Effect of the Synthesis Conditions and Microstructure for Highly

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Effect of the synthesis conditions and microstructure for highly effective electron shields production based on Bi coatings Daria I. Tishkevich, Sergey Grabchikov, Stanislau Lastovskii, Sergey Trukhanov, Tatsiana Zubar, Denis Vasin, and Alex V. Trukhanov ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.8b00179 • Publication Date (Web): 28 Mar 2018 Downloaded from http://pubs.acs.org on April 3, 2018

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ACS Applied Energy Materials

Effect of the Synthesis Conditions and Microstructure for Highly Effective Electron Shields Production Based on Bi Coatings Daria I. Tishkevich1*, Sergey S. Grabchikov1, Stanislav B. Lastovskii1, Sergey V. Trukhanov1,2, Tatyana I. Zubar3, Denis S. Vasin4, Alex V. Trukhanov5 1

SSPA “Scientific and Practical Materials Research Centre of NAS of Belarus”, 220072, Minsk, P. Brovki str., 19, Belarus, *corresponding author e-mail: [email protected]

2

National University of Science and Technology MISiS, 119049, Moscow, Leninsky Prospekt, 4, Russia

3

A.V. Luikov Heat and Mass Transfer Institute of the NAS of Belarus, 220072 Minsk, P. Brovki str., 15, Belarus

4

Belarusian State University of Informatics and Radioelectronics, 220013, P. Brovki str., 6, Belarus

5

South Ural State University, 454080, Chelyabinsk, Lenin Prospect, 76, Russia

Keywords: electrodeposition, bismuth, gelatin, X-ray diffraction, microstructure, shielding properties, electron radiation Abstract Microelectronic products are very sensitive to the ionizing radiations (electrons, protons, heavy charged particles, X-ray and gamma radiation). Lead is the commonly used material for radiation protection. Bismuth deposition has become an interesting subject for the electrochemical community because of bismuth’s unique electrical, physical and chemical properties. There is a limited number of authors dealing with deposition of continuous bismuth films onto metallic substrates by electrodeposition method. The conditions of Bi electrochemical deposition and the structure of Bi coatings were examined. X-ray diffraction patterns for all samples were indexed to

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rhombohedral Bi. Coatings with a signified texture (012) are formed in electrolyte without additives. With gelatin the growth texture changes and the most intense reflex becomes (110). It was found that increasing gelatin concentration from 0.1 to 0.5 g/L leads to Bi microstructural refinement from 4-20 µm to 50 nm-2 µm, respectively. The protection efficiency of Bi-based shields under 1,6–1,8 MeV electron radiation energy was measured. The electron beam attenuation efficiency was estimated by the changing of current-voltage characteristics of semiconductor test structures which were located behind the shields and without them. It has been determined that optimal protection effectiveness and mass-dimensional parameters is enabled by Bi shields with 2 g/cm2 reduced thickness and 156 attenuation coefficient. PACs: 61.05.C-, 81.05.Bx, 68.35.bd, 81.15.Pq, 61.82.Bg.


