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Thin Solid Films 583 (2015) 60 – 69 Contents lists available at ScienceDirect Thin Solid Films

Contents lists available at ScienceDirect

Thin Solid Films

journal homepage: www.elsevier.com/locate/tsf

Solid Films journal homepage: www.elsevier.com/locate/tsf Layer-by-layer assembled highly absorbing hundred-layer fi

Layer-by-layer assembled highly absorbing hundred-layer lms containing a phthalocyanine dye: Fabrication and photosensibilization by thermal treatment

Alena S. Sergeeva a ,b , , Elena K. Volkova a , Daniil N. Bratashov a , Mikhail I. Shishkin a , Vsevolod S. Atkin a , Aleksey V. Markin a , Aleksandr A. Skaptsov a , Dmitry V. Volodkin b , Dmitry A. Gorin a

a , Dmitry V. Volodkin b , Dmitry A. Gorin a a Saratov State University, Astrakhanskaya

a Saratov State University, Astrakhanskaya 83, 410012 Saratov, Russia

b Fraunhofer Institute for Cell Therapy and Immunology, Branch Bioanalytics and Bioprocesses (Fraunhofer IZI-BB), Muehlenberg 13, 14476 Potsdam, G ermany

article info

Article history:

Received 14 November 2013 Received in revised form 15 March 2015 Accepted 20 March 2015 Available online 28 March 2015

Keywords:

Layer-by-layer assembly Copper phthalocyanine Polyelectrolytes Multilayer thin lms Absorption spectra Surface morphology Thermogravimetry analysis

abstract

Highly absorbing hundred-layer lms based on poly(diallyldimethylammonium chloride) (PDADMAC) of various molecular weights and on sulfonated copper phthalocyanine (CuPcTs) were prepared using layer-by- layer assembly. The multilayer lms grew linearly up to 54 bilayers, indicating that the same amount of CuPcTs was adsorbed at each deposition step. This amount, however, was dependent on the molecular weight of PDADMAC in the range 100 500 kDa: the higher the molecular weight, the more CuPcTs molecules were adsorbed. This can be explained by the larger surface charge number density specic to longer polymer chains. Domains of pure PDADMAC and of the PDADMAC/CuPcTs complex were formed in the lms during the assembly. Uniform distribution of CuPcTs over the lms could be achieved by thermal treatment, leading to an α β phase transition in phthalocyanine at 300 °C. Annealing caused changes in the lm absorbance spectra, resulting in a 30-nm red shift of the peak maxima and in a strong (up to 62%) decrease in optical density. Thermogravimetric analysis revealed thermodegradation of PDADMAC during annealing above 270 °C, giving rise to micrometer- sized cracks within the lms, as evidenced by scanning electron microscopy. © 2015 Elsevier B.V. All rights reserved.

1. Introduction

Nano- and microstructured thin lms containing organic materials (such as phthalocyanine dyes) serve as components of highly integrated devices in different elds of science and technology, including optoelec- tronics [17]. A wide variety of methods can be used to fabricate such coatings. Layer-by-layer (LbL) assembly is one of the simplest tech- niques to design multilayer lms with controlled thickness and chemi- cal composition [8] . This approach makes it possible to use substrates of various shapes and dimensions (up to the micro- and nano-scale) for the fabrication of planar and curved nanomaterials with required properties [9 16] . The LbL technique has been employed to pattern surfaces with various particles, including microcapsules, micelles, and nanoparticles [1722]. The nature of the polyelectrolytes used in LbL assembly is important, owing to the strong in uence of inter- polyelectrolyte complexation [23,24]. The thickness of deposited layers

Corresponding author at: 410012, Saratov State University, Astrakhanskaya St. 83, Saratov, Russia. Tel.: +7 845 2511181, +7 927 1399975. E-mail addresses: alenasergeeva@mail.ru (A.S. Sergeeva), ekvolkova87@rambler.ru (E.K. Volkova), dn2010@gmail.com (D.N. Bratashov), shishkin1mikhail@gmail.com (M.I. Shishkin), ceba91@list.ru (V.S. Atkin), markinav@mail.ru (A.V. Markin), skaptsov@yandex.ru (A.A. Skaptsov), dmitry.volodkin@izi-bb.fraunhofer.de (D.V. Volodkin), gorinda@mail.ru (D.A. Gorin).

0040-6090/© 2015 Elsevier B.V. All rights reserved.

depends strongly on polyelectrolyte molecular weight (MW), surface charge density, and polymer transport to the lm surface [2528]. The formation of domains or phase separation can take place during layer deposition [27,29,30] or as a result of some post-treatment [31 33] , leading to lm microstructurization. In the case of phthalocyanine polymer lms, thermal treatment can cause both phase separation and formation of a homogeneous phase [29]. LbL lms containing conductive polymers, carbon nanostructures (single- or multiwall tubes, fullerenes), and dyes can serve as electrodes or photoactive layers in multilayer photovoltaic converters [7,3440]. Indeed, the hybrid photoelement structure can be fabricated only by all-solution processes [7,34 40] . The main advantages of such multilayer organic elements are that they are cheap, easy to process, and ecologically safe; however, the photovoltaic characteristics are not satisfactory. Therefore, the next promising direction in optoelectronics (apart from the creation of thin-lm hybrid solar cells) is the develop- ment of unconventionally constructed photoelements [4146]. Modern approaches to modifying photovoltaic converters are based on the use of textured templates [41], nanowire arrays [42], plasmonic nano- particles [45] , spherically shaped elements [43] , and photonic crystal st ructures [44] . Alternative constructions with the abovementioned changes in design can provide enhanced photovoltaic converter ef ciency. The performance improvement can be achieved both by

