SINTERING OF PRINTED NANOPARTICLE STRUCTURES USING LASER TREATMENT

N205 Petri Laakso1, Saara Ruotsalainen1, Eerik Halonen2, Matti Mntysalo2, Antti Kemppainen3
2

VTT Technical Research Centre of Finland, Lappeenranta, 53850, Finland Tampere University of Technology, Institute of Electronics, Tampere, 33101, Finland 3 VTT Technical Research Center of Finland, Oulu, 90571, Finland

Abstract Printed intelligence is a promising new technology to produce low-cost electronics. Non-conductive circuits can be printed using nanoscale metal particle inks. Due to the nanoscale size of the particles, the typical sintering temperatures of 100300 C are only a fraction of the macroscopic melting point of the corresponding materials, thus allowing the use of paper or plastic substrates. Sintering of printed nanoparticle structures using laser treatment has been investigated at VTT. Laser sintering can be utilized in manufacturing of printed conductor structures such as antennas, circuits and sensors. A drop-on demand printer was used to print patterns with metallo-organic silver nanoparticles on a flexible polyimide substrate. Laser sintering was made with a 940 nm CW fiber coupled diode laser. Process was optimized using different laser power levels, line separation and repetition rounds. Conductivity of laser sintered samples was compared to conductivity of samples sintered in convection oven. Introduction One of the driving forces in printed electronics is the cheap way to produce large amounts of low cost electronics. Then solution is the roll-to-roll production for really high throughput. There are only few potential methods which are truly capable for R2R processing. Laser sintering offers possibility to do R2R sintering. If one wants to combine multiple different printed electronic components one needs a way to create contacts between the components. There are several ways to print the contacts but in this paper we chose the ink jet printing of nanoparticles. Metallic nanoparticle inks are used in making of conductors in printed electronics [1]. These inks

typically consist of silver or gold nanoparticles (nominal particle diameters 250 nm). Particles are encapsulated with a thin protective shell and dispersed in a liquid solvent [2, 3]. After printing a conducting structure can be obtained by sintering, i.e. by partially melting and fusing the adjacent nanoparticles together. Due to the nanoscale size of the particles, the typical sintering temperatures of 100300 C are only a fraction of the macroscopic melting point of the corresponding materials [4]. This allows the use of paper or plastic substrates. Recent studies have demonstrated thermally sintered silver and gold conductors with conductivities approaching half of the bulk material conductivity [1, 2, 5]. Since electronics are printed on plastic or fiber based substrates and multiple different materials are used to produce conducting and insulating properties it might not be possible to use oven heating to sinter the nanoparticle ink due other printed materials or substrate may suffer from the heat. Oven sintering is also time consuming. Of course there are also other alternative methods to enable sintering such as electrical sintering [6], UV or microwave [7] illumination. In this research, we have studied laser sintering with diode laser at 940nm. The resistivity of ink-jetprinted tracks on polyimide is demonstrated to be close to bulk silver resistivity, providing same improvement to tracks that were oven-sintered at high temperatures. Benefits for laser sintering are the accurate heat load only where it is needed, the absorbance to the substrate being really low, the short processing time and last but not least it is possible to connect laser to quality monitor to see if the process works like it should. After all laser sintering seems really promising technique.

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Experimental Printing of sintered conductors The samples for the laser sintering trials were inkjet printed in Tampere University of Technology. The used printer was iTi XY2.0 Material Deposition System, in figure 1 below. The printer has a repeatability of 1 m and the maximum substrate size is 305 mm x 305 mm. Generally the printing speed is somewhere around 100-200 mm/s. The print head was Spectra SQ-128 (Figure 2), which creates drops of 10 pl. There are 128 nozzles in the head and the nozzle spacing is 508 microns and the diameter of a nozzle 35 m.

printing. The pattern that was printed consist several ponsa (shown in figure 3) structures. In all structures the constant A was 15 mm and the constant B was 100 m, 200 m, or 350 m. The one layer patterns were printed at the resolution of 600 dpi. The temperature of the printing plate of the printer was 60 C. So the ink dried a bit but did not sinter.