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1. INTRODUCTION Nowadays, the synthesized materials spectrum is quite large and many of them may be promising for use as shields from ionizing radiation. Aluminum, iron, copper, tungsten, lead, silicate glass etc. are used to protect against electron, X-ray, heavy charged particles and gamma radiation. Heavy elements are commonly used to effectively absorb high-energy radiation. Lead is the most widely used heavy metal. This is a highly toxic material with high density values (ρ=11.35 g/cm3). Currently, bismuth electrodeposition has become an interesting subject for the electrochemical community because of bismuth’s unique chemical, physical and electrical properties. The Bi films have shown thermoelectric efficiency [1], large magnetoresistance [2-4] and interesting quantum effects [5]. Bismuth is also used for contact formation on semiconductors [6] and for perspective electrochromic material for electronic devices [7,8], and like the material for films with a giant magnetoresistive effect for magnetic field sensors [9]. Quantum spin Hall (QSH) insulators based on 2D bismuthylene films and hydrogenated arsenene showed potential applications in spintronic devices at room temperature [10,11]. Functionalized Bi/Sb (111) films (SbNH2 and BiNH2) demonstrated a promising platform for realizing practical application in dissipationless transport devices. This topological phase in Bi/SbNH2 films showed a favorable robustness against strain engineering, perpendicular electric field, and rotation angle of amidogens, accompanied with effectively modulated bulk gap [12]. The tunable QSH state of a Bi(110) films with a black phosphorus structure obtains a tunable large bulk gap by strain engineering and its QSH effect shows a favorable robustness within a wide range of combinations of in-plane and out-of-plane strains, although a single in-plane compression or out-of-plane extension may restrict the topological phase due to the self-doping effect [13]. Bismuth has found application in electroanalytical chemistry as a new promising environmentally safe electrode for the heavy metals analysis in place of a poisonous mercury



dropping electrode [14-18]. Bismuth deposited on various metals is used as protective and antifriction coatings due to chemical resistance and mechanical properties [19]. Bismuth submonolayers on some noble metal surfaces have shown enhanced catalytic activity, particularly the two-electron reduction of H2O2 to H2O, the reduction of O2 in aqueous fuel cells [20,21], as well as the oxidation of formic on Pt [22-26]. Uses of bismuth composites offer a very attractive alternative to lead protection from gamma irradiation due to the much more environmentally friendly bismuth [27]. Thus, glasses based on bismuth oxide Bi2O3 are used as gamma radiation shields [28] and textile materials with Bi2O3 particles are applied in the overalls manufacture for medical personnel working on X-ray and gamma-ray systems [29]. The coatings based on multilayer structures with light (Sn, Sb, Ba) and heavy (W and Bi) elements on the polymer substrate provides a weakening equivalent to the case of pure lead, yet with mass dimensions lower by 25% [30]. There is a limited number of authors dealing with deposition of continuous Bi films onto metallic substrates by electrochemical method [31,32]. The main goal is to obtain thick-layer bismuth coatings on aluminum substrates, because aluminum is the one of the main materials for packages of microelectronic and radio-electronic devices. Our purpose is bismuth coatings production by the electrochemical deposition method and investigation of the shielding efficiency from electron radiation. The electrodeposition method has a significant number of advantages: the possibility of a controlled microstructure changing (the grain size, coatings density and texture) due to technological parameters variation; high growth rate and the possibility of thick coatings producing; electrolyte composition changing owing to the adding of various organic additives. The electrochemical deposition method also makes it possible to obtain Bi-based coatings and thereby obtain non-Pb materials. Electrodeposited coatings based on bismuth are ecology friendly, chemically stable, do not require the use of expensive and vacuum equipment, and coatings production is technologically simple.


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In this paper, we examine the electrodeposition of bismuth coatings from an acid perchlorate electrolyte in galvanostatic regime with 300-2580 µm as a promising material for radiation protection. 2. EXPERIMENT Samples of Bi coatings were electrodeposited from an acid perchlorate electrolyte. Electrolyte was prepared from concentrated perchlorate acid solution (400 mL/L) and bismuth (III) oxide (40 g/L) with rapid mixing. Bismuth deposition was produced in galvanostatic regime at the 23°C temperature onto aluminum substrates 0.4 mm thickness. The operating current density was 150 mA/cm2. Bismuth rods were used as anodes. The electrochemical experiments were carried out using a power source B5-78/6 as a stabilized current source. Organic additive – gelatin was added into the bismuth electrolyte at a concentration of 0.1-0.5 g/L. Electrochemical Cu deposition was carried out before Bi deposition to improve the Bi coating adhesion to the aluminum substrate. Electrodeposition of copper sublayer was performed in electrolyte of the following composition: CuSO4 – 35 g/L, K4P2O7 – 145 g/L, Na2HPO4 – 95 g/L, KNa tartrate – 25 g/L. Electrolyte pH was 8.0-8.5 and temperature range 32-35ºC. Copper electrodeposition was produced with current density 8 mA/cm2 during 10 min. Cu thickness of sublayer was 2.5 µm. Three series of experimental samples were produced: – the 1st series for the structural properties of coatings studying (thickness dependence) – three samples obtained from electrolyte without additives with Bi thicknesses of 100, 300 and 600 µm (Samples № 1-3); – the 2nd series for the structural properties of coatings studying (chemical composition dependence) – five samples obtained from electrolyte with gelatin adding in its different concentration 0.1-0.5 g/L with Bi thickness 300 µm (Samples № 4-8);



