Ion-beam synthesis of copper nanoparticles in transparent ceramics of aluminum-magnesium spinel

Journal Pre-proof Ion-beam synthesis of copper nanoparticles in transparent ceramics of aluminummagnesium spinel A.F. Zatsepin, A.N. Kiryakov, D.A. Zatsepin, N.V. Gavrilov, B.L. Oksengendler PII:

S0042-207X(20)30080-4

DOI:

https://doi.org/10.1016/j.vacuum.2020.109243

Reference:

VAC 109243

To appear in:

Vacuum

Received Date: 4 October 2019 Revised Date:

23 January 2020

Accepted Date: 30 January 2020

Please cite this article as: Zatsepin AF, Kiryakov AN, Zatsepin DA, Gavrilov NV, Oksengendler BL, Ion-beam synthesis of copper nanoparticles in transparent ceramics of aluminum-magnesium spinel, Vacuum, https://doi.org/10.1016/j.vacuum.2020.109243. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2020 Published by Elsevier Ltd.

Ion-beam synthesis of copper nanoparticles in transparent ceramics of aluminum-magnesium spinel A.F. Zatsepin1, A.N. Kiryakov1*, D.A. Zatsepin1, N.V. Gavrilov2, B.L. Oksengendler1,3 1

Ural Federal University (UrFU), Yekaterinburg, Russia

2

Institute of Electrophysics (IEP UB RAS), Yekaterinburg, Russia

3

Institute of Ion-Plasma and Laser Technologies (IPLT UAS), Tashkent, Uzbekistan

*

e-mail: [email protected]

Abstract: Experimental studies of aluminum-magnesium spinel modified by Cu2+ ions as a result of pulsed ion bombardment were carried out. The analysis of the modified samples with X-ray photoelectron spectroscopy (XPS) revealed the presence of metallic copper (Cu0) along with a small amount of oxidized copper at implantation doses of F = 5x1016 cm-2. It has been found with optical spectroscopy methods that, intrinsic (F, F+, anti-site) and impurity (Cu-related) optically active centers are formed in the matrix under the action of a beam of accelerated ions, and a complex dependence of the optical absorption intensity of these centers is observed with the increase of the annealing temperature. Experimental data allows us to conclude that the synthesis and evolution of metal nanoparticles formed in the surface layer of transparent ceramics MgAl2O4 showed a number of paradoxical properties, to interpret which a number of new physics of solid state concepts turned out to be adequate: the intermittency concept, which found its implementation in the Mott-Gurney kinetics, and the hierarchy of defective structure, which was realized in the trophic chains of defects. Keywords: transparent ceramics MgAl2O4, pulsed ion implantation, copper nanoparticles, complexity, modified Mott-Gurney kinetics, trophic chains of defects. 1. Introduction Oxide dielectrics are promising materials for photonics and optoelectronics due to their high radiation resistance and the presence of light transmission in a wide range of wavelengths. The possibilities of using such materials as radiation converters, heat-resistant windows, and also host materials for various ions are currently being studied. Ion technologies of doping dielectrics allow realizing very precisely controlled optical properties by varying the parameters of the ion implantation in manufacturing process. This method of creating optically active centers in the surface layer is interesting not only because it allows modification of the material with the type of ion of interest, but also because during the modification process it is possible to create nanostructures with a small spread in the depth of the surface layer [1]. Because of ionic modification of such materials, first of all, new optical properties arise, which allow us to expand the boundaries of their applicability. Wide-gap oxide dielectrics are interesting because of having significant radiation resistance, which makes it possible to carry out ion implantation into such materials under high radiation loads, which provides not only a high concentration of impurity ions in the surface layer, but also the growth of metal nanoclusters. In particular, during the ion implantation of

