State of the Art Printing With Water Based Ink
Nanotechnol Sci Appl. 2016; 9: 1–xiii.
Argent nanoparticle ink engineering: state of the art
Krishna Rajan
Center for Space Human Robotics, Italian Constitute of Technology, Turin, Italia
Ignazio Roppolo
Center for Infinite Human being Robotics, Italian Institute of Technology, Turin, Italy
Annalisa Chiappone
Center for Space Homo Robotics, Italian Establish of Technology, Turin, Italy
Sergio Bocchini
Center for Space Human being Robotics, Italian Institute of Applied science, Turin, Italian republic
Denis Perrone
Center for Space Man Robotics, Italian Institute of Technology, Turin, Italy
Alessandro Chiolerio
Center for Space Human Robotics, Italian Institute of Technology, Turin, Italy
Abstract
Printed electronics will bring to the consumer level great breakthroughs and unique products in the near future, shifting the usual prototype of electronic devices and circuit boards from hard boxes and rigid sheets into flexible thin layers and bringing disposable electronics, smart tags, and so on. The most promising tool to achieve the target depends upon the availability of nanotechnology-based functional inks. A certain delay in the innovation-transfer procedure to the market place is now being observed. Nevertheless, the most widely diffused product, settled technology, and the highest sales volumes are related to the silvery nanoparticle-based ink market, representing the all-time example of commercial nanotechnology today. This is a meaty review on synthesis routes, chief backdrop, and practical applications.
Keywords: silver nanoparticles, surface plasmon resonance, nanocomposites, inks, printed electronics
Introduction
Argent nanoparticle (NP)-based inks represent the most important commercial nanotechnology-derived product and the most widely studied worldwide. To better clarify the motivation of this review, nosotros should therefore focus on the iii points highlighted: the raw material (Ag), the morphology it takes (NPs), and the compound through which it is used in practical applications (ink).
Let united states first with silver. Why Ag in place of other raw materials? Because information technology is a noble metallic, featuring undisputed advantages in terms of electrical conductivity, resistance to oxidation, and providing interesting plasmonic and antibacterial properties, as we will run across further in the text. The topic is far also wide to be synthesized in a single sentence, and there is no single source from which to extract information regarding the different materials that could exist used to set up conductive inks (Au,ane Cu,two brass,3 nickel,four Cr,5 Atomic number 26,6 Ti,7 intrinsically conductive polymers,8 thin conductive oxides,9 carbon-based materials).10 It is hard to imagine a future without the use of Ag, at least for certain disquisitional systems that cannot lose efficiency. The market share will exist reduced in favor of other nanoengineered, less expensive materials, only it is non possible to avoid the apply of metals to transport electricity without losses.
And then, why NPs? The most important feature is connected with their scale, bringing surface tension and ionic forces to that level of importance that allows a play against gravity, giving stability to a suspension. But many other interesting phenomena occur: collective electron resonances, the so-called plasma waves enabling surface plasmon resonance (SPR), and interactions with the electromagnetic field;11 , 12 a huge enhancement of diffusivity of the surface atoms, enabling "melting" (sintering) at extremely low temperatures,xiii and then on. In a world where nanoengineered materials could take broad awarding, from the consumer electronics market, building industry, pharmaceutical and corrective products, to food and the environs, nosotros tin can easily imagine that the part of NP synthesis and modification activities will exist huge.