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– the 3d series for the attenuation coefficients determining from electron irradiation – six bismuth samples obtained in electrolyte with 0.5 g/L gelatin concentration with thicknesses of 970, 1340, 1560, 1950, 2240, 2580 µm (Shields №1-6). Shields production was carried out from electrolyte with gelatin adding in a concentration of 0.5 g/L in order to obtain uniform, flat, dense and close grained coatings. The Bi coatings reduced thickness was calculated using:

drth=d·ρBi,

(1)

Where ρBi – Bi density. Coatings surface morphology investigation was realized on scanning electronic microscope (SEM) LEO 1455VP. X-ray diffraction (XRD) analysis of Bi coatings was performed on a PanAnalytical Empyrean diffractometer using monochromatized CuKα radiation. Samples radiation using a linear electron accelerator ELA-4 was carried out. The nominal electron energy after the output window was Ee = 4 MeV, the fluence was F = (0,5÷50)·1013 cm2

. The electron flux density was 4·1011 cm-2s-1, which was controlled by a Faraday cylinder. It is known [33], that with radiation exposure, the attenuation coefficient by the substance

irradiation (according to the absorbed dose) essentially depends on the energy spectrum. A duralumin plate of 5 mm thickness was placed between the target and the electron output window (Figure 1) to approximate the accelerator ELA-4 electron spectrum characteristics to the spectrum of electrons of the Earth's radiation belt (ERB). The electron beam emerging from the accelerator output window falls on the moderating duralumin shield and then, with 1.6-1.8 MeV energy and concomitant braking radiation is directed to the investigated shield. The test sample is located behind the radiation shield. The shielding efficiency was evaluated by estimating the behavior of the volt-ampere characteristics (VAC) of test p-MOS transistor (p-MOST).


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The electron flux attenuation coefficient was determined from the ratio of the fluences of the electron flux incident on the shield and the electron flux transmitted through the shield. This method of determining the radiation absorbed dose is based on a change in radiation-sensitive parameters of p-MOST and is quite convenient from the point of view of practical application [33]. The measurements of the drain-gate VAC of the p-MOST were carried out before and after each irradiation dose on the MISD-1/6 measuring instrument for semiconductor devices. Radiation changes in the p-MOST characteristics are connected, firstly, with the scavenging of free charge carriers in deep centers in the dielectric bulk and, secondly, with the formation of surface states at the dielectric-semiconductor interface. The scavenging of charge carriers in the SiO2 bulk and on the levels of surface states causes a shift in the threshold voltage. The increasing in the surface states density leads to an additional scattering of mobile charge carriers and decreasing in the slope of the drain-gate VAC. The absorbed dose was determined from the changing of the VAC curve shift – the changing in the threshold voltage drop (∆U) at leakage current Ic = 10-7 A for p-MOST. The separate microcircuit was used for each dose of electron radiation. The values of ∆U were averaged over six transistors. The ∆U value was calculated for the shielded p-MOST to find the absorbed dose of the transmitted radiation and in case of unshielded p-MOST for the absorbed dose of the incident radiation. The shielding efficiency was evaluated from the change in the VAC, namely, the threshold voltage for the pMOST located behind the shield and without shield. The shielding coefficient values (the attenuation coefficient) (Ka) were simulated from ratio (2) Кa = F/F0,

(2)

Where F – the electron fluence corresponding to a parametric failure of a shielded test pMOST; F0 – the electron fluence corresponding to a parametric failure of unshielded test p-MOST. The parametric failure of p-MOST was fixed with threshold voltage changing ∆U = 0.05 V.