copper into crystals of wide-gap oxides, such as Al2O3, SiO2, MgAl2O4, the growth of copper metal nanoparticles is observed in the surface layer [2, 4, 5]. At the same time, modern trends show that the use of transparent ceramics is more promising from the economic point of view due to shorter production time and scalability of production [3]. The authors [4, 5] showed that doping of a non-stoichiometric MgAl2O4 single crystal with Cu– ions leads to the growth of copper metal nanoparticles with the simultaneous formation of intrinsic defects; however, no growth models for such nanoparticles have been proposed. The question of appearing copper nanostructures in the ceramic modification of MgAl2O4 also remains open. The study of copper oxide and metallic copper nanoparticles is being actively carried out in the view of their possible application in various sensors, biomedicine, and solar cells [6, 7]. The evolution of the process of nanoparticle formation from individual ions upon doping of oxide dielectrics is an important aspect of modern solid state physics. However, the description of metallic nanoparticle formation is always accompanied with a number of controversial points [1, 8, 9]. So questions requiring clarification in this case can be formed as following: How do the passivation of individual impurity ions and their agglomeration take place? What determines the shape of the nanoparticle? What factors limit the growth of nanoparticles in solids? Is it possible to control the growth of nanoparticles during ion doping? In this regard, the goal of this work was to synthesize copper nanoparticles in the surface layer of MgAl2O4 optical ceramics study its electro-optical properties and develop a conceptual model for the formation of such nanoparticles and their temperature evolution. The following tasks were set out: to perform the modification of optical ceramics with copper ions in a pulsed ion accelerator; carry out certification by X-ray photoelectron spectroscopy; to evaluate the optical characteristics at various doses of implantation; to study the temperature dependence of intrinsic and impurity optically active centers; to develop a new conceptual approach to explain the observed effects, because of their paradoxical behavior. 2. Materials and methods The matrix used for modification was transparent MgAl2O4 ceramics obtained by uniaxial hot pressing of nanopowder. Certification of the original matrix was performed using XRD. All reflections correspond to 100% MgAl2O4 with the space group Fd-3m. MEVVA-type ion source used for pulsed ion implantation with predominantly Cu2+ ions. Ion implantation has been conducted in Ar atmosphere at 1х10-1 Pa pressure. The accelerating voltage was 30 kV, the pulse duration was 0.4 ms and the arc current was 60 A. Copper cathode with 99,9% purity was used as target. A setup for ion implantation was described in more detail in [10]. Samples were irradiated with implantation doses from 1x1015 cm-2 to 1x1017 cm-2. The analysis of the electronic states of the surface layer was carried out on a Thermo Scientific K-Alpha+ XPS spectrometer. For measurements, we used a monochromatic X-ray source Al Kα with a probe diameter of 400 μm at a pressure of 5x10–6 Pa. Electron

paramagnetic resonance spectra (ESR) were recorded using ELEXSYS 580 spectrometer (Bruker, Germany) with resonator frequency set at 9.88 GHz and in 3100-3900 G range. Standard glass tubes from Bruker were used for spectra recording. Obtained ESR signal was normalized by samples mass. Optical absorption spectra were measured on a PerkinElmer Lambda 35 spectrophotometer. The sample was heated in a SNOL muffle furnace for 10 min in a corundum crucible; the temperature setting error was ± 10°С. 3. Experimental Results Calculation of Cu ions penetration depth in spinel matrix was done using full-profile SRIM modeling, figure 1 [11]. The thickness of implanted layer is about 40 nm. Ions distribution maximum in near surface layer was 20 nm.

Figure 1. SRIM modeling of Cu2+ ions implantation in MgAl2O4 matrix The certification of samples by XPS allows us to conclude that the studied objects were aluminum-magnesium spinel, with its characteristic bands of electron emission of aluminum, magnesium and oxygen [12, 13]. To confirm the presence of copper in the surface layer of ceramics, XPS spectra of core Cu 2p levels were recorded in the energy range 920 - 960 eV (Figure 2).

Figure 2. Electronic states of the ground level Cu 2p in the sample irradiated with a 1x1016 cm-2 fluence (upper spectrum). The XPS spectra of Cu2+, Cu0, and Cu+ are given below for comparison. It can be seen that both Cu 2p3/2 and Cu 2p1/2 bands are registered in the studied samples [14]. The presence of weak satellites typical of Cu+ [15] shows that, at the implantation dose of F = 1x1016 cm-2 copper ions are oxidized. At the same time, it is worth noting that the high-energy shoulder of the Cu 2p3/2 band is broadened, compared with the same band in the sample of metallic copper, which points at its non-elementarity and the possible presence of slightly oxidized copper. Thus, the obtained results indicate that, at the implantation dose F = 5x1016cm-2, metallic inclusions of copper are formed in the surface layer as well as a small amount of oxidized copper. Due to the small intensity ratio of satellites to the bands Cu 2p3/2 and Cu 2p1/2, it can be assumed that metallic inclusions are slightly oxidized on their surface. Presence of differently charged state of copper ions in spinel matrix was studied by electron spin resonance (ESR) technique. This method has high sensibility to low concentrations of paramagnetic ions. In case of studied samples, it was expected that there would be Cu2+ paramagnetic ions signal at ESR spectra resulting from Cu2+ implanted in spinel dielectric matrix [16]. ESR spectra of implanted ceramics are shown in figure 3.

