Elsevier

Applied Surface Science

Volume 258, Issue 7, 15 January 2012, Pages 2289-2296
Applied Surface Science

Laser assisted embedding of nanoparticles into metallic materials

https://doi.org/10.1016/j.apsusc.2011.09.132Get rights and content

Abstract

This paper reports a methodology of half-embedding nanoparticles into metallic materials. Transparent and opaque nanoparticles are chosen to demonstrate the process of laser assisted nanoparticle embedding. Dip coating method is used to coat transparent or opaque nanoparticle on the surface of metallic material. Nanoparticles are embedded into substrate by laser irradiation. In this study, the mechanism and process of nanoparticle embedding are investigated. It is found both transparent and opaque nanoparticles embedding are with high densities and good uniformities.

Highlights

► Half-embedding nanoparticles with diameter less than 100 nm into metallic materials. ► Large area and uniform distribution of half-embedded nanoparticles are achieved using a pulsed laser irradiation to induce substrate melting. ► This process works for both transparent and opaque nanoparticles ► Various types of surface properties of metallic materials can be introduced by these half-embedded nanoparticles.

Introduction

Nanoparticles with unique, size-dependent properties are of increasing interest for both fundamental research and industrial applications. Substrates based on noble metal nanoparticles are currently the subject of extensive research in areas such as biological sensing, medicine, optical microscopy, optoelectronic devices and nano-photonics [1]. In general, it is possible to create a thin layer of new nanostructured material with promising new properties. In many applications, a thin layer of new nanostructured material may increase one or more functional properties [2].

Embedding nanoparticles into materials to study and improve material properties has attracted much attention. Noble metal nanoclusters embedded into a polymer is developed as a new probe to study the dynamic properties of the polymer surface near the glass transition [3], [4]. From a material point of view, it is advantageous to embed the metal nanoparticles in thin polymer films for optical and nonlinear applications [5]. Ag nanoparticles are integrated into polymer matrices to study surface enhanced Raman spectroscopy [1]. Optical absorption of solar cell is enhanced by embedding metal nanoparticles in the active layer [2]. Cu nanoparticles are embedded in Co to introduce magnetic moment by so-called buffer-layer-assisted growth (BLAG) [6]. Magnetic nanoparticles are embedded into polydimethylsiloxane (PDMS) for generating heat under an externally applied AC magnetic which holds the potential for using as a hyperthermia material for killing tumors [7]. Also, nanoparticle dispersed composite thin films have demonstrated improved mechanical properties [8].

In order to realize the above advantages, several methods were developed to embed nanoparticles into sorts of materials. The layer-by-layer (LBL) assembly of alternating layers of polycations with silica nanoparticles was successfully utilized to create antifogging, superhydrophilic surfaces [9]. Electrostatic layer-by-layer assembly technique was used make uniform, conformal multistack nanoparticle thin films for optical applications with precise thickness control [10]. Using the smallest possible high-index nanoparticles and achieving low large-scale surface roughness was the key point for the success of their method. Co nanoparticles were reoriented to become coherent with Cu(1 0 0) matrix and only semicoherent in Ag(1 0 0) matrix at different high temperature [11]. The capillary forces and surface tension of nanoparticle must be high enough to drive atoms away from underneath the cluster to achieve this purpose. Pt nanoparticles were burrowed into SiO2 thin films by iron-beam irradiation [12]. The driving force for the embedding behavior was the high-surface energy of the Pt particles relative to the energy of Pt/SiO2 interface. Au nanopaticles can be embedded into poly (methyl methacrylate) (PMMA) by heating substrate up to the melting temperature [13]. A thin polystryrene wetting layer covered the nanoparticle rapidly to fulfill this embedding process. Gold nanoparticles were embossed into polymeric film by laser irradiation [14]. The nanoparticles absorbed laser energy, converted it to heat, and sinked into a locally softened polymer film. This method had an impact on ultrahigh-density data storage, measurements of fundamental thermal parameters of materials, etc. [14]. A fabrication process of Au film exposed by a Nd:YAG (yttrium aluminum garnet) laser (wavelength =355 nm) was introduced to embed Au nanoparticles into Si substrate [15]. A golden thin film with thicknesses of a few nanometers needed to be coated prior to laser irradiation. This method is only feasible for limited materials which restrict its application. Unfortunately, above nanoparticle embedding process techniques are often costly and time consuming, or on a prohibitively small scale, uniformity, reproducibility [15], and the substrates are often fragile and suffer from poor temporal stability [1]. Also, above methods do not fit for embedding nanoparticles into metallic materials.

Transparent and opaque nanoparticles are two fundamental classes with different optical properties which are important for the embedding process. In this paper, we report an improved process for half-embedding nanoparticles of these two classes of nanoparticles into metallic matrix. This process includes first dipping the parent material into a solution in which nanoparticles are dissolved. Then laser irradiation is applied after that. This improved process is more flexible in terms of the materials and processes feasibilities. In this project, transparent (SiO2) or opaque (TiN) nanoparticles are coated on metallic matrix surfaces to demonstrate the laser assisted nanoparticle embedding process. This process has the potential to change matrix surface properties of fluorescence, catalyze, wettability, magnetism, biology and sterilization.

Section snippets

Experiment setup

Fig. 1 shows the schematic representation of the laser-assisted nanoparticle embedding process. The Q-switched pulse laser is irradiated on the nanoparticles. The nanoparticles are coated on sample surface prior to the laser irradiation. In order to coat nanoparticles on substrate surface, nanoparticles are dissolved in pure ethanol with Polyvinyl Pyrrolidone as the dispersing agent. Nanoparticles are separated in solution by the ultrasonic device before coating on the sample surface by dip

Numerical modeling

Optical fields are changed after laser passing nanosized particles. The optical enhancement by nanospheres in the near-field region can be explained by Reyleigh scattering and Mie scattering mechanisms [16]. Reyleigh scattering occurs when the size of nanoparticles is smaller than the wavelength of the light, while Mie scattering takes place when the size of nanoparticle is larger than the wavelength of light. In this study, the sizes of SiO2 and TiN nanoparticles (20 nm) are both much smaller

Laser embedding conditions

Laser fluence and pulse number are two of the most important parameters in the laser embedding process. There are three main parameters to control the thickness of coated nanoparticles: nanoparticle density in solution, dip coating speed and dip coating times. Silicon oxide and titanium nitride nanoparticles are chosen to perform the embedding process since they are two different embedding mechanisms. They are transparent or opaque to the laser with wavelength of 1064 nm. The SiO2 nanoparticle

Conclusion

This paper represents a process of half-embedding nanoparticles in metallic materials by laser assisted irradiation. It is found this process works for both transparent and opaque nanoparticles. It shows that nanoparticles can be embedded into metallic materials with high density and good uniformity. With this technology, different kinds of surface properties of metallic materials can be introduced by these half-embedded nanoparticles.

Acknowledgements

The authors appreciate the financial support NSF grant (CMMI 0900327). Results reported here do not necessarily reflect the views or opinions of the agency. The authors also thank the support of Purdue graduate school via Rose Fellowship.

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