Received: 25 October 2017; Accepted: 18 December 2017; Published: 20 December 2017

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2 s Article Morphological Structural Analysis Polyaniline Poly(o-anisidine) Layers Generated in a DC Glow Discharge Plasma by Using an Oblique Angle Electrode Deposition Configuration Bogdan Butoi 1,2, Andreea Groza 2, *, Paul Dinca 1,2, Adriana Balan 3 Valentin Barna 1, * 1 Faculty Physics, University Bucharest, 405 Atomistilor Street, Magurele, Romania; bogdan.butoi@g.unibuc.ro (B.B.); dincapaulpavel@yahoo.com (P.D.) 2 National Institute for Laser, Plasma Radiation Physics, 409 Atomistilor Street, Magurele, Romania 3 Nano-SAE Research Centre, Faculty Physics, University Bucharest, Magurele, Romania; ronie@3nanosae.org * Correspondence: reea.groza@inflpr.ro (A.G.); barnavalentin@yahoo.com (V.B.); Tel.: (V.B.) Received: 25 October 2017; Accepted: 18 December 2017; Published: 20 December 2017 Abstract: This work is focused on structural morphological investigations polyaniline poly(o-anisidine) s generated in a direct current glow discharge plasma, in vapors monomers, without a buffer gas, using an oblique angle-positioned substrate configuration. By atomic force microscopy scanning electron microscopy we identified formation worm-like interlinked structures on surface polyaniline layers, layers being compact in bulk. The poly(o-anisidine) layers are flat with no kind structures on ir surfaces. By Fourier transform infrared spectroscopy we identified main IR bs characteristic polyaniline poly(o-anisidine), confirming that polyaniline chemical structure is in emeraldine form. The IR b from 1070 cm 1 was attributed to emeraldine salt form polyaniline as an indication its doping with H +. The appearance IR b at 1155 cm 1 also indicates conducting protonated polyaniline. The X-ray diffraction revealed formation crystalline domains embedded in an amorphous matrix within polyaniline layers. The interchain separation length 3.59 Å is also an indicator conductive character s. The X-ray diffraction pattern poly(o-anisidine) highlights semi-crystalline nature layers. The electrical conductivities polyaniline poly(o-anisidine) layers ir dependence with temperature are also investigated. Keywords: polyaniline layers; poly(o-anisidine) films; DC plasma ization method; conductivity measurements 1. Introduction Polyaniline poly(o-anisidine) are conducting s that present a well-known interest in different research areas due to ir high potential applications in displays molecular devices, smart windows, energy storage systems, as corrosion protective layers [1]. The polyaniline can be syntized in different chemical structural forms, such as leucoemeraldine, emeraldine base, pernigraniline or emeraldine salt that present specific electrical behaviors. Leucoemeraldine is electrically insulated with no double bonds between aromatic rings N H groups. Emeraldine base has few N H groups in its main chain being partially oxidized insulated. A fully-oxidized compound is pernigraniline having no N H groups in its main chain structure, thus, no conducting properties. Protonation emeraldine base to emeraldine salt Polymers 2017, 9, 732; doi: /polym

3 Polymers 2017, 9, induces an insulator to conductor conversion, transition taking place on NH groups [2,3]. The poly(o-anisidine) is a derivative form aniline, having a methoxy ( OCH 3 ) group substituted at ortho-position on benzene ring [4]. Over time, se conducting s have been produced by chemical, electrochemical, or plasma ization techniques [5 7]. Their synsis represents an attractive topic as ir structural properties, like morphology chemical form, are influenced by type ization method specific generation conditions. By DC or RF plasma deposition methods, ization conducting monomers involves complex chemical reactions mainly due to electron impact dissociation ionization chemical species. In [1] it was showed that ization organic compounds in glow discharges take place by a free radical mechanism, ionization being small. Thus, radicals produced in plasma are combined high molecular weight cross-linked s can be generated. In this paper we present results on morphological physicochemical characterization polyaniline () poly(o-anisidine) (POA) layers generated in a DC glow discharge plasma. The electrode discharge configuration has particularity that substrate holder can be positioned at different oblique inclination angles to anode. The vaporized aniline or o-anisidine monomers are injected into plasma through anode. The influence deposition plasma conditions, such as monomer injection temperature into plasma, anode-substrate inclination angle, discharge current intensity, on physical chemical properties layers are analyzed. The morphology layers was investigated by scanning electron microscopy (SEM) atomic force microscopy (AFM). The structure chemical composition s were analyzed by Fourier transform infrared spectroscopy (FTIR) X-ray diffraction (XRD). The dependence with temperature electrical conductivities polyaniline poly(o-anisidine) layers was also analyzed. 2. Materials Methods 2.1. Materials Aniline o-anisidine monomers in liquid form (Sigma-Aldrich Chemistry, Dorset, UK) were used as precursors for synsis polyaniline poly(o-anisidine) ic layers in a DC glow discharge plasma using various deposition parameters Deposition Technique Polyaniline Poly(o-Anisidine) Layers The layers polyaniline () poly(o-anisidine) (POA) were synsized in plasma a DC glow discharge produced in vapors monomers, with no buffer gas, using experimental setup presented in Figure 1. The DC plasma reactor consists two ring-shaped electrodes, mounted in parallel, namely anode, through which a vaporized liquid monomer is directly injected, cathode, through which sample s substrate holder is positioned, as shown in Figure 1. The liquid monomers (aniline o-anisidine) were heated to 20 C, consecutively to 50 C, vapors were injected (due to pressure difference between vacuum chamber monomer container) through a pipe from top reactor centrally positioned to anode. There is no buffer gas in vacuum chamber, pressure being about torr. The sample substrates were placed on holder at 5 10 cm from anode. The position samples holder relatively to anode its angle inclination (0, 45, 90 ) are controlled precisely through a six servo-mechanism system. In se experimental conditions, applying a voltage between anode cathode, a glow discharge plasma in aniline or o-anisidine vapors is produced. The experimental conditions used for plasma deposition polyaniline () poly(o-anisidine) (POA) layers on Si substrates are presented in Table 1.