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optimizing absorbance spectra and by enlarging the space-charge region (increasing the photogenerated charge separation area). Surface patterning reduces the reection and increases the number of adsorbed photons [4144], leading to enhanced efciency. A nonconventional design for a thin-lm photovoltaic converter was suggested recently by Regan et al. [46] . The proposed construction is a screening-engineered eld-effect photoelement based on a single- doped inorganic semiconductor [46] . The multilayer architecture is similar to the metal insulator semiconductor structure and consists of a bottom contact on a solid substrate, a single-doped semiconductor layer, an ultrathin top contact, and two transparent layers: a gate contact and a gate insulator. This unconventional construction shows acceptable characteristics, which can be additionally improved by ap- plying an external voltage to the gate contact and blocking the recombi- nation current [46]. Regan et al.'s [46] work inspired us and became a starting point for this research. Si and Cu 2 O lms can be replaced with an organic layer (such as a sulfonated phthalocyanine complex acting as a single- doped semiconductor), so that the described construction [46] could be fabricated using an all-solution process. One challenge is to obtain the LbL photoactive organic layers with a proper thickness of about 30200 nm [13] in general for hybrid solar cells based on fullerenephthalocyanine evaporated lms. Thus, to prepare suf ciently thick phthalocyanine lms by LbL assembly, one should use an acceptable cationic polyelectrolyte [e.g., poly(diallyldimethylammonium chloride) (PDADMAC), poly(ethyleneimine) (PEI), poly(allyl amine hydrochloride) (PAH), or polyaniline] coupled to an anionic phthalocyanine to consecu- tively deposit the necessary number of layers. For a single LbL bilayer, a thickness of 0.81.2 nm has been reported for MPcTs/PDADMAC and MPcTs/PAH structures [4749] (here, MPcTs is sulfonated phthalocya- nine of a certain metal). Thus, it is important to fabricate hundred-layer structures to achieve a proper thickness for a photoactive semiconductor lm. Note that CuPcTs/PDADMAC multilayers possess electrochromic as well as photovoltaic properties [49]. Fabrication of thick micrometer-sized polyelectrolyte multilayers with large numbers of bilayers (tens or more) has been demonstrated previously for different polymers [8,50]. Such thick lms usually serve as reservoirs for bioactive molecules and are utilized in various biologi- cal applications to load, store, and release biomolecules to biological cells [5154], also upon external stimulation [55,56]. However, the liter- ature describing the LbL fabrication of hundred-layer lms, especially thick coatings containing phthalocyanines, is very limited [47,49]. LbL assembly was applied to fabricate highly absorbing hundred- layer organic semiconductor coatings from PDADMAC as a cationic component and from sulfonated copper phthalocyanine (CuPcTs) as an anionic single-doped organic semiconductor. PDADMACs of different MWs were used to examine the effect of the polymer MW on the thick- ness of deposited lms [25,50,54,5762]. The choice of phthalocyanine as an anion is driven by its photo- voltaic properties and its strong optical absorbance between 550 and 750 nm [47,63 73]. In fact, phthalocyanine lms can be in the amor- phous α -phase or in the crystalline β -phase, depending on the fab- rication approach. As both α - and β -phthalocyanines demonstrate photogeneration, both forms are used in photovoltaic devices. In both cases, the planar phthalocyanine macrocyclic molecules are arranged in one-dimensional stacks; however, the relative arrangement of these stacks and the stacking overlap of adjacent molecules differ between α- and β-phases. The main distinction between the two phases is the difference in the stacking axis of the phthalocyanine molecules and the normal to the surface plane of the dye molecule; this can be distin- guished by using a strong diffractive peak near 6.9° in X-ray diffraction spectra of phthalocyanine lms [69,70] . The overlap between the neighboring molecular stacks in the β-phase is smaller (0.38 nm), as compared with that for the α -phase (0.48 nm). The closer spacing of the molecular stacks and the orientation of molecules lying at (face- down) on the substrate (in contrast to the standing-up (on-edge)

molecule arrangement) facilitate the electron transport that is of importance for photovoltaic converter ef ciency. The usual way to obtain β -phase phthalocyanine lms is to employ high-temperature evaporation techniques and special conditions (i.e., heating of sub- strates), resulting in high crystallinity and good electrical properties of the structures. Alternatively, a high-temperature postannealing is applied to amorphous phthalocyanine lms (e.g., those prepared by wet chemical deposition techniques) to cause an α β phase transition accompanied by improvement of the molecular structure as well as spectral and electrical characteristics. The in uence of annealing on evaporated pure phthalocyanine lms has been studied [66 70] . For 30 150-nm-thick coatings prepared by vacuum evaporation, a phase transition was achieved if the temperatures from 240 to 250 °C [68,69] to 300 °C [66] were used. The minimum known phase transition temperature is 200 °C for 80-nm-thick vacuum-evaporated ZnPc lms [70] . The phase transition point for phthalocyanine polyelectrolyte multilayer lms may differ from that for pure phthalocyanine owing to the presence of the polyelectrolyte matrix, which can lead to phase separation [27,2933] and affect phthalocyanine thermostability [47]. In this work, we examine the high-temperature behavior of hundred-layer PEI/CuPcTs/(PDADMAC/CuPcTs) n lms, taking into account lm composition and morphology.

2. Experimental details

The general denition of the LbL method, used to prepare multilayer thin-lm structures on solid substrates, was rst given by Decher and Hong [8] . A detailed description of this process in the context of this work is given below.