Finally, why inks? Inks and writing/press engineering date dorsum to the 23rd century BC (near 4,500 years ago), presumably beingness invented in the People's Republic of China by Tien Chu under the empire of Huang Ti.fourteen Probably the offset nanotechnology ever discovered and practical was that of black ink based on carbon black and os black, containing fullerenes and a wide multifariousness of aromatic small molecules. Today, printing technology has expanded its horizon toward the realization of electron devices on any substrate, according to two chief approaches: 1) analog printing, involving the use of linear/rotary machines that are able to realize multiple copies of the same pattern at a rather high speed (serigraphy, gravure, outset, flexography), involving generally microstructured inks; and two) digital printing, where raster machines realize at rather tedious speed a single copy of a design that could exist changed merely working at the software level (inkjet printing, 3-D press), involving nanostructured inks. In Figure 1, an instance of a complex circuit realized on an unconventional substrate (borosilicate glass) is shown: cheers to a silver NP-based ink submitted to a sintering treatment and to a bonding phase, it was possible to join the conductive track with detached traditional components. This is the present cutting-border level of inquiry. What will exist in that location in the future? We recollect that in one case the processes and techniques to produce pure and controlled Ag NPs are settled, more complicated systems involving multimaterial processing could exist studied, producing multifunctional, adjustable, and adaptive smart materials. Information technology could be squeamish to run into "futu-retro" technological objects, based on principles as old as 4,500 years but able to realize those functions that are at the basis of our modern "east-society".
Silver nanocomposite ink afterwards sintering and resin bonding of discrete electronic components.
Notes: Printed on borosilicate glass. Image courtesy of Politronica Inkjet Printing SRL.
Now that the application domain is clear, to come back to the first question we asked: why is silverish so of import among nanostructured inks? Silver has optimal electron conductivity and a lower analogousness for oxygen if compared to copper, it is 25 times more abundant than gold on Earth's crust, and hence is less expensive. Argent NPs and nanocomposites (NCs) possess interesting electrical, optical, and chemical properties used in catalysis, surface-enhanced Raman spectroscopy (SERS), nanoelectronics, photonics, and biological and physical sensing.fifteen – 21 Shape and dimension of Ag NPs are easily controllable, resulting in tunable backdrop.22 We will meet how silver NP inks are produced and applied in the following sections.
Synthesis methods
Nanocrystals tin can exist fabricated using ii different approaches (Figure ii): the starting time, known as "elevation-down", utilizes concrete methods to reduce crystal size, while the other, the "bottom-up" approach, is based mainly on solution-stage chemistry and also named wet chemistry.23 Physical methods usually permit the production of a large quantity of nanocrystals, only is very hard to control geometry or have a uniform size. In dissimilarity, wet chemic synthesis allows the synthesis of nanocrystals with controlled particle size. Furthermore, as we will see, several nanocrystal shapes tin can exist synthesized by varying the reaction weather. In the case of inks, the command is actually of import, considering of the dependency of specific properties on the size and shape of the nanocrystal. For these reasons, wet chemic synthesis is by and large preferred. In this context, a wide variety of wet-synthesis techniques have been proposed to produce metallic nanocrystals and in particular Ag nanocrystals, including chemical reduction,24 – 26 electrochemical and photochemical reduction,27 – 29 sonochemistry, and oestrus evaporation.30 , 31
Height-down and bottom-upwards approaches to the synthesis of nanocrystals.
Notes: Adapted from "Ion Substitution Technologies", book edited by Ayben Kilislioğlu, ISBN 978-953-51-0836-eight, Published: November vii, 2012 under CC By 3.0 license. © Domènech et al.32
The chief road involves the bottom-up synthesis, starting from the silver salts and leading to the final nanocrystals. Three distinct stages tin be roughly recognized (Figure iii).32 , 33 Nucleation, the clustering of few atoms and/or ions, is the first phase of any crystallization process.34 In the second step, a seed is formed through cantlet-by-atom addition to the initial nuclei. In the final step, the seeds grow mainly in size while the shape is largely determined by the structure of the seed.
Plot of atomic concentration against time, illustrating the generation of atoms, nucleation, and subsequent growth.
Notes: Reprinted with permission from LaMer VK, Dinegar RH. Theory, production and mechanism of formation of monodispersed hydrosols. J Am Chem Soc. 1950;72(11):4847–4854. Copyright 1950 American Chemical Society.35
NP properties, such as catalytic, optical, magnetic, and electronic, have been demonstrated to exist size- and shape-sensitive.35 – 38 Nowadays, research efforts are put into not only controlling size and suspension stability but also developing unconventional crystal geometry, eg, synthesizing well-defined anisotropic and/or organized nanostructures. For ink production, usually it is easier to use wet synthesis, considering the final NPs are employed in intermission, and thus only bottom-up solution-phase synthesis methods will be discussed.
