Article

Digital selective growth of ZnO nanowire arrays from inkjet printed nanoparticle seed on a flexible substrate
Seung Hwan Ko, Daeho Lee, Nico Hotz, Junyeob Yeo, Sukjoon Hong, Koo Hyun Nam, and Costas P. Grigoropoulos
Langmuir, Just Accepted Manuscript DOI: 10.1021/la203781x Publication Date (Web): 30 Nov 2011 Downloaded from http://pubs.acs.org on November 30, 2011

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Digital selective growth of ZnO nanowire arrays from inkjet printed nanoparticle seed on a flexible substrate
Seung Hwan. Ko1,2, Daeho Lee2, Nico Hotz2,3, Junyeob Yeo,1, Sukjoon Hong,1, Koo Hyun Nam,1, Costas P. Grigoropoulos2
1

Applied Nano Technology and Science Lab, Department of Mechanical Engineering, KAIST, 291

Daehak-ro, Yusong-Gu, Daejeon 305-701, KOREA

2

Laser Thermal Lab, Department of Mechanical Engineering, University of California, Berkeley, CA

94720-1740, USA.
3

Duke University, Department of Mechanical Engineering and Materials Science, Thermodynamics and

Sustainable Energy Lab, 303 Hudson Hall, Durham, NC 27708-0300, USA maxko@kaist.ac.kr, cgrigoro@me.berkeley.edu

RECEIVED DATE 9/27/2011 CORRESPONDING AUTHOR FOOTNOTE Prof. Seung Hwan Ko (maxko@kaist.ac.kr) Applied Nano Technology and Science lab, Graduate School of EEWS (Energy, Environment, Water & Sustainability), KAIST, 373-1 Gusung-Dong, Yusong-Gu, Daejeon 305-701, KOREA. Prof. Costas P. Grigoropoulos (cgrigoro@me.berkeley.edu) Laser Thermal Lab, Mechanical Engineering, University of California, Berkeley, CA 94720, USA
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ABSTRACT

In this paper, we introduce a fully digital selective ZnO nanowire array growth on the inkjet printed seed patterning. Through proper natural convection suppression during the hydrothermal growth, successful ZnO nanowire local growth could be achieved. Without any need for photolithographic process or stamp preparation, the nanowire growth location can be easily modified when the inkjet printing process is integrated with CAD (computer aided design) system to allow high degree of freedom when the design needs to be changed. Current proposed process is very fast, low cost, environmentally benign, and low temperature. Therefore it can be applied for flexible plastic substrate and scaled up for larger substrate for mass production or roll-to-roll process.

KEYWORDS ZnO nanowire, direct patterned growth, digital selective growth, hydrothermal growth, flexible substrate, low temperature.

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1. Introduction Extended and oriented nanostructures are desirable for many applications, including microelectronic devices, chemical and biological sensing and diagnosis, light emitting displays, energy conversion and storage, catalyst, drug delivery, separation and optical storage. [1-5] Among the nanorods, ZnO nanowires (NW) have attracted much attention due to their direct band gap of 3.37eV and a large exciton binding energy of 60 meV, which make them a promising candidate for applications in various optoelectronics. The synthesis of nano/microstructures of ZnO has been carried out using various methods, such as evaporation and condensation [6], physical vapor deposition [7], chemical vapor deposition [8], and solvothermal [9] and hydrothermal method [10]. Among them, the hydrothermal method is one of the most attractive candidates for industrial use due to rapid, low-cost, low temperature, environmentally friendly process nature [1]. The ability to build functional nanostructured assemblies at predetermined locations requires both control of their growth structure and morphology and their placement at a specific location [4]. Usual approach use entails a series of multi-steps for growth, harvest and placement of nanowires, which are very time consuming, expensive, and low yield. To overcome the difficulties encountered in multi-step serial processes, new approaches use the direct growth at specific location with desired nanowire morphology. For site selective patterned nanowire growth, photolithographic method is usually applied to pattern the catalyst layer for local growth [1,5,11,12,13]. Other approaches used microcontact printing method for surface modification by patterned self-assembled monolayers with hydrophobic and hydrophilic end groups on silver or silicon substrate [3, 4, 14] or microcontact printing of seed nanoparticles [15]. However, these approaches are subject to practical limitations because they need a photomask for photolithography or mold for contact printing, which cannot be modified once they are fabricated. Furthermore, photolithographic method cannot be applied for heat and corrosive chemical sensitive plastic substrates. In this research we introduce fully digital selective ZnO nanowire growth using inkjet printed seed patterning and hydrothermal ZnO local growth. The proposed process is very fast, low cost,
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environmentally benign, and low temperature. Therefore it can be applied for flexible plastic substrate and scaled up for larger substrate for mass production or roll-to-roll process. Most of all, the nanowire growth location can be easily modified when the inkjet printing process is integrated with CAD (computer aided design) system to allow huge degree of freedom at the development stage.