2.1. Materials

Poly(ethyleneimine) (MW 600 1000 kDa), poly(diallyldimethyl- ammonium chloride) (MW b 100 kDa, 35 wt.%), poly(diallyldimethyl- ammonium chloride) (MWs 100200 kDa, 200350 kDa, and 400500 kDa; 20 wt.%), and tetrasulfonated copper phthalocyanine (CuPcTs) were purchased from Sigma-Aldrich and used without further puri cation. Aqueous polymer solutions (2 mg mL 1 ) and homoge- neous dispersions of CuPcTs (0.25 mg mL 1 ) were prepared in deion- ized water. Glass slides coated with uorine-doped tin oxide (FTO) (20 × 30 × 3.2 mm 3 ; surface resistance, 8 Ω square 1 ; transmittance, 8081.5% in the visible range; Sigma-Aldrich) were used as substrates to assemble the lms.

2.2. Deposition of multilayer thin lms

Thin lms of polyelectrolytes and sulfonated copper phthalocyanine were prepared by LbL assembly [8] on ethanol-precleaned glass slides coated with conductive FTO [74,75] . Films were deposited onto the slides by vertical immersion of the glass substrate into PDADMAC and CuPcTs solutions at a controlled rate (5 mm min 1 ) by using a dipping mechanism (part of the KSV Nima Langmuir Blodgett Trough). The rst layer was made by adsorption of the cationic polyelectrolyte (2 mg mL 1 water solution), with subsequent three rinsing steps in deionized water. The second layer was prepared by adsorption of anionic copper phthalocyanine (0.25 mg mL 1 water solution) followed by three rinsing steps. The fabricated multilayer structure was air dried during a variable period after each bilayer deposition. Either long-time drying (1 min for every layer and 20 min after every 3 bilayers) or short-time drying (1 min for every layer) was used during LbL de- position. The deposition procedure was repeated n times to assem- ble (PDADMAC/CuPcTs) n lms. In this way, glass/FTO/PEI/CuPcTs/ (PDADMAC/CuPcTs) n structures (n, 1554) were obtained (Table 1).

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A.S. Sergeeva et al. / Thin Solid Films 583 (2015) 6069

Table 1 Structure of the fabricated LbL multilayers and data about an average MW of the used PDADMAC polyelectrolytes.

Multilayer structure of thin lms formed on the FTO-coated substrates

Polyelectrolyte

Number of

MW, kDa

layers

PEI/CuPc/(PDDA/CuPc)15

PDDA,

b 100

32

PEI/CuPc/(PDDA/CuPc)15

PDDA, 100 200 PDDA, 200 350 PDDA, 400 500

32

PEI/CuPc/(PDDA/CuPc)15

32

PEI/CuPc/(PDDA/CuPc)54

110

2.3. Thermal treatment

The hundred-layer lms were annealed in air at 200 300 °C. The oven with the samples was heated from 25 °C to the required tempera- ture at a rate of ~20 °C min 1 ; this temperature was kept constant for 3 h. Various annealing temperatures were used to examine the in u- ence of heating temperature on the PDADMAC/CuPcTs multilayers and to achieve an α β phase transition [6670].

2.4. Research methods

The surface morphology of the fabricated multilayer lms was stud- ied by atomic force microscopy (AFM), scanning electron microscopy (SEM), and optical microscopy (OM). AFM images of the coatings were obtained in the tapping mode with a NTEGRA Spectra microscope (NT-MDT, Russia) and with a CombiScope scanning probe microscope (AIST-NT, Russia). The AFM images were processed using Gwyddion open source software. OM images were obtained in the bright- eld transmission mode with an Olympus IX71 microscope (part of the NTEGRA Spectra Setup). For imaging and laser irradiation, a 100×/ 0.90 M Plan FL N objective was used. An Altami MET 5 optical micro- scope was also used to obtain optical images of multilayer structures (in the reection and transmission modes). All optical images were cap- tured from the video signal of the microscope camera. SEM analysis was performed with a MIRA II LMU scanning electron microscope (TESCAN, Czech Republic) operated at an accelerating voltage of 730 kV. A Lambda 950 UVvis spectrophotometer (PerkinElmer, USA) was used to obtain UVvis absorbance spectra of the fabricated multilayer lms. For Raman spectroscopy analysis, a NTEGRA Spectra Setup (NT-MDT, Russia) was used. A heliumneon laser (wavelength, 632.8 nm; maxi- mum power, 5 mW) was used for sample irradiation. Thermogravimetric analysis (TGA) was performed on a TGA Q500 V20.10 Build 36 thermogravimetric analyzer (TA Instruments, USA) under argon gas ow. TGA measurements were performed between 24 and 1000 °C, and the temperature increase rate was adjusted for each sample according to the intrinsic properties of a given substance. For PDADMAC, the temperature increase rate was 1 °C min 1 in the range 25250 °C and 10 °C min 1 in the range 250998 °C; for CuPcTs, it was 10 °C min 1 for the temperature ranges 25 270 °C and 6001000 °C and was 1 °C min 1 for the range 270600 °C.

3. Results and discussion

3.1. Film fabrication

The actual work describes the formation of the hundred-layer lms based on a water-soluble copper phthalocyanine dye and polyelectro- lytes. The central metal atom and substituents on the benzene rings of the phthalocyanine molecule in uenced UV vis absorbance; CuPcTs had strong absorption bands around 650 nm (Q bands) [63 67, 7073]. The characteristic maxima of CuPcTs were in the 300800 nm range of the absorbance spectra, which was convenient for the analysis of the semitransparent thin PEI/CuPcTs/(PDADMAC/CuPcTs) n lms.

