Controlled Growth of Stable β-Glycine via Inkjet Printing | Crystal

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Controlled Growth of Stable β‑Glycine via Inkjet Printing V. Slabov,†,‡ D. Vasileva,§ K. Keller,† S. Vasilev,§,∥ P. Zelenovskiy,§,⊥ S. Kopyl,‡ V. Ya. Shur,§ A. Vinogradov,† and A. L. Kholkin*,‡,§

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†

Laboratory of Solution Chemistry of Advanced Materials and Technologies, ITMO University, St. Petersburg 197101, Russian Federation ‡ Department of Physics & CICECO-Aveiro Institute of Materials and ⊥Department of Chemistry & CICECO−Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal § School of Natural Sciences and Mathematics, Ural Federal University, Ekaterinburg 620000, Russian Federation ∥ Department of Chemical Sciences, Bernal Institute, University of Limerick, V94 T9PX Limerick, Ireland S Supporting Information *

ABSTRACT: Glycine is a well-known polymorphic amino acid extensively used as a precursor for proteins and a drug for treating various neurological diseases. Recently, a giant piezoelectric response and ferroelectricity found in its βphase have prompted intensive research aimed at controlled growth of this polymorph and at creating biocompatible piezoelectric sensors and actuators able to work in direct contact with a biological environment. In this work, a standard inkjet printing method was used to deposit stable isolated crystals of β-glycine in predefined locations without using special conditions such as nanoconfinement. Narrow size distribution, notable piezoelectric response, and 100% phase control of the grown crystals allow using simple inkjet technology for the creation of various sensor and actuator architectures required for the next generation of flexible bioelectronic devices.

1. INTRODUCTION Piezoelectric materials are widely used in modern electronic devices as sensors, actuators, acoustic transducers, and energy harvesters.1 Most of them are based on inorganic ceramics and films, such as BaTiO3 (BTO) and Pb(Zr,Ti)O3 (PZT), which dominate many applications including ferroelectric memories, storage capacitors, electrocaloric coolers, nonlinear optical devices, etc.2−5 Organic compounds in general and biomolecular materials in particular are attractive alternatives of inorganic perovskites for biomedical applications. These materials are lightweight, low cost, mechanically flexible, structurally tunable, and easy to process.6 Moreover, they consist of the same building blocks (amino acids, peptides, and proteins) and thus can be used as biocompatible components of biomedical devices, e.g., piezoelectric microactuators, tiny sensors, or nerve stimulators after injuries.7−10 One of these materials, the simplest amino acid glycine was recently found to be strongly piezoelectric11,12 when grown in its β-form. Piezoelectric coefficients were found to be comparable with those of BTO ceramics, the voltage piezoelectric coefficient being much greater than in any other single-phase material.13 Unfortunately, these crystals are thermodynamically unstable and under normal conditions can be grown only as a mixture with more stable α- and γpolymorphs.14 Some polarity of initially centrosymmetric α © 2019 American Chemical Society

glycine crystals can be induced by doping with polar guest molecules15 or by a nonclassical growth method,16 but their piezoelectricity is yet to be evaluated. Preferential growth of the ferroelectric β-phase can be achieved by nanoconfinement17 or by a dewetting process that allows formation of isolated islands of this polymorph on Pt substrates.18 Recently, there has been an attempt to form ferroelectric metastable glycine by inkjet printing.19 The β-phase was also achieved from microdrops,but without precise emulsion deposition.20,21 However, even in the picoliter printed volumes there was some amount of other phases, thus preventing using this method for the fabrication of piezoelectric sensors and actuators with predefined architectures. Three-dimensional printing of ferroelectric/piezoelectric materials is becoming a mainstream of modern technologies. In this way, piezoelectric metamaterials can be realized with high piezoelectric coefficients, controlled anisotropy, and flexibility for specific applications.10 However, printing of inorganic perovskites involves a lot of difficulties because the sintering step should be done after printing the green ceramics and huge shrinking and apparent porosity results.22 Printing organic and polymer piezoelectrics is much Received: March 9, 2019 Revised: May 21, 2019 Published: May 30, 2019 3869