4 Polymers 2017, 9, Polymers 2017, 9, The Theization process process aniline aniline o-anisidine monomers in ina glow glow discharge plasma plasma follows follows a free free radical mechanism [8]. [8]. When When discharge dischargeis isignited ignitedbetween between anode cathode cathodeat ata apotential V ( V ( substrate substrate holder holder being being at floating floating potential), potential), monomer monomer vapors do vapors not drop do not directly drop onto directly onto substrate substrate as y enter as y into enter plasma into plasma are involved arein involved collisions in with collisions plasma with electrons. plasma As electrons. a result this As aprocesses, result thischemical processes, reactive chemical species (radicals) reactive initiate species (radicals) fragmentation initiate stage fragmentation plasma stageization plasma ization reaction. The reaction. aniline The aniline o-anisidine fragmentation o-anisidine fragmentation takes place takes via place monoradical via monoradical (by detaching (by detaching from a from hydrogen a hydrogen atom atom eir eir by forming/detaching by forming/detaching an amino an amino group group on/from on/from aromatic aromatic ring) ring) biradical biradical (by (by opening opening aromatic aromatic ring ring π-bond π-bond scission) scission) species species formation, formation, thus thus initiating initiating propagation propagation stage stage ization ization process. process. These These radicals radicals deposited deposited on on substrate substratepromote promote classical chain chain ization izationprocess. process. In In final finalstage stage ization izationprocess, process, termination, termination, re reis isa simultaneous destruction destruction two two radicals radicals by by ir ir coupling, coupling, ending ending reaction. reaction. Usually Usually in this process, in this process, hydrogen hydrogen is transferred is transferred from onefrom one radical to radical anorto killing anor killing active end, active duringend, during discharge [8]. discharge [8]. As As ions ions temperature temperature into into plasma plasma does does not not exceed exceed K, K, plasma plasma heating heating deposited depositedlayers layerson on substrate substrateis isavoided [7]. [7]. Figure Figure Experimental Experimental setup setup employed employed DC DC plasma plasma reactor reactor [6,7]. [6,7]. Table Table Experimental Experimental deposition deposition conditions conditions for for ic ic films. films. Sample Sample Voltage Voltage Current Intensity Anode-Substrate Substrate Monomer Time Time No. No. (V) (V) Intensity (ma) Distance Distance (cm) (cm) Inclination Angle Temperature ( C) ( C) (min) (min) POA POA Structural, Morphological, Electrical Characterization Polyaniline Poly(o-Anisidine) Layers 2.3. Structural, Morphological, Electrical Characterization Polyaniline Poly(o-Anisidine) Layers The morphological features polyaniline poly(o-anisidine) layers, namely growing process The evolution morphological features s function polyaniline experimental poly(o-anisidine) depositionlayers, parameters, namely were growing analyzed process with an evolution SPM-NTegra Prima s AFM (NT-MDT) function atomic force experimental microscope deposition (AFM, NT-MDT, parameters, Moscow, were analyzed with an SPM-NTegra Prima AFM (NT-MDT) atomic force microscope (AFM, NT-MDT,

5 Polymers 2017, 9, Russia), which operates in semi-contact mode, using a NSG 01 cantilever (resonance frequency: khz, force constant: N/m). The topology polyaniline poly(o-anisidine) coatings deposited on Si substrates have been investigated by scanning electron microscopy (SEM) using a FEI Inspect S scanning electron microscope ( Hillsboro, Oregon, OR, USA) in both high- low-vacuum modes. The IR spectra polyaniline poly(o-anisidine) layers obtained on Si substrate were acquired in spectral range cm 1 using a SP100 IR Perkin Elmer spectrometer (Waltham, MA, USA) equipped with an attenuated total reflection (ATR) accessory. The structure layers was investigated by means a X-ray computerized diffractometer having a X-ray source Cu-Kα on a nm in a Bragg-Bretano configuration. The diffractograms were performed in a 5 70 angle range with an accuracy for 36 h. The method used for determining electrical conductivities polyaniline poly(o-anisidine) layers was previously reported in [9]. The measurements were performed by means a Keithley 2400 source meter controlled by LabView stware (custom made stware). The dependence conductivities on temperature was also established. The temperature control was granted by an INSTEC mk1000 high-precision Peltier stage controller (Boulder, Colorado, CO, USA). The solubility s was analyzed using following organic solvents acquired from Sigma Aldrich Chemistry: methanol, ethyl alcohol, chlororm, acetone, distilled water. 3. Results 3.1. AFM Analysis Atomic force microscopy allowed investigation morphological surface features POA layers deposited on Si optically-polished surfaces, as a function experimental deposition conditions presented above in Table 1. The ic layers have been obtained at a pressure about torr inside vacuum chamber. In Figures 2 3 are presented 2D 3D images POA layers. The layers form worm-like interlinked structures that change ir characteristics as a function experimental deposition conditions (Table 1). In Figure 2a,b it can be observed that, for 1 2 layers, an increase in substrate inclination angle to anode does not affect surface morphology. By increasing monomer injection temperature up to 50 C substrate inclination angle to anode up to 90, (Figure 2c e), it can be observed that worm like interlinked structures begin to form. The maximum dimension a worm-like structure is about 1.8 µm for a 90 inclination angle. As experimental conditions for ic layers pattering were established, role anode substrate distance was investigated. The role anode substrate distance on ic layers networking, (Figure 2f h) was studied it was observed that by decreasing from 10 to 5 cm, for an inclination angle C monomer injection temperature, dimension worm-like structures attain a value about 5 µm. The analysis AFM images poly(o-anisidine) layers indicate that no kind structures form on ir surfaces even when substrate inclination angle to anode monomer injection temperature were varied. In Figure 2i an AFM image a POA layer is presented, obtained for experimental conditions mentioned in Table 1. Recently [10], it was shown that polyaniline synsized in emeraldine salt formed in strong acidic medium present a wrinkled structures on ir surfaces. These structures are similar with those presented in Figure 2. Thus, we assume that DC glow discharge ignited in vapors aniline monomers can act as a strong oxidizing medium for ization aniline.

6 Polymers 2017, 9, Polymers 2017, 9, In ization process aniline, oxidation monomers takes place due to oxidizing agents, consecutively, generated aniline aniline cation cation radicals radicals initiate initiate process. process. The nitrogen The nitrogen atoms atoms usually usually act as oxidation act as oxidation centers centers [11]. [11]. In comparison, free electrons DC glow discharge which interact with monomer vapors produce fragmentation monomer. The The most probable reactions inside inside plasma plasma are are detaching detaching hydrogen hydrogen atoms atoms by fragmentation by fragmentation N H/C H N H/C H molecules molecules oxidation oxidation Nitrogen Nitrogen atoms. These atoms. fragments These fragments consisting consisting in cations, in anions, cations, anions, reactive species reactive that species reachthat reach substrate substrate holder canholder initiatecan initiate chain ization chain ization process. Theprocess. recombination The recombination cation radicals cation or radicals electrophilic or substitution electrophilic (oxidizing substitution nitrogen-containing (oxidizing nitrogen-containing structure attacksstructure phenyl attacks ring anphenyl aniline ring molecule an aniline substitutes molecule one proton substitutes one ring) proton can promote ring) can ic promote chain ic growth. During chain growth. chainduring growth ization, chain growth ization, monomer units monomer are continuously units are added continuously to added to chain bearing active chain endbearing groups. The active chainend growth groups. implies athe continuous chain oxidation/reduction growth implies a continuous oxidation/reduction chain during glow discharge. chain during glow discharge. Figure 2. 2D images (a) 1; (b) 2; (c) 3; (d) 4; (e) 5; (f) 6; (g) Figure 2. 2D images (a) 1; (b) 2; (c) 3; (d) 4; (e) 5; (f) 6; (g) 7; 7; (h) 8; (i) POA ic layers. (h) 8; (i) POA ic layers.

