Applied Surface Science 257 (2011) 83968401

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

ZnO nanoparticles produced by reactive laser ablation

V.V. Gaychuk a , B.K. Ostaychuk b , D.I. Popovych a, , I.D. Popovych a , A.S. Serednytski a
a b

Institute of Applied Problems of Mechanics and Mathematics NASU, 3b, Naukova Str., Lviv 79060, Ukraine Vasyl Stefanyk Precarpathian National University, 57, Shevchenko Str., Ivano-Frankivsk, 76000, Ukraine

a r t i c l e

i n f o

a b s t r a c t
The paper presents the results of theoretical and experimental researches of the analysis of nanopowder ZnO and ZnO-based structures formation mechanisms by means of pulse laser reactive technology ( = 1.06 m, = 107 to 105 s). The developed 2D model combines non-stationary heat transfer and uid motion along with the calculated prole of surface deformation. The characteristics of the dispersive and chemical compositions and structural parameters of the synthesized nanopowder together with the inuence of the energy of laser impulse evaporation, its duration and gas pressure in the reaction chamber have been studied using X-ray diffractrometry (XRD), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM). Particle size distribution analysis of ZnO has shown that the majority of them range from 5 to 60 nm in size. The photoluminescence emission spectra of the initial ZnO nanopowder at room temperature have been identied. 2011 Elsevier B.V. All rights reserved.

Article history: Received 14 February 2011 Received in revised form 11 April 2011 Accepted 17 April 2011 Available online 27 April 2011 Keywords: Nanopowders oxides Cluster formation Luminescence Laser annealing Gas sensors

1. Introduction Zinc oxide is a wide-gap semiconductor material (Eg = 3.37 eV), the interest which has especially grown recently, because this material is considered to be the one of the most prospective ones both for creating light-emitting structures, lasers and for gas sensors [1]. As it is known, gas adsorption processes are associated with electronic transitions on the surface of the material, and this leads to various effects in luminescence [2], and these processes are particularly strongly pronounced in nanopowder materials which have a big effective surface. One of the prospective methods of creating wide-class nanopowder materials is pulse laser reactive technology [3]. There are a lot of methods of nanopowder synthesis including the synthesis using CO2 laser during evaporation of metal oxide targets [4]. However, in this method there is no dosed control of pressure and reactive gas composition, which fact does not enable to form composite nanopowder materials and barrier structures on their basis during evaporation of metal targets. Besides, for evaporation of mainly transparent targets of metal oxides it is necessary to use CO2 or eximer lasers, and that limits the use of accessible and low-price solid-state powerful lasers which work in visible or close infrared spectral regions for that purpose. In this paper we suggest the method of formation of nanopowder materials and barrier structures on their basis by means of pulse laser reactive evaporation of material targets which can effectively be used for nanopowder production. The above method enables to

regulate technological parameters of the process and, accordingly, the characteristics of synthesized nanopowders. And there takes place formation of disperse phase in the conditions of high rates of growth and speeds of the process which leads to the formation of non-equilibrium structure of ZnO material which possesses a clearly manifested self-defective structure [5]. On the other hand, properties of the material can additionally be modied by different laser-alloyed admixtures. At present there is no generally accepted model of laser ablation of material from the target, that is why the issue of metal targets evaporation mechanism, in particular, at high density of laser impulse energy, remains unanswered. It is often considered that particles are mainly formed as a result of coagulation of clusters which are formed at early stages of evaporation [6]. Since during the evaporation products expansion process the liquid phase does not completely evaporate, the particle formation process can occur both with involvement of condensation and coagulation mechanisms. The establishment of the mechanism which dominates at nanoparticles formation is of fundamental and applied interest. 2. Mathematical modeling The suggested model enables us to determine the ablated matter size and the character of substance distribution on the Zn-target (Fig. 1) [7] in oxygen ambient. To study this, we use the equations of the non-stationary heat transfer and the uids mechanics. The process was simulated with a nite element method (FEM) by means of the software package Comsol 3.5 [8]. Analogical problem, without standard enthalpy of formation has been considered in ref. [9] (Table 1).

