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Article

Characterization of ZrBSiTaNx Films

by
Kuo-Hong Yeh
1,
Li-Chun Chang
2,3 and
Yung-I Chen
1,*
1
Department of Optoelectronics and Materials Technology, National Taiwan Ocean University, Keelung 202301, Taiwan
2
Department of Materials Engineering, Ming Chi University of Technology, New Taipei 243303, Taiwan
3
Center for Plasma and Thin Film Technologies, Ming Chi University of Technology, New Taipei 243303, Taiwan
*
Author to whom correspondence should be addressed.
Coatings 2024, 14(4), 487; https://doi.org/10.3390/coatings14040487
Submission received: 25 March 2024 / Revised: 12 April 2024 / Accepted: 14 April 2024 / Published: 15 April 2024
(This article belongs to the Special Issue Multilayer and Functional Graded Coatings—2nd Edition)
Browse Figures
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Abstract

:
In this study, ZrBSiTa and (ZrBSiTa)Nx films were deposited on silicon wafers through direct current magnetron cosputtering. The nitrogen flow ratio (RN2) of the reactive gas and the sputter power applied to the Si target (PSi) were the variables in the fabricating processes. The influence of the N and Si contents on the mechanical properties, thermal stability, and oxidation behavior of the ZrBSiTa and (ZrBSiTa)Nx films were investigated. All the as-fabricated films exhibited amorphous structures. The RN2 set at 0.1, 0.2, and 0.4 caused the ZrBSiTaNx films to exhibit high N contents of 52–55, 62–64, and 63–64 at.%, respectively. The Si content of the ZrBSiTa films increased from 0 to 42 at.% as PSi increased from 0 to 150 W, and this was accompanied by decreases in hardness and Young’s modulus values from 19.1 to 14.3 GPa and 264 to 242 GPa, respectively. In contrast, the increase in Si content of the (ZrBSiTa)Nx films from 0 to 21 at.% increased the hardness from 11.5 to 14.0 GPa, and Young’s modulus from 207 to 218 GPa. Amorphous BN and SiNx phases in the (ZrBSiTa)Nx films varied the structural and mechanical properties. The thermal stability of the (ZrBSiTa)Nx films was evaluated by annealing at 800–900 °C for 10–30 min in Ar. The oxidation behavior of the (ZrBSiTa)Nx films was evaluated in the ambient air at 800 °C for 0.5–24 h. The amorphous (ZrBSiTa)Nx films with a high Si content had high thermal stability and oxidation resistance.

1. Introduction

Si-contained amorphous and nanocomposite transition metal (TM) nitride films have been developed due to their outstanding antioxidative [1,2,3,4] and anticorrosive properties [5,6,7,8]. One of the vital characteristics of amorphous materials is the lack of grain boundary. Grain boundaries with high defect density provide diffusion paths for elements in crystalline materials, whereas the lack of grain boundaries for amorphous structures improve the diffusion resistance of protective coatings [9,10,11]. Amorphous nitride thin films have been utilized as diffusion barriers in microelectronics [12,13,14], and oxidation-resistant coatings for protective purposes at elevated temperatures [11,15,16,17,18]. The thermal stability of amorphous material in inert gas is crucial in applications such as diffusion barriers. Doping of Si or B into TM nitrides stabilizes the amorphous or nanocomposite structures [19,20,21]. Musil et al. [16] reported that ZrSiN films with a Si content > 25 at.% formed a stable amorphous structure when annealed at >1000 °C. The formation of non-volatile silicon oxide (SiOx) improves the antioxidative properties of TM–Si–N films at elevated temperatures [11,17,18]. However, the mechanical properties of TM–Si–N films decline with increasing Si content because of a high volume ratio of the amorphous phase. TM boride thin films have been developed to replace TM nitride thin films in various applications [22,23,24,25]. Bakhit et al. [26] stated that Zr1−xTaxBy thin films had a hardness of 42 GPa and Young’s modulus of 504 GPa. However, TM diborides are inherently hard but brittle, accompanied by crack formation during deformation [27]. Moreover, BN tends to form amorphous structures, as reported in sputtered Ti–B–N [28], Cr–B–N [29], and Zr–B–N [30] films. Combining the characteristics of TM–Si–N and TM–B–N films applied as protective coatings is essential. In this study, we fabricated ZrBSiTa and (ZrBSiTa)Nx films through direct current (DC) magnetron cosputtering using ZrB2, Ta, and Si targets. The mechanical properties, thermal stability, and oxidation behavior of ZrBSiTa and (ZrBSiTa)Nx films were investigated.