7 Polymers 2017, 9, Polymers 2017, 9, Figure 3. 3D images: : (a) (a) 1; 1; (b) (b) 2; (c) 2; (c) 3; (d) 3; (d) 4; (e) 4; (e) 5; (f) 5; (f) 6; (g) 6; (g) 7; (h) 7; (h) 8; 8; (i) POA (i) POA ic layers. layers. The The increase increase monomer monomer injection injection temperature temperature up up to to C, C, holder holder inclination inclination angle angle to to anode anodeup upto to90 decrease decrease anode-holder anode-holder distance distance to 5 tocm 5 cm (Table (Table 1) support 1) support generation generation an increased an increased amount amount oxidizing oxidizing agents agents on on substrate substrateholder holderwhich enhanced enhanced chain chain growth growth during during DC DC plasma. plasma. In this In this way, way, patterning patterning layer surfaces layer surfaces is slightly is changed, slightly changed, dimension dimension worm-like worm-like structure structure increasing increasing (Figure (Figure 2). Thus, 2). it Thus, can be it can explained be explained that that formation formation evolution evolution worm-like worm-like interlinked interlinked structure structure layers layers as a function as a function deposition deposition plasma plasma conditions. conditions. In In same same time, time, it it must must be be consider consider that that as as substrate substrate holder holder is at is a at floating a floating potential, potential, its superficial its superficial electrostatic electrostatic charging charging,, consecutively, consecutively, charge charge distribution distribution on on growing growing layer layer surface surface during during deposition deposition process process assist assist worm-like worm-like interlinked interlinked structure structure formation formation evolution. evolution. Previously, Previously, formation formation similar similar structures structures due due to to building building a charge charge density density on on free free surface surface a ic ic layer layer in in initial initial phase phase ization ization process process was was reported reported [12,13]. [12,13]. The The roughnesses roughnesses POA POA layers layers were calculated were calculated from from 2D AFM 2D images AFM presented images presented in Figure 2 in using Figure image 2 using processing image processing stware. The stware. results The are results shown are in Table shown 2. in Table 2. Table Table Roughness Roughness measurements measurements POA POA layers. layers. Sample POA Peak Sample to peak (nm) POA 8.1 Peak Average to peak (nm) Average (nm) SEM Analysis The topology generated POA layers on Si substrates with optically-polished surfaces in a DC glow discharge plasma using an oblique angle substrate configuration, in experimental deposition conditions presented in Table 1, were analyzed by scanning electron microscopy.

8 Polymers 2017, 9, SEM Analysis The topology generated POA layers on Si substrates with optically-polished surfaces in a DC glow discharge plasma using an oblique angle substrate configuration, in experimental Polymers 2017, 9, deposition conditions presented in Table 1, were analyzed by scanning electron microscopy. Figure 4a h 4a h presents SEM SEM images images ic ic layers layers worm-like worm-like structures pattering structures evolution pattering function evolution function experimental experimental conditions presented conditions in presented Table 1. The in layers Table do 1. The not present layers do any not cracking present on any ir cracking surfaces. on ir surfaces. In Figure 4i 4i it it can be be observed that that POA POA layer layer generated in in experimental conditions similar similar to those to those used used for for synsis synsis 8 layer 8 layer do not do not present present any any worm-like worm-like interlinked interlinked structures structures on its on surface. its surface. Figure Figure SEM SEM images images : : (a) (a) 1; 1; (b) (b) 2; 2; (c) (c) 3; 3; (d) (d) 4; (e) 4; (e) 5; (f) 5; (f) 6; (g) 6; (g) 7; (h) 7; (h) 8; (i) 8; (i) POA POA layers. layers. The layer thicknesses were established by analyzing with SEM technique, transversal The layer thicknesses were established by analyzing with SEM technique, transversal cross cross section each ( right corner inset image from Figure 4). The s are compact section each ( right corner inset image from Figure 4). The s are compact in in ir bulks, worm-like interlinked structures being formed only on layer surfaces. The ir bulks, worm-like interlinked structures being formed only on layer surfaces. The sample sample 1 2 generated for a monomer temperature 20 C inclination angles 1 2 generated for a monomer temperature (Table 1) have thicknesses about nm C inclination angles 0 flat surfaces. The increase in 45 monomer (Table 1) have thicknesses about nm flat surfaces. The increase in monomer temperature up to 50 C for an inclination angle 0 do not affect structuring 3 sample surface, it thickness being 310 nm. There are no structures on surface 6 sample obtained in deposition condition presented in Table 1. The increase thickness can be due to increase current intensity to decrease anode-substrate distance. The deposition conditions (Table 1) used for generation samples 4, 5, 7, 8 are