DOI: 10.1021/acs.cgd.9b00308 Cryst. Growth Des. 2019, 19, 3869−3875

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Figure 1. Experimental scheme of the crystal formation from the drops with different contact angles and compositions (see section 3.2 for ink parameters). Sessile drop images of the glycine water-based drop: (a) in initial time and (c) after 30 s of drying. Optical images of the glycine crystals: (e) from the water-based drop, scale bar 50 μm. Sessile drop images of the solvents mixture-based drop: (b) in the initial time and (d) after 30 s of drying. (f) Optical images of the glycine crystals from the solvents mixture-based drop, scale bar 50 μm. (g) Schematic of the drying and crystallization processes in the drops with different contact angles. subsequent analysis by scanning electron microscopy (SEM) and piezoresponse force microscopy (PFM). 2.3. Piezoresponse Force Microscopy. To characterize the topography and local piezoelectric properties of printed glycine crystals, we used semicontact topography and PFM modes of the commercial atomic force microscope (AFM) Asylum MFP-3D (Asylum Research, Oxford Instruments, UK). PFM images of the surface of glycine microcrystals were acquired by applying a range of ac voltages (0.1−10 V, peak-to-peak) with a frequency of 20 kHz. Conductive probes (with stiffness 5 N/m and resonance frequency 180 kHz) were used for the PFM measurements under ambient conditions. The cantilever response due to electromechanical coupling was detected using an internal lock-in amplifier of the AFM.

easier because crystallization (or subsequent poling) can be done in a single step using commercial inkjet printing (IJP) technology.23 Recently, it has been demonstrated that strongly piezoelectric peptide microribbons can be printed using IJP by controlling the solution chemistry and inkjet printing parameters.24 In this work, we used inkjet printing technology to form stable isolated crystals of β-glycine of a controlled size. As distinguished from recently reported printing attempts19 that produced coffee-ring structures with a mixture of α- and βphases, our work is focused on the printing of microdrops with controlled rheological properties on hydrophobic substrates. We demonstrate the formation of isolated glycine crystals in the predetermined positions formed by IJP. Crystal growth process was precisely controlled by using a system of two solvents (water and diethylene glycol) where amino acid is dissolved only in one of them. At the same time, these solvents have different evaporation temperatures and glycine is insoluble in a solvent with higher evaporation temperature. Thus, we formed a shell without air for crystal growth in each printed drop. The methodology described above is important to preserve the metastable β-phase of glycine and opens up new possibilities for the controlled growth of piezoelectric functional materials.

3. RESULTS AND DISCUSSION 3.1. Inkjet Printing of the Isolated Crystals. Printing and subsequent crystallization of the isolated crystals from a printed microdrop require a deep understanding of the accompanying processes.25,26 One of the most important parameters is a surface contact angle and vapor pressure of used solvents. Vapor pressure impacts the evaporation rate, and the contact angle controls the molecules flow inside the drop. Glycine powder is very soluble in water (2.9 mol/L) and has poor solubility in alcohols (0.004−0.009 mol/L).27 In this paper, we focus on creating a method for the growth of isolated single crystals of the ferroelectric β-phase in each printed drop. In the case of drying water-based glycine solution, the crystallization normally starts from the drop edge, where supersaturation condition is fulfilled. Accelerated growth of the metastable β-phase is engendered by the Marangoni effect, which induces circulation and sedimentation of the particles in a drying drop.28 The Marangoni effect originates from the gradient of surface tension in a drying drop in such a way that the particles seek drying edges, thus inducing accelerated growth. Figure 1g illustrates the effect of the contact angle on the particles’ flow and growth conditions. For a low contact angle, the flow of the glycine particles is close to the substrate. Because of the flat wedge geometry, the evaporation of the solvent is much faster at the drop edges, and glycine crystals appear around the drop edges growing toward the center (Figure 1a,c,e). This is a well-known coffee-ring effect, and, as has been previously shown,24 the growth of diphenylalanine polycrystals is strongly accelerated. In contrast, by mixing two solvents with different vapor pressures (3.1 kPa for water and 0.0003 kPa for diethylene glycol29), the mixture of two solutions is formed which dries much more slowly in comparison with pure water solution and has a bigger contact