2. Materials and Methods

ZrBSiTa and (ZrBSiTa)Nx films were fabricated on silicon wafers through cosputtering. The cosputtering apparatus has been described in a previous study [31]. The target-substrate distance was 90 mm. The substrate holder, without heating, was rotated at 30 rpm. The DC powers applied to the ZrB2 and Ta targets were fixed at 100 and 50 W, respectively, whereas the DC power on the Si target (PSi) varied from 0 to 50, 100, and 150 W. All the targets were 50.8 mm in diameter. The total flow rate of N2 and Ar was 20 sccm, and the nitrogen flow ratio [RN2 = N2/(N2 + Ar)] was set at 0, 0.1, 0.2, and 0.4 for fabricating various batches of A, B, C, and D samples, respectively. The thermal stability test was performed at 800 and 900 °C for 10–30 min under purged Ar gas in a rapid thermal annealing (RTA, eRTP50, Giant-Tek, Miaoli, Taiwan) furnace with a ramping speed of 10 °C/s. Moreover, the oxidation behavior was evaluated after (ZrBSiTa)Nx samples were annealed at 800 °C in the air for 0.5–12 h.
The chemical compositions of the ZrBSiTa and (ZrBSiTa)Nx films were analyzed using a field-emission electron probe microanalyzer (FE-EPMA, JXA-iHP200F, JEOL, Akishima, Japan) at a 12-kV accelerating voltage on the surface. The bonding characteristics of films were analyzed using an X-ray photoelectron spectroscope (XPS, PHI 5000 Versaprobe II, ULVAC–PHI, Kanagawa, Japan) with a monochromatic Al Kα X-ray beam operated at 15 kV. The C 1s line from the carbon contamination on the free surface of a Zr10B9Ta18N63 sample was 284.33 eV. The XPS spectra of Zr 3d, B 1s, Si 2p, Ta 4f, and N 1s core levels were recorded. The splitting energies were 2.43 and 1.91 eV for Zr 3d and Ta 4f doublets [32], respectively. The intensity ratios of I(3d5/2):I(3d3/2) and I(4f7/2):I(4f5/2) were set as 3:2 and 4:3 for the Zr and Ta doublets, respectively. An Ar+ ion beam of 3 keV was used to sputter the films for depth profiling; the sputter etching rate was 8.2 nm/min for SiO2. XPS analyses were conducted at depths of 8.2, 16.4, 24.6, 32.8, 41.0, and 49.2 nm. The backgrounds were corrected via a Shirley function, and the peaks were fitted with a mixed Gaussian–Lorentzain function. The phases of the films were verified using X-ray diffraction (XRD; X’Pert PRO MPD, PANalytical, Almelo, The Netherlands) with Cu Kα radiation using a grazing incidence technique at an incidence angle of 1°. The applied accelerating voltage and current of XRD were 45 kV and 40 mA, respectively. The nanostructures of the films with a protective C layer were observed using transmission electron microscopy (TEM, JEM-2010E, JEOL, Akishima, Japan). The mechanical properties of the films were measured using a nanoindentation tester (TI-900 Triboindenter, Hysitron, Minneapolis, MN, USA) equipped with a Berkovich diamond probe tip and calculated using the Oliver–Pharr method [33]. The indentation depth was 80 nm. The residual stress on the films was determined using the curvature method [34,35].