2. Experimental Section Direct patterned ZnO NW arrays were selectively grown from the inkjet printed ZnO NP nuclei through the hydrothermal decomposition of a zinc complex. The process is mainly composed of two simple steps as shown in Figure 1(a); (1) ZnO NP inkjet printing on a substrate, and (2) subsequent selective ZnO NW hydrothermal growth on the inkjet printed ZnO NP seeds. All of the processes were carried out at plastic compatible low temperature (<95C) without using any conventional photolithography or vacuum deposition processes. 2.1 ZnO NP seed synthesis. ZnO NPs are used as seeds for the subsequent selective ZnO NW growth. ZnO NP ink was prepared by modifying the original method by Pacholski. [16]. A NaOH solution in 32.5mL of ethanol (0.03 mM) was added slowly to a solution of zinc acetate dihydrate (0.01mM) in 62.5mL of methanol at 60C and stirred for two hours. The resulting ZnO NP solution in ethanol is approximately 30nM and stable for at least two weeks in solution. The ZnO NPs were 5~10 nm in diameter with spherical shape characterized by TEM (transmission electron microscope) as shown in Figure 1. 2.2 ZnO NP seed inkjet printing. The ZnO NP solution was inkjet printed by a piezo-electrically driven DOD (drop-on-demand) inkjet head (MicroFab, Figure 1(b)) integrated with CAD system [17-18] to draw arbitrary digital patterns of ZnO NPs. The detailed jetting system set up and jetting parameters can be found in the supporting materials [Figure S1]. The various size of droplets (1~200 m) could be generated by changing nozzle diameter, jetting parameter (applied voltage waveform and amplitude), and substrate heating condition.