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In general, the Ka (drth) dependences can be approximated by a second-order polynomial: Ka = A + B1drth +B2drth2,

(3)

Where A = -28.046; B1 = 137.15884; B2 = -23.9592.

3. RESULTS AND DISCUSSION Previous simulation using the Geant4 software package showed that to ensure effective radiation protection it is necessary to produce shields with the drth values not less than 1 g/cm2. Moreover, in the shields production, it is important to guarantee a good Bi adhesion to the substrate, as well as plasticity increase and the dense and uniform coatings formation. Bi electrodeposition from perchlorate electrolyte without introduction of organic surface-active substances (SAS) leads to coarse-grained Bi coatings on the cathode. It is recommended to introduce SASs (such as glue or gelatin, dextrin, peptone etc. [34]) for the cathodic polarization increase resulting in close grained coatings in the electrolyte. Figure 2a shows the X-ray diffraction (XRD) spectra of bismuth coatings with various thicknesses (1st series samples №1-3). The number of reflexes increases with coatings thickness rising, but their intensity falls, which indicates the crystallites formation of different orientations. XRD data shows that the all structure of Bi samples was characterized by a rhombohedral crystal lattice (space group R-3m). All of the diffraction patterns can be indexed to bismuth with lattice parameters a = 0.450 nm and с = 1.179 nm. There is also a Cu(200) peak, which corresponds to a technological copper sub-layer deposited to improve the bismuth adhesion onto aluminum substrate. It is important to emphasize that coatings with a signified texture (012) are formed in the electrolyte without additives. However, in the presence of gelatin, the growth texture changes (Figure 2b) for all samples №4-8 and the reflex becomes most intense (110). In this case the grain size decreases, new peaks do not arise, but the peaks intensity reduces and they become wider.


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It appears that gelatin forms stable adsorption cation-organic complexes with Bi ions and provides the microstructure formation in a sample with a preferred grain orientation (texture). Cathodic polarization increase is required. The interaction of gelatin is mainly related to their adsorption at the metal-solution interface. The process of Bi reduction during deposition leads to destruction of cation-organic complexes at equilibrium electrochemical potential values, which results in the crystallites formation with preferable orientation. The intensity of diffraction peaks is different for the samples obtained in pure electrolyte and with gelatin adding, which indicates the crystalline size variations and lattice strain in the presence of additive. A locally positive charge formed on the nitrogen atom (-NH3+) promotes passivation of the cathode surface (the source of electrons), which prevents the grains growth and contributes the formation of a finegrained structure. However, the carboxy group (-COO-) leads to nucleation of new crystallization centers by adsorption of bismuth ions on unsaturated bonds –COO-…Bi3+... –COO- (Figure 3). Bismuth coatings with 100 µm thickness have an open-grained structure (Figure 4a). Dendrides grains with sizes from 10 to 30 µm form a faceted shape and sharp boundaries. Since the grains longitudinal dimensions are comparable to the coating’s thickness, it can apparently be assumed that in Figure 4a shows the first bismuth layer grown on an aluminum substrate. Cross-sectional SEM image of 100 µm Bi coating with technological sublayers is demonstrated in Figure 5. It can be seen that the bismuth coating has a dense structure and good adhesion to the copper sublayer. The nature of the surface morphology varies considerably with the coatings thickness increasing. Βi coatings with 300 and 600 µm thicknesses do not have dendrides (Figure 4b, c). SEM surface images are a combination of a large-scale component with oval formations ranging with sizes from 80 to 120 µm and a fine-grained component with 4 to 12 µm crystallites size ranging. Figure 6 shows SEM images of bismuth coatings with different gelatin concentration 0.10.5 g/L in the perchlorate electrolyte. Bi thickness for all samples is 300 µm.