3. Results

3.1. Chemical Compositions and Phase Structures of ZrBSiTa and (ZrBSiTa)Nx Films

Table 1 lists the chemical compositions of as-deposited ZrBSiTa and (ZrBSiTa)Nx films. The Si content revealed an increasing trend with increasing PSi. In contrast, the Zr, B, and Ta contents demonstrated a decreasing trend with increasing PSi for each batch sample, which implied that the sputtering yield of these sputter guns in the cosputtering apparatus was independent. The N content of batch B films decreased from 59.4 at.% to 54.5, 54.6, and 51.4 at.% as increasing PSi from 0 to 50, 100, and 150 W, whereas the N content of the batch C and D samples remained constant at 61.4–64.6 and 63.0–63.5 at.%, respectively. For example, the batch D samples exhibited chemical compositions of Zr10B9Ta18N63, Zr7B6Si10Ta13N64, Zr5B6Si17Ta9N63, and Zr4B4Si21Ta8N63 when the applied PSi was 0, 50, 100, and 150 W, respectively, which were accompanied by a deposition rate increasing from 4.7 to 5.7, 6.9, and 8.1 nm/min, respectively. The stoichiometric ratio (x) was higher than 1 for all the (ZrBSiTa)Nx films. However, in a previous study [36], the value of x was less than 0.5 for (NbTaMoW)Nx films, even for the sample fabricated under a high RN2 value of 0.4. This variation was attributed to the evident difference in affinity between N and the other elements. Mo2N and W2N are the preferentially formed Mo–N and W–N compounds during sputtering. The standard formation enthalpies for BN, TaN, ZrN, Si3N4, TaB2, and ZrB2 at 298 K are −254.4, −252.3, −365.3, −744.8, −209.2, and −322.6 kJ/mol [37], respectively. N should preferentially bond to Zr and then bond to B, Ta, and Si, whereas B should preferentially bond to N, Zr, and Ta. Moreover, the ZrN, BN, and TaN had a stoichiometric ratio of 1, whereas the x value is 1.33 for Si3N4. Therefore, the x values were >1 for all the (ZrBSiTa)Nx films. ZrBy, as well as TiBy [38], tended to form overstoichiometric diboride thin films through sputtering [26]. In our previous study [39], a ZrB2.5 (28.4% Zr–70.5% B–1.1% O) film was fabricated using a ZrB2 target. However, all the ZrBSiTa and (ZrBSiTa)Nx films had understoichiometric B/Zr ratios of 0.9–1.6, which could be attributed to scattering and resputtering of light B atoms during cosputtering [26].
Table 2 lists the thicknesses and deposition rates of the fabricated ZrBSiTa and (ZrBSiTa)Nx films. The deposition rate increased with the increasing PSi level for all the films. The deposition rate decreased with increasing RN2, which was attributed to the target poisoning effect [40] and the low sputtering efficiency of N correlated to that of Ar ions [41,42]. For example, the deposition rates for the Zr10B11Ta19N60 (B1), Zr9B12Ta14N65 (C1), and Zr10B9Ta18N63 (D1) samples decreased from 10.7 to 6.6 and 4.7 nm/min as RN2 increased from 0.1 to 0.2 and 0.4. Figure 1 displays the GIXRD patterns of the as-fabricated ZrBSiTa and (ZrBSiTa)Nx Films. The broad peaks observed at 2θ of 36–38° for ZrBSiTa films and at 2θ of 34° for (ZrBSiTa)Nx films indicated that all the as-fabricated ZrBSiTa and (ZrBSiTa)Nx films formed amorphous structures. In our previous study [43], TaZrN films crystallized into a face-centered cubic phase and revealed a columnar structure. The addition of B and Si into TaZrN films affected the phase structures. Multicomponent alloys could form distinct structures (solid solution, intermediate phase, and bulk metallic glasses) depending on their atomic size difference (δ), mixing enthalpy (ΔHmix), and mixing entropy (ΔSmix) [44]. Multicomponent bulk metallic glasses have larger δ (6%–18%) and more negative ΔHmix (−25–−37 kJ/mol) [44]. The batch A (ZrBSiTa) samples exhibited high δ values of 24.0%, 22.6%, 24.2%, and 19.6%, significant and negative ΔHmix values of −48, −58, −65, and −66 kJ/mol, and medium mixing entropy values of 8.6, 10.7, 11.3, and 10.7 J/K.mol for Zr21B30Ta49 (A1), Zr20B24Si13Ta43 (A2), Zr18B29Si21Ta32 (A3), and Zr15B15Si42Ta28 (A4), respectively, which resulted in forming amorphous structures. Moreover, sputtered BN [28,29] and SiNx films tended to be amorphous, which resulted in the formation of amorphous structures for the (ZrBSiTa)Nx films.
Figure 2 displays the XPS spectra and curve fitting of Zr 3d, B 1s, Si 2p, and Ta 4f for the batch A samples at a sputter depth of 49.2 nm. The XPS analysis results of batch A samples at sputter depths of 16.4–49.2 nm are listed in Table 3. The binding energies of Zr 3d5/2 at 178.49–178.70 eV were recognized as Zr–B bonds in a ZrB2 compound. The B 1s signals were determined at 187.01–187.33 eV, identified as B–Zr bonds. The reported Zr 3d5/2 and B 1s binding energies for an epitaxial ZrB2 film were 178.9 and 187.9 eV [45], respectively. The binding energy of Si–Si bonds was 98.43–98.77 eV. The binding energy of Ta 4f7/2 for the Ta–Ta bonds was 21.88–22.08 eV, comparable to metallic Ta at 21.9 eV [32]. The Zr 3d5/2 was also reported to be 178.8 eV in ZrSi2 [46]. However, the standard formation enthalpy of ZrSi2 at 298 K is −159.4 kJ/mol [32], which is lower than that of ZrB2. ZrSi2 should be not the preferentially formed compound.
Figure 3 displays the XPS spectra of Zr 3d, B 1s, Si 2p, Ta 4f, and N 1s core levels for batch D films at a depth of 49.2 nm. Table 4 lists the XPS analysis results of the batch D samples at sputter depths of 16.4–49.2 nm. Figure 3a shows the curve fitting of the Zr profiles, which were split into two 3d doublets, representing Zr–N bonds for ZrN and Zr3N4 components. The average Zr 3d5/2 values at sputter depths of 16.4–49.2 nm were 179.60–180.52 and 180.84–181.46 eV, respectively. The B 1s signals of 189.74–190.44 eV were identified as B–N bonds comparable with reported values of 190.3 eV [28,47]. The Si signals of the Zr7B6Si10Ta13N64, Zr5B6Si17Ta9N63, and Zr4B4Si21Ta8N63 films comprised two components whose binding energies were 99.02–99.34 and 101.15–101.28 eV for the Si–Si and Si–N bonds, respectively. Previous studies [32,48,49] have reported Si 2p signals at 99.2, 101.80, 102.60, and 103–103.50 eV to be Si–Si, Si–N, Si–N–O, and Si–O bonds, respectively. Therefore, only Si–N and Si–Si bonds were detected for the batch D films. Figure 3d shows the Ta signals, split into two 4f doublets, representing Ta–N bonds for TaN and Ta3N5. The Ta 4f7/2 signals were determined at 22.56–22.95 and 23.89–24.38 eV for TaN and Ta3N5, respectively, which were comparable with reported 22.2–23.0 [50,51] and 24.2 [52] eV. All the aforementioned binding energies of the Zr10B9Ta18N63 (D1) sample were lower than those of the Zr7B6Si10Ta13N64, Zr5B6Si17Ta9N63, and Zr4B4Si21Ta8N63 samples, which could be attributed to a charge effect for the Si-containing films with high resistivity.