Corresponding author. E-mail address: popovych@iapmm.lviv.ua (D.I. Popovych). 0169-4332/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2011.04.084

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Fig. 2. Geometry and boundaries.

u t [( u + u) ] + (u )u + p = f t u = 0 qchem = qK0 eEa /KT

(3) (4)

Fig. 1. Schematic representation of boiling process at pulsed laser ablation.

where density, k specic conductivity, Cp heat capacity, qchem reaction heat, power density, viscosity, q standard enthalpy of formation, Ea activation energy, f volume force, u liquid velocity. The difference between the solid condition and liquid manifests itself in a very high value of viscosity when the material is in a solid state (temperature lower than the melting point). The effect of recoil pressure on the free part of the uid layer is described in the Laplaces equation: p= C (5)

Table 1 Materials data of ZnO used in calculation [10]. Parameter Latent heat of vaporization (kJ kg1 ) Temperature of vaporization (K) Emissivity Latent heat of fusion (kJ kg1 ) Temperature of fusion (K) Surface tension (N m1 ) Density (kg m3 ) Conductivity (W m1 K1 ) Heat capacity (J kg1 K1 ) Thermal dilatation (K1 ) Standard enthalpy of formation (kJ mol1 ) Activation energy (kJ mol1 ) Symbol Lv Tv Lm Tm Value 25.499 1179 0.6 111 692.5 0.8 7133 110.95 0.383 64 106 350 361

with p difference in pressures, surface tension factor, C curvature of surface. Boundary conditions (Fig. 2). Thermal conductivity conditions. For boundaries 13 we impose the following limiting conditions: - constant ow on the surface until the temperature of the surface is T = Tv . - stable temperature T = Tv of the surface until the end of the pulse (T < las ). - cooling by advection and radiation of air (T = T0 ) for T > las . Hydrodynamic conditions. Boundary 1 is subjected to the effect of two forces. The rst one is due to recoil pressure formed by the ejected vapour, while the second one is due to surface tension force. pI + ( u + ( u) ) n = Pr n Pr n t =0 s
t

k Cp q Ea

We consider that during the irradiation phase the surface receives specic power with a Gaussian distribution: = 2PC (2x2 /r 2 ) e r2 (1)

(6) (7)

where Pc specic power, emissivity, r beam radius. However, the surface of the layer of molten metal quickly reaches the irradiation temperature. This vapour ow means that: - the surface remains with the temperature of vaporization; - the vapour ejected creates a recoil pressure on the liquid layer. To model this effect, it is necessary to know the evolution of the recoil pressure generated by this vapour ejection. Our purpose is to model a thermal cycle, i.e., the heating during 120 ns and then the cooling under the effect of the environment. In this paper we have developed a 2D model coupling the nonstationary heat transfer and the uid motion. We assume that this is a Newtonian uid and incompressible. In this case, in order to model the movement of the liquid under the effect of recoil pressure, use the NavierStokes equation. The heat conductivity equation takes account of the uid motion through an advection item. Cp T + (k T ) + Cp u T + qchem = t (2)

with, n normal, t tangential vectors and Pr recoil pressure. Boundaries 2 and 3 are subjected to neutral boundary conditions. For boundaries 4, 5 and 6 we impose a condition of displacement which results in the components of speed normal being equal to zero. Boundaries 1, 2 and 3 correspond to the free part of the material. In this case, because of free surface movement, it is necessary to set the surface speed normal components as equal to normal components of the material motion speed. Fig. 3 shows the calculated prole of deformation of the surface. It is noticed that the depth of the crater is weak at the end of the pulse. However, after the end of the pulse, the surface remains deformed. This phenomenon can also be observed in the experimental section of the crater after a series of impulses. Crater formation is accompanied drops ablation from crater edges. This conrms that in our case the effect of recoil pressure is denitely more important than the effect of surface tension. The offered model describes a partial version of possible formation of drops.

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Fig. 3. Calculation of deformation processes of surface.