2. EXPERIMENTAL SECTION 2.1. Preparation of the Inks for IJP. The ink for the printing process was prepared from water-based glycine solutions (glycine was purchased from Sigma-Aldrich, Inc. (St. Louis, Missouri)) with different concentrations (25, 50, and 100 mg/mL) and then diluted by diethylene glycol to adjust the rheological properties of the mixture. To control the surface tension change, we used cationic surfactant Dynax 4000N (1% wt). The detail description of ink preparation is explained in Results and Discussion. The viscosity measurements of the ink were carried out using a rotational viscometer (Fungilab Expert, Spain) with a simple adapter (Fungilab APM) allowing measuring small volumes. Surface tension of produced inks and contact angle of printed drops on different substrates were measured using a drop shape analyzer DSA-25 (KRUSS, Germany). Morphology of printed drops was examined using Scanning Electron Microscope (Tescan Vega 3, Czech Republic) and standard optical microscope (LOMO, Russia). 2.2. Inkjet Printing of Glycine Arrays. For glycine-based ink deposition, we used a Dimatix Materials printer (DMP 2831, Fujifilm, USA) with 10 pl cartridges and conductive Pt-coated Si substrates. The optimized printing conditions were jetting frequency of 5 kHz and resolution 423 dots per inch (dpi). The resulting drop velocity was 8 m/s. The printed samples were kept in dry conditions for the 3870

DOI: 10.1021/acs.cgd.9b00308 Cryst. Growth Des. 2019, 19, 3869−3875

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angle with a Pt-coated substrate (Figure 1b). In this way, during the evaporation process the water evaporates faster from the mixture and allows for local supersaturation conditions for water-soluble glycine in the printed drop. Since the speed of water evaporation is higher than that of ethylene glycol at room temperature, the edges of drop are fixed (i.e., diethylene glycol defines the drop area), and the nuclei of the beta phase do not appear anymore at the circumference of the drop as in the case of pure water-based solution. As such, a sufficiently big contact angle of the printed drop facilitates the flow of glycine particles in the entire volume of the drop (Figure 1g). And supersaturated solution of glycine in such a closed system promotes efficient crystallization from single nuclei inside the diethylene glycol shell (Figure 1b,d,f). Figure S1 shows the frame-by-frame images from video of the isolated crystal formation in the printed drop. In our work, we used a hydrophobic Pt-coated silicon wafer which can also help as a catalyst for β-phase formation.30 Apparently, a variation of the glycine concentration in ink composition influences the number of crystals formed in drops. 3.2. Ink Preparation and Characterization. To chose the optimal parameters for the inkjet printing process, the Ohnesorge theory was used.31,32 This theory is based on the calculation of the hydrodynamic constants that adapt to inkjet technology. Thus, equations of Reynolds (1) and Weber (2) numbers, that show the ratios between inertial and viscous forces, and between inertial and surface forces, respectively, were used. The Ohnesorge number Oh (eq 3) represents jetting conditions of the individual drop, while the Z number (4) is the inverse of the Ohnesorge number. Since the viscosity of the glycine water solution is not high enough for printing, diethylene glycol and cationic surfactant Dynax DX4000 were used to change its rheological parameters, because it was required to fit ink for stable and controlled jetting of the drops. Diethylene glycol was chosen as a solvent because of its high viscosity (35.7 cP at 20 °C) and low evaporation rate that allows the crystals to form the necessary structure until complete evaporation of the solvents. Thus, diethylene glycol allows preparing a mixture with a higher content of the water solute glycine. Figure 2a shows the viscosity as a function of the solvent/glycine solution ratio. The surfactant Dynax DX4000 was chosen due to the linear dependence of its surface tension on the concentration, which would ensure the usability and stable printing (Figure 2b). Re =

ρVd η

(1)

We =

ρV 2d γ

(2)

Oh =

We Re

(3)

Z=

1 Oh

Figure 2. Inks conditions and printing settings. (a) Dependence of the viscosity on the solvent/glycine solution ratio. (b) Properties of the surfactant Dynax dx 4000. (c) Waveform used to print glycine inks. (d) Demonstration of the drop-live formed by the used waveform.

composition of the inks must be in the range 1−10.33,34 At the same time, we obtained the optimum glycine concentration in the drop. After optimization, the final ink composition has the following parameters: viscosity 3.1 cP, surface tension 35 mN/ m. Full ink parameters and hydrodynamic numbers are given in Table S1. These values correspond to Z number 8.7 and, at the same time, contain the maximum value of the watersolution of glycine. The velocity of the drop 7 m/s and the diameter of the nozzle d = 21 μm were used in all calculations. Figure 2c shows the waveform setting that was used for glycine ink printing. Figure 2d demonstrates the stable spherical drop generation without satellites that confirms optimum rheological and waveform settings for the printer. For water-based solutions, a standard waveform from the Dimatix Material Printer software was used (Figure S2). The cartridge with a drop volume of 10 pL was used for printing in all cases. 3.3. Phase Determination. The polymorphic phase of the grown crystals was determined by confocal Raman microscopy using a previously reported method12 based on determination of phase fingerprints in Raman spectra placed in three separate spectral regions: 100−260 cm−1, 1200−1600 cm−1, and 2800− 3200 cm−1 (Figure S3). These regions include lattice vibrations, torsion vibrations of CH2 group (line at about 1327 cm−1), and symmetrical stretching of the CO2 group (line at about 1414 cm−1); and symmetric stretching vibrations of CH2 group, respectively. Raman spectra were measured in one point of more than 50 isolated crystals, and all of them were found to belong to the ferroelectric β-phase without any change of the spectra from crystal to crystal. Moreover, Raman mapping of microcrystals sets grown from the ink with 100 mg/mL glycine concentration also confirmed the appearance of the β-phase for all crystals (Figure S4). 3.4. Optical and Scanning Electron Microscopies. In our method, one of the main parameters for isolated crystal