3.2. Mechanical Properties

Table 5 lists the mechanical properties of the ZrBSiTa and (ZrBSiTa)Nx films. The ZrBSiTa films with a Si content of 0–21 at.% maintained a hardness (H) of 18.4–19.1 GPa, elastic modulus (E) of 256–264 GPa, and elastic recovery (We) of 31%–34%, whereas the A4 sample with a high Si content of 42 at.% exhibited a lower H value of 14.3 GPa, E value of 242 GPa, and We value of 18%. Adding N into the ZrBSiTa matrix did not enhance the mechanical properties. For most transition metal nitride with crystalline structures, their mechanical properties were higher than corresponding metallic films due to the variation in bonding structures. SiNx and BN tended to form amorphous structures fabricated through sputtering processes; therefore, the (ZrBSiTa)Nx films exhibited amorphous structures and had low mechanical properties. The increase in Si content of the (ZrBSiTa)Nx films increased the mechanical properties, which were accompanied by increased residual stresses. For example, the H of batch C samples increased from 11.0 to 12.3, 14.0, and 15.0 GPa as the compressive residual stress increased from 0.61 to 0.81, 0.87, and 1.09 GPa. Residual stress was recognized as a minor effect on the mechanical properties of crystalline films, in which crystalline size and phase structure were the major factors. In contrast, residual stress dominated the mechanical properties of amorphous films. Figure 4 exhibits the relationship between H and residual stress of the ZrBSiTa and (ZrBSiTa)Nx films. Linear fitting lines for each batch sample are shown in this figure. The hardness values decreased with the increasing N content in the films. The batches C and D samples exhibited a similar N content of 62–65 at.%, and their hardness–stress fitting lines were almost overlapped.

3.3. Thermal Stability of ZrBSiTa and ZrBSiTaN Films

The thermal stability tests were performed at 800 and 900 °C within purged Ar gas in an RTA furnace. Figure 5 shows the GIXRD patterns of the ZrBSiTa films after 10 min annealing at 800 °C, which exhibits the formation of tetragonal ZrO2 (t-ZrO2) (ICDD 00-042-1164); monoclinic ZrO2 (m-ZrO2) (ICDD 00-037-1484); and orthorhombic Ta2O5 (ICDD 00-025-0922) phases for the annealed Zr21B30Ta49 (A1), Zr20B24Si13Ta43 (A2), and Zr18B29Si21Ta32 (A3) films. A TaSi2 (ICDD 00-038-0483) phase was observed for the annealed Zr15B15Si42Ta28 (A4) film with a high Si content. The O originated from the residual contamination in the chamber. The SiO2 and B2O3 which was possibly present should be amorphous and not shown in these XRD patterns. The aforementioned four ZrBSiTa films were annealed at the same time, which implied that Zr15B15Si42Ta28 had higher oxidation resistance among the ZrBSiTa films. In contrast, all the (ZrBSiTa)Nx films maintained an amorphous phase in their GIXRD patterns after 10 min annealing at 800 °C. After extending the annealing time to 20 and 30 min, all the (ZrBSiTa)Nx films were amorphous except for the Zr9B12Ta14N65 (C1) and Zr10B9Ta18N63 (D1) films. The C1 and D1 samples exhibited ZrO2 and Ta2O5 phases after 30 and 20 min annealing, respectively. Table 6 lists the XRD analysis results of the ZrBSiTa and (ZrBSiTa)Nx films annealed at 800 and 900 °C in Ar gas.
The oxidation and crystallization of the Zr10B11Ta19N60 (B1) and Zr9B11Si11Ta15N54 (B2) films occurred after 10 min annealing at 900 °C. In contrast, crystallization reflections became evident for the Zr7B9Si17Ta12N55 (B3) films after 20 min annealing, and the Zr6B9Si22Ta11N52 (B4) films maintained an amorphous phase after annealing for up to 30 min, as Figure 6a shows. The oxide phases of the (ZrBSiTa)Nx films comprised m-ZrO2, t-ZrO2, and Ta2O5. The oxidation and crystallization of the Zr9B12Ta14N65 (C1) and Zr7B8Si9Ta12N64 (C2) films occurred after 10 min annealing at 900 °C. In contrast, crystallization reflections became evident for the Zr5B7Si14Ta10N64 (C3) films after 30 min annealing, and the Zr4B6Si20Ta8N62 (C4) films maintained an amorphous phase after annealing for up to 30 min. The oxidation and crystallization of the Zr10B9Ta18N63 (D1) films occurred after 10 min annealing at 900 °C, whereas the Zr7B6Si10Ta13N64 (D2), Zr5B6Si17Ta9N63 (D3), and Zr4B4Si21Ta8N63 (D4) films maintained an amorphous phase after annealing for up to 30 min. Figure 6b,c display the GIXRD patterns of the 900 °C and 30 min annealed batches C and D samples, respectively.
Figure 7a shows a cross-sectional TEM (XTEM) image of the Zr10B9Ta18N63 (D1) film after 30 min annealing at 900 °C in Ar. The Zr10B9Ta18N63 film detached from the Si substrate after annealing. The original Zr10B9Ta18N63 film/Si substrate interface exposed the underlying carbon film on the TEM sample holder. Figure 7b displays the selected area electron diffraction (SAED) pattern of the annealed Zr10B9Ta18N63 sample revealing ring patterns of the Ta2O5, m-ZrO2, and t-ZrO2 phases. Figure 7c displays a high-resolution TEM (HRTEM) image of the annealed Zr10B9Ta18N63 film, which depicts lattice fringes correlating to d-spacing values of 0.308, 0.389, 0.364, and 0.283 nm for Ta2O5 (200), Ta2O5 (001), m-ZrO2 (011), and m-ZrO2 (111) planes, respectively. The lattice fringes with a d-spacing of 0.315 nm could represent either Ta2O5 (1 11 0) or m-ZrO2 (−111) planes. Figure 8a shows the XTEM image of the Zr4B4Si21Ta8N63 (D4) film after 30 min annealing at 900 °C in Ar. The Zr4B4Si21Ta8N63 film was detached from the Si substrate. Figure 8b shows an amorphous SAED pattern. The HRTEM image observes no crystalline lattice fringes (Figure 8c). The Zr4B4Si21Ta8N63 film maintained an amorphous phase for up to 30 min as annealed at 900 °C.