Bottom-up self-assembly approach
Bottom-up solution-phase synthesis of metallic nanocrystals starts from zerovalent metallic compounds or salts dissolved in a solvent. In particular for silver, these precursors are in the +1 oxidation country (Ag+), and thus, during the reaction, Ag0 atoms are produced as metal nanocrystal building blocks. Two synthetic pathways are at present under discussion. The beginning possibility consists in reducing the precursor compound into zerovalent atoms, which and then aggregate into the nuclei and abound into nanocrystals. In the 2nd possible reaction pathway, the unreduced metal species acquaintance with nuclei and then are reduced to zerovalent metal species.33
Generally, the mechanism depends on reaction conditions: college forerunner concentrations and mild reducing agents shift the reaction from the first to the second pathway. A low reduction rate and high concentration of metallic ions forbid the complete reduction into the zerovalent state. A nanosize cluster surface results thus positively charged, and could be stabilized by the capping effect of ionic species, such as halide or carboxylic anions, too as solvent molecules or polymeric species.33
Kinetic command is achieved when the crystal germination is directed by a moderate driving forcefulness, thus nether atmospheric condition far away from the thermodynamic equilibrium. Under kinetically controlled synthesis, the reaction proceeds considerably more than slowly than under normal weather condition, thus, slowing down the forerunner decomposition or reduction.39
Silver salts are unremarkably insoluble in whatever solvent, and thus the most used precursor for Ag nanocrystal product is silver nitrate (AgNO3), which has good solubility in polar solvents. The preferential seed shapes from argent salt reduction are icosahedral and decahedral, thermodynamically favored from the face up-centered cubic lattice of metallic argent.
Surfactant-assisted synthesis
Nanocrystal shape can be controlled past the addition of capping agents (Effigy 4). Surfactants, polymers, biomolecules, pocket-size organic molecules, and metal ions or atoms can be used as capping agents. They operate mainly by being adsorbed on a specific crystal plane and thus reduce surface free energy, changing the relative growth rate and inducing growth on the uncapped surfaces. Despite their importance in controlling shape, their mechanism of action is still not completely understood, and thus knowledge on the produced shapes is mainly obtained by trial-and-error attempts.40
Role of a capping agent in decision-making the evolution of Ag seeds into nanocrystals with different shapes.
Notes: Starting with single-crystal seeds, it is possible to selectively obtain Ag octahedrons enclosed past {111} facets by adding sodium citrate (Na3CA) and nanocubes/nanobars enclosed by {100} facets by adding polyvinylpyrrolidone (PVP). Reprinted with permission from Zeng J, Zheng Y, Rycenga M, et al. Controlling the shapes of silver nanocrystals with different capping agents. J Am Chem Soc. 2010;132(25):8552–8553. Copyright 2010 American Chemic Society.45
Abbreviation: AA, 50-ascorbic acid.
Capping agents are used according to ii different approaches. In the first arroyo, the seeds are grown directly into the solution and the capping agents used to orient the addition of the metal atoms on the surface, where the capping agents are either weakly or not bonded. In the 2nd arroyo, preformed seeds in which capping agents orient the growth are added in the synthesis solution.
The nearly used capping agents for Ag NPs are polyvinylpyrrolidone (PVP), a polymeric capping agent, and bromine anions. Both the agents tend to be selectively adsorbed onto the {100} facets of Ag nanocrystals, driving the addition of new Ag atoms to other crystal facets.41 , 42 Both capping agents induce the formation of nanocubes, rectangular nanobars, and octagonal nanorods. Bromine ions are much smaller than PVP, and thus the crystals obtained with this capping amanuensis are normally smaller than 25 nm in size. By slowing the reduction rate, thus using balmy reducing agents, such as ascorbic acrid, it is also possible to obtain Ag nanoplates.43 , 44 , 45
UV-induced synthesis of silver NPs
Since the 19th century, argent salts, eg, silver halides, have been used as photosensitive compounds for photography applications. In fact, their calorie-free exposure leads to the generation of metallic particles that were used in photography emulsion.46 Therefore, light radiation is a common fashion to synthesize silver colloids and NPs.