Fig. 5. Formation depletion (a and b) and enriched (c and d) layers in case of metal contact with semiconductor n-type (a and c) and p-type (b and d) (AM , As , A s -work functions of metal and semiconductor of n- and p-type accordingly). Fig. 4. Block diagram of installation for nanopowder production (RC reaction chamber, T target, C cyclone, EF electric lters, MF mechanical lters, P nanopowder collection).

3. Experimental setup Researches of phase and structural analyses of nanopowders we obtained were done using an X-ray diffractometer DRON-4, where Distribution of particles Cu K1 radiation in used ( = 1.54180 A). by size was determined on the basis of images received by means of electron microscope PEM-125K. Bar charts of particles distribution by size were based on the data of electron microscopy. Researches of chemical and phase structures of nanoparticles were done by means of micro-X-ray analysis and Auger-spectroscopy. For excitation and photoluminescence registration typical installation with double monochromator DMR-4 was used. Excitation was done by means of mercury-discharge lamp DRT-240 with light lter UVS-2. 4. Results and discussion In suggested method the process of pulse laser evaporation of target material and formation, accordingly, along with of microdrops fraction gasvapour phase is carried out by means of the Nd: YAGlaser ( = 1.06 m, = 107 to 105 s, q = 106 5 107 W/cm2 ) in the directed stream at atmospheric pressure of the mixture of reactive O2 (99.999%) and inert gases e, Ar (99.9999%) in the set proportion (PO2 : PHe = 0.1 0.4), which is directed in parallel to the evaporating target (Fig. 4). Directed by means of the fan with the set speed the stream (1030 m/s) of gas mixture ensures transfer and separation of nanopowder with its subsequent gathering on the exit from the reaction chamber through the use of a special cyclone and lters. By regulation of partial pressure of reactive gas (PO2 ) full or partial (near-surface) oxidation of nanopowder

and creation, accordingly, of a complex nanopowder material or barrier structures of metalsemiconductor type on its basis (e.g., ZnZnO at evaporation of Zn-target in oxygen environment) are ensured. Such barrier structures of Schottky-junction type predetermine occurrence of contact eld in the transition system with respective modication of electronic condition. In Fig. 5 there are energy diagrams of metalsemiconductor contact. In case of n-type semiconductor contact with metal, when the correlation of their work function AS < AM , concentration of electrons in the surface n(x) = n0 exp (Ep (x)/(kT)), where n0 stands for equilibrium concentration of electrons in the volume of semiconductor, Ep potential barrier value [11]. If AM < AS , then electron concentration in the contact area of the semiconductor increases, becomes equal to n(x) = n0 exp (Ep (x)/(kT)) and the contact layer of the semiconductor becomes enriched. In case of contact of metal with p-type semiconductor the depletion layer is formed at AM < AS , and the enriched one at AM > AS . Thickness of the depletion layer dn = (2 0 Ep0 /(ne2 ))1/2 , where Ep = AM AS . That is the smaller the difference between the work functions of metal and semiconductor and the larger concentration of charge carriers in the semiconductor, the smaller the depth of contact eld penetration into the semiconductor. Electron depletion or enrichment of the conductivity zone of the surface layer of granules promotes changes, in particular, in the intensity of the surface luminescence component. Therefore, changing chemical composition of the surface layer and the concentration of charge carriers in it as well as its conductivity type, it is possible to purposefully modify electronic properties of nanopowder materials. The use of the method suggested enables to effectively produce nanopowder materials of compounds and barrier structures on their basis (Schottky-junction type) with average diameter up

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Fig. 6. TEM image of the ZnO nanoparticles. Fig. 8. XRD pattern. (a) ZnO (Po2 /PHe 1/3), (b) ZnO + Zn (Po2 /PHe 1/5), (c) Zn (PHe 1 Pa).

Fig. 7. Distribution of ZnO nanopowder particles by size (Ei = 4.9 J/cm2 , (Po2 /PHe = 1/3).