9 Polymers 2017, 9, temperature up to 50 C for an inclination angle 0 do not affect structuring 3 sample surface, it thickness being 310 nm. There are no structures on surface 6 sample obtained in deposition condition presented in Table 1. The increase thickness can be due to increase current intensity to decrease anode-substrate distance. The deposition conditions (Table 1) used for generation samples 4, 5, 7, 8 are proper for pattering surfaces, which can be associated to increase layer thicknesses. The thickness sample 5 is higher than one corresponding to 4 Polymers 2017, 9, (Figure 4d,e) as inclination angle substrate holder to anode has been increased from 45 to 90 thicknesses.. The AFM The pictures thickness in Figure 3d,e sample indicate also 5 is higher increasing than one corresponding dimension to worm-like 4 structure (Figure with 4d,e) as inclination inclination angle. angle substrate holder to anode has been increased from 45 In to 90. comparison The AFM pictures with in deposition Figure 3d,e indicate conditions also increasing 5 sample dimension (Figure 4e), maintaining wormlike structure time with 10inclination min, angle. inclination angle substrate holder to anode 90, deposition decreasing In comparison anode with substrate deposition distance conditions to 5 cm, 75 sample was (Figure obtained, 4e), maintaining with surface features deposition presented time in Figure 10 min, 4g. Theinclination thicknessangle ic substrate layer holder ( to 8) has anode furr 90, increased up decreasing anode substrate distance to 5 cm, 7 sample was obtained, with surface to 2.36 µm (Figure 4h) as current intensity was set to 30 ma. features presented in Figure 4g. The thickness ic layer ( 8) has furr increased For all samples, differences in ir pattering were also analyzed by up to 2.36 μm (Figure 4h) as current intensity was set to 30 ma. AFM measurements. For all samples, differences in ir pattering were also analyzed by AAFM high-resolution measurements. SEM image transversal cross-section 8 sample is presented in FigureA 5. high-resolution This is an indication SEM image a surface transversal effect cross-section that appear during 8 sample growing is presented process polyaniline in Figure 5. layer This is onan Si indication substrate in a surface a DC glow effect discharge that appear plasma during produced growing inprocess absence a bufferpolyaniline gas, in layer vapors on Si substrate monomers, in a DC glow usingdischarge an oblique plasma angle-positioned produced in electrode absence configuration. a buffer Previously gas, in [14,15], vapors worm-like monomers, interlinkedusing structures an oblique in plasma angle-positioned s volume electrode due configuration. to buckling effectpreviously have been[14,15], reported. worm-like interlinked structures in plasma s volume due to buckling effect have been reported. Figure 5. SEM images transversal cross-section 8 sample. Figure 5. SEM images transversal cross-section 8 sample FTIR Analysis 3.3. FTIR Analysis The structural analysis two types conducting s produced by plasma The ization structural processes analysis was performed two by types infrared spectroscopy. conducting s produced by plasma In Figures 6 7 are presented IR spectra liquid precursor layers ization processes was performed by infrared spectroscopy. obtained by plasma ization. In Figures 6 7 are presented IR spectra liquid precursor layers obtained In case both liquid polyaniline layers, (Figures 6 7), IR bs specific to N H by plasma bond vibrations ization. (3370, 3200, 3023 cm 1 ), C H vibrations (2961, 2921, 2862, 1373, 995, 971, 909 cm 1 ), In C=N bond casevibrations both liquid (1650 cm 1 ), polyaniline C N bond vibrations layers, (Figures (1310, cm7), 1 ), IRC=C bs bond specific vibrations to N H bond(1597, vibrations 1515, 1496, (3370, , cm ) are cm observed 1 ), C H [16 20]. vibrations (2961, 2921, 2862, 1373, 995, 971, 909 cm 1 ), By comparing IR bs identified in spectra with those observed in liquid precursor spectrum, one can obtain information about molecular bond arrangements. The IR bs assigned to N H bond vibrations (3370, 3200, 3023 cm 1 ) C H vibrations (2961, 2921, 2862, 1373, 995, 971, 909 cm 1 ) are broader in spectra than in liquid one.

10 Polymers 2017, 9, C=N bond vibrations (1650 cm 1 ), C N bond vibrations (1310, 1255 cm 1 ), C=C bond vibrations (1597, 1515, 1496, 1450 cm 1 ) are observed [16 20]. By comparing IR bs identified in spectra with those observed in liquid precursor spectrum, one can obtain information about molecular bond arrangements. The IR bs assigned to N H bond vibrations (3370, 3200, 3023 cm 1 ) C H vibrations (2961, 2921, 2862, 1373, 995, 971, 909 cm 1 ) are broader in spectra than in liquid one. Polymers 2017, 9, Polymers 2017, 9, Figure 6. FTIR spectra liquid precursor. Figure Figure FTIR spectra liquid precursor. Figure 7. FTIR spectra : (a) 1; (b) 2; (c) 3; (d) 4; (e) 5; (f) 6; (g) Figure 7; 7. FTIR (h) spectra : 8. (a) 1; (b) 2; (c) 3; (d) 4; (e) 5; (f) 6; (g) Figure 7. FTIR spectra : (a) 1; (b) 2; (c) 3; (d) 4; (e) 5; (f) 6; 7; (h) 8. (g) 7; (h) 8. As inclination angle between substrate anode is varied from 0 to 45, (Figure 7a,b; As Table 1), inclination for a monomer angle between injection temperature substrate 20 C, in anode is varied from cm 1 range 0 to 45, (Figure 7a,b; 2 IR Table spectrum, 1), for it a can monomer be observed injection that temperature intensities 20 C, in vibrational bs cm 1 range N H groups are 2 higher IR spectrum, than those it can specific be observed to C H that groups. intensities Contrarily, as vibrational monomer bs injection N H temperature groups are is higher increased than up those to 50 C, specific in to IR spectra C H groups. Contrarily, 3, 4, 5, 6, 7, as 8 samples, monomer (Figure injection 7c h) temperature intensities is increased C H up IR to bs 50 C, from in 2961, IR spectra 2921, , cm 4, 5, 1 are 6, 7, comparatively 8 samples, higher (Figure than 7c h) those intensities specific to N H IR C H bs IR bs from 3370, from 2961, 3200, 2921, 3023 cm cm Thus, 1 are it comparatively is possible that higher number than those N H specific broken to N H IR bs from 3370, 3200, 3023 cm 1. Thus, it is possible that number N H broken

11 Polymers 2017, 9, As inclination angle between substrate anode is varied from 0 to 45, (Figure 7a,b; Table 1), for a monomer injection temperature 20 C, in cm 1 range 2 IR spectrum, it can be observed that intensities vibrational bs N H groups are higher than those specific to C H groups. Contrarily, as monomer injection temperature is increased up to 50 C, in IR spectra 3, 4, 5, 6, 7, 8 samples, (Figure 7c h) intensities C H IR bs from 2961, 2921, 2862 cm 1 are comparatively higher than those specific to N H IR bs from 3370, 3200, 3023 cm 1. Thus, it is possible that number N H broken bonds inside plasma can be enhanced with increase monomer injection temperature. In same time, ratio between intensities C H N H IR bs is higher as inclination angle between anode substrate holder is increased up to 90 anode substrate distance is decreased to 5 cm (Figure 7f h, Table 1). The IR b from 1650 cm 1 assigned to C=N bond vibrations IR bs characteristic to C=C bond vibrations (1597, 1515, 1496, 1450 cm 1 ) are broader in spectra than in liquid one, for all samples. The IR bs from cm 1 are characteristic to protonated polyaniline attributed to C=C stretching vibrations quinoid benzoid rings. The broadening IR bs observed in spectra suggests cross-linking formation samples as a result ir synsis in a DC glow discharge plasma. The intensities IR bs specific to vibrations quinoid benzoid units allow estimation ir ratio in ic layer. As ir intensities are almost same, se groups are formed in in approximately equal proportions. This could be an indication ization in an emeraldine form [16]. Moreover, it is shown that 1070 cm 1 b is a characteristic b for emeraldine salt, being attributed to doping with H +. By this process an excitation b between valence conduction b can be formed, having an important role in electrical conduction samples. At same time, IR b from 1155 cm 1 also indicates conducting protonated process [17]. As can be observed in IR spectra from Figure cm 1 IR bs characteristic to emeraldine salt form are formed in all analyzed samples, having smallest intensity in 2 sample higher one in 8 sample. At same time, it can be noticed that intensity cm 1 IR bs increase with monomer injection temperature anode-substrate inclination angle, attaining a maximum value identified in 8 IR spectrum, (Figure 7h). These results, related to intensities molecular vibrational bs samples, can be correlated with variation in thickness ic layers in agreement with data presented in Section 3.2. The thickness 1 sample is about 390 nm that 8 sample attains a value 2.36 µm. The IR bs observed in sample spectra in cm 1 range are similar with those observed in liquid precursor spectrum. The C H out plane bending modes in cm 1 spectral region indicate all substitutions present in benzene ring as a result ization process, (Figure 8) [16 20]. The intensity IR bs observed at 747 cm 1 (ortho substitutions in benzene ring) 692 cm 1 (meta substitutions in benzene ring) are almost equal in all investigated samples (except 2 sample) in comparison with that from 830 cm 1 assigned to para substitutions. As chain conducting contains a high proportion para substitutions in benzene ring [11], it results that 2 sample has smallest conductivity, higher conductivity being attributed to 8 sample. In Figure 7 can be observed that intensity 830 cm 1 IR b has highest value in case 8 sample IR spectrum smallest one in case 2 sample IR spectrum. The dependence intensity IR b from 830 cm 1 on plasma deposition conditions (Table 1) can also be observed in Figure 8. The monomer injection temperature 50 C ( 3, 5, 6, 7, 8), a substrate inclination angle about 90 ( 5, 7, 8), anode substrate distance 5 cm ( 7, 8) are most favorable plasma deposition conditions for a high degree aniline ization in para substitutions in benzene ring.