Photoreduction occurs when photogenerated free electrons react with Ag+ ions, forming the respective Ag0 metal atom. Ag+ ions in solution and efficient photogeneration are the master issues to control in order to have an effective production of Ag NPs.
By changing precursors and electron donors, it is possible to command both the dimension and the shape of the NPs synthesized. One of the outset syntheses of argent NPs in aqueous and alcohol solution was performed past Hada et al in the 1970s past ultraviolet (UV)-induced photoreduction using the photooxidation of water and alcohols under a deep-UV irradiation.47 Nowadays, the near common used electron donors are aromatic ketones: they undergo cleavage under UV irradiation, producing radicals that induce reduction of silverish.48 – 51 Other molecules reported equally photoreducing agents or other parameters have been involved in the reduction procedure, such every bit the use of acrylic monomers,52 sodium citrate to control the pH,53 reaction performed in nonaqueous media or fifty-fifty applying magnetic fields.54 , 55
Electrons tin be also photogenerated past photoactive semiconductors: under UV irradiation, they are able to promote a free electron that can reduce Ag+; usually, in this case the redox reaction is balanced past oxidation of the solvent, mostly water. The most investigated materials have been titanium dioxide and zinc oxide.56 – 59
Ag NP structural, morphological, and functional backdrop
As reported in the previous department, in order to exploit the potential of metal NPs fully and to provide effective strategies to tune electronic and optical backdrop of materials, the command of size and morphology of nanostructures are of central and technological interest.60 Noble metal NPs (Ag, Au, Pt) are extremely interesting because of their unique backdrop, and amidst them Ag possess the highest electrical and thermal conductivity, along with other backdrop, which promote its extensive employ in a wide range of applications. Nowadays, Ag NPs are largely used to produce conductive tracks with inkjet printing, cheers to the loftier conductivity and thermal stability of such materials.61 – 63
Conductive inks normally are aqueous or organic solvent dispersions of silver NPs that are stabilized past surfactants and polymers that undergo printing, a drying step, and at the finish a sintering process that is commonly accomplished by heating the printed substrates to a temperature ordinarily college than 200°C. Alternatively, more unconventional techniques, such as microwave,64 light amplification by stimulated emission of radiation radiation,65 flash sintering,66 plasma,67 and electrical- or chemic-induced sintering, can be pursued.68 , 69
Sintering at 200°C is much below the melting point of silver (960°C), and information technology can be attributed to the enhanced surface diffusion of atoms and to surface premelting; therefore, even in the sintering process, the dimension and shape of Ag NPs are one of the offset backdrop to be investigated.70
Ag NPs used for inks generally have spherical shape with diameters ranging from 5 to approximately 100 nm with narrow dimensional distribution. Several works are presented in the literature using such NPs. Fuller et al described an inkjet ink based on colloidal silver NPs of spherical shape with a diameter of approximately 5–7 nm dispersed 10 wt% in α-terpineol, which was sintered at 300°C on a hot plate, giving conductive lines of 80 µm and presenting a resistivity of 3 µΩ/cm.71
Lee et al proposed a conducting ink composed of silver NPs with diameter around 50 nm dispersed in a water-and-diethylene glycol cosolvent system. Continuous and shine lines of 130 µm width were printed, and after baking at 260°C for three minutes, these lines exhibited a resistivity of 16 µΩ/cm.72
Chiolerio et al explored the effects of NP-diameter distribution and limerick of Ag NP-based inks for the realization of inkjet-printed microwave circuits.73 Dissimilar NP sizes were measured by numerical analysis of field-emission scanning electron microscopy images, and electrical measurements after annealing gave a surface resistance ranging from 19.4 up to 30 mΩ/□, equally specified in Tabular array one. The best-performing composition was found to be the i containing an added copolymer, and field-emission scanning electron microscopy assay showed a peculiar NC structure with a percolating network of NP agglomerates, with an extremely low density of metal into the polymeric network.