= 120 ns,

Fig. 9. EDX spectrum of ZnO nanopowders. The composition of ZnO: [Zn] 53.36, [O] 46.64 (at%).

to 510 nm and specic surface area of more than 80190 m2 /g at productivity to 50 g/h. Electron microscope analysis of produced ZnO nanopowders has shown that all of them are poorly conglomerated and contain mainly nanofractions in the form of spherical particles 1060 nm in size and larger (Fig. 6). Obtained distribution of ZnO nanopowder particles by size is close to normal-logarithmic one (Fig. 7). In the larger fraction there occur shapeless particles 810 m in size and more, which obviously constitute target splinters. These particles were separated in the process of nanopowder production by means of mechanical lter. Separation and collection of nanopowders were carried out basically on the electric lter which was charged and caught nanoparticles of a certain size on the basis of their surface charge for the given speed of gas mixture insufation. ZnO nanopowder materials (Fig. 8a) or barrier structures ZnZnO of metalsemiconductor type (Fig. 8b) were formed in the reaction chamber depending on the ratio of gas pressure (PO2 /PHe ). XRD pattern and EDX spectrum of nanopowder is shown in Fig. 8 and Fig. 9, respectively. The XRD pattern reveals that the powder is ZnO with hexagonal wurtzite structure and no peaks except ZnO is detected. From the XRD patterns, the lattice parameters of a- and c respectively. These axis are estimated to be 3.2498 and 5.2058 (A), are consistent with the values of bulk ZnO. Research into the phase composition and structure of ZnO nanopowders have shown that all of them were produced under optimum conditions (PO2 /PHe 0.3), were single-phase ones (Fig. 8). EDX spectrum of nanopowder is shown in Fig. 9. The EDX spectrum indicates that only peaks associ-

ated with Zn and O atoms are seen in the spectrum, indicating that the powder is pure ZnO material. Research has shown that particles are formed in the course of material ablation from the target [12] and its coagulation and cluster coalescence in the plume [13]. Association of clusters takes place during agitation of the major part of evaporated substance with the environmental gas. Concentration of coagulation clusters and value of laser irradiation energy inuence the nature of particles growth. Nanoparticles coagulation takes place at temperatures below the fusion temperature of the material, and oxidation heat which appears as the result of it promotes particles agglomeration and leads to their growth in size. It has been traced that ZnO formation takes place owing to chemical reaction of oxygen on the surface of zinc particles, thus, further on, layers of oxidation reaction product restrict nanoparticles in their growth. Comparative analysis of chemical compound formation heat value and metal target evaporation value shows that chemical compound formation proceeds in the vapour-phase ZnO area or on the particle surface, owing to diffusion of active oxygen component. The size of particles and oxide content in nanopowder are determined by energy density and duration of laser irradiation, gas pressure and concentration of the reactive component. Particles growth becomes more intensive with the rise of pressure and oxygen concentration in the inert atmosphere. Researches of the form of ablated particles have shown that their shape changes depending on the size and can have both spherical and irregular shapes. Oxygen concentration in a nanogranule is determined by the value of laser irradiation energy density, reac-