Each step of phthalocyanine deposition changed the absorbance peak in the lm's spectra. Optical spectra (absorption and transmission) were measured for the prepared lms after every bilayer deposition in the whole process of multilayer structure fabrication. The absorbance spectra of the PEI/CuPcTs/(PDADMAC/CuPcTs) 54 structures (PDADMAC MW, 400500 kDa) fabricated on FTO-coated glass substrates are shown in the inset in Fig. 1. The graphs demonstrate spectra of the deposited coat- ing with the subtraction of the native spectrum of FTO-coated glass. In good agreement with typical spectra of phthalocyanine [47,66 68, 70 73] , the absorbance spectra had peaks in the range 300 400 nm (Soret band) and in the 550750 nm region (Q bands) (Fig. 1), with a maximum at 330 nm and a dominant peak near 620 nm (with a prom- inent shoulder at 670 nm), respectively. Absorbance increased for all peaks (inset in Fig. 1), and this increase was accompanied by a decrease in transmission (data not shown). The dependence of the intensity (absorbance peak at 620 nm) on the number of deposited bilayers was linear throughout the fabrication of the hundred-layer structures (Fig. 1). This means that the same amount of phthalocyanine molecules was adsorbed onto the substrate during every PDADMAC/CuPcTs bilayer deposition. This straight trend line is given by the equation A = 0.048 n ( R 2 = 0.99) ( Fig. 1 ), where A is the absorbance at the peak near 620 nm and n is the number of deposited PDADMAC/CuPcTs bilayers. As shown by many research groups [25,27,50,54,5761], the relative molecular weight and the surface charge density (σ) of polyelectrolytes in uence the adsorption process. However, the effect of the polymer MW on LbL assembly with CuPcTs has not been studied before. Thus, three other relative MWs (b 100 kDa, 100200 kDa, and 200350 kDa) were used in addition to the 400500 kDa PDADMAC to study the effect of the polymer MW on lm deposition. The optical spectra of the multi- layer lms fabricated using PDADMAC of three MWs were similar in terms of the peak maximum position. Linear growth of intensity at absorbance maxima with an increasing number of PDADMAC/CuPcTs bilayers was observed for the 100500 kDa MW (Fig. 2(a)). However, the slope magnitudes for the three MWs differed perceptibly. The higher the relative MW was, the greater was the tilt angle, with the maximal value being observed for the 400 500 kDa MW ( Fig. 2 (b)). These data demonstrate the in uence of the polymer MW on CuPcTs adsorption: a higher concentration of CuPcTs has been found in lms based on higher-MW polymers. This agrees with the previous results [25,27] showing that lms are deposited better when polyelectrolytes of higher MWs and with higher σ values are used. Indeed, the thickness

and with higher σ values are used. Indeed, the thickness Fig. 1. Dependence of the absorbance

Fig. 1. Dependence of the absorbance (at maximum near 620 nm) on the number of de- posited bilayers n for PEI/CuPc/(PDADMAC/CuPc) 54 lms; the inset demonstrates the cor- responding absorbance spectra. MW of PDADMAC is 400500 kDa.

A.S. Sergeeva et al. / Thin Solid Films 583 (2015) 6069

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Sergeeva et al. / Thin Solid Films 583 (2015) 60 – 69 63 Fig. 2. (a)

Fig. 2. (a) Dependence of the absorbance (at maximum near 620 nm) on the number of de- posited bilayers n for PEI/CuPc/(PDADMAC/CuPc) 15 lms and (b) dependence of the slope angle on MW of the PDADMAC for the straight lines in (a). Circles containing various num- ber of PDADMAC molecules with the different chain length illustrate that at equal concen- tration of polymer solutions (2 mg·mL 1 ) the PDADMAC content is not equal; the amount of molecules is different in solutions of PDADMAC with various MWs. MWs of PDADMAC are b100 100200="" 200350="" kda="" and="" 400500="" span=""N.

of multilayers can be affected by various factors such as substrate prop- erties, deposition conditions, and ionic strength of polyelectrolytes, and it is always strongly determined by σ and MW of the polyelectrolytes used [25] . The dependence of the deposited layer thickness on the surface charge density σ is nonmonotonic for different adsorption regimes [25]. Initially, it is inversely proportional to surface charge num- ber density (σ 1 ); in the second regime, it decreases according to σ 1/3 because the thickness of the adsorbed layer is determined by the energy gain from electrostatic attraction to the charged surface and the con- nement entropy loss from chain compression [25]. Within the third interval, σ increases as σ 1/3 , and, nally, the thickness of the adsorbed layer saturates at high surface charge densities when the surface coun- terions dominate the screening of the surface potential. Moreover, an addition of salt lowers the amount of polymer adsorbed, because the salt ions also take part in the screening of the surface charge [25] . At the same time, surface overcharging exhibits a nonmonotonic salt- concentration dependence, rst increasing until a critical salt concentra- tion and then decreasing with further rising salt concentration [25] . Thus, most high-molecular-weight polymers (including PDADMAC) adsorb better owing to the larger surface charge number density, which provides stronger surfacesubstance interaction because of the larger amount of ions per chain [25,27]. This is why the 400500 kDa PDADMAC adsorbed best, as compared with the lower-MW polyelec- trolytes, and, as seen from the absorbance spectra ( Figs. 1 and 2), the CuPcTs concentration in the fabricated lms was the highest. Note

in the fabricated fi lms was the highest. Note Fig. 3. (a) Absorbance spectra of the