Table one
Collection of relevant data for inks according to UV-vis measurements, FESEM assay, and electrical measurements afterwards annealing
| Ink name | NP diameter main mode ten ± s (nm)a | NP bore main mode 2 × ± south (nm)a | Main peak x ± w (nm)b | Secondary acme 10 ± west (nm)b | Third height x ± west (nm)b | Surface resistance (mΩ/□) |
|---|---|---|---|---|---|---|
| C10 (46) | 10±five | NA | 409.seven±48.9 | NA | NA | thirty.0 |
| C10 (47) | 15±5 | 100±50 | 400.1±31.0 | 365.9±43.five | NA | 30.0 |
| C10 (52) | 6±two | 15±5 | 420.v±65.7 | NA | NA | 30.0 |
| C20 (48) | 25±15 | NA | 439.2±77.iv | 555.three±193.2 | 365.9±43.5 | 19.four |
| C30 (49) | vi±2 | 40±x | 469.7±115.0 | NA | NA | xxx.0 |
| C40 (41) | 12±2 | 100±50 | 441.0±285.ane | NA | NA | 22.4 |
| C40 (51) | 12±two | 100±10 | 470.0±177.6 | NA | NA | 22.4 |
| C100 (7) | 12±two | xc±ten | NA | NA | NA | 30.iv |
Unlike kinds of NP shapes are also presented for the fabrication of conductive inks, such equally silver nanowires, which have huge potential applicability in transparent electrodes, just can give rise to problems, such as clogging of the printhead nozzles.74 , 75 In one of the about recent works, Finn et al75 presented the controlled degradation of networks of silver nanowires (average diameter of 55 nm and an average length of 8.one µm) in well-divers patterns by inkjet press from an optimized isopropyl alcohol–diethylene glycol dispersion. The resultant networks, after an evaporation/annealing process at 110°C, presented sheet resistance of 8 Ω/□ and conductivity of 105 S/chiliad, achieved for line widths of 1–x mm and network thicknesses of 0.v–2 µm deposited from ~ten–20 passes. In this case, the thinner networks showed semitransparency.
In 2012, Tung et al proposed shape-controlled synthesis of Ag NPs by 10-ray irradiation for inkjet press with which various shapes, including spheroidal, prism, rod, and multifaceted NPs, were produced by varying the initial concentration of PVP and AgNO3.60 It was demonstrated that at an optimized reagent ratio, a mixture of high-attribute-ratio rods (tunable to ~50), and spheroidal particles could be obtained, and such a mixture was proven to have a melting point and dispersive properties suited to inkjet press of conductive tracks. The resistivity of the printed lines decreased to 77.7 µΩ/cm and 33.i µΩ/cm after heating to 200°C and 350°C. Nanoplatelets were as well proposed for ink applications,76 , 77 allowing the formation of tracks with relatively low resistivity (7.4 µΩ/cm compared to 30 µΩ/cm of a like rails fabricated by NPs), with good stability after external repetitive angle stress (Figure 5). The authors attributed the electric resistivity and mechanical stability values to the dense microstructure resulting from the NP shape. It was besides demonstrated that the pulsed-laser sintering was able to control the shape of the Ag NPs, avoiding the typical "coffee stain" effect and realizing patterned lines with electrical conductivity very close to that of Ag majority.78
TEM and AFM of silver nanoplatelets.
Notes: (A) TEM image, (B) high-resolution TEM images with selected-area electron-diffraction patterns (inset), (C) FESEM prototype with edge-length distribution (inset graph), and (D) AFM epitome and thickness contour of silver nanoplatelets synthesized by the solvothermal method. Reprinted with permission from Lee YI, Kim Due south, Jung SB, Myung NV, Choa YH. Enhanced electrical and mechanical backdrop of silver nanoplatelet-based conductive features direct printed on a flexible substrate. ACS Appl Mater Interfaces. 2013;5(thirteen):5908–5913. Copyright 2013 American Chemic Social club.76
Abbreviations: TEM, manual electron microscopy; FESEM, field-emission scanning electron microscopy; AFM, diminutive force microscopy.