12 Polymers 2017, 9, In ization process coupling phenyl nuclei with respect to amino groups is mainly performed in meta ortho positions. The difference in intensities se bs that from 830 cm 1 can also be an indication a branched structure s [18 20]. Polymers 2017, 9, Figure Figure8. 8. Details Details samples samplesftir FTIRspectra spectrain in cm 1 1 range. range. The IR spectra polyaniline syntized DC glow discharge plasma, (Figures 7 8), The IR spectra polyaniline syntized DC glow discharge plasma, (Figures 7 8), showed influence deposition parameters on s structure. The spectra showed influence deposition parameters on s structure. The spectra 1, 1, 2 samples are distinct in terms b intensities, especially in cm 1 range, as a result 2 samples are distinct in terms b intensities, especially in cm variation inclination angle between anode holder substrate 1 range, as a result for a monomer variation inclination angle between anode holder substrate for a monomer injection temperature 20 C. The IR spectra 3 8 samples generated at 50 C monomer injection temperature 20 injection temperature do not C. The IR spectra 3 8 samples generated at 50 present such differences in ir IR spectra even when C monomer inclination injection temperature do not present such differences in ir IR spectra even when inclination angle between anode substrate holder was increased up to 90. As se ic layers angle between anode substrate holder was increased up to 90 are spectrally identified to be in emeraldine salt form polyaniline (Figure. As se ic 7), it seems that layers are spectrally identified to be in emeraldine salt form polyaniline (Figure 7), it seems inclination angle between anode substrate holder affect mainly proportion between that inclination angle between anode substrate holder affect mainly proportion para, ortho, meta substitutions in benzene rings, as a consequence, conductivity between para, ortho, meta substitutions in benzene rings, as a consequence, conductivity samples. samples. Figure 9 presents spectra poly(o-anisidine) liquid precursor (black line) POA layers Figure 9 presents spectra poly(o-anisidine) liquid precursor (black line) POA layers (red line). The IR bs assignment identified within spectra are shown in Tables 3 4. (red line). The IR bs assignment identified within spectra are shown in Tables 3 4. Table 3. IR spectral bs identified in spectra. Wavenumber (cm 1 ) IR Vibrational Unit 3370, 3200, 3023 N H stretching vibrations [16,18] 2961, 2921 C H stretching vibrations in CH3 [16] 2862 C H vibrations in CH2 [16] 1650 C=N stretching vibrations quinoid ring [16] 1597 C=C stretching vibrations quinoid ring [5,16,19] 1515, 1496, 1450 C=C stretching vibrations benzoid ring [1,5,16] 1405 C N + stretching vibrations [16] 1373 C H symmetric deformation vibrations in CH3 [19] 1310 C N stretching vibrations aromatic ring [19] 1255 C N stretching vibrations in aromatic primary amine [16,20] 1173, 1109, 1026 In-plane bending vibrations aromatic C H [19]

13 Polymers 2017, 9, Polymers 2017, 9, Figure 9. FTIR spectrum poly(o-anisidine) liquid precursor (black line) (red line). Figure 9. FTIR spectrum poly(o-anisidine) liquid precursor (black line) (red line) X-Ray Diffraction Analysis Table 3. IR spectral bs identified in spectra. The crystalline structure s was investigated for all samples produced in experimental Wavenumber conditions (cm presented ) in Table 1 by means IR Vibrational an X-ray diffraction Unit (XRD) setup. The XRD patterns 3370, 3200, 8 sample 3023 are presented in Figure N H stretching 10. vibrations [16,18] 2961, 2921 C H stretching vibrations in CH 3 [16] 2862 C H vibrations in CH 2 [16] 1650 C=N stretching vibrations quinoid ring [16] 1597 C=C stretching vibrations quinoid ring [5,16,19] 1515, 1496, 1450 C=C stretching vibrations benzoid ring [1,5,16] 1405 C N + stretching vibrations [16] 1373 C H symmetric deformation vibrations in CH 3 [19] 1310 C N stretching vibrations aromatic ring [19] 1255 C N stretching vibrations in aromatic primary amine [16,20] 1173, 1109, 1026 In-plane bending vibrations aromatic C H [19] 1155 C N stretching vibrations in benzoid ring [17] 1070 Quinoid ring NH + benzoid ring stretching vibrations [16] 995, 971, 909 C H out plane bending vibrations [18] 873, 692 meta substitutions, 1,3 disubstitution in benzene ring [18] 830, 554 para substitutions, 1,4 disubstitution in benzene ring [2,18] 747, 506 ortho substitutions, 1,2 disubstitution in benzene ring [16,19] 613 vibrations in aryl nitro compounds [5] Table 4. IR spectral bs assignments identified in poly(o-anisidine) spectrum. Wavenumber Figure cm10. 1 XRD diffraction patterns IR Vibrational 8 sample. Unit 3350 N H stretching vibrations [18,21] The main reflections 2930, correspond 2882 to a pseudo C H orthorhombic stretching vibrations phase in. CH 3 [20] Crystallinity samples could account 1597 for superior conductive C=C stretching properties vibrations thin quinoid groups layers. [18,21] Thus, a highlyordered structure, similar 1501, 1455 to metals, will most C=C stretching likely have vibration enhanced benzoid conductivity. groups [4,18,21] Our results present 1335 N H group vibration [22] a textured film made up two components from crystalline point view. The first one 1270, 1240 Carboxyl groups vibrations on benzene ring [4,22] formed from (010), 1217, (200) 1177, with 1152broad appearance 1,2,4 trisubstituted low intensity benzene due ring to [21] reduced crystalline dimension with a low 1117, degree 1020 organization, 1,4 substitution or on one composed benzene ring [4] intense narrow reflections corresponding 848, 805, to 740 a highly-ordered 1,2 structure. 1,3-substitutions Additionally, in benzene latter ring case, [4] crystallite size increased with a factor 550 ~10. These results 1,4 disubstitution indicate that on benzene ic ring [2,20] layers are formed by crystalline domains embedded in an amorphous matrix.