3.4. Oxidation Behavior of (ZrBSiTa)Nx Films

The (ZrBSiTa)Nx samples were annealed at 800 °C in air for 0.5, 1, 2, and 12 h. Figure 9 shows the GIXRD patterns of the batch B films after annealing at 800 °C in air. The t-ZrO2, m-ZrO2, and Ta2O5 phases formed for the annealed Zr10B11Ta19N60 (B1) sample, whereas the Zr9B11Si11Ta15N54 (B2), Zr7B9Si17Ta12N55 (B3), and Zr6B9Si22Ta11N52 (B4) samples maintained an amorphous phase after annealing for 0.5 h. The one h annealed samples revealed XRD patterns similar to those of the 0.5 h annealed samples. After 2 h annealing, the Zr9B11Si11Ta15N54 sample crystallized, and the Zr7B9Si17Ta12N55 and Zr6B9Si22Ta11N52 samples maintained an amorphous phase. The Zr7B9Si17Ta12N55 and Zr6B9Si22Ta11N52 samples crystallized after 12 h annealing. The oxidation behavior of batches C and D samples was similar to those of the batch B samples. The Si content affected the oxidation resistance of (ZrBSiTa)Nx films. The B1, C1, and D1 samples without Si content oxidized after 0.5 h annealing at 800 °C, whereas the B2, C2, and D2 samples with Si contents of 9–11 at.% oxidized after 2 h annealing. The B3, C3, D3, B4, C4, and D4 samples with Si contents of 14–22 at.% maintained an amorphous phase after 2 h annealing. In this study, B and Si in the (ZrBSiTa)Nx films stabilized the amorphous phase. However, the oxidation resistance of (ZrBSiTa)Nx films was determined by the amorphous Si3N4 content, which was comparable with the oxidation behavior of ZrSiN films with a high Si content (≥25 at.%) [16].
Figure 10a depicts an XTEM image of the Zr4B4Si21Ta8N63 (D4) film after 12 h annealing at 800 °C in the air. An oxide scale of 531 nm (zone A) was observed, and the SAED pattern (Figure 10b) indicated that this scale was crystalline and consisted of t-ZrO2 and Ta2O5 phases. Beneath the oxide scale, zone B of the annealed Zr4B4Si21Ta8N63 film exhibited a dense structure, and its SAED pattern showed an amorphous phase (Figure 10c). Figure 10d shows an HRTEM image of the surface oxide scale, and lattice fringes identified for tetragonal ZrO2 (101) and orthorhombic Ta2O5 (001) planes are indicated. Figure 10e depicts the EDS analysis of the annealed Zr4B4Si21Ta8N63 film, which suggests that the Zr4B4Si21Ta8N63 film is partially oxidized. Zone A was oxide-dominant, and zone B was amorphous nitride-dominant after 12 h annealing at 800 °C in the air.
Figure 11a displays an XTEM image of the Zr4B4Si21Ta8N63 film after 24 h annealing at 800 °C in the air. The oxide scale (zone A) expanded relative to that of the 12 h annealed Zr4B4Si21Ta8N63 film. The SAED patterns of regions I, II, and III indicated in Figure 11a are shown in Figure 11b–d, respectively. Region I, the outermost part of the oxide scale, exhibits diffraction rings of m-ZrO2, t-ZrO2, and Ta2O5 phases. In contrast, the inner part of the oxide scale (Region II) and the unoxidized film (Region III) are amorphous. Figure 11e shows an HRTEM image of region I displaying crystalline lattice fringes. Figure 11f displays the EDS analysis results of the 24 h annealed Zr4B4Si21Ta8N63 sample.

4. Conclusions

This study fabricated ZrBSiTa and (ZrBSiTa)Nx films through cosputtering. The main findings of this study are as follows:
(1)
All the as-fabricated ZrBSiTa and (ZrBSiTa)Nx films exhibited amorphous structures due to incorporating B and Si. The overstoichiometric ratio (x > 1) was obtained for the (ZrBSiTa)Nx films.
(2)
The as-fabricated ZrBSiTa films exhibited hardness values of 14.3–19.1 GPa and Young’s modulus values of 242–264 GPa. The hardness and Young’s modulus values of the (ZrBSiTa)Nx thin films decreased to 11.0–15.0 and 181–223 GPa, respectively.
(3)
The amorphous (ZrBSiTa)Nx films with high Si contents exhibited high thermal stability when annealed at 800 and 900 °C for up to 30 min in an Ar-purged atmosphere.
(4)
The Si content dominated the oxidation resistance of (ZrBSiTa)Nx films. The (ZrBSiTa)Nx films with Si contents of 14–22 at.% maintained an amorphous phase after 2 h annealing at 800 °C in air. The lower part of the Zr4B4Si21Ta8N63 film held amorphous nitride after extending the annealing time to 24 h.