Fig. 3. (a) Absorbance spectra of the two identical PEI/CuPc/(PDADMAC/CuPc) 54 lms fab- ricated using the various drying times during LbL assembly (the long-time drying means 1 min air drying after each layer deposition and 20 min after every 3 bilayers; the short- time drying means 1 min air drying after each layer adsorption). (b) Absorbance spectra of PEI/CuPc/(PDADMAC/CuPc) 54 lms before and after annealing at different tempera- tures (200300 °C) during 3 h. MW of PDADMAC is 400500 kDa.

that the amount of PDADMAC molecules was different for solutions with the different MWs, despite the weight concentrations of the poly- mer solutions being equal (Fig. 2(b)). However, all PDADMAC solutions had an excess concentration (2 mg mL 1 ), so adsorption did not depend on the polymer concentration even if the amount of molecules differed between solutions of the different MW polymers. The drying time during the lm formation inuenced the deposition process also. This fact can be proven by the analysis of absorbance spectra of two sim- ilarly structured (PEI/CuPcTs/(PDADMAC/CuPcTs) 49 coatings fabricated under different drying conditions (Fig. 3(a)). Long-time drying (1 min for every layer, 20 min for every 3 bilayers) was applied in the fabrica- tion of the rst lm, and the total time of coating formation was 9.5 days (including stand-by periods during the night). Short-time drying (1 min for every layer) was used for the second lm, and the total fabrication time was 4 days. As a result, the total absorbance of the lm subjected to long-time drying was almost two times higher than that for the lm subjected to short-time drying ( Fig. 3 (a)). The difference in absorbance means that longer drying during LbL deposi- tion provided better adsorption of the phthalocyanine molecules on the surface (Fig. 3(a)).

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A.S. Sergeeva et al. / Thin Solid Films 583 (2015) 6069

3.2. Film thermal treatment

As stated before, it would be better for photovoltaic applications to use phthalocyanine in the β -phase, because high crystallinity gives

good photoconductive properties. The β -phase can be obtained from an α-lattice by high-temperature annealing, which improves the molec- ular structure of lms. LbL-assembled lms with a hundred layers are amorphous; hence, annealing is necessary for an α β phase transition of CuPcTs contained in the fabricated lms. Thermal treatment was per- formed at different temperatures to determine if any domain formation or phase transition took place in the multilayer lms. The annealing temperature regime for the fabricated hundred- layer lms was chosen for the following reason: it was reported that an- nealing of 80-nm-thick ZnPc lms at 200 °C for 3 h leads to structure modi cations and to a transition to the photoactive β -phase [70] . This is the minimum known temperature for the α β transition of thin (30 150 nm) ZnPc lms [66 70] . In our study, therefore,

200 °C was chosen as a starting annealing point for PEI/CuPcTs/

(PDADMAC/CuPcTs) n lms. However, this temperature was insufcient for an α β phase transition to occur, probably owing to the presence of the PDADMAC matrix, which can affect the properties of phthalocya-

nine [47] . Further, the temperature was increased step by step until phthalocyanine transformed into the β-phase (at 300 °C). The processes taking place during the annealing of the hundred-layer PEI/CuPcTs/ (PDADMAC/CuPcTs) n lms were investigated and are described below. The phase transition causes some changes in both crystallinity and optical spectra of coatings, which helps to determine the phase-

transition point [6670,76]. According to the obtained results, thermal treatment caused a red shift of the absorbance peaks from 633 and

695 nm to 650 and 752 nm, respectively. Moreover, an intensity

decrease was observed for these peaks, as shown earlier [70,76] . Fig. 3 (b) shows the absorbance spectra of the fabricated PEI/CuPcTs/ (PDADMAC/CuPcTs) n lms before and after annealing. The treatment time was 3 h, and the temperature range was 200 300 °C. The back- ground spectrum used for the analysis of these UV vis spectra was a spectrum of pure phthalocyanine, because PDADMAC does not make a strong contribution to absorbance within the analyzed wavelength range [47,77,78] . Annealing at 200 °C did not modify the molecular structure of the lms, because there were no changes in the absorbance spectra ( Fig. 3 (b)). This means that the presence of PDADMAC in the multilayers affected the thermal sensitivity of CuPcTs and that as a result of the PDADMAC/CuPcTs interactions, the phase-transition tem- perature increased [47] . A possible reason for this effect might be a phase separation during the LbL assembly or a kind of domain formation in the lms ( Fig. 5 ). A 50 °C increase in the annealing temperature induced no signi cant changes in the spectra (~12% absorbance de-

crease and 12-nm red shift for the peak near 615 nm), demonstrating that the lm was highly stable. Under annealing at 270 °C, the molecular structure underwent a change and the absorbance decreased by 47% (Q band maximum) without a wavelength shift ( Fig. 3 (b)). Raising the annealing temperature to 300 °C induced a stronger modication of the crystal lattice, which was accompanied by an approximately 30-nm red shift of the Q-band peaks to longer wavelengths (from

615 nm to 645 nm and from 670 nm to 700 nm), with a decrease in

absorbance (to 62%) and with intensity redistribution between the two peaks of the Q band ( Fig. 3 (b)). As explained above, such changes in UVvis spectra of phthalocyanine indicate that an α β phase transi- tion has occurred.

