of CuBTC
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35 CuBTC was synthesized by traditional solvothermal route as reported elsewhere15, since
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the solvothermal method gives high purity, surface area and yield of the MOFs than other
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38 methods25. . Solutions of Cu(NO3)2,3H2O (3.1gm) in 36 ml of HPLC grade D. I. water and
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40 benzene-1,3,5-tricarboxylic acid (BTC) (0.81 gm) in 36 ml of ethanol prepared separately and
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42 mixed with constant stirring at room temperature. After observing precipitate, 2.4 ml of N,N
43 dimethyl formamide (DMF) was added dropwise. Above mixture was transferred in Teflon lined
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45 autoclave and kept at 100 oC for 20 hrs. After completion of reaction, autoclave allowed to cool at
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room temperature. Then blue crystals of CuBTC were collected and washed with D. I. water and
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ethanol 5 times to remove unreacted reactants. CuBTC powder dried at room temperature and
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50 activated at 120 oC to remove solvent molecules from the pores of CuBTC and kept in desiccator
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52 for further use. After activation color of CuBTC changes from faint blue to dark blue.
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3 1.3.Synthesis of Im@CuBTC
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6 For the synthesis of proton conductive MOF, 0.5 gm of activated CuBTC inserted in 4 ml of
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1M imidazole solution in methanol for adsorption of imidazole molecules inside the CuBTC MOF
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9 pores, we called this material as Im@CuBTC. Then crystals were dried and stored for further use

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11 and characterization.
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13 1.4.Substrate Preparation and development of FET device:
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16 SiO2 (100 nm) coated p-type Si wafer used as a substrate on which electrodes were prepared

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via. Photolithography method. Firstly, Si/SiO2 coated wafer washed with acetone followed by 2-
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19 propanol and dried using N2 flow gun and dehydrated at 120oC. On the cleaned wafer photoresist
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21 was coated via. Spin coating and pre-baked at 100 oC. Then wafer was exposed to UV light
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through mask and developed in the developer solution. On the developed wafer, chromium (20
nm) was coated via. E-beam and gold (180 nm) via. Thermal coating method. Using Lift-off
technique desired electrodes were prepared on the Si/SiO2 wafer and used as substrate for Field
Effect Transistor (FET). Proton conductive metal organic framework (Im@CuBTC) was drop
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casted in between two gold electrodes as shown in fig. 10, which was used as a field effect
31 transistor (FET) device. Electrical contacts were made by using West Bond wire bonder ( 7476
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33 D) ( between Gold microelectrode contact pad and epoxy printed circuit board (PCB) for the
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35 further electrical measurements)
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37 1.5. Material characterization
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Fourier Transform Infrared (FTIR) spectra of as-synthesized CuBTC and Im@CuBTC were
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41 recorded on Bruker Alpha ATR having ZnSe window material in the range of 4000 – 500 cm-1.
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43 Powder X-ray diffraction (PXRD) measurements were performed in angle dispersive mode at
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45 beamline-11 of INDUS-2 synchrotron source at Raja Ramanna Center for Advanced Technology
46 (RRCAT), Indore, India using λ = 0.61 Ao. X ray Photoelectron Spectroscopy (XPS)
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48 measurements were carried out at RRCAT, Indore.
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Room temperature X-ray absorption near-edge structure (XANES) measurements around
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52 C K-edge, O K-edge, N K-edge and Cu L-edge were carried out in total electron yield (TEY) mode
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54 at Polarized light soft X-ray absorption spectroscopy beamline BL-01, at Indus-2, RRCAT, India.
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3 All the measurements were carried out at maximum current of 122 mA and 2.5 GeV of ring energy
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Nitrogen adsorption experiments were performed on Nova Station A instrument at room
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9 temperature. Thermogravimetric analysis of as synthesized CuBTC and Im@CuBTC were carried

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11 out in nitrogen atmosphere at 10 oC/min rate. All alternating current impedance spectroscopy
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13 measurements were carried out on CHI 660C electrochemical workstation in the frequency range
14 of 1 Hz to 100 KHz in anhydrous atmosphere. Powder samples pressed in KBr press having 0.2
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16 mm thick, 0.4 mm diameter and these pallets used for the alternating current impedance