14 Polymers 2017, 9, The FTIR spectra poly(o-anisidine) liquid precursor ic film obtained in DC plasma Polymers 2017, reactor 9, 732 are shown in Figure 9. The corresponding IR b assignments are presented in Table in agreement with reference data [4,18,20,22]. In ic layer, main characteristic bs are attributed to: N H stretching vibrations (3350 cm 1 ) in poly(o-anisidine) group; vibrations quinoid (1597 cm 1 ) benzoid (1501, 1455 cm 1 [18]) rings which confirm plasma ization o-anisidine to poly(o-anisidine); carboxyl groups (1270, 1240 cm 1 ) presence on benzene rings; 1,2,4 trisubstituted benzene ring (1217, 1177, 1152 cm 1 ); 1,4 substitution on benzene rings (1117, 1020 cm 1 ); 1,2 1,3 substitutions on benzene ring (848, 805, 740 cm 1 ) [4]; 1,4 disubstitution on benzene ring (550 cm 1 ) can be clearly noticed. In comparison with IR bs characteristic to liquid precursor it can be observed that in POA spectrum, in spectral range cm 1, IR bs characteristic to N H stretching vibrations (3350 cm 1 ) C H stretching vibrations (2930, 2882 cm 1 ) are overlaid as an indication ir broadening. The C=C stretching vibrations quinoid groups appear in spectrum at 1597 cm 1, not at 1612 cm 1 as in liquid precursor spectrum. The C=C stretching vibration benzoid groups has similar IR b features in both liquid spectra. In cm cm 1 spectral ranges IR bs are better evidenced in precursor liquid spectrum than in one. This can be an indication that, in, IR bs are broader overlaid. The broadening IR bs is an indication cross-linking. In comparison to IR spectrum, IR spectrum poly(o-anisidine) from Figure 9 shows that IR b specific to benzoid group is more intense than one quinoid group, indicating Figure that 9. FTIR ir spectrum proportions are poly(o-anisidine) not equal. liquid precursor (black line) (red line) X-Ray Diffraction Analysis The crystalline structure s was investigated for all samples produced in experimental conditions presented in Table 1 by means an X-ray diffraction (XRD) setup. The XRD patterns 8 sample are presented in in Figure Figure 10. XRD diffraction patterns 8 sample. The The main main reflections reflections correspond correspond to to a pseudo a pseudo orthorhombic orthorhombic phase phase.. Crystallinity Crystallinity samples samples could account could account for superior for superior conductive conductive properties properties thin thin layers. Thus, layers. a highlyordered Thus, a highly-ordered structure, structure, similar to similar metals, to will metals, most will likely most have likely enhanced have enhanced conductivity. conductivity. Our results Our present results present a textured a textured film made film up made two up components two components from crystalline from point crystalline view. point The first view. one The formed first from one formed (010), (200) from with (010), broad (200) appearance with broad appearance low intensity low due intensity to reduced due to crystalline reduced dimension with a low degree organization, or one composed intense narrow reflections corresponding to a highly-ordered structure. Additionally, in latter case, crystallite size increased with a factor ~10. These results indicate that ic layers are formed by crystalline domains embedded in an amorphous matrix.

15 Polymers 2017, 9, crystalline dimension with a low degree organization, or one composed intense narrow reflections corresponding to a highly-ordered structure. Additionally, in latter case, crystallite size increased with a factor ~10. These results indicate that ic layers are formed by crystalline domains embedded in an amorphous matrix. Defects in crystal symmetry are most likely caused by lattice strain which represents a measure both defects dislocation. This, in turn, leads to a lattice deformation that causes residual stress in crystalline matrix. Moreover, lattice strain induces an effect line broadening in XRD spectra. Assuming that crystallite size lattice strain have an independent contribution to line broadening, we calculated strain induced in crystalline structure with following relation [23]: β = 4εtanθ (1) where ε is lattice strain induced in crystalline particles β full width at half maximum value. The crystalline plane lattice strain associated to diffraction peaks identified in Figure 10 are summarized in Table 5. Table 5. Crystallinity proprieties 8 sample. hkl Diffraction Peak (2θ) d (nm) Lattice Strain (010) (005) (111) (022) (200) The crystalline domain size was evaluated using Scherrer formula [16]: d = 0.89λ/βcosθ (2) where d represents crystallite dimension, λ specific X-ray wavelength. The interchain separation length was determined from Equation (2) for highest intensity crystalline orientation. This parameter can give a measure ic layers conductivity it represents hopping distance electrons from one chain to anor. Thus, probability for a layer to be conductive increases as distance between chains decreases [16]. In our case, interchain separation length value was 3.59 Å, which is in good agreement with literature for conductive polyaniline [16]. R = 5λ 8 sin θ As presented in Figure 11 diffraction pattern POA sample exhibits a medium broad peak at 2θ = 12.5, a broad intense peak with its maximum centered at 25. These peaks are attributed to semi-crystalline nature [24]. In case POA samples obtained for a substrate inclination angle 0 degree, namely, 1, 3, 6, re were no observed diffraction patterns. (3)

16 Polymers 2017, 9, Polymers 2017, 9, Figure 11. XRD diffraction patterns POA sample. Figure 11. XRD diffraction patterns POA sample Solubility Analysis 3.5. Solubility Analysis The solubility behavior plasma ic films can give useful knowledge about ir degree The solubility behavior plasma ic films can give useful knowledge about ir degree cross-linking. For example, a well cross-linked is typically insoluble in organic solvents cross-linking. For example, a well cross-linked is typically insoluble in organic solvents [24]. [24]. The solubility POA thin films was investigated using four organic solvents, The solubility POA thin films was investigated using four organic solvents, namely: methanol, ethyl alcohol, chlororm, acetone, distilled water. It was analyzed qualitatively namely: methanol, ethyl alcohol, chlororm, acetone, distilled water. It was analyzed by recording FT-IR spectra layers before after ir submerging in organic solvents for qualitatively by recording FT-IR spectra layers before after ir submerging in organic 5 min. By comparing se spectra for each, we observed that intensities IR bs, solvents for 5 min. By comparing se spectra for each, we observed that intensities specific to poly(aniline) to poly(o-anisidine) kept in organic solvents, become partially (50%), IR bs, specific to poly(aniline) to poly(o-anisidine) kept in organic solvents, become completely (100%), or not diminished. In terms solubillity we interpret se results as partially partially (50%), completely (100%), or not diminished. In terms solubillity we interpret se results soluble, soluble, or insoluble samples. The results are shown in Table 6. as partially soluble, soluble, or insoluble samples. The results are shown in Table 6. Table 6. Solubility POA samples. Table 6. Solubility POA samples. Sample Sample Organic Solvent CH 3 CH3OH C 2 HC2H6O 6 O CHCl3 3 C3H6O C 3 H 6 O H2O H 2 O 1 1 p p p p p s s i i 2 2 p p p p p s s i i 3 3 p p p p p s s i i 4 p p p s i 4 p p p s i 5 p p p s i 6 5 p p p p p s s i i 7 6 p p p p p s s i i 8 7 p p p p p s s i i POA s s s s i 8 p p p s i POA Where s soluble, s p partially s soluble s i insoluble. s i where s soluble, p partially soluble i insoluble Electrical Conductivity Measurements 3.6. Electrical Polyaniline Conductivity s Measurements synsized by chemical, electrochemical or plasma methods, can have electrical Polyaniline conductivities s ranging synsized between by 10 chemical, 10 electrochemical 10 S/cm. The electrical or plasma conductivity methods, can have electrical depend onconductivities it oxidation state ranging (pernigraniline, between 10 emeraldine ors/cm. leucoemeraldine) The electrical conductivity degree protonation. depend on it oxidation state (pernigraniline, emeraldine or leucoemeraldine) degree protonation. The undoped form polyaniline usually has an electrical conductivity in ~10 9 S/cm