An alternative use of Ag inks is related to NP optical backdrop. Information technology is well known that Ag NPs possess a feature plasmon resonance in the visible range that could be controlled by properly tuning their dimensions, number, and relative distance.79 – 82 This property could be exploited for producing optical waveguides.83 Another property well exploited in the literature is the high transparency that could exist obtained from sparse films (over 95%) that is necessary in some applications.84 , 85 Also, homogeneous films of Ag NPs show high reflectivity in the visible range; this property was well exploited in order to produce reflective electrodes for solar cells, enhancing considerably solar cell performances.86 , 87
Applications
The following sections bargain with the most of import applications of Ag NP-based inks.
Surface-enhanced Raman spectroscopy
SPR is an consequence commonly seen in metals where free electrons collectively oscillate in stage with the incident low-cal,88 driven past the alternating electric field when irradiated by low-cal of proper wavelength. SPR enables an effective handful and absorption of calorie-free under a resonant condition. For example, this gives to metal colloids, like Ag, their brilliant colors. Concurrently, surface charges are polarized under the excitation of incoming low-cal. In the case of metal NPs, the generated charges cannot propagate every bit a wave along a flat surface as in bulk metals, only are bars to and full-bodied on the NP surface, and thus, this phenomenon is called localized SPR (LSPR).88
In these conditions, if organic molecules are adsorbed on the surface of metallic NPs, LSPR leads to intense local electrical fields within a few nanometers from the particle surface, and thus tin exist used for the enhancement of the Raman-scattering cross sections of molecules. This would provide an enhanced "fingerprint" spectrum of the molecule, rich in chemical information. This technique is widely known equally SERS, and was showtime demonstrated past Fleischmann and Van Duyne in the 1970s.89 – 92
It is also known that not simply the nanosize dimensions simply also the shape of a nanocrystal affects its interaction with electromagnetic waves. Therefore, the intensity and position of LSPR peaks can be fine-tuned by shape control, and a significant Raman-betoken enhancement tin be achieved by only selecting nanocrystals with an advisable shape. The detection of diluted analytes is possible by the indicate enhancement of organic molecules. Therefore, the sensitivity of SERS can exist greatly enhanced by many orders of magnitude by tailoring the shape of Ag nanocrystals and thus their plasmonic features,93 , 94 ie, LSPR.95 , 96 Particularly, branched argent nanocrystals with tips, such as stars, flowers, and dendrites, accept attracted increasing interest for their awarding in SERS, due to the enhanced plasmonic features.97
Ag polymer NCs by direct embedding of silvery NPs in polymers
Conductive NCs
Embedding highly conductive nanofillers in polymer is a common strategy for producing conductive polymer NCs. 1 of the common strategies used in order to characterize a noble metal–polymer composite is to evaluate its electrical resistivity. Many works take been reported in literature in this regard.
Silver conductive NCs were synthesized by embedding silver NPs of different shapes in diverse matrices, such as high-density polyethylene,98 polymethyl methacrylate,99 polyvinyl booze,100 , 101 bisphenol F diglycidyl ether,102 polyvinylidene difluoride, and polydimethylsiloxane,103 but likewise in inks and conductive polymers, such as poly(3,4-ethylenedioxythiophene).104
Sensors
Taking reward of the electrical electrical conductivity of silver-based NCs that arise upon mechanical stress variation, unlike pressure and tactile sensors have been produced. These NCs were recently reviewed by Nambiar and Yeow.105
In situ synthesized Ag NCs