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18 spectroscopy and proton conductivity measurement experiment. Conductivity and FET
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measurements were carried out on Keithley 4200 SCS semiconductor parameter analyser in
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2. Results and discussion
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FTIR spectra of CuBTC is as shown in Fig. 1. Bands at 2890 cm-1 and 1446 cm-1 are
corresponding to the asymmetric C-H stretching vibration and asymmetric stretching of the
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carboxylic groups. The peak at 1446 cm-1 attributed to bending vibrations of C=C26. The sharp peak
31 observed at about 730 cm-1 attributed to Cu-O stretching vibration. The peak observed at 1373 cm-
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33 indicating stretching VC=O, VC-O and bending O-H present bands respectively, which shows the
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35 presence of a carboxylic acid group3a. This confirms the formation of CuBTC. Similarly, for
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Im@CuBTC apart from above mentioned peaks some extra strong peaks observed at 1066 cm-1
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38 and 1644 cm-1attributed to C-N stretching of amine group27 and peaks at 1266 cm-1 and 1324 cm-
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40 attributed to C-N stretching of aromatic amine group of imidazole , which confirms successful
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Fig. 1. FTIR Spectra of as-synthesized CuBTC and Im@CuBTC
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31 The X-ray diffraction (Fig. 2) peaks of as-synthesized CuBTC are well matched with the
32 reported literature28 and matched with ICDD database no. PDF 00-065-1028 and also having very
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34 sharp peaks which indicates highly crystalline nature of solvothermally synthesized CuBTC
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36 (crystallinity – 97.6%). The diffraction pattern (2θ peak position) of imidazole molecules adsorbed
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CuBTC i.e. Im@CuBTC having same peak position but decreased intensity which depicts no
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39 change observed in the crystal structure of as-synthesized CuBTC but decrease in the intensity of
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41 the diffracted peaks due to adsorption of imidazole molecules inside pores and decrease in
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43 crystallinity Im@CuBTC (crystallinity – 93.7%). No substantial change observed in the crystallite
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size29 of CuBTC and Im@CuBTC (~117.4nm) due to only absorption of imidazole molecules
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46 inside the CuBTC framework. It is calculated by classical Scherrer formula30 by considering peaks of
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48 the XRD pattern,
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50 𝑲𝝀
𝑫 = β𝑪𝒐𝒔𝜽 ………………. Eq. 2
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3 where, D is the average crystallite size, λ is the wavelength of the X-ray radiation (λ = 0.61 Ao),
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5 K is the Scherrer constant (0.89 for cubic shape), θ is the Bragg diffraction angle and β is the full
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30 Fig. 2. XRD patterns of as-synthesized CuBTC and Im@CuBTC
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FE-SEM images clearly shows distinct change s in morphology and crystalline nature of
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38 of CuBTC as shown in Fig. 3. The elemental confirmation of as-synthesized CuBTC and proton
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40 conductive Im@CuBTC was carried out using Energy-dispersive X-ray spectroscopy (EDS). EDS
41 spectra (Fig. 4) clearly shows presence of nitrogen in Im@CuBTC which confirms presence of
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Fig. 3. FE-SEM images of (A) CuBTC and (B) Im@CuBTC
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XPS spectra was recorded to verify interaction between CuBTC and imidazole molecules.
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48 The survey spectra of CuBTC, Im@CuBTC and Cu-holder (to avoid background interference) is
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50 shown in Fig. 5 (A). The spectra for N 1s (Fig. 5 (B)) of CuBTC and Im@CuBTC clearly indicates
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52 absence of peaks for nitrogen in CuBTC, while N 1s peak observed in Im@CuBTC, clearly
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53 indicates presence of imidazole inside CuBTC. Spectra for Cu 2p (Fig. 5 (C)) of pure CuBTC and
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3 Im@CuBTC samples at B.E. 937.9 eV is due to imidazole molecules dominated CuBTC on
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5 surface at the time of recording of data. The peaks of pure CuBTC and Im@CuBTC at 937.9 eV
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oxidation state31. The same spectra of O 1s (Fig. 5 (D)) was recorded observed for CuBTC and

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10 Im@CuBTC. Two peaks observed at 531.1 eV and 535.91 eV indicates presence of carboxylic
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3 Pre- post edge corrected normalized XANES spectra at Cu L-edge, N K-edge, C K-edge
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5 and O K-edge for CuBTC and Im@CuBTC samples are shown in Fig. 6. The spectra at Cu L-edge,
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indicate that there is no chemical effect of adsorbed imidazole molecules on CuBTC. On the other

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10 hand, we have observed the features related to Imidazole at N K-edge absorption spectra of
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45 Figure 6. Room temperature XANES spectra at (A) Cu L-edge, (B) N K-edge, (C) C K-edge and
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50 N2 adsorption-desorption isotherm of CuBTC and Im @CuBTC and corresponding BJH
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52 pore size distribution shown in Fig.7 (A & B). The both the MOFs deggased in vacuum to remove
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3 microporous structure having type IV adsorption-desorption isotherm27, 32. While, Im@CuBTC
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adsorption of imidazole molecules inside the pores of CuBTC.

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Fig. 7 (A) N2 adsorption-desorption isotherm of CuBTC and Im@CuBTC (B) BJH pore size
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3 Fig. 8. shows Thermogravimetric analysis of as synthesized CuBTC and Im@CuBTC. Small
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5 weight loss (11.41%) observed in CuBTC samples between 49 oC and 129 oC due to removal of
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CuBTC MOF and very small weight loss (3.98%) between 129 oC to 322 oC is due to the