Author Contributions

Conceptualization, Y.-I.C.; validation, L.-C.C.; formal analysis, K.-H.Y.; investigation, K.-H.Y.; resources, L.-C.C. and Y.-I.C.; supervision, Y.-I.C.; project administration, Y.-I.C.; funding acquisition, L.-C.C. and Y.-I.C. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Science and Technology Council, Taiwan, grant numbers 112-2221-E-019-014-MY3, 111-2221-E-019-064, and 111-2221-E-131-028. The APC was funded by National Taiwan Ocean University.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data are contained within the article.

Acknowledgments

The analysis support from the Instrumentation Center at the National Tsing Hua University for the EPMA and XPS characterizations is acknowledged. The analysis support from the Joint Center for High Valued Instruments at NSYSU for the FIB (EM025100) is acknowledged.

Conflicts of Interest

The authors declare no conflicts of interest.

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Figure 1. GIXRD patterns of the as-fabricated (a) ZrBSiTa and (ZrBSiTa)Nx films prepared at RN2 of (b) 0.1, (c) 0.2, and (d) 0.4, respectively.
Figure 1. GIXRD patterns of the as-fabricated (a) ZrBSiTa and (ZrBSiTa)Nx films prepared at RN2 of (b) 0.1, (c) 0.2, and (d) 0.4, respectively.
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Figure 2. XPS patterns of (a) Zr 3d and B 1s, (b) Si 2p, and (c) Ta 4f signals of the as-deposited A1 (Zr21B30Ta49), A2 (Zr20B24Si13Ta43), A3 (Zr18B29Si21Ta32), and A4 (Zr15B15Si42Ta28) samples at a sputter depth of 49.2 nm.
Figure 2. XPS patterns of (a) Zr 3d and B 1s, (b) Si 2p, and (c) Ta 4f signals of the as-deposited A1 (Zr21B30Ta49), A2 (Zr20B24Si13Ta43), A3 (Zr18B29Si21Ta32), and A4 (Zr15B15Si42Ta28) samples at a sputter depth of 49.2 nm.
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Figure 3. XPS patterns of (a) Zr 3d, (b) B 1s, (c) Si 2p, (d)Ta 4f, and (e) N 1s signals of the as-deposited D1 (Zr10B9Ta18N63), D2 (Zr7B6Si10Ta13N64), D3 (Zr5B6Si17Ta9N63), and D4 (Zr4B4Si21Ta8N63) samples at a depth of 49.2 nm.
Figure 3. XPS patterns of (a) Zr 3d, (b) B 1s, (c) Si 2p, (d)Ta 4f, and (e) N 1s signals of the as-deposited D1 (Zr10B9Ta18N63), D2 (Zr7B6Si10Ta13N64), D3 (Zr5B6Si17Ta9N63), and D4 (Zr4B4Si21Ta8N63) samples at a depth of 49.2 nm.
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Figure 4. Relationship between hardness and residual stress of ZrBSiTa and (ZrBSiTa)Nx films.
Figure 4. Relationship between hardness and residual stress of ZrBSiTa and (ZrBSiTa)Nx films.
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Figure 5. GIXRD patterns of ZrBSiTa films, Zr21B30Ta49 (A1), Zr20B24Si13Ta43 (A2), Zr18B29Si21Ta32 (A3), and Zr15B15Si42Ta28 (A4), after annealing in Ar at 800 °C for 10 min.
Figure 5. GIXRD patterns of ZrBSiTa films, Zr21B30Ta49 (A1), Zr20B24Si13Ta43 (A2), Zr18B29Si21Ta32 (A3), and Zr15B15Si42Ta28 (A4), after annealing in Ar at 800 °C for 10 min.
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Figure 6. GIXRD patterns of (a) batch B, (b) batch C, and (c) batch D films after annealing in Ar at 900 °C for 30 min.
Figure 6. GIXRD patterns of (a) batch B, (b) batch C, and (c) batch D films after annealing in Ar at 900 °C for 30 min.
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Figure 7. (a) XTEM image and (b) SAED pattern of the Zr10B9Ta18N63 film after 30 min annealing at 900 °C in Ar, (c) HRTEM image of the area shown in (a).
Figure 7. (a) XTEM image and (b) SAED pattern of the Zr10B9Ta18N63 film after 30 min annealing at 900 °C in Ar, (c) HRTEM image of the area shown in (a).