Homogeneous dispersion of metal NPs in polymer matrices remains a critical event for NC preparation, due to their high surface energy. A mutual strategy in order to disperse NPs in polymeric matrices is to functionalize the surface of the NPs. An alternate style adult over the last few years envisages the direct dispersion of silver photosensitive precursors in photocurable monomers (often using a cosolvent) followed by UV irradiation, which results in the germination of a polymeric network and in the germination of metal NPs. In literature, several studies take used silvery hexafluoroantimonate (in acrylates,106 – 108 epoxies,109 , 110 thiol-ene,111 and divinyl ether systems),112 and also in engineered structures,113 using silver nitrate for synthesizing silver NCs.114
Unconventional Ag NCs
In this section, some innovative strategies for the synthesis of silver NCs are presented in guild to illustrate possible future trends in this field. The start strategy concerns the command of the shape of NPs in the solid-bulk phase. Trandafilović et al reported nigh the synthesis of argent nanoplates in polyampholyte copolymers.115
Tunneling conductive fillers in piezoresistive composites
Piezoresistive composite materials have recently found interesting applications in the fields of microsensors,116 , 117 electromechanical devices, circuit breakers,118 touch-sensitive screens, and tactile sensors for robotics.119 With respect to commercially available devices, these composite systems tin provide cheaper, faster, and more accurate alternatives. Past varying the nature and morphology of the type of polymeric matrix and the conductive particles that are used as functional fillers,120 the properties of these composite materials can be tuned. The percolation issue tin be used to explain the conduction mechanism in the case of contact between particles,121 , 122 and the tunneling mechanism where each conductive particle is separated from the others past a thin layer of insulating polymer, which represents the tunneling bulwark.123 , 124 In the instance of piezoresistive composites, which are based on the tunneling mechanism, a huge modify in electrical conductivity is caused, due to an external load-induced deformation.125 , 126 The applied mechanical strain induces a subtract in polymer thickness betwixt the particles, thus reducing the tunneling barrier. In this way, a big reduction in majority electric resistance takes place by an increased probability of tunneling.
Silverish nanostructures accept also been studied and employed equally conductive fillers for functional sensing composites. Recently, Hong et al127 investigated the electrical and thermal conductivities of a silvery flake–thermosetting polymer blended. The influence of silver-flake size, distribution, and filler loading on the electrical book resistivity and thermal conductivity of the composite was studied in detail by the authors.
Ag-based inks for inkjet-press flexible electronics
Concentrated argent (Figure half-dozen) NPs are well-recognized materials with potential applications in the field of printing technology. These are used for the preparation of metallic structures on various substrates, because of their high electrical conductivity and resistance to oxidation. Such inks should encounter some important requirements: for example, they should non dry out and clog when in the printhead, they should have good adhesion to the substrate with limited java-ring result and reduced particle aggregation, and they should be characterized by suitable viscosity and surface tension, as they determine drib size, drop-placement accurateness, satellite formation, and wetting of the substrate.128 These requirements are very well met by Ag NP-based inks.
FESEM image of a h2o-based Ag nanoink.
Notes: Deposited on an Si wafer (A); numerically extracted size distribution of nanoparticle population (B). Reprinted from Microelectronic Engineering, Volume 97 edition 9, Chiolerio A, Cotto M, Pandolfi P, et al, Ag nanoparticle-based inkjet printed planar transmission lines for RF and microwave applications: considerations on ink composition, nanoparticle size distribution and sintering time, Pages 8–15, Copyright 2012, with permission from Elsevier.73
Abbreviations: FESEM, field-emission scanning electron microscopy; ED, equivalent diameter.