Fig. 3: Test geometry. The first used silver nanoparticle ink in printing was Ink 1 whose curing conditions in convection oven are 100-350 C for 1-60 minutes. However there were some problems with the jetting of the ink and hence the imprint was not as good as desired. Some results were got but many of the lines were broken. Broken wires were neglected in sintering. The second set of trials was made with Ink 2 that was also a silver nanoparticle ink. Metal content was about two times higher than in Ink 1 and therefore it offers better conductivity. The advantage of it was also that it is jetting better with our print heads. Normal sintering conditions of the ink are 210220 C for 60 minutes. The imprint was better with this ink and the results were also easier to get. Fig. 1: iTi XY2.0 material deposition system Laser sintering The laser sintering experiments were performed at VTT in Lappeenranta. The laser system (fig. 4) used in the experiments was a Laserline LDF400-200 fiber coupled diode laser, where the laser beam was guided via an 400 m optical fiber to a scanhead. The diode laser is operated at 940 10 nm wavelength and the focal length used was 163 mm resulting an 1.0 mm focal spot on the work piece. The beam profile used was top hat beam. Sintering tests were done at the focal point and in some tests the beam was defocused -32 mm to achieve ca. 6 mm spot to work piece. Beam profiles in the focal spot and defocused beam profile are presented in the figure 5. In the sintering tests the film was placed on the top of two glass plates so that the pattern to be sintered was hanging on free space. Samples were sintered from the printed side of the film.

Fig. 2: Spectra print head The chosen substrate was Kapton (Polyimide). There was not made other surface treatments to the substrate than cleaning with isopropanol before

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Laser Sintering Process When thinking about the laser sintering process one would need a smooth heat input with minimum amount of differences and small absorbance to the base material. Laser has this advantage to bring very localized heat input [8, 9, 10, 11, 12]. Smooth input comes from the beam spatial profile and top hat mode then would be preferred. Diode lasers offer normally this top hat mode and the chosen 940nm does not have too high absorbance to the used PI substrate. Also pulsing of the laser is not preferred and that is why continuous wave laser is good alternative. If high average powers are used the intensity might get quite high. This can be adjusted so that the beam size is the same as the width of the conductor and then sintering can be made only with one pass. If it is not possible to bring enough energy to the material with one pass, it is possible to heat up material gradually with several passes. For example if ink contains too much solvent and the vaporization of solvent interferes with the sintering process, then multiple passes is the right approach. Another method is to use line wise method so that beam is scanned back and forth over the whole area to be sintered. This way the sintering has to be even faster due the sintering has to happen within less than 1 ms at a time and the process window is a lot smaller due really fast process. In this line wise method sintered lines can be overlapped so that conductors are heated gradually and also cooled gradually. Laser moving speed has to be some meters per second and then material does not have time to cool down too much between passes. Still it is common for all strategies to heat up the material quickly and locally to enable the sintering, low process times and minimal heat effect to the substrate. Results and Discussion In sintering tests two different inks were tested and test geometry was like what is shown in Figure 3. Three different line thicknesses were printed to see what the effect of line width is. First sintering tests were made with Ink 1 printed geometries using hatch technique. Laser speed was 1000 mm/s and line to line distance 0.2 mm. Beam size was 1 mm in diameter. After series of pre tests it was found out that the optimal range could be between 20 50 W average powers. From table 1. one can see the effect of average power to sheet resistance.

Fig. 4: Laser sintering setup.

Fig. 5: Beam profiles a) focal spot (beam 1 mm) b) defocused -32 mm (beam 6 mm). Samples were sintered by scanning multiple vertical lines across the ponsa pattern, line spacing was 0.2mm (figure 6). Tests were done in focal plane and also in defocus.
0,2 mm 5 mm

20 mm

Fig. 6: Sintering path when laser beam was used in the focal spot. Sintering experiments were performed using different laser powers and number of sintering times to found out the optimal sintering parameters. In all tests the scanning speed was 1000 mm/s. When the focused laser beam was used laser powers were between 20 and 50 W. When defocused laser beam was used laser powers were between 30 and 197 W. Some tests were done also by sintering samples 1, 2, 5 and 10 times. In these tests used laser powers were 50 or 80 W. These tests were done in defocus.

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Table 1 Sheet resistance values with different average powers. 50 W 40 W 30 W 20 W 100 m 200 m 350 m 0,16 0,17 0,16 0,18 0,27 0,19 0,29 0,31 0,28 0,52 0,59 0,38