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Figure 8. (a) XTEM image and (b) SAED pattern of the Zr4B4Si21Ta8N63 film after 30 min annealing at 900 °C in Ar, (c) HRTEM image of the area shown in (a).
Figure 8. (a) XTEM image and (b) SAED pattern of the Zr4B4Si21Ta8N63 film after 30 min annealing at 900 °C in Ar, (c) HRTEM image of the area shown in (a).
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Figure 9. GIXRD patterns of the batch B films, Zr10B11Ta19N60 (B1), Zr9B11Si11Ta15N54 (B2), Zr7B9Si17Ta12N55 (B3), and Zr6B9Si22Ta11N52 (B4), after annealing at 800 °C in the air for (a) 0.5, (b) 1, (c) 2, and (d) 12 h.
Figure 9. GIXRD patterns of the batch B films, Zr10B11Ta19N60 (B1), Zr9B11Si11Ta15N54 (B2), Zr7B9Si17Ta12N55 (B3), and Zr6B9Si22Ta11N52 (B4), after annealing at 800 °C in the air for (a) 0.5, (b) 1, (c) 2, and (d) 12 h.
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Figure 10. (a) XTEM image, (b) and (c) SAED patterns, and (e) EDS analysis of the Zr4B4Si21Ta8N63 film after 12 h annealing at 800 °C in the air, (d) HRTEM image of the area shown in (a).
Figure 10. (a) XTEM image, (b) and (c) SAED patterns, and (e) EDS analysis of the Zr4B4Si21Ta8N63 film after 12 h annealing at 800 °C in the air, (d) HRTEM image of the area shown in (a).
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Figure 11. (a) XTEM image, (b–d) SAED patterns, and (f) EDS analysis of the Zr4B4Si21Ta8N63 film after 24 h annealing at 800 °C in the air, (e) HRTEM image of the area shown in (a).
Figure 11. (a) XTEM image, (b–d) SAED patterns, and (f) EDS analysis of the Zr4B4Si21Ta8N63 film after 24 h annealing at 800 °C in the air, (e) HRTEM image of the area shown in (a).
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Table 1. Chemical compositions of ZrBSiTa and (ZrBSiTa)Nx films.
Table 1. Chemical compositions of ZrBSiTa and (ZrBSiTa)Nx films.
SamplePower PSi (W)RN2 aChemical Composition (at.%)
ZrBSiTaNO
A1 Zr21B30Ta490020.9 ± 0.429.3 ± 0.3–48.6 ± 0.7–1.2 ± 0.9
A2 Zr20B24Si13Ta4350019.1 ± 0.424.1 ± 0.412.9 ± 0.142.8 ± 0.2–1.1 ± 0.2
A3 Zr18B29Si21Ta32100017.7 ± 0.128.8 ± 0.320.7 ± 0.231.0 ± 0.4–1.8 ± 0.1
A4 Zr15B15Si42Ta28150014.5 ± 0.115.0 ± 0.041.4 ± 0.326.9 ± 0.4–2.2 ± 0.1
B1 Zr10B11Ta19N6000.110.3 ± 0.211.3 ± 0.2–18.7 ± 0.459.4 ± 0.30.3 ± 0.5
B2 Zr9B11Si11Ta15N54500.18.7 ± 0.110.9 ± 0.010.6 ± 0.114.8 ± 0.354.5 ± 0.40.5 ± 0.6
B3 Zr7B9Si17Ta12N551000.17.0 ± 0.08.8 ± 0.317.4 ± 0.312.0 ± 0.154.6 ± 0.50.2 ± 0.3
B4 Zr6B9Si22Ta11N521500.16.4 ± 0.08.4 ± 0.322.1 ± 0.411.3 ± 0.251.4 ± 0.50.4 ± 0.1
C1 Zr9B12Ta14N6500.28.8 ± 0.111.9 ± 0.4–14.3 ± 0.464.6 ± 0.90.4 ± 0.4
C2 Zr7B8Si9Ta12N64500.26.5 ± 0.18.0 ± 0.29.2 ± 0.112.4 ± 0.163.4 ± 0.30.5 ± 0.4
C3 Zr5B7Si14Ta10N641000.25.1 ± 0.16.7 ± 0.114.3 ± 0.29.6 ± 0.164.0 ± 0.20.3 ± 0.4
C4 Zr4B6Si20Ta8N621500.24.4 ± 0.16.0 ± 0.119.8 ± 0.17.5 ± 0.161.4 ± 0.20.9 ± 0.1
D1 Zr10B9Ta18N6300.49.4 ± 0.19.1 ± 0.0–18.2 ± 0.163.0 ± 0.30.3 ± 0.4
D2 Zr7B6Si10Ta13N64500.46.8 ± 0.06.2 ± 0.210.3 ± 0.113.0 ± 0.263.5 ± 0.10.2 ± 0.3
D3 Zr5B6Si17Ta9N631000.45.0 ± 0.15.6 ± 0.117.1 ± 0.08.8 ± 0.263.3 ± 0.10.2 ± 0.3
D4 Zr4B4Si21Ta8N631500.44.2 ± 0.14.1 ± 0.220.7 ± 0.17.5 ± 0.163.2 ± 0.20.3 ± 0.1
a RN2: nitrogen flow ratio.
Table 2. Thicknesses and deposition rates of ZrBSiTa and (ZrBSiTa)Nx films.
Table 2. Thicknesses and deposition rates of ZrBSiTa and (ZrBSiTa)Nx films.
SampleThickness (nm)Deposition Time (min)Deposition Rate (nm/min)
A18151206.8
A210731208.9
A39831009.8
A48818011.0
B1160815010.7
B2153012012.8
B3168412014.0