(4)

where ρ is the ink density, η is the viscosity of the solution, γ is the surface tension, V is the velocity of the drop, and d is the diameter of the nozzle. The most crucial parameters impacting the hydrodynamic numbers are viscosity and surface tension. In accordance with the equations of Ohnesorge theory, the Z number in final 3871

DOI: 10.1021/acs.cgd.9b00308 Cryst. Growth Des. 2019, 19, 3869−3875

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Figure 3. Optical images of glycine microcrystals grown from printed drops with (a) 25, (b) 50, and (c) 100 mg/mL of glycine residue. Scale bar is 20 μm.

μm. The agglomerates of the small crystals with a broader size distribution were produced for higher glycine concentrations. Therefore, our method is more efficient for the precise control of crystal size in comparison with the simple droplet method (for example, from micropipette). Moreover, the used ink provides 100% β-phase glycine crystals grown in the predetermined positions inside the drops (see section 3.3 for more detail). The length distributions of isolated and polycrystals samples were obtained from SEM (Figure 4a) and optical microscopy images (e.g., Figure 1e,f). Only the length of each crystal (along the crystal direction b, the direction of spontaneous polarization) was determined using a graphical editor (in pixels). Obtained values were then recalculated to the micrometer using a scale bar from each image. Afterward, measured crystal sizes were statistically processed. In particular, mean crystal length, standard deviation, and normal distribution function were calculated based on the measured data. 3.5. Time Stabilities. It is well-known that the less-stable polymorphic phase can spontaneously transform into a more stable phase with time. For example, glycine β-phase transforms into the γ-phase under increased humidity35 or in the presence of NH3. Our isolated glycine microcrystals stored in the open air at a controlled temperature and humidity (about 50%) remained in the metastable β-phase for at least two months. The phase stability was verified by Raman spectroscopy as it will be described below.14 3.6. Piezoresponse Force Microscopy. The topography of the printed microcrystals was studied by the semicontact AFM. It was shown that the crystal morphology is similar to the crystals grown from a drying droplet of aqueous solution (Figure 5). The growth steps are clearly visible on the crystal surface. The typical crystal thickness is about 3−5 μm.

growth is a glycine concentration in the ink. To optimize this parameter, we tested the water-based solutions with different initial glycine concentrations 100, 50, and 25 mg/mL, which were used for the ink preparation. Obviously, the solvents evaporation in the printed drop leads to the saturation of glycine solution. Adjusting the glycine concentration allows decreasing the number of grown crystals. Figure 3 demonstrates that the number of crystals in the printed drop significantly decreases with concentration. Therefore, for further investigation we used the ink with a concentration of 25 mg/mL of water-based glycine solution. Figure S1 illustrates the process of the crystal formation in the printed drop. The crystal growth starts at the edge of the drop, where the glycine concentration reaches its maximum due to a higher evaporation flux. All other crystals in the printed array grow in the same way but in random orientations. Scanning electron microscope (SEM) images of the printed samples (Figure 4a−c) show that the crystals are grown in each isolated drop. All crystals have slightly different shapes (Figure 4b−c) probably due to the irregular drop drying which leads to the differences in local glycine concentration. Figure 4d demonstrates the distribution of the crystal lengths for two different solvent concentrations. The average length is 29.4 ± 4

Figure 4. SEM images of the printed isolated crystals produced from the ink with a glycine concentration of 25 mg/mL: (a) general view, (b) and (c) different shapes of isolated crystals, (d) size distribution of printed crystals.