3.3. Raman spectra characterization

The annealing-mediated changes in the lm molecular structure could be seen in the Raman scattering spectra (RS) owing to the inu- ence of thermal treatment on the chemical bonds within the lms. Fig. 4 presents both calculated spectrum of CuPcTs by itself and spectra of the PEI/CuPcTs/(PDADMAC/CuPcTs) n lms experimentally measured

n fi lms experimentally measured Fig. 4. Raman scattering spectra of CuPcTs and

Fig. 4. Raman scattering spectra of CuPcTs and PEI/CuPc/(PDADMAC/CuPc) 54 lms annealed at different temperatures during 3 h; spectra obtained using on-resonance (633 nm) excitation. MW of PDADMAC is 400500 kDa.

by using resonance excitation (wavelength, 633 nm). Resonance excitation was chosen because it excites the electron states of phthalo- cyanine, giving well-dened peaks over the frequency range examined (500 1800 cm 1 ). The strongest peaks were observed for chemical bonds with a central copper atom, corresponding to Raman shifts of 756, 860, 978, 1158, 1200, 1293, 1341, 1459, and 1547 cm 1 . All measured spectra had several indicative peaks between 500 and 1800 cm 1 corresponding to certain chemical bonds of CuPcTs, and they were in the agreement with the results reported previously [70 72] . As seen from the obtained data, most of the band positions observed in the Raman spectra were similar for the analyzed samples (both as-prepared and annealed) in the examined frequency range (5001800 cm 1 ) (Fig. 4). Consequently, there was no strong difference between the Raman spectra of the α- and β-phthalocyanines in the 5001800 cm 1 interval. The shifts of several cm 1 and the different intensities were not sufcient to identify the CuPcTs crystalline structure by Raman spectroscopy [72]. However, the preservation of the character- istic peaks of CuPcTs in Raman spectra could be evidence of the thermal stability of the used phthalocyanine (resistance of a molecule to decom- position) in the examined temperature range [79,80]. Composite polymer-containing multilayers giving well-dened RS can be used for molecular analysis by Raman spectroscopy [81,82] . Raman-sensitive platforms have been fabricated with CaCO 3 micro- spheres [83]. Calcium carbonate microspheres can serve as templates to prepare protein-loaded particles [8487], opening a way to employ these complexes for theranostic applications.

3.4. OM, AFM, and SEM characterization

The morphology of the fabricated hundred-layer lms was exam- ined by OM, AFM, and SEM to investigate the effect of thermal treat- ment. The optical images obtained for the prepared FTO/PEI/CuPcTs/ (PDADMAC/CuPcTs) n multilayers show a morphology typical of organic LbL thin lms ( Fig. 5 (a b)). The surface of the multilayers is rough and has no macroscopic defects. Both the re ection-mode and the transmission-mode images ( Fig. 5 (a,b)) show colored areas. In both images, it is possible to distinguish small dark dots and a two-colored networkconsisting of elongated islands (some islands are indicated by the arrows in Fig. 5 (a,b)). Various colors from pink to light blue ( Fig. 5 (a)) are observed owing to the difference in density between the corresponding areas: a denser structure provides a darker pattern (black arrows in Fig. 5 (a)), whereas softer places give light islands

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Sergeeva et al. / Thin Solid Films 583 (2015) 60 – 69 65 Fig. 5. Optical

Fig. 5. Optical images of PEI/CuPc/(PDADMAC/CuPc) 54 lms before (ab) and after (cf) annealing at 300 °C. MW of PDADMAC is 400500 kDa. Pictures were obtained using re- ection (a,c,e) and transmission (b,d,f) mode. Scale bar is 10 μm.

(white arrows in Fig. 5(a)). Such a patterned surface can be explained by the formation of domains within the lm. The dark grains in Fig. 5 might be large aggregates of CuPcTs molecules, whereas the pinkblue patterns consist of pure PDADMAC islands (lighter) and CuPcTs PDADMAC areas (darker). In fact, phthalocyanine molecules tend to

aggregate in a kind of phase separation, e.g., if they are surrounded by a polymer matrix [29]. Under some conditions, phthalocyanine aggrega- tion takes place in various complexes, including phthalocyanine- aggregated Pluronic nanoparticles, used in photodynamic therapy [88], and phthalocyaninefullerene complexes, used to fabricate bulk heterojunctions for photovoltaic applications [6365]. Thermal treatment at 300 °C led to a change in lm morphology ( Fig. 5 (c,d)). The lm structure was light blue, with nanosized dark dots ( Fig. 5 (c,d)) similar to the dots observed before annealing ( Fig. 5(a,b)). The colored network disappeared, probably because the polymer matrix had melted, resulting in a uniform component redistri- bution within the lms. Moreover, some defects were formed in the lms (Fig. 5(e,f)). This can be explained by the different thermal behav- iors of pure CuPcTs aggregates, pure PDADMAC, and CuPcTsPDADMAC complexes with various component ratios. Whereas thermal treatment at 300 °C led to an α β phase transition of the CuPcTs molecules, the surrounding phases of CuPcTsPDADMAC and pure PDADMAC started to melt (see the TGA data). Thus, thermal treatment gave rise to a liquid polymeric phase with uniformly distributed nanosized solid CuPcTs ag- gregates (Fig. 5(c,d)). At the same time, the islands of pure PDADMAC (white arrows in Fig. 5 (a)) degraded at above 270 °C (see the TGA data) and microdefects were formed in the corresponding places (Fig. 5(e,f)). The microcracks and pores in the annealed lms were bet- ter visible in the SEM images. It was difcult to study the multilayer lms by AFM and SEM owing to the granular nature of the conductive FTO coating that covered the glass substrate ( Figs. 6 and 7 ). The average size of the FTO granules was 100500 nm, in agreement with the data described previously [74, 75]. It was possible to observe the microstructure of the hundred-layer PEI/CuPcTs/(PDADMAC/CuPcTs) 54 lms by AFM (Fig. 6). Thermal treat- ment induced the following changes in lm morphology (Fig. 6(bd)):