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because experiment was conducted in protective N2 atmosphere that prevents oxidation, means
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43 Fig. 9 (A) Impedance spectrum of Im@CuBTC (B) Arrhenius plot of proton conductivity of
44 Im@CuBTC, in anhydrous conditions at different temperatures
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Alternating current (AC) impedance spectra recorded at different temperature to determine
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50 the proton conductivity of Im@CuBTC is as shown in fig 9 (A). And Fig 9 (B), shows conductivity
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52 versus temperature plot of Im@CuBTC in anhydrous conditions at different temperature. The
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54 proton conductivity increases as temperature increases. Moreover, increase in conductivity of
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3 Im@CuBTC upto 1.04 x 10-4 S cm-1 was observed for Im@CuBTC at 70 oC at the anhydrous
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Field Effect Transistors (FETs) performance
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21 Fig. 10. Proton Conductive MOF (Im@CuBTC) Field Effect Transistor
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49 Fig. 11. FET study of Im@CuBTC based FETs : (A) Output characteristics on linear scale (B)
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51 Output characteristics on linear scale at absolute value of drain-source current (C) Output
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53 characteristics on log scale at absolute value of drain-source current (D) Transfer

54 characteristics at Vds = 2V
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3 Fig. 10 shows schematic of proton conductive MOF Field Effect Transistor. Fig. 11 (A),
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5 (B), (C) and (D) shows the output and transfer characteristics of the proton conductive MOFs
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7 (Im@CuBTC) FET device at 50 oC in anhydrous atmosphere. The output characteristics curves of
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the FET device shifted from origin (i.e. at 0 ) and for negative gate voltage there is complete

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10 shifting of origin as well as curves in Ist and IInd quadrant. This is due to proton (charges)
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12 accumulation/depletion at the Au contacts (an imperfect Im@CuBTC/SiO2 interface34) and
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14 capacitance formed between the electrodes (i.e. source, gate and drain) restrict the accumulated
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charge carriers to disappear immediacy during the quick and continuous voltage scanning of the
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17 devices. The output characteristics (Fig. 11 (A), (B), (C)) shows p-type (holes) charge carriers in
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19 positive Vds and n-type (electrons) charge carriers in negative Vds. Also, the transfer characteristics
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21 (Fig. 11 (D)) shows V shape curve on semilog scale ( | Ids | ), these confirms ambipolarity in the
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FET device35.

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We believe that, in Im@CuBTC MOF although imidazole molecules act as proton source,
but when external electric field is applied between source – drain terminals there is accumulation
of protons at drain electrode in negative Vds and anions at the source electrode due to separation of
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30 protons (i.e. cations) and anions takes place. This is the main reason for ambipolarity in
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32 Im@CuBTC MOF. The threshold voltage at 2V Vds is approximately 7.0 V. The On/Off ratio was
33 calculated from transfer characteristics and found to be ~826. The charge carrier mobility of the
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35 FET device was calculated from the equation (2) mentioned elsewhere36 and found to be ~0.04 x
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37 10-3 cm2 V-1 s-1 at Vds 2V.
38
𝜕𝜎 𝑡
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39 ………………. Eq. 2
40 µ𝐻 + = ± .
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𝜕𝑉𝐺𝑆 𝐶𝐺𝑆
42 𝜕𝜎
43 where, 𝜕𝑉 is the linear fit slope of transfer characteristics, t is the thickness of Im@CuBTC film
𝐺𝑆
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45 (approx. 50 µm) and CGS is the capacitance per unit area of the 100 nm SiO2 dielectric layer
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47 calculated by using following equation:

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49 3.9 . Ԑ0 ………………. Eq. 3
50 𝐶𝐺𝑆 =
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𝑡0
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where, Ԑ0 is the permittivity of free space and t 0 is the oxide (SiO2) thickness
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3 Conclusions:
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6 In this work, MOF (Im@CuBTC) based FET is successfully demonstrated. The MOF
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(CuBTC) was synthesized by solvothermal route and significant increase in conductivity of the
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9 insulating MOFs (CuBTC) was observed by adsorption of imidazole molecules inside the pores of

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11 the CuBTC MOF. Increase in conductivity of Im@CuBTC (at 70 oC) was observed upto 1.04 x
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13 10-4 S cm-1 in the anhydrous conditions which is better than Nafion at 30 oC at 98% RH. The FET
14 based on Proton conductive MOF (Im@CuBTC) exhibit ambipolarity with excellent FET
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16 characteristics (gate voltage control, drain current, On/Off ratio, threshold voltage).

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Acknowledgements:
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21 Authors extend their sincere thanks to UGC – DAE CSR (RRCAT), Indore (Project no.:
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CSR-IC-BL66/CRS-183/2016-17/847), for providing financial support and XPS, FE-SEM and
XAS, EDAX and XRD facilities on synchrotron beamlines. Inter University Accelerator Center
(IUAC), New Delhi, India (UFR no. 62320) and DST - SERB, New Delhi (Project no.:
EEQ/2017/000645), Rashtria Uchachatar Shiksha Abhiyan (RUSA), Government of Maharashtra,
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UGC-SAP Programme (F.530/16/DRS-I/2016(SAP-II) Dt.16-04-2016) for providing financial
31 support. Prof. P. S. Patil, Department of Physics, Shivaji University, Kolhapur (MS), India for
32
33 providing BET surface area characterization facility.
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35
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