It was found that gelatin concentration increase (0.1-0.5 g/L) leads to bismuth microstructural refinement from 4-20 µm (Figure 6a) to 50 nm-2 µm (Figure 6, c). The enlarged fragment Figure 6f of image Figure 6c demonstrates bismuth with adsorbed gelatin on the coating surface. As shown in Figure 6f the adsorption of gelatin with its concentration increasing in some cases prevents the growth of crystallites. Influence of organic additives introduction into electrolyte on the structure of bismuth coatings is investigated in more detail in [35]. The drain-gate characteristics of electron irradiated test p-MOST shift to negative values when the radiation dose increases. The charge carriers capture in the SiO2 volume and on the surface states levels causes a shift in the threshold voltages. Surface state density increase leads to an additional scattering of mobile charge carriers and decrease in the drain-gate steepness of p-MOST VAC [29]. The p-MOST leakage current growth with increasing fluence is due to the protective diodes leakage current increment in microcircuits input and output. Figure 7a shows the dependence of threshold voltage shift ∆U (in absolute value) on the electron radiation fluence of the p-MOST, which is not shielded. The electron fluence causing parametric failure of unshielded p-MOST was determined from the obtained results. The fixed value of the parametric failure ∆U = 0.05 V corresponds to an electron fluence of order F0 = 2.3·1012 cm-2. Figure 7b shows the threshold voltage shift dependence of electron irradiated p-MOST which is protected by Bi shield. The increasing of ∆U for all shielded p-MOSTs is observed in the entire investigated range of electron radiation fluences. However, for the same electron fluence values, the changes in the threshold voltage are significantly smaller for protected pMOST compared to unprotected p-MOST. This effect is enhanced with thickening of the Bi shield. From the results presented in Figure 7b, it follows that all used shields have sufficiently high values of attenuation coefficients. Attenuation coefficient Ka was calculated using (2) with the value of a parametric failure ∆U = 0.05 V. The calculation results of the Кa values of Bi shields № 1-6, depending on the drth, are given in the Table 1.


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As can be seen from the data in table 1, the Ka values increase with the shields drth rising. In this case, the Bi thickness increasing to the values drth = 2.0 g/cm2 has a stronger effect on the Ka changing, than at drth > 2.0 g/cm2. Results analysis shows that even at shield thickness drth = 1.6 g/cm2, the dose accumulated by the sample is reduced in Ka = 130 times. The excessive Bi thickness build-up does not give a clear advantage in the radiation protective properties of shields. It can be concluded that shields with Bi thicknesses of the 1.6 ÷ 2.0 g/cm2 are the most optimal for protection against electrons from the point of view of mass-dimensions parameters. The nature of the Ka (drth) dependences in the experiment is observed due to the interaction of electrons and braking radiation with matter. Thickness increasing in the range of values drth ≤ 2.0 g/cm2 effectively reduces the electron component contribution to the absorbed dose of the protected p-MOST, which is observed in the experiment (see Figure 7b and Table 1). All electrons are scattered by the shield material with the Bi drth ≈ 2.0 g/cm2. In this case, and for drth > 2.0 g/cm2 the secondary types of radiation contribute to the absorbed dose, the predominant of which is braking radiation. This radiation has a high penetrating power and the protection of electronic components with local shields becomes ineffective against it. Therefore, with the reduced thickness values of shields (drth ≈ 2 g/cm2) and its further growth, the behavior of the curves ∆U = ∆U (F) for drth = 2.0; 2.3 and 2.6 g/cm2 practically coincides (Figure 7b) and the values of Ka differ insignificantly (Table 1).