the prepared amorphous PEI/CuPcTs/(PDADMAC/CuPcTs) 54 lms were characterized by a surface nanopatterned with some spherical nanograins ~ 30 nm in size ( Fig. 6 (b)). The spherical grains probably were solid CuPcTs aggregates sur rounded by the PDADMAC matrix (dark dots in Fig. 5 , bright dots in Fig. 6 (b,c)). Such a surface pattern is characteristic of phthalocyanine coatings, which typically consist of small spherical particles [9,66] . Annealing the PEI/CuPcTs/(PDADMAC/CuPcTs) 54 lms at 250 °C caused changes in coating morphology ( Fig. 6 (b,c)). The average

changes in coating morphology ( Fig. 6 (b,c)). The average Fig. 6. AFM-images: (a) the granular

Fig. 6. AFM-images: (a) the granular conductive FTO-coated glass substrate; (b) the air dried PEI/CuPc/(PDADMAC/CuPc) 54 lm on the FTO-coated substrate; (cd) the glass/FTO/PEI/ CuPc/(PDADMAC/CuPc) 54 lm after thermal treatment at 250 °C (c) and 300 °C (d). Images (a) and (d) show a real surface relief; images (b) and (c) were treated with a high-pass lter for the better morphology visualization. Scale bar is 200 nm.

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A.S. Sergeeva et al. / Thin Solid Films 583 (2015) 6069

A.S. Sergeeva et al. / Thin Solid Films 583 (2015) 60 – 69 Fig. 7. SEM-images:

Fig. 7. SEM-images: (a) the granular conductive FTO-coated glass substrate; (b) the air dried PEI/CuPc/(PDADMAC/CuPc) 54 lm on the FTO-coated substrate; (c) the glass/FTO/ PEI/CuPc/(PDADMAC/CuPc) 54 lm annealed at 300 °C during 3 h.

size of the nanograins (aggregated CuPcTs molecules surrounded by PDADMAC) was reduced from 30 to 20 nm ( Fig. 6 (b,c)). This can be explained by the lm behavior under the applied temperature. First, all water molecules evaporated from the lm. Moreover, as found by TGA, the PDADMAC matrix did not degrade at 250 °C, but the polymer structure became more compact. As a result, solid aggregates of heat- stable phthalocyanine molecules, which are dispersed in the polymer matrix, were seen better (Fig. 6(b,c)). As noted above, annealing of the hundred-layer structure at 300 °C led to changes in molecular structure (Fig. 5) and to an α β phase transition of CuPcTs ( Fig. 3 (b)). The obtained AFM images show that increasing the annealing temperature from 250 to 300 °C modi ed the lm morphology further. After thermal treatment at 250 °C, the PEI/CuPcTs/(PDADMAC/CuPcTs) 54 lms became more compact and pat- terned with 20-nm nanograins. Conversely, after annealing at 300 °C, the 20-nm patterns disappeared (Fig. 6(d)) and the surface of the coat- ed FTO granules became similar in appearance to that of the uncoated ones ( Figs. 6 (a), 7 (a)). This effect can be explained by the different thermal sensitivities of the lm constituents (described in the rst paragraph of this section). Briey, at 300 °C, CuPcTs is stable, whereas the PDADMAC/CuPcTs complex starts to melt and pure PDADMAC degrades at above 270 °C [89,90]. As a result, the melted polymer matrix with dispersed CuPcTs aggregates spreads over the FTO surface to create a uniform layer repeating the relief of the FTO granular surface. The SEM images gave no information about the nanomorphology of the freshly prepared lms, because the lm multilayer structure was transparent for SEM observation. The blurred borders of the FTO granules were the only visible result of layer deposition ( Fig. 7 (a,b)). However, thermal treatment at 270 300 °C changed the structure of

treatment at 270 – 300 °C changed the structure of Fig. 8. TG-curves measured for (a)

Fig. 8. TG-curves measured for (a) PDADMAC of MW 400500 kDa (the temperature in- crease rate is 1 °C/min for the range 25250 °C and 10 °C/min for the range 250998 °C); (b) CuPcTs (the temperature increase rate is 10 °C/min for the ranges 25 270 °C and 6001000 °C, and 1 °C/min for the range 270600 °C).

the hundred-layer coatings. The lms developed holes and microcracks, which could be seen by SEM (Fig. 7(c)) and OM (Fig. 5). The formation of such micropores was complex and was caused only by the melting and decomposition of the pure polymer (white arrows in Fig. 5(a)) at above 270 °C (TG measurements, Fig. 8(a)). Indeed, annealing of CuPcTs at 300 °C could not destroy the lms or give rise to microcracks, because this material is heat resistant and decomposes at above 450 °C (TG measurements, Fig. 8(b)). The presence of characteristic peaks in the absorbance (insets in Figs. 1 and 3 (b)) and Raman ( Fig. 4 ) spectra after annealing also con rms that CuPcTs was thermally stable. Most polymers, including PDADMAC, are not heat resistant, and the organic matrix decomposes completely at 300 500 °C, depending on the precursors employed [8993]. Therefore, the only possible reason for such microdefects to form in the PEI/CuPcTs/(PDADMAC/CuPcTs) n lms ( Figs. 5 and 7 ) was the degradation of the PDADMAC at above 270 °C. As a result, the lms were broken in certain places (islands of the pure polymer, white arrows in Fig. 5 ) and the FTO granules could be seen through the emerged differently shaped and sized pores (Fig. 7(c)).