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After inkjet printing, the substrate was dried and annealed at 95C for 20 minutes to ensure the seed particle adhesion to the substrate. 2.3 ZnO NW selective growth. ZnO NWs were selectively grown only on the inkjet printed ZnO NP seed by immersing seed-inkjet printed substrates in aqueous solutions containing 25 mM zinc nitrate hydrate, 25 mM hexamethylenetetramine (HMTA) and 57 mM polyethylenimine (PEI, branched, low molecular weight) at 92 C for 2.5 hours. [19] 3. Results and Discussion Solution-grown ZnO NW arrays reported previously have been limited to aspect ratios of less than 20. PEI, a cationic polyelectrolyte, could boost the aspect ratio of ZnO NW above 125 by hindering only the lateral growth of the nanowires in solution, while maintaining a relatively high nanowire density [1920]. The substrate was suspended upside-down in an open crystallizing dish filled with solutions to remove the unexpected precipitation of homogeneously grown ZnO NW on the substrate. However, the inkjet printed ZnO NP seeds could become mobile due to strong natural convective flow and could diffuse to the unpatterned (unseeded) adjacent substrate region as shown in Figure 2(a). This, in turn, can induce secondary ZnO NW growth at unwanted areas resulting in wavy random white patterns of ZnO NWs as shown in Figure 2(b-d). To remove this secondary growth on the unseeded area, a thin cover glass was added to the substrate with 2 mm spacer to control and suppress the natural convection flow (Figure 2(e)). Figures 2(f-h) signify that current approach can successfully reduce the secondary ZnO NW growth and produce highly selective ZnO NW growth on the inkjet printed ZnO NP drop arrays. Figure 3 show the SEM (scanning electron microscope) and TEM (transmission electron microscope) pictures of selectively grown ZnO NW array on the inkjet printed ZnO NP seeds. Figure 3(a) and (b) show the ZnO NW growth on the 120 m dot arrays of inkjet printed ZnO seed NP ink droplets. The DOD inkjet print head originally generated 50 m diameter ZnO NP ink droplets (~100 pico-liter), and they spread out and dried to various sized ZnO NP circular pattern depending on the substrate heating
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condition. Smaller diameter ZnO NP seed patterns could be achieved by applying substrate heating. The usual length of the ZnO NW was around 10~12 m with 100~150 nm diameter after one time growth as shown in the cross section pictures (Fig. 3(c,d)). Longer ZnO NW could be obtained by introducing the samples repeatedly into fresh solution baths every several hours. The arrays were then rinsed with deionized water and dried in N2 for SEM imaging. ZnO NWs have hexagonal cross sections and grow along the c-axis of the wurtzite crystal. TEM characterization of individual NWs indicates that they are single-crystalline and grow in the [0001] direction (Figure 3(e): TEM picture, inset: SAED (selected area electron diffraction) pattern). More detailed characteristics of ZnO NW selective growth on the inkjet printed ZnO NP seed droplet can be explained in the Figure 4. Figure 4(a) shows a tilted SEM image and Figure 4(b-d) show cross sectional view. The ZnO NWs are grown vertically within 10 deviation angle on the central part of a circular pattern (Figure 4(b)) while urchin-like ZnO NWs are grown at the edge of the circular pattern (Figure 4(c)). The urchin-like dense ZnO NWs show highly ordered outward radial directional growth that can be explained as follows. Firstly, urchin-like radial growth minimizes the interaction among each ZnO NWs. In