B415369017.1
C111891806.6
C215931808.8
C3137712011.5
C4154712012.9
D17491604.7
D210291805.7
D311671706.9
D412111508.1
Table 3. XPS analysis results of batch A films at sputter depths of 16.4–49.2 nm.
Table 3. XPS analysis results of batch A films at sputter depths of 16.4–49.2 nm.
SampleZr 3d5/2 (eV)B 1s (eV)Si 2p (eV)Ta 4f7/2 (eV)
A1178.52 ± 0.01187.02 ± 0.02—21.93 ± 0.02
A2178.49 ± 0.04187.01 ± 0.0498.43 ± 0.0221.88 ± 0.04
A3178.68 ± 0.07187.23 ± 0.0698.75 ± 0.1622.03 ± 0.04
A4178.70 ± 0.06187.33 ± 0.0398.77 ± 0.0622.08 ± 0.02
Table 4. XPS analysis results of batch D films at sputter depths of 16.4–49.2 nm.
Table 4. XPS analysis results of batch D films at sputter depths of 16.4–49.2 nm.
SampleZr 3d5/2 (eV) B 1s (eV)Si 2p (eV) Ta 4f7/2 (eV)
(ZrN)(Zr3N4) (Si)(Si3N4)(TaN)(Ta3N5)
D1179.60 ± 0.02180.84 ± 0.03189.74 ± 0.04——22.56 ± 0.0223.89 ± 0.03
D2180.06 ± 0.02181.12 ± 0.02190.26 ± 0.0499.02 ± 0.05101.15 ± 0.0522.95 ± 0.0224.34 ± 0.03
D3180.52 ± 0.05181.46 ± 0.03190.44 ± 0.0499.34 ± 0.05101.28 ± 0.0522.91 ± 0.0424.35 ± 0.01
D4180.42 ± 0.02181.46 ± 0.02190.42 ± 0.0699.25 ± 0.07101.28 ± 0.0522.95 ± 0.0324.38 ± 0.02
Table 5. Mechanical properties of ZrBSiTa and (ZrBSiTa)Nx films.
Table 5. Mechanical properties of ZrBSiTa and (ZrBSiTa)Nx films.
SampleH a (GPa)E b (GPa)H/EH3/E2 (GPa)We c (%)σ d (GPa)
A118.5 ± 0.2256 ± 30.0720.09632−0.80 ± 0.15
A219.1 ± 0.3264 ± 70.0720.09934−0.84 ± 0.01
A318.4 ± 0.3261 ± 40.0710.09231−0.54 ± 0.08
A414.3 ± 0.2242 ± 50.0590.05018−0.26 ± 0.05
B113.0 ± 0.1215 ± 60.0610.04844−0.45 ± 0.05
B214.5 ± 0.2221 ± 50.0660.06347–0.60 ± 0.03
B314.9 ± 0.1223 ± 20.0670.06749−0.75 ± 0.23
B414.9 ± 0.3221 ± 40.0670.06852−0.84 ± 0.05
C111.0 ± 0.1181 ± 50.0610.04143−0.61 ± 0.12
C212.3 ± 0.3187 ± 40.0660.05446−0.81 ± 0.08
C314.0 ± 0.2195 ± 30.0720.07249−0.87 ± 0.16
C415.0 ± 0.2197 ± 30.0760.08752−1.09 ± 0.10
D111.5 ± 0.5207 ± 60.0560.03515−0.64 ± 0.03
D212.3 ± 0.4213 ± 40.0580.04119−0.77 ± 0.01
D313.5 ± 0.2219 ± 60.0620.05123−0.92 ± 0.08
D414.1 ± 0.3218 ± 50.0650.05825−0.90 ± 0.12
a H: hardness. b E: elastic modulus. c We: elastic recovery. d σ: residual stress.
Table 6. Phases of the ZrBSiTa and (ZrBSiTa)Nx films annealed at 800 and 900 °C in Ar gas.
Table 6. Phases of the ZrBSiTa and (ZrBSiTa)Nx films annealed at 800 and 900 °C in Ar gas.
SampleAnnealing Time (min)
102030
annealed at 800 °C
A1, A2, A3ZrO2 a + Ta2O5——
A4TaSi2——
B1, B2, B3, B4amorphousamorphousamorphous
C1amorphousamorphousZrO2 + Ta2O5
C2, C3, C4amorphousamorphousamorphous
D1amorphousZrO2 + Ta2O5-
D2, D3, D4amorphousamorphousamorphous
annealed at 900 °C
B1, B2ZrO2 + Ta2O5ZrO2 + Ta2O5ZrO2 + Ta2O5
B3amorphousZrO2 + Ta2O5ZrO2 + Ta2O5
B4amorphousamorphousamorphous
C1, C2ZrO2 + Ta2O5ZrO2 + Ta2O5ZrO2 + Ta2O5
C3amorphousZrO2 + Ta2O5ZrO2 + Ta2O5
C4amorphousamorphousamorphous
D1ZrO2 + Ta2O5ZrO2 + Ta2O5ZrO2 + Ta2O5
D2, D3, D4amorphousamorphousamorphous
a ZrO2: t-ZrO2 + m-ZrO2.
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Yeh, K.-H.; Chang, L.-C.; Chen, Y.-I. Characterization of ZrBSiTaNx Films. Coatings 2024, 14, 487. https://doi.org/10.3390/coatings14040487

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Yeh K-H, Chang L-C, Chen Y-I. Characterization of ZrBSiTaNx Films. Coatings. 2024; 14(4):487. https://doi.org/10.3390/coatings14040487

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Yeh, Kuo-Hong, Li-Chun Chang, and Yung-I Chen. 2024. "Characterization of ZrBSiTaNx Films" Coatings 14, no. 4: 487. https://doi.org/10.3390/coatings14040487

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