3.5. Characterization by TGA

TGA was conducted to conrm whether the pores emerged because of the nature of the PDADMAC polymer. TGA measurements were made between 24 and 1000 °C to determine the individual decomposition temperatures of the 400 500 kDa PDADMAC ( Fig. 8 (a)) and CuPcTs (Fig. 8(b)). During annealing, the PDADMAC went through a sequence of exothermic processes with continuous weight loss. It is possible to detect three curve segments in Fig. 8(b) within the following tempera- ture limits: 24 260 °C, 260 470 °C, and 470 1000 °C. These three

A.S. Sergeeva et al. / Thin Solid Films 583 (2015) 6069

67

segments are characterized by different tilt angles describing the specif- ic behavior of the PDADMAC in the corresponding temperature range. The rst segment (24270 °C) demonstrates that the sample weight was reduced to approximately 11% of its initial value. This slow and uniform weight reduction can be due to the release of the inner water molecules, making the polymer matrix more compact without degrading it. These data agree with the obtained AFM images of the hundred-layer lms, showing that annealing at 250 °C made the lms textured and compact (Fig. 6(b,c)). The second curve segment (270470 °C) shows a rapid weight loss of ~77% ( Fig. 8 (a)). This strong constant decrease is responsible for the decomposition of the PDADMAC matrix and for the oxidation of organic carbonaceous residues [89 93] . The PDADMAC polymer be- comes soft and then liquid and its constituents are burned away [89]. These processes brought the sample to the nal stable weight of the third curve segment (4701000 °C) (Fig. 8(a)). The observed thermal degradation of PDADMAC agrees with the previous results [89,90] and explains the behavior of the multilayer PEI/CuPcTs/(PDADMAC/CuPcTs) n lms under annealing. The TG curve obtained for sulfonated phthalocyanine consists of two main sections within the temperature ranges 20 455 °C and 455 1000 °C. The rst segment (20 455 °C) demonstrates that the dye was resistant to temperatures of up to ~455 °C (Fig. 8(b)). Between 20 and 455 °C, the sample lost ~9% of its initial weight. Moreover, 8% of this weight loss at 20200 °C was associated with water evaporation (similarly to what is observed in the TG curve of PDADMAC) (Fig. 8(b)). Subsequently, all water molecules were released and the weight of CuPcTs became almost constant at 200 455 °C. This effect could be due to the heat resistance of phthalocyanines. The second segment of the curve (4551000 °C) is characterized by constant weight loss during the whole period. Between 455 and 535 °C, the weight of the sample underwent a large (~15%) decrease (Fig. 8(b)). Weight decreased by 40%, with several visible steps being observed between 540 and 1000 °C. Note that 1000 °C is not enough to bring the sample to the nal stable weight and even higher temperatures are needed to decompose it. As a result, the total weight loss by CuPcTs was 54% of its initial value after annealing at 241000 °C (Fig. 8(b)). In summary, the organic PDADMAC matrix decomposed completely between 270 and 470 °C (Fig. 8(a)), whereas CuPcTs was stable in this range ( Fig. 8 (b)). This proves our assumption that the pores in the annealed hundred-layer lms emerged in the areas of pure PDADMAC (Fig. 5).

4. Conclusions

LbL assembly has been employed to fabricate highly absorbing hundred-layer PEI/CuPcTs/(PDADMAC/CuPcTs) n lms ( n , 15 54) on FTO-coated slides. Four PDADMAC MWs ( b 100 kDa, 100 200 kDa, 200 350 kDa, and 400 500 kDa) have been used to study the effect of the polymer MW on the adsorption of CuPcTs molecules. Film depo- sition has been monitored by absorbance spectra measurements. The absorbance of the lms depended linearly on the number of deposited PDADMAC/CuPcTs bilayers, which means that the same amount of CuPcTs molecules was adsorbed at each deposition step. The absor- bance of the lms was enhanced by increasing the MW of the PDADMAC, with maximal absorbance observed for the highest-MW polymer (400 500 kDa). This might be because longer PDADMAC molecules, having higher surface charge number density, adsorbed more phthalocyanine molecules. Moreover, it has been possible to enhance absorbance almost twofold by using long-time drying during the LbL assembly. The thin hundred-layer lms were annealed at high temperatures, leading to an α β phase transition in CuPcTs at 300 °C. Thermal treatment has resulted in the formation of domains within the lms that were composed of pure CuPcTs aggregates, pure PDADMAC, and complex CuPcTs/PDADMAC mixtures, as found by morphological and TG analyses.

Acknowledgments

This work was supported by an individual grant of the Foundation for Assistance to Small Innovative Enterprises in Science and Technology under the program U.M.N.I.K. (project no. 17259) and by grant of the Russian Scientic Foundation (project no. 14-12-00275) (work related to phase separation and the effect of thermal treatment on phase separa- tion in the nanostructured lms). We thank Mikhail Trusov (AIST-NT) for supplying the equipment used in this study and for helping with AFM microscopy. We are also grateful to Ilya Gorbachev (Scientic Re- search Institute of Nanostructures and Biosystems, Saratov State Univer- sity, Saratov, Russia) for his help with TG measurements and to Roman Sergeev for his help with OM imaging of samples after thermal treatment.

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