the interior of the seed pattern and away from the edges, the NWs preferentially grow vertically aligned as shown in Figure 4(b). However, on the edge, urchin-like radial growth mode can favorably minimize the interaction between the NWs while increasing the distance as they grow. Secondly, ZnO NWs preferentially grow toward the high concentration precursor supply. The affluent precursor supply from outside of the circular ZnO NP seed pattern redirects the NW growth to the outward direction compared with the ZnO NWs in the central part. The high density and the bigger length of ZnO NWs grow on the edge due to those effects. Various diameter circular patterns of ZnO NWs were successfully grown on the inkjet printed ZnO NP seeds as shown in Figure 5. The ZnO NW array pattern (Figure 5(b) left picture) was slightly bigger than the original inkjet printed ZnO NP seed (Figure 5(b) right picture indicated by red dotted line) because the horizontal ZnO NWs from the urchin-like radial growth at the edge of the NP seed pattern added extra length. The diameter of the initial inkjet printed ZnO NP seed pattern determined the final
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configuration of ZnO NW selective growth. As shown in top view SEM images (Figure 5(a) and (c)), there are two length regimes; the diameter of the inkjet printed ZnO NP seed (indicated by red dotted circles) and the length of the urchin-like ZnO NW growth at the edge of the circle (indicated by blue dotted circles.). When the diameter of the inkjet printed ZnO NP seed (indicated by red dotted circles) is larger than 20 m, the general configuration of the ZnO NWs grown on the inkjet printed seed looks alike. As the diameter of the inkjet printed ZnO NP seed decreases (Figure 5(c)) and especially when it becomes smaller than the length of the urchin-like ZnO NW growth, the latter growth mode became more dominant as shown in Figure 5(c)-v. The usual length of individual ZnO NW was around 10 m. However, when the inkjet printed seed NP pattern are very small, the individual ZnO NW length almost doubled (Figure 5(C)-v). This may be because the Zn precursor supply was enough for growing longer for ZnO NW array with fewer number and smaller density of ZnO NWs. On the other hand, the precursor consumption was not as competitive as in the densely packed ZnO NW array growth. The growth process could be conducted multiple times to grow longer NWs by simply repeating with fresh precursor solution. Figure 6(a) shows the ZnO NWs grown twice from the original NWs (Figure 6(b)). The length of NW was increased from 12 m to 20 m while the diameter was increased from 150 nm to 250 nm. By repeating the hydrothermal process, over 50 m long ZnO NW arrays can be grown. Just like an office inkjet printer, ZnO seed NP inkjet printing process is a fully digital process enabling the arbitrary micro patterning from single micro-droplets with the CAD geometry data. When the overlapping between the inkjet printed ZnO NP seed drops increases, ZnO NW array could be grown in a continuous line pattern (Figure 7(a)) or in a 2D checker pattern (Figure 7(d,e)). When the two droplets slightly touched, the urchin-like ZnO NWs meet to make NW bridges (Figure 7(b-c)). All of the processes were carried out at low temperature under 95C and no corrosive chemical etching or developing steps are applied. Therefore, current process can be directly applied for the ZnO NW patterned growth on a polymer substrate. Figure 8 shows line and dot patterned ZnO NW arrays on a polyimide substrate. This implies that current process can be applied for flexible electronics.