Figure 3. ESR spectroscopy of studied samples. Spectra are presented in order of implantation dose increase (downwards).

From the ESR spectra, an interesting trend is seen with an increase of fluence: the signal of divalent copper (g = 2.207) passes through the extremum at an implantation dose of 1x1016cm-2. It means that the matrix is mostly saturated by copper in 2+ states resulting from low dose implantation. There are mechanisms initiated during concentration critical values for implanted copper where the latter in indicated 2+ state almost disappears. One of the most probable Cu2+ concentrations decrease channels is clustering with the formation of metallic nanoparticles. Metal nanoparticles are characterized by plasmon resonance due to collective in-phase oscillations of electrons in the nanoparticle. As a result of the coincidence of the vibrational frequencies of the electrons and the quantum of the electromagnetic (EM) wave, its resonance absorption by the nanoparticle occurs with the appearance of a characteristic dipole [17].

Noble metal nanoparticles (gold, silver, copper) exhibit resonance absorption in the visible part of the spectrum, while for most other metals the absorption is observed in the ultraviolet range. Optical absorption spectroscopy makes it possible to establish the energy of the EM wave participating in such a resonance. Figure 4 shows the absorption spectrum of transparent ceramics irradiated with implantation doses of 5x1015cm-2 and 5x1016cm-2.

Figure 4. Spectra of induced optical absorption of MgAl2O4 transparent ceramics irradiated with copper ions. Insert shows the values of ion fluence.

It can be seen that because of the exposure to a low dose of implantation (F = 5x1015cm2 ), radiation annealing in the visible part of the spectrum, as well as in the UV range, occurs. As the fluence grows to the values of F = 5x1016cm-2, the formation of intrinsic centers optically active in the UV, called F+ and F – centers (with one or two trapped electrons on the anion vacancy) takes place [18]. At the same time, there is an increase in a wide absorption band in the range from 3 to 4 eV, characteristic for intrinsic defects of cationic mixing. Such anti-site defects are an aluminum ion in the position of magnesium ([Al3+]Mg2+) and vice versa [19]. When an anti-site defect capture an electron or hole, an optically active center is formed in the optical absorption spectrum. A narrow peak with the energy of 2 eV is associated with the absorption of copper through the surface plasmon resonance (SPR) mechanism and it indicates about the formation of metal nanoparticles in the surface layer. Analysis of SPR peak position (position, halfwidth) allows concluding that synthesized nanoparticles were less than 5 nm [4]. However, the question still remains - how do charged ions form neutral clusters? Annealing of ceramics in a muffle furnace leads to the decrease in the optical absorption of intrinsic F and F+ – centers with overcoming of the local maximum at 280 - 300 ° C, fig. 5.

Figure 5. Graphs for the intensity of the absorption bands dependence on the annealing temperature in the range of SPR, F+ and F- centers. Right scale is the dependence of SPR energy peak position on the temperature annealing

Such thermally stimulated ionization of intrinsic centers is possible during electron injection. It is believed that broken bonds in metallic copper nanoparticles can act as an electron source. It is seen that in the indicated temperature range the SPR band intensity decreases, which indicates about the decrease in the number of nanoparticles. It was shown in [20] that metallic copper nanoparticles obtained from a solution oxidize at temperature above 140 ° C over time, which is characterized by a shift of the SPR peak. There is also the same dependence of SPR peak position on annealing temperature for our samples. Energy position shift of plasmonic resonance in low energy range proclaims copper nanoparticles oxidation. Besides, shift of plasmonic resonance energy peak is minimal both at initial (below 200 оС) and last stages (above 400 оС). We assume that, as a result of ceramic thermal stimulation, a competition occurs between the dissolution and aggregation of nanoparticles in the matrix. Also, there is a considerable contribution of metallic nanoparticles oxidation to this process. The question remains: how does the copper nanoparticles disintegration with the increase of annealing temperature? 4. Discussion of results, conceptual models Last 25 years of investigation of many processes in alive and non-alive nature revealed a special type of phenomena which understanding demanded the development of a new and very special approach. Along with the studied objects, which possessed the properties of multi componentness, hierarchy, nonlinearity, strong non equilibrium and a special type of disorder this direction was called complexity.

A number of problems, which were formerly referred to as paradoxical, within the framework of new ideas, have found adequate understanding. This judgment, as will be shown below, can be fully applied to the processes experimentally observed in this work.