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tive gas concentration in the inert atmosphere and gas environment pressure. Average size of ZnO particles gets larger along with gas pressure increase and the increase in the percentage of oxygen contained in the inert environment. In particular, with the increase of oxygen concentration in gas from 1020%, average particles size increases from 40 to 60 nm, and in case oxygen concentration in the inert atmosphere increases to 30%, content of zinc oxide in the produced nanopowder increases to 100%. The size of the major part of nanogranules is determined by the target laser irradiation energy density, chemically active gas pressure and laser pulse duration. With the increase in the energy of laser irradiation on the surface of zinc target, scattering speed of ablation products increases, concentration of coagulating clusters quickly decreases, and average size of particles produced becomes smaller. On the other part, growth of laser radiation energy leads to growth of ejection of big particles directly from crater and to formation of additional peak (Fig. 7). In case gas environment pressure increases, evaporation products are cooled faster, however concentration of coagulating clusters also increases. With the increase of oxygen pressure in gas there increases oxidation speed and drops evaporation speed, this leading to the growth of vapour concentration, up to their oversaturation and condensation on the cluster-forming centres. That is, as pressure increases, there accumulate more and more clusters, and the average size of particles increases. In its turn, coagulation process is also determined by the duration of laser pulse. The smaller duration of the laser impulse, the faster the products of evaporation get cooled and the smaller concentration of coagulating particles. Fast cooling of evaporation products leads both to the decrease in the speed of cluster coagulation, and to the reduction of the size of produced ZnO nanoparticles. Research of the synthesis and structure formation mechanism of nanopowders deposited in the reaction chamber in oxygen atmosphere has shown high reactivity of the technological process. We have traced that in case of evaporation of the zinc target in oxygen atmosphere already at Po2 1.3 Pa ZnO nanogranules were always formed. Such a high reactivity of the technological process is obviously accounted for by a high degree of ionisation and excitation of oxygen gas component by high-energy ions of the zinc target material. This is conrmed by the spectroscopic studies of the erosive plume of the zinc target which have discovered in the emission spectra at 513 mm distance from the target surface spectral lines of Zn0 , Zn+ , Zn2+ [14]. It stimulates formation of molecular complexes in the reaction space. However, obviously, with the indicated partial pressure of oxygen in the collision chamber there can appear to be an insufcient amount of ZnO to form ZnO nanogranules. At the pressure of gases applied ( 105 Pa) there take place intensive recombination processes of ions and excited atoms. Besides that, when molecular complexes are being formed, the corresponding energy relations relating to reaction heat and kinetic energy of atoms must be achieved, otherwise, as the result of energy deposition during complex formation it can break up. Besides, as it is generally known [15], excitation of atoms and molecules of the vapour ow changes the activation energy of physical adsorption on the surface of nanogranules, increases the activation energy of diffusion and the degree of their chemical bonding ionicity, thus stimulating transition through energy barriers in the elementary processes of synthesised nanogranules structure formation. And the surface of nanogranules is subject to bombardment by oxygen atoms with the stream density exceeding 1019 mol/cm2 s. That is, during nanogranule formation, up to 105 monolayers of the lacking poor component (oxygen) per second can interact with it. This can signicantly effect the correlation of components in synthesised nanogranules. On the other part, as we have traced, when the zinc metal plate is radiated with the target laser radiation impulses in the Q-switching mode (t = 120 ns) in oxygen atmosphere with a

Fig. 10. Photoluminescent spectres of ZnO nanopowders.

luminous ux density sufcient for surface fusion, embedding of oxygen atoms in the target surface layer at the depth to 0.51 m takes place. Besides, as micro-X-ray investigations have shown, in the zinc target, after multiple (n 5) irradiations in the oxygen atmosphere, the mixture of phases ZnZnO can be traced. Its quantity increases sharply with the growth of oxygen pressure in the chamber and the number of laser impulses. Since the process of laser evaporation, in our case, is normally carried out going through a liquid phase, it follows from the above that evaporation of Zn-target in oxygen atmosphere takes place from the layer saturated to some extent by oxygen, which essentially determines the structure and correlation of powder nanogranules components. Depending on oxygen pressure in the reactive chamber formation of ZnO can proceed (or to be dominating) either on the surface of the target (Po2 /PHe 1/3) or in the process of nanogranules transition to a cyclone (Po2 /PHe < 1/3). Thus, the formation mechanism for nanopowder oxide materials during evaporation of the metal target in oxygen atmosphere is of a complex nature. Ionisation and excitation of zinc and oxygen atoms, as well as oxygen implantation into the irradiated target constitutes a crucial factor. It has been traced that for initial ZnO at room temperature intensive ultraviolet ( max = 385 nm) and yelloworange ( max = 605 nm) luminescence and weak green ( max = 515 nm) luminescence were observed (Fig. 10). 5. Conclusions Theoretical and experimental analysis of the mechanism of ZnO nanopowder formation by means of pulse laser reactive technology has been made. The developed 2D model combines non-stationary heat transfer and uid motion along with the calculated prole of surface deformation. It has been established that nanoparticles are formed in the process of material ablation from the target and its coagulation as well as cluster coalescence in the plume. Coagulating cluster concentration inuences particles growth nature, and the size of the majority of nanogranules is determined by energy density and duration of laser pulse as well as pressure of chemically active gas. The peculiarities of photoluminescence of initial ZnO nanopowder have been studied (d 4060 nm). References
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