17 Polymers 2017, 9, Polymers 2017, 9, range while conductivity H + doped polyaniline varies from ~10 5 S/cm to 10 S/cm The [9,11,16,22]. undoped form polyaniline usually has an electrical conductivity in ~10 9 S/cm range while conductivity The electrical conductivities H + doped polyaniline were measured variesfor from all ~10 5 samples S/cm to produced 10 S/cm in [9,11,16,22]. experimental condition The electrical presented conductivities in Table 1. At were room measured temperature, for all conductivity samples produced 2 insample experimental is about 3.8 condition 10 5 S/cm presented conductivity in Table 1. At room temperature, 8 sample is 5 10 conductivity 5 S/cm. There are smaller 2 sample differences is about in 3.8 conductivities 10 5 S/cm or conductivity samples. In 8 principle, sample is 5 sequence 10 5 S/cm. in There increase are smaller in ir differences conductivities in follow conductivities behavior or intensity samples. In830 principle, cm 1 IR b sequence (attributed in increase to para insubstitutions ir conductivities in benzene follow ring) as behavior it was observed intensity FTIR 830 spectra cm 1 from IR b Figure (attributed 8. On to or para substitutions h, intensities benzene ring) IR bs as it was from observed 1070 in 1155 FTIR cmspectra 1 could from indicate Figure 8. On differences or in h, concentration intensities IRemeraldine bs fromsalt 1070 formed 1155 in cm 1 samples. could indicate The spectra differences from Figure in 7 concentration indicates that emeraldine 2 sample salt formed has in smallest samples. concentration The spectra emeraldine from Figuresalt, 7 indicates while that 8 sample 2 sample has has highest smallest one. concentration emeraldine salt, while 8 sample has highest one. The dependence electrical electrical conductivity conductivity polyaniline polyaniline ( 8( sample) 8 sample) poly(o-anisidine) anisidine) onsamples temperature on temperature is presentedis inpresented Figure 12. in The Figure conductivities 12. The conductivities all samples all have samples similar samples dependences have similar ondependences temperature. on temperature. The poly(o-anisidine) sample shows an abrupt increase conductivity with temperature, reaching aa value S/cm at at K, K, in incomparison with that polyaniline ( 8 sample) that only increases up up to to S/cm, Figure Figure 12. Dependence 8 POA samples electrical conductivity on temperature. Figure 12. Dependence 8 POA samples electrical conductivity on temperature. 4. Conclusions 4. Conclusions In this study we investigated from physicochemical morphological points view polyaniline In this study poly(o-anisidine) we investigated from physicochemical layers generated in a morphological direct current glow points discharge view plasma polyaniline in absence poly(o-anisidine) a buffer gas, in vapors layers generated monomers, in a direct using current an glow oblique discharge angle positioned plasma in substrate absence configuration. a buffer gas, In in comparison vapors with monomers, poly(o-anisidine) using an layer oblique surfaces angle which positioned are flat, substrate on configuration. surface In polyaniline comparison films with we poly(o-anisidine) identified formation layer surfaces worm-like which are interlinked flat, on surface structures having polyaniline dimensions films we identified a spatial distribution formation dependent worm-like on interlinked plasma structures ization having experimental dimensions conditions. a spatial For distribution 0 degree dependent inclination on angle plasma between ization anode experimental substrate conditions. holder, re For was 0 no degree observed inclination structure angle on between anode surfaces any substrate kind. holder, re was no observed structure on The main advantage surfaces any this kind. plasma ization technique is ease synsis (10 min) The main possibility advantage different this plasma patterning ization polyaniline technique is ease surfaces synsis only by (10 varying min) deposition possibility conditions, different namely patterning inclination polyaniline angle substrate surfaces only holder by varying to anode deposition conditions, monomer namely injection temperature. inclination angle This does substrate not imply holder any to supplementary anode chemical monomer or injection physical treatments which can affect layer surface morphologies, mainly by cracking.