4.1 The growth and evolution of metal (Cu) nanoparticles in the solid phase and the concept of "intermittency" The Cu+ ions introduced during implantation into spinel and their agglomeration into nanoparticles inevitably require an answer to the question: how the “Coulomb blockade” is overcome for each new Cu ion joining a positively charged copper nucleus. Nanoclusters formation ideas based on Ostwald ripening type models and Gibbs-Thompson effect can be utilized in our experiment during passivation of individual ions in spinel matrix. Therefore, we would observe classic oversaturated solution with formation of subseeds and supersedes which evolution could be described by discussing Gibbs-Thompson equations for phase formation theories. Though, XPS and ESR spectroscopy prove that implanted ions keep their charged state in the matrix. Thus, known models for cluster formation from liquid melt and saturated solutions won’t convey the point fully. One of the most radical approaches to this paradox solution (where the positive charge goes) can be found in the intermittency model, according to which the deposition always takes place in pairs. First Cu+ deposits onto the [Cu S]+ (where S – neutral sink) trap with further neutralization of this complex by an electron. Then everything repeats until the certain moment (moment of growth cessation) when a metal nanoparticle is grown and this is a special issue (see below). A similar scheme in a simple qualitative form was proposed by Mott and Gurney to the problem of latent photographic images [21]. A specific kind of kinetics, where copper and electron flows are adjacent, is shown in Figure 6.

Figure 6. Mott-Gurney kinetics (for copper ions and electrons). The time intervals of events are marked as - t. The diffusion times of an electron and a positively charged ion are marked as ̅ and – respectively.

The time interval (0: t1) corresponds to the deposition of A+ on a drain S. The time interval (t1: t2) corresponds to the following recharge time [ ] → [ ] . The time interval (t2: t3) corresponds to an increase in the number of particles in a growing neutral cluster up to two. The dashed line in the figure 6 shows the interpolation curve of nanoparticle growth. Thus, at all odd moments tj (j = 1, 3, 5, ...) there is an increase in the number of atomic particles (abruptly). The horizontal sections of the curve in the figure correspond to the duration of the recharging of positive clusters to neutral ones at even moments ti (i = 2, 4, 6, ...). The kinetics of the Mott-Gurney type shown in the figure can be calculated analytically in very different models (for example, in the Ham model [22]). However, the following is significant: the real growth time of a copper nanoparticle is much less than the total experiment time: − where ϰ < 1.

̅

+

= ̅

̅

≡ ∗ ;

+

Following the mentioned Ham model [22], we can obtain the expression for the size of the nanoparticle: −

=

!

.

Here: ! (

! #$% &−ϰ(

=

);

And: =

(

2+

!

;

where C0 is the average concentration of the initially implanted ions, Cinit is the concentration of the substance in the nucleus, D is the diffusion coefficient of the implanted ion, re is the radius of the equivalent sphere during implantation. Basing on the above formula for C(t), a regular nucleus of a nanoparticle can be estimated. An interesting point is that such an intermittency scheme allows us to propose a method for controlling the maximum size of a nanoparticle, for which it is enough to keep it in a positively charged state all the time, which in turn can be carried out by laser irradiation with an energy quantum equal to: ℎ- ≥ |0 | = 12

3;

where {Ei} is a charge trap energy in nanoparticle. Another non-trivial result manifested during the growth of metal nanoparticles is a violation of the Curie-Prigozhine symmetry principle (on the correlation of cause and effect of symmetry) [23]. Here it refers to the form which the nanoparticle grows - spherical or non-spherical. The solution to this paradox is possible with the involvement of the ideas of synergetics and nanofractals [24].

4.2. The temperature evolution of a defective system and the concept of trophic chains of defects In a number of experiments, when studying the effect of temperature on the properties of simple and complex defects, the quasi-oscillatory behavior of the corresponding dependences was discovered, and the number of oscillations could be controlled [25]. Noting first of all that if these oscillations occur not in time but in temperature, then we have to abandon the usual synergetic models. An adequate explanation was obtained within the framework of another concept based on the hierarchy of energy characteristics of defects (exclusively temperature variant [25, 26]; variant involving radiation [26-28]). Our idea is that if there are a large number of different types of defects, a hierarchy in energy (energy characteristics of defects in the sample) can be established between them in accordance with which the kinetics can be written in the form similar to the interaction among organisms in ecosystems developed by Svirezhev [29]. Similarly, in the investigated system the interaction of defects is interpreted in the framework of the ideology of "predator-prey", and so it is possible to write the following system of equations: 45 = 6 − 7 ∗ 4 + 7