From these results can be seen that the higher the average power was the lower the resistance was. If higher than 50 W average power was used, nanoparticle ink starts really easily to burn and conductivity is not as good anymore. Bulk resistance of silver is 1.6 Ohmcm. If accurate layer thickness of tested samples would be known, the bulk resistance of the sintered samples could be calculated. Layer thickness is around 1-2 m which would mean almost the same bulk resistance as with the bulk silver. Laser sintering is quite sensitive if any dust particles etc. are on the substrate during sintering. These impurities would absorb laser light more than the ink and this is why a serious damage may occur to the surface of ink or substrate. After laser sintering and measuring of samples they where put to convection oven to sinter the materials thoroughly. Small increase in conduction was noticed but this still needs further testing to get reliable data. Anyway this indicates that laser sintering did not sinter the nanoparticle ink fully. When ink 1 was only oven sintered 60 minutes at 160C, the average sheet resistance of 12 samples after sintering was 0.46 ohm. This is a bit worse than what was obtained with laser but due PET substrate oven temperature was not as high as would be needed to sinter ink fully. This value for oven sintering is also only couple times higher value than with bulk silver which is good result. Due nanoparticle ink 1 was not so easy to print it was decided to change the ink to Ink 2 to get better print quality. With the new ink it was immediately noticed that this ink does not allow as high laser intensity as the ink 1. In figure 7 we can see the damage to sintered Ink 2 due too high intensity.

Fig. 7: Ink 2 sintered with 40W in focus with hatch method. Because as high intensities could not be used as with Ink 1, the laser beam was decided to be enlarged to make intensity lower and to give process more time. Sintering seemed to work better even if sintering was done multiple times. Again after short pre tests it was found out that right parameter window was between 80 and 197 W with the 6 mm beam used. From table 2 one can see how conductivity changes when average power is changed. Less than 80 W average power sintering does not seem to work. Table. 2 Different average powers and corresponding sheet resistance values of 100 m wide sintered lines. Average power Resistance [W] [Ohm] 197 180 160 140 120 100 90 80 70 14,3 16,8 17,1 20,3 25,3 24,9 33,5 148 N/A

With multiple scanning technique was tried to see if quasi-simultaneous sintering could be done. From Figure 8 we can see that laser powers below sintering threshold with one pass does sinter the material by

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multiple passes. This makes process also more gentle for the ink. Of course this kind of operation takes more time but also it would enable more solvent containing inks to be sintered. It is notable that if ink is already once sintered it does not sinter more with multiple passes with the same laser power and speed. This might be also due after first sintering the surface of line changes color to human eye from light blue to silver like outlook. This silver surface will most probably reflect near infrared light really well which in fact lets lower amount of light to the process itself and may explain why multiple passes does not help if first pass sinters the conductor. Well a way around this might be the increase in power in consecutive passes but this may lead to substrate damage and that is why it was not tested. With ten passes and high average power material may suffer due high heat input (see figure 8 lowest right and the red arrow).
50 W x1 N/A 80 W x1 ~ 0,11

One issue in both tested inks was that solvent from the ink evaporates when sintering. It can be seen after process with microscope that evaporated ink spreads on both sides of the conductor which might cause problems in the next steps of whole production process. In figure 7 one can also see this evaporated residue near the sintered conductor. Another issue seen as a problem in laser sintering is the thickness variation of printed ink. In figure 9 we can see a picture about differences in printing quality and thickness before laser sintering. At some points thickness of the printed ink is so thin that one can even see through.

50 W x5 ~ 0,42

80 W x5 ~ 0,08

Fig. 9: After printing, thickness differences of ink. If one can see through the printed layer it is clear that the absorbance of laser light into this printed area has to be different than places where thickness is so thick that one cannot see through the printed conductor. In figure 10 we can see the thickness variation after sintering. Picture is not exactly at the same position than in figure 9 but thickness variation is similar. It is obvious that ink is only partially sintered. Sintered material have silver outlook and blue parts are unsintered. It is certain that laser has passes all areas due multiple similar tests made.

50 W x10 ~ 0,34

80 W x10 ~ 0,11

Fig. 8: Multiple pass tests with consecutive sheet resistance. When ink 2 was only oven sintered 60 minutes at 260C the average sheet resistance of 12 samples after sintering was 0.05 ohm. This is again a bit better than what was obtained with laser. Again measurement was done in different place so confirmation is needed. This value also is really close to bulk silver value.

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temperatures in process. Camera was operated at 500 frames per second. From the measurements it was easy to see how heat diffuses to PI substrate from the conductor after laser has passed by. Due the surface change from light blue outlook to silver outlook may explain why thermal camera does not see the actual temperature from sintered conductor. Also silver has really good heat conducting properties and that is why temperatures are roughly measured from PI and silver interface (figure 12).

Fig. 10: After sintering, thin sections unsintered. By doing multiple passes one can sinter a bit better the thinner areas also but it still does not help completely. In figure 11 we can see on the left with 80W and 1 pass sintered pattern, which has unsintered areas on the edges. With the same power if the sintering was done five times edges are almost fully sintered. Ten times would not anymore make the situation any better.