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4. Conclusions In conclusion, we introduce a fully digital selective ZnO NW array growth on the inkjet printed seed patterning. Through the proper natural convection suppression during the hydrothermal growth, successful ZnO NW local growth could be achieved. Without any need for photolithographic process or stamp preparation, the nanowire growth location can be easily modified when the inkjet printing process is integrated with CAD system to allow high degree of freedom when the design need to be changed. The herein proposed process is very fast, low cost, environmentally benign, and low temperature. Therefore it can be applied for flexible plastic substrate and scaled up for larger substrate for mass production or roll-to-roll process.

Acknowledgement. Financial supports to KAIST by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (grant No. 2011-0005321 and 2011-0028662), and the support to the University of California, Berkeley by the NSF STTR (grant No. 0930594) through AppliFlex LLC are gratefully acknowledged.

Supporting Information Available: This material is available free of charge via the Internet at http://pubs.acs.org.

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REFERENCES (1) J.H. Kim, D. Andeen, F. F. Lange, Adv. Mater. 18, 2453-2457, 2006. (2) Z.R. Tian, J.A. Voigt, J. Liu, B.Mckenzie, M.J. Mcdermott, M.A. Rodriguz, H. Konishi, H. Xu, Nat. Mater. 2, 821, 2003. (3) S.J. Kwon, J.H. Park, J.G. Park, Appl. Phys. Lett. 87, 133112, 2005. (4) J.W.P Hsu, Z.R. Tian, N.C. Simmons, C.M. Matzke, J.A. Voigt, J. Liu, Nano Lett. 5, 83-86, 2005. (5) J.J. Cole, X. Wang, R.J. Knuesel, H.O. Jacobs, Adv. Mater. 20, 1474-1478, 2008. (6) P.A. Hu, Y.Q. Liu, L. Fu, X.B. Wang, D.B. Zhu, Appl. Phys. A. 109, 13091, 2005. (7) S. Kumar, V. Gupta, K. Sreenivas, Nanotechnology 16, 1167, 2005. (8) T. Hirate, S. Sakai, W.C. Li, H. Miyashita, T. Kimpara, T. Satoh, Thin Solid Films 487, 35, 2005. (9) D.B. Wang, C.X. Song, J. Phys. Chem. B, 109, 12697, 2005. (10) L. Vayssieres, K Keis, S.E. Lindquist, A. Hagfeldt, J. Phys. Chem. B, 105, 3350, 2001. (11) X. Hu, Y. Masuda, T. Ohji, K. Kato, Langmuir 24, 7614, 2008. (12) H.J. Fan, P. Werner, M. Zacharias, Small, 2, 700-717, 2006. (13) T.L Sounart, J. Liu, J. A. Voigt, J.W.P. Hsu, E.D. Spoerke, Z. Tian, Y. Jiang, Adv. Func. Mater. 16, 335-344, 2006. (14) Y. Masuda, N. Kinoshita, F. Sato, K Koumoto, Cryst. Growth Des. 6. 75, 2006. (15) H.W Kang,J.Y Yeo,J.O Hwang,S.J Hong,P Lee,S.Y Han,J.H Lee,Y.S Rho,S.O Kim,S.H Ko, H.J Sung, J. Phys. Chem. C 115,1143511441, 2011. (16) C. Pacholski, A. Kornowski, H.Weller, Angew. Chem. Int. Ed. 41, 1188, 2002. (17) S . H . Ko , H. Pan, Nanotechnology 18, 345202, 2007. (18) S.H.Ko, H. Pan, C.P. Grigoropoulos, Applied Physics A 92,579-587, 2008. (19) L. Greene, M. Law, J. Goldberger, F. Kim, J. Johnson, Y. Zhang, R. Saykally, P. Yang, Angew. Chem. Int. Ed. 42, 3031, 2003. (20) S.H. Ko, D.H. Lee, H.W. K, K.H. Nam, J.Y. Yeo, S.J. Hong, C.P. Grigoropoulos, H.J. Sung, Nano Lett. 11,666-671, 2011.

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SYNOPSIS TOC Digital Selective patterned ZnO nanowires growth is demonstrated by inkjet printed ZnO NP seed and subsequent hydrothermal ZnO NW growth without any photolithographic processes. The ZnO NW growth location can be easily modified when the inkjet printing process is integrated with CAD (computer aided design) system to allow high degree of freedom when the design needs to be changed.

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Figures

Figure 1. (A) Process schematics of the direct patterned ZnO NW growth from the inkjet printed ZnO NPs. Inset picture shows the TEM image of the ZnO seed NPs prepared by modified Pacholski method. (B) Time resolved image of the ZnO seed NP inkjet printing by piezo-electrically driven drop-ondemand inkjet printing system.

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Figure 2. Selective ZnO NW growth (A-D) without natural convection suppression and (E-H) with natural convection control. Note the secondary growth in (A-D) and the absence of the secondary growth in (E-H).

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Figure 3. (A,B) SEM pictures of selective ZnO NW growth on the inkjet printed ZnO NP seeds. (C,D) Cross-sectional SEM pictures of ZnO NWs. (E) TEM and SAED picture of the single ZnO NW.

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Figure 4. SEM pictures of the ZnO NW grown on a single drop of inkjet printed ZnO seed NPs. (A) Tilted view. (B,C) Magnified cross sectional view at the center and at the edge. (D) Cross sectional view of the ZnO NW array on one inkjet droplet.

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Figure 5. (A) SEM pictures of ZnO NW arrays with various diameters from few microns to several hundreds microns. (B) SEM pictures of the inkjet printed ZnO seed NPs (right) and actual ZnO NW growth (left) on the seed NPs. (C) Magnified SEM picture of small diameter ZnO NW arrays in blue box in Figure 5(A). Red and blue dotted circles represent original inkjet printed seed diameter and total diameter of ZnO NW patterned growth respectively.

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Figure 6. (A) 2 times grown and (B) original one time grown ZnO NWs at the edge of the inkjet printed NP seed.

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Figure 7. (A) SEM pictures of the ZnO NW growth at various droplet spacing. (B,C) ZnO NW bridges between two circular ZnO NP seed droplets. (D) Check shape ZnO NW growth. (E) 3 times grown check shape ZnO NW growth.

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Figure 8. Line and dot patterned ZnO NW arrays on a plastic substrate.

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