4(5 = 6( − 7

,(

,(

∗ 4 ∗ 4( − 4 /

∗ 4 ∗ 4( + 7(,! ∗ 4( ∗ 4! − 4( /

(

. . . . . . . . . . . . . . . . . . . . . . . . 4:5 = 6; − 7;<

,;

with initial conditions:

∗ 4;< ∗ 4; + 7;,;

∗ 4; ∗ 4;

− 4; /

;

→ 0; 4; = 4; ; > = 1, 2, 3 … B.

where Nj – is the defect of a certain type, λj – is the probability of defect creation, ;< – sinks for defects, all k – are coefficients that determine the corresponding quasi-chemical interactions If the drains can be neglected ( equations will take the form:

< ;

→ 0), then the solution of the above system of kinetic N

C = DEFG HI −1 ;O

;

Q

6; exp [−0; /7M]P

where Ej is the activation barrier for the reaction j. Obviously, with an increase in T(oC) from T1 to Tm, the size of the clouds R will exhibit a quasi-oscillatory character.

Taking into account external sinks ;< ≠ 0 deforms a qualitatively important effect - the quasi-dynamic nature of the formula: the earlier the action of drains is turned on (in temperature), the less oscillations can occur.

Returning to the experimental data in the figure 5, we see that there are both oscillations of the characteristics of the defects and their monotonic relaxation. Thus one can conclude that increasing the annealing temperature decay of nanoparticles concentration occurs, with the simultaneous appearance of degradation products such as oxidized copper, as evidenced by the drop in intensity SPR peak in the optical absorption spectrum, and its offset in the low-energy part of the spectrum. Obviously, detailed monitoring allows for the complete certification of defects involved in the predator-prey game. 5. Conclusion The carried out experimental and theoretical studies are related to a rather new field of physics of condensed matter, which has gained fame under the term complexity. The objects of such studies are multicomponent disordered nonequilibrium systems characterized by both small (nano) sizes and reduced (including fractional) dimensions. The new theoretical approaches using fractality and synergetics proved to be adequate for understanding the numerous phenomena considered paradoxical. In the new conceptual approach, which clearly reveals nonlinearity, nanofractality, intermittency, dynamic chaos, and hierarchy of complex systems, many paradoxes have been understood. In the present work, the multicomponent MgAl2O4 spinel substantially removed from the equilibrium state by the implantation of copper ions was selected as a complex object. As a result, copper nanoparticles were formed, the generation and evolution of which demonstrated a number of paradoxical properties. For their interpretation a number of new physics of solid state concepts appeared to be adequate: the intermittency concept, which found its implementation in the Mott-Gurney kinetics and the hierarchy of the defective structure, which was realized in the trophic chains of defects. Specifically, the following was carried out: pulsed ion implantation of transparent MgAl2O4 ceramics by Cu2+ ions was performed. The effect of small doses (F = 5x1015 cm-2) stimulates radiation annealing of intrinsic structural defects formed as a result of the synthesis of microceramics. Due to implantation with a dose of F = 5x1016 cm-2, defect formation processes dominate over radiation annealing, leading to the growth of intrinsic anionic and cationic optically active centers. In the near-surface layer, copper nanoparticles are formed, with a small fraction of oxidized copper (probably at the metal-insulator interface). Such nanoparticles exhibit resonance absorption of electromagnetic energy through the mechanism of surface plasmon resonance. Thermal disaggregation of copper nanoparticles characterized by complex kinetics was discovered. New conceptual models of formation of clusters of metallic copper nanoparticles in the surface spinel layer have been proposed, implying a two-stage process of cluster growth. As a result of the first stage, the ion joins to a neutral sink. As a result of the second stage, the excess charge of the cluster is passivated by an electron. Thermo stimulated processes in copper nanoparticles can be considered in terms of trophic chains of defects with one or two quasi-vibrational iterations. Acknowledgments The reported study was funded by RFBR and Sverdlovsk region, project number 20-42-660012 and by Act 211 Government of the Russian Federation, contract № 02.A03.21.0006.

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Highlights 1. It is shown that, as a result of ion implantation of MgAl2O4 transparent ceramics by copper ions, the synthesis of copper metal nanoparticles occurs in the matrix. 2. After the thermal treatment of the spinel implanted with copper ions, the concentration of copper nanoparticles changes. The nature of the change in concentration from temperature is complex. 3. A conceptual model of the growth of copper nanoparticles as a result of ion implantation is proposed. 4. The complex nature of the dependence of the concentration of nanoparticles on temperature is explained using the model of trophical chains of defects.