In this regard, there are several approaches to codify Ag-based inks for piezoelectric and thermal inkjet printing that tin can produce low resistivity and high-resolution conductive traces on unlike substrates.73 , 129 , 130 The primary components for all conductive inks include an advisable amount of highly conductive metal precursor, such as Ag, Cu, and Au NPs, and a carrier vehicle. The majority of the inks are water-based, and water used in these inks should be very pure so as to limit contaminants. Inks may too comprise other additives, such as humectants, binders, surfactants, and bactericides/fungicides. The additives are typically a pocket-size percentage with respect to the composition of the ink, and are used to tune ink properties or to add specific properties, thus increasing its performance. Compatibility of the selected ink with a detail inkjet system chosen for degradation is very important, as this influences the interaction among NPs.131
In club to avert atmospheric precipitation and agglomeration of metallic NPs in colloidal inks, dispersants are added to the formulation, which helps to stabilize metal colloids. This helps to increase the loading rate of NPs, thus leading to the synthesis of conductive inks of higher quality. Surfactants and polymers are added to inks in society to interact with the surface of NPs and to class a coating of variable composition and thickness. The resulting modified particle surfaces either attract or repel each other, leading to flocculation or stabilization, respectively. Apart from these, humectants, including alcohols and glycols, are besides added to the ink as an boosted vehicle or carrier for metallic NPs. These control the evaporation of the ink, and help in the reduction of the coffee-band effect.132
Ink transfer to dissimilar substrates is facilitated with the help of binder components, which are typically resins that will remain on the substrate or surface along with the NPs. Another important ingredient used in conductive inks is the surfactant, molecules that contain both a hydrophilic and a hydrophobic portion. The primary office of a surfactant is to adjust the surface tension of the resultant ink. The addition of a surfactant to a water-based ink will have the result of drastically lowering the surface tension, due to the orientation furnishings at interfaces caused by the hydrophilic and hydrophobic portions of the surfactant. Loftier surface tension of the ink leads to reduced wettability of the cartridge as well as the substrate, resulting in poor reproduction of the geometry.127 Growth of leaner and fungi are mutual in inks, and this tin can exist avoided by the addition of biocides and fungicides, though with Ag conductive inks information technology is not necessary, since Ag NPs themselves take antibacterial properties.
One of the most of import parameters of an ink is its viscosity. In order to accommodate the viscosity to the desired value, a polymeric thickening agent can be used (eg, polyvinyl alcohol).133 In the case of piezoelectric printheads, the ink viscosity should be in the range of five–20 cP, while thermal printheads require a viscosity ranging from 1 to five cP.
After inkjet printing of a metal NP-based ink, a sintering procedure has to be performed in order to form a conductive printed pattern. Sintering is the process of welding particles together at temperatures below the corresponding bulk-metal melting bespeak, which involves surface-diffusion phenomena rather than phase change between the solid and the liquid. The conventional arroyo to sintering metal NPs is heating either with a hot plate or an oven driven by conduction/convection mechanisms (thermal sintering).72
In add-on to thermal sintering, at present some emerging sintering techniques are being studied and used, such as laser-induced sintering,134 flash sintering (photonic sintering),66 microwave oven sintering,64 and depression-pressure level Ar plasma sintering (plasma sintering).67 Sintering can too be obtained by the addition of a positively charged polyelectrolyte, such equally polydiallyldimethylammonium chloride, which promotes the coalescence of the NPs due to a decrease in their zeta potential (chemic sintering).135
Thermal sintering has been discussed by several authors as a method to optimize the quality of printed silver ink lines, in view of their use as electrodes. A critical drying temperature was found to determine an optimal contour of the printed line, thus also improving the electrical properties of the electrode. In these studies, the authors besides considered the effect of other factors on the properties of the printed electrodes, such as drop volume,136 different substrates, and thicknesses of the printed layers.137 , 138
The apply of inkjet-printed electrodes is of import in view of their integration in complex electronic circuits like organic thin-flick transistors.139 In contempo years, argent NP-based inks have found a broad range of applications, such every bit sparse-film photovoltaic solar cells,140 screen printing (which tin can replace some printed circuitboard interconnections),141 membrane touch switches, touch screens,140 automotive sensors,142 , 143 and automatic radio-frequency identification.144
Determination
Among metal nanostructures, Ag-based ones are the most diffused (and discussed) from both an academic and commercial point of view. This leads to the formulation of a wide range of nanostructured inks for a huge range of applications. Such inks are mainly employed in the field of printed electronics, promising to bring to the consumer great breakthroughs and unique products, shifting the usual epitome of electronic devices and circuit boards and allowing the realization of flexible functional sparse layers. The most of import synthesis techniques, functional backdrop, and practical applications have been reviewed in the present manuscript.
Footnotes
Disclosure
Ac was the founder of the company Politronica Inkjet Printing SRL, which is involved in printed electronics; his studies are at the ground of some of the products patented and commercialized by the company. AC and SB are shareholders of the aforementioned Politronica. The other authors written report no conflicts of interest in this work.
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Source: https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4714735/
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