Figure 5. AFM image of the topography of the glycine crystals: (a) printed and (b) grown from the drying droplet. 3872

DOI: 10.1021/acs.cgd.9b00308 Cryst. Growth Des. 2019, 19, 3869−3875

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Figure 6. PFM images of the printed glycine crystals: (a) surface topography and domain structure: (b) amplitude, and (c) phase of the piezoelectric response, (d) 3D image of the surface topography, (e) same image with domain structure. b is the polar axis, Ps is the direction of the spontaneous polarization.

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The printed crystals demonstrate mostly a lateral piezoelectric response and a ferroelectric domain structure typical for β-glycine (Figure 6b,c).36 The observed domains are elongated in one direction lying in the plane of the substrate and have a similar shape as compared to the domains observed on the nonpolar cuts of other uniaxial ferroelectric crystals.2,11,37 The domain shape suggests that the polar axis b in the printed β-glycine crystals lies in the plane of the substrate, and its direction coincides with the apparent direction along which the domains are elongated (Figure 6b). The charged head-to-head and tail-to-tail domain walls are perpendicular to the polar axis (Figure 6c), and their position frequently coincides with the edges of the surface steps (Figure 6d,e). The values of effective piezoelectric coefficients were determined by the previously published method31 (deff = 2− 4 pm/V) using the same procedure as for the β-glycine crystals grown from the drying droplet of glycine solution. Giant piezoresponse due to d16 piezoelectric coefficient12 could not be observed in the used geometry.

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.9b00308. Frame-by-frame image of the crystal growing process. Waveform used to print water-based glycine solutions. Typical Raman spectrum of β-glycine. Raman analysis of the representative ensemble of glycine crystals. Table with the typical printing parameters (PDF)

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AUTHOR INFORMATION

Corresponding Author

*Phone: +351 234247025. Fax: +351 234 370089. E-mail: [email protected]. ORCID

K. Keller: 0000-0002-9188-5646 S. Vasilev: 0000-0002-3103-1438 P. Zelenovskiy: 0000-0003-3895-4785 S. Kopyl: 0000-0003-3347-8628 V. Ya. Shur: 0000-0002-6970-7798 A. L. Kholkin: 0000-0003-3432-7610 Notes

4. CONCLUSIONS

The authors declare no competing financial interest.

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In this work, we presented a novel method for the growth of stable isolated microcrystals of β-glycine by inkjet printing. By varying the ink composition and printing conditions, we could promote the growth of individual single crystals of thermodynamically metastable β-glycine without an admixture of other (more stable) phases. The stability of the grown phase for more than two months was demonstrated. The existence of the β-phase of glycine was confirmed by piezoresponse force microscopy and confocal Raman spectroscopy methods. The obtained results will facilitate the application of inkjet technology in controlling the polymorphic crystal forms, which is of paramount importance in materials science, solidstate chemistry, mineralogy, pharmacology, and so on. Several applications based on the high piezoelectric response and polarization switchability of β-glycine are also envisaged.

ACKNOWLEDGMENTS This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, FCT ref. UID/CTM/ 50011/2019, financed by national funds through the FCT/ MCTES. P.Z., S.K., and A.K. were partly supported by FCT (Portugal) through the Project PTDC/CTM-CTM/31679/ 2017. Part of this work was funded by national funds (OE), through FCT − Fundaçaõ para a Ciência e a Tecnologia, I.P., in the scope of the framework contract foreseen in the numbers 4, 5, and 6 of the article 23, of the Decree-Law 57/ 2016, of August 29, changed by Law 57/2017, of July 19. S.V. thanks Russian Science Foundation (Project 18-72-00053) for financial support. Part of the work was supported by the Government of Russian Federation (Act 211, Agreement 02.A03.21.0006). Ministry of Education and Science of 3873

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Russian Federation is acknowledged for the support within Projects Nos. 418244 (V.S.) and 16-19-10346 (A.V. and V.S.). The research was carried out using equipment of Ural Center for Shared Use “Modern Nanotechnology” of Ural Federal University. V.S. and K.K. are grateful to the Erasmus+ exchange program for funding their stay at University of Aveiro.

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DOI: 10.1021/acs.cgd.9b00308 Cryst. Growth Des. 2019, 19, 3869−3875

Crystal Growth & Design

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(37) Lu, H.; Li, T.; Poddar, S.; Goit, O.; Lipatov, A.; Sinitskii, A.; Ducharme, S.; Gruverman, A. Statics and Dynamics of Ferroelectric Domains in Diisopropylammonium Bromide. Adv. Mater. 2015, 27, 7832−7838.

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DOI: 10.1021/acs.cgd.9b00308 Cryst. Growth Des. 2019, 19, 3869−3875