Fig. 12: Thermal camera image just after laser has passed by with Ink 1. When comparing different average power results from 20 to 50 Watts, the 50 W average power seems to have a bit smaller temperature after laser has passed by than 40 W. This is maybe because surface has melted due laser heat and that is why it is seen cooler by the thermal camera (Fig 13).

Fig. 11: On left 1x and on right 5x sintered. If these kinds of samples are processed after laser sintering in convection oven one hour at 220C everything is sintered. So we can note that too thin printed layer is a challenge for the laser and also big thickness differences within printed layers might also be problematic for CW diode laser sintering. At high powers even the thickest prints might be left partially unsintered if optical penetration depth and heat diffusion is a lot smaller than print thickness. Normally then printing is done layer by layer to achieve high thicknesses. Due at high average powers the substrate starts to deform we decided to analyze the absorbance of PI which was measured with spectrometer to be around 5 %, reflectance around 15 % and transmission 80 %. So according to this diode wavelength is a good choice. To find out what kind of temperatures are in the process during sintering, we used high speed thermal camera CEDIP Titanium 560BB to see roughly the

Fig. 13: Measured temperatures with different average powers with Ink 1. Conclusions Laser sintering of nanoparticle inks seems to be promising technique if substrate cannot be put to an oven or R2R production would be needed. Choosing the right ink for the process and keeping the substrate clean are the key factors to successful operation. Continuous CW diode laser seems to be a good choice for sintering due no problems with ablation was not seen. Of course too high intensity will

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vaporize the ink. Since samples were a bit pre dried next step might be sintering of these conductors right after printing when they contain much more solvent. This high amount of solvent might be a problem if the same laser parameters would be tested. Laser sintering seems to be really sensitive if printed layer is too thin or there is too much variation in thickness. Resistance values are already quite close to what bulk silver has so this is good thing, but still process has to be improved and testing is to be done also in real Roll to Roll environment in the near future. References [1] Redinger D, Molesa S, Yin S, Farschi R and Subramanian V 2004 IEEE Trans. Electron Devices 51 197883 [2] Kim D and Moon J 2005 Electrochem. SolidState Lett.8 J303 [3] Lee H-H, Chou K-S and Huang K-C 2005 Nanotechnology 16 243641 [4] Buffat P and Borel J-P 1976 Phys. Rev. A 13 228798 [5] Fuller S B, Wilhelm E J and Jacobson J M 2002 J. Microelectromech. Syst. 11 5460 [6] Allen, M.; Aronniemi, M.; Mattila, T.; Alastalo, A.; Ojanper, K.; Suhonen, M.; Sepp, H.: Electrical sintering of nanoparticle structures. In: Nanotechnology 19 (2008) 175201 [7] Perelaer J, deGans B-J and Schubert U S 2006 Adv. Mater. 18 21014 [6] Bieri N R, Chung J, Haferl S E, Poulikakos D and Grigoropoulos C P 2003 Appl. Phys. Lett. 82 3529 31 [7] Chung J, Ko S, Bieri N R, Grigoropoulos C P and Poulikakos D 2004 Appl. Phys. Lett. 84 8013 [8] Khan, A.; Rasmussen, N.; Marinov.; Svenson, O.: Laser Sintering of Nanomaterial on Polymer Substrates. In: journal of Microelectronics and electronic Packaging (2008)5, 77-86 [9] Khan, A.; Rasmussen, N.; Marinov.; Svenson, O.: Laser Sintering of Direct Write silver nano-ink conductors for microelectronic applications. In: Photon Processing in Microelectronics and Photonics VII, edited by Andrew, S. et al. Proc of SPIE Vol. 6879, 687910, (2008).

[10] Ko S.; Pan H.; Grigoropoulos C.; Luscombe C.; Frechet J.; Poulikakos D.: All-inkjet-printed flexible electronics fabrication on a polymer substrate by lowtemperature high-resolution selective laser sintering of metal nanoparticles, Nanotechnology 18 (2007) 345202. [11] Ko S.; Pan H.; Grigoropoulos C.; Luscombe C.; Frechet J.; Poulikakos D.: Air stable high resolution organic transistors by selective laser sintering of inkjet printed metal nanoparticles, Applied Physics Letters 90, 141103, 2007. [12] Auyeung, R.; Kim H, Mathews, S.; Piqu, A.: Laser Direct-Write of Metallic Nanoparticle Inks, JLMN-Journal of Laser Micro/Nanoengineering Vol. 2, No. 1, 2007. Meet the Author Petri Laakso works as research scientist at VTT and has worked with several different fields of laser materials processing such as cutting, welding of polymers, laser ablation with ultra fast lasers and systems integration.

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