4. CONCLUSIONS The electrodeposition conditions and Bi coatings structure studies showed the following: the Bi coatings structure for all samples has a rhombohedral type of crystal lattice; the microstructure changes from a dendritic, coarse-grained crystal with 10-30 µm grain sizes to a fine-crystalline with 4-12 µm grain sizes with an increasing in thickness from 100 to 600 µm for samples obtained in electrolyte without additives. Coatings with a signified texture (012) are



formed in electrolyte without additives, but with gelatin presence the growth texture changes and the most intense reflex becomes (110). It was found that gelatin concentration increase from 0.1 to 0.5 g/L leads to Bi microstructural refinement from 4-20 µm to 50 nm-2 µm, respectively. The radiation-protection properties of Bi shields with electron irradiated p-MOST with an energy of 1.6-1.8 MeV and exposure doses up to 5 × 1014 cm-2 have shown that with drth values increasing from 1.0 to 2.6 g/cm2, the value of the shielding efficiency Ka rises from 95 to 165. The most optimal, from the point of view of the mass-dimensional parameters, are 1.6 ÷ 2.0 g/cm2 drth values. Bi shields thickness increase to more than 2 g/cm2 does not lead to a significant rising in Ka, which is due to braking radiation contributing to the shield absorbed dose.

ACKNOWLEDGEMENT The work was carried out with financial support of Belarusian Republican Foundation for Fundamental Research (Grant No. T17M-046), in part from the Ministry of Education and Science of the Russian Federation in the framework of Increase Competitiveness Program of NUST «MISiS» among the leading world scientific and educational centres (No. П02-2017-2-4, No. К3-2017-059). In SUSU this work was supported by Act 211 Government of the Russian Federation, contract № 02.A03.21.0011. Additionally the work was partially supported by the Ministry of Education and Science of the Russian Federation (10.9639.2017/8.9).


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TABLE 1 - The electron fluence corresponding to the parametric failure (∆U = 0,05 V) of the pMOST, and the Кe of the Bi shields with different drth. Shield №

Reduced thickness, drth [g/cm2]

Fluence, F [cm-2]

Efficiency coefficient, Кa = F/F0

1

1,0

2,2⋅1014

95

2

1,4

2,7⋅1014

117

3

1,6

3,0⋅1014

130

4

2,0

3,6⋅1014

156

5

2,3

3,8⋅1014

162

6

2,6

3,8⋅1014

165



Figure 1. The testing scheme of radiation shields based on Bi with test p-MOST.


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35000

¹ 4

(110) 30000

Intensity [a.u.]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


b

Bi+gelatin

25000 20000

(220)

1500

(122)

1000

(202)

500

(312)

0 25 30

40

50

60

70

80

90

100

2 Θ [deg.] Figure 2. XRD spectra of the 1st series samples (a) and 2nd series (b).



Figure 3. The mechanism of gelatin additive interaction with the bismuth surface.


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а

b

c

Figure 4. SEM-images of the 1st series samples surface with Bi thickness 100 µm (a), 300 µm (b) and 600 µm (c), obtained from perchlorate electrolyte without additives.



Figure 5. Cross-sectional SEM image of 100 µm Bi coating with technological sublayers.


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Figure 6. SEM-images of the 2nd series samples surface, obtained in perchlorate electrolyte with different gelatin concentration: 0.1 g/L (a), 0.2 g/L (b), 0.3 g/L (c), 0.4 g/L (d), 0.5 g/L (e); (f) – adsorbed gelatin on the Bi surface – insert from image (c).



Figure 7. Threshold voltage changing ∆U under electron irradiation of p-MOST without shield (a) and with Bi shields with different drth (b).


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Table of Contents/Abstract Graphics


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The testing scheme of radiation shields based on Bi coatings 588x276mm (72 x 72 DPI)


Effect of the Synthesis Conditions and Microstructure for Highly

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