18 Polymers 2017, 9, temperature. This does not imply any supplementary chemical or physical treatments which can affect layer surface morphologies, mainly by cracking. The analysis physical chemical properties ic layers has been performed by infrared X-ray diffraction spectroscopy. The FTIR spectral analysis polyaniline layers indicates, besides main IR bs, conductive character polyaniline. The intensities IR bs specific to conducting protonated samples ascertain it emeraldine salt form (1070, 1155 cm 1 ) increase with thicknesses layers. At same time, intensity molecular b from 830 cm 1, characteristic to para substitutions in benzene ring, can give information about conductivities layers. The FTIR analyses are in agreement with conductivity measurements which show that 8 sample has highest conductivity ( S/cm) 2 sample has lowest one ( S/cm). This results in conductivity investigated samples increasing as concentration emeraldine salt in s increases. The electrical conductivity polyaniline is higher than poly(o-anisidine) in a C temperature range. In contrast, conductivity poly(o-anisidine) layers increase to higher values than that polyaniline in C temperature range. Anor advantage this plasma ization technique was identified by XRD spectra analysis that show formation crystalline domains embedded in an amorphous matrix in 8 sample. The X-ray diffraction pattern poly(o-anisidine) highlighted semi-crystalline nature layers. The s obtained for a 0 degree inclination angle between anode substrate holder are amorphous. Usually, polyaniline layers are obtained by different plasma deposition techniques, chemical or electrochemical methods are amorphous. Polymers with crystalline or semi-crystalline structure can be obtained only by physical or chemical treatments layers using supplementary methods. Acknowledgments: The research activities were supported from RO PN-II-RU-TE grant. Author Contributions: Bogdan Butoi, Andreea Groza, Valentin Barna conceived designed experiments. Bogdan Butoi, Paul Dinca, Adriana Balan performed experiments. Bogdan Butoi, Andreea Groza, Paul Dinca, Adriana Balan, Valentin Barna analyzed data wrote paper. All authors discussed results, edited agreed final form manuscript. Conflicts Interest: The authors declare no conflict interest. References 1. Lakshmi, G.B.V.S.; Dhillon, A.; Siddiqui, A.M.; Zulfequar, M.; Avasthi, D.K. RF-plasma ization characterization polyaniline. Eur. Polym. J. 2009, 45, [CrossRef] 2. Cruz, G.J.; Morales, J.; Castillo-Ortega, M.M.; Olayo, R. Synsis polyaniline films by plasma ization. Synth. Met. 1997, 88, [CrossRef] 3. Ameen, S.; Akhtar, M.S.; Song, M.; Shin, H.S. Metal Oxide Nanomaterials, Conducting Polymers Their Nanocomposites for Solar Energy. In Solar Cells-Research Application Perspectives; Intech: Rijeka, Croatia, 2013; Chapter Chaudhari, S.; Sainkar, S.R.; Patil, P.P. Anticorrosive properties electro synsized poly(o-anisidine) coatings on copper from aqueous salicylate medium. J. Phys. D Appl. Phys. 2007, 40, [CrossRef] 5. Gong, X.; Dai, L.; Mau, A.W.; Griesser, H.J. Plasma-Polymerized Polyaniline Films: Synsis Characterization. J. Polym. Sci. A 1998, 36, [CrossRef] 6. Staicu, D.; Butoi, B.; Armeanu, C.; Barna, E.S. Influence key deposition control parameters on structure thin films in a direct current cold plasma reactor for photonics applications. Dig. J. Nanomater. Biostruct. 2016, 11, Butoi, B.; Berezovski, C.; Staicu, D.; Berezovski, R.; Marin, A.M.; Barna, E.S. Direct Current Plasma Polymerization Reactor for Thin Duromer Film Deposition. J. Optoelectron. Adv. Mater. 2014, 16,

19 Polymers 2017, 9, Jatratkar, A.A.; Yadav, J.B.; Deshmukh, R.R.; Barshilia, H.C.; Puri, V.; Puri, R.K. Impact low-pressure glow-discharge pulsed plasma ization on properties polyaniline thin films. Phys. Scr. 2016, 91, [CrossRef] 9. Shi, G.; Rouabhia, M.; Wang, Z.; Dao, L.H.; Zhang, Z. A novel electrically conductive biodegradable composite made polypyrrole nanoparticles polylactide. Biomaterials 2004, 25, [CrossRef] [PubMed] 10. Xie, J.; Zong, C.; Han, X.; Ji, H.; Wang, J.; Yang, X.; Lu, C. Redox-Switchable Surface Wrinkling on Polyaniline Film. Macromol. Rapid Commun. 2016, 37, [CrossRef] [PubMed] 11. Sapurina, I.Y.; Shishov, M.A. Oxidative Polymerization Aniline: Molecular Synsis Polyaniline Formation Supramolecular Structures. In New Polymers for Special Applications; InTech: Rijeka, Croatia, 2012; Chapter 9; ISBN Groza, A.; Surmeian, A.; Diplasu, C.; Luculescu, C.; Chapon, P.; Tempez, A.; Ganciu, M. Physico-chemical processes occurring during ization liquid polydimethylsiloxane films on metal substrates under atmospheric pressure air corona discharges. Surf. Coat. Technol. 2012, 212, [CrossRef] 13. Groza, A.; Ciobanu, C.S.; Popa, C.L.; Iconaru, S.L.; Chapon, L.; Luculescu, C.; Ganciu, M.; Predoi, D. Structural properties antifungal activity against Cida albicans biilm different composite layers based on Ag/Zn doped hydroxyapatite-polydimethylsiloxanes. Polymers 2016, 8, 131. [CrossRef] 14. Wang, X.; Grundmeier, G. Morphology Patterning Processes Thin Organosilicon Perfluorinated Bi-Layer Plasma Polymer Films. Plasma Process. Polym. 2006, 3, [CrossRef] 15. Tsai, T.C.; Staack, D. Low-Temperature Polymer Deposition in Ambient Air Using a Floating-electrode Dielectric Barrier Discharge Jet. Plasma Process. Polym. 2011, 8, [CrossRef] 16. Du, X.; Xu, Y.; Xiong, L.; Bai, Y.; Zhu, J.; Mao, S. Polyaniline with high crystallinity degree: Synsis, structure, electrochemical properties. J. Appl. Polym. Sci. 2014, 131, [CrossRef] 17. Jarad, A.N.; Ibrahim, K.; Ahmed, N.M. Synsis characterization thin films conductive () for optoelectronic device application. AIP Conf. Proc. 2016, 1733, Coates, J. Interpretation Infrared Spectra, A Practical Approach. In Encyclopedia Analytical Chemistry; Meyers, R.A., Ed.; John Wiley & Sons Ltd.: Chichester, UK, 2000; pp Tamirisa, P.A.; Liddell, K.C.; Pedrow, P.D.; Osman, M.A. Pulsed-Plasma-Polymerized Aniline Thin Films. J. Appl. Polym. Sci. 2004, 93, [CrossRef] 20. Ohsaka, T.; Ohnuki, Y.; Oyama, N.; Katagiri, G.; Kamisako, K. IR absorbtion spectroscopic identification electroactive electroinactive polyaniline films prepared by electrochemical ization aniline. J. Electroanal. Chem. Interfacial Electrochem. 1984, 161, [CrossRef] 21. Nabid, M.R.; Zamiraei, Z.; Sedghi, R. Water-soluble Aniline/o-Anisidine Co: Enzymatic Synsis Characterization. Iran. Polym. J. 2010, 19, Shah, K.; Iroh, J. Poly(o-anisidine) Coatings Electrodeposited onto AL-2024: Synsis, Characterization, Corrosion Protection Evaluation. Adv. Polym. Technol. 2004, 23, [CrossRef] 23. Mote, V.D.; Purushotham, Y.; Dole, B.N. Williamson Hall analysis in estimation lattice strain in nanometer-sized ZnO particles. J. Theor. Appl. Phys. 2012, 6. [CrossRef] 24. Özdemir, C.; Kaplan Can, H.; Colak, N.; Güner, A. Synsis, Characterization, Comparison Self-Doped, Doped, Undoped Forms Polyaniline, Poly(o-anisidine), Poly[aniline-co-(o-anisidine)]. J. Appl. Polym. Sci. 2006, 99, [CrossRef] 2017 by authors. Licensee MDPI, Basel, Switzerl. This article is an open access article distributed under terms conditions Creative Commons Attribution (CC BY) license (

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