Influence of N₂ flow rate on structure and properties of TiBCN films prepared by multi-cathodic arc ion plating and studied with ion beam scattering spectroscopy

Influence of N 2 flow rate on structure and properties of TiBCN films prepared by multi-cathodic arc ion plating and studied with ion beam scattering spectroscopy 1 first-author 1 1 1 2 1 1 corresp Corresponding author. E-mail address: djfu@whu.edu.cn Corresponding author. E-mail address: djfu@whu.edu.cn djfu@whu.edu.cn Key Laboratory of Artificial Micro- and Nano-Materials of Ministry of Education and School of Physics and Technology, Wuhan University, Wuhan 430072, China Key Laboratory of Artificial Micro- and Nano-Materials of Ministry of Education and School of Physics and Technology, Wuhan University, Wuhan 430072, China School of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, China School of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, China TiBCN films were deposited on Si(100) and cemented carbide substrates by using multi-cathodic arc ion plating in C 2 H 2 and N 2 atmosphere. Their structure and mechanical properties were studied systematically under different N 2 flow rates. The results showed that the TiBCN films were adhered well to the substrates. Rutherford backscattering spectroscopy was employed to determine the relative concentration of Ti, B, C and N in the films. The chemical bonding states of the films were explored by X-ray photoelectron spectroscopy, revealing the presence of bonds of TiN, Ti(C,N), BN, pure B, sp 2 C-C and sp 3 C-C, which changed with the N 2 flow rate. TiBCN films contain nanocrystals of TiN/TiCN and TiB 2 /Ti(B,C) embedded in an amorphous matrix consisting of amorphous BN and carbon at N 2 flow rate of up to 250 sccm. TiBCN nanocomposite N 2 flow rate Rutherford backscattering spectroscopy (RBS) X-ray photoelectron spectroscopy 1. Introduction 1 Nitride-based protective films have been extensively studied due to their excellent properties such as high hardness and resistance against wear, erosion, and corrosion. TiBCN is a promising nanocomposite film with good tribological properties, super high hardness, and high resistance to oxidation and corrosion [ 1 1 - 5 5 1-5 ] . It is synthesized by chemical vapor deposition (CVD) [ 1 1 , 2 2 ] , cathodic arc plasma evaporation [ 3 3 ] , thermal plasma CVD [ 4 4 ] , and magnetron sputtering [ 5 5 ] . Depending on deposition conditions, the films of different microstructures, phase contents, morphologies, and grain sizes, can be produced. Multiphase coatings of TiBCN consist of TiN, TiC, TiB 2 , TiB and amorphous BN, C and CN x , etc . By taking advantage of the high hardness phase of TiB 2 and TiC, and the low friction coefficient phase BN and CN x , it is possible to fabricate TiBCN coatings with excellent mechanical properties by adjusting the atomic concentration of Ti, B, C and N. Researchers TiBCN films have been prepared on Si(100) substrate by reactive cathodic arc evaporation from the graphite/ boron-containing composite target and Ti target in N 2 and C 2 H 2 atmosphere. The cathode current of the target influenced composition and structure of the TiBCN films [ 3 3 ] . Shimada et al . studied the composite TiBCN films deposited on WC-Co tools at 800 o C by varying the N 2 flow rate from 0 to 1000 mL/min and found that the N content in TiCN increased with the N 2 flow rate, but TiB 2 content decreased [ 4 4 ] . Lin et al . synthesized Ti-B-C-N nanocomposite films by sputtering compound target containing 80 mol.% TiB 2 and 20 mol.% TiC in Ar/N 2 plasma using a pulsed closed-field unbalanced magnetron sputtering system [ 5 5 ] . They found that when the N content was low (3 at.%), the coating was characterized as a mixture of nano-columnar grains of Ti(B,C) and small volume fractions of amorphous free carbon, BN and CN x , while increasing the N content to 10at.%–13at.%, the N atoms would replace the B sites in Ti(B,C) leading to reduced Ti(B,C) phase and the formation of Ti(C,N), and an increase in the volume fraction of amorphous BN. When N content reached 36 at.%, the hard Ti(B,C) phase diminished completely, accompanied by the formation of a large volume fraction of amorphous BN. Film compositions can be examined by several methods. X-ray photoelectron spectroscopy (XPS) is an efficient tool for determining the type of bonding states involving each element [ 6 6 ] . When the environment of the central atom becomes more electropositive, the peaks shift to lower energy; while it shifts to higher energy if the atom is bound to more electronegative neighbors [ 6 6 ] . XPS provides a relative amount of different phases, such as the carbon-containing phase as a function of the total carbon content [ 7 7 ] . It also provides depth profiles of elements by layer-etching (which takes much time and energy), but it is unable to provide accurate concentration of light elements, whereas they can be detected with Rutherford scattering spectroscopy (RBS), including non-elastic RBS, by using especially MeV protons to do nondestructive depth profiling with better sensitivity, smaller straggling and greater penetrability for light element detection. In this work, TiBCN films were deposited by multi-cathodic arc ion plating at different flow rates of N 2 . The samples were measured by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic field microscopy (AFM), high-resolution transmission electron microscopy (HRTEM), RBS and XPS, to observe the influence of N 2 flow rate. 2. Experimental section 1 All the samples were prepared by cathode ion plasma deposition, which are described in a previous report [ 8 8 ] . The Si (100) and cemented carbide substrates were ultrasonically cleaned by acetone, alcohol and de-ionized water. The sputtering targets were TiB 2 and metal Ti, with a target-sample distance of 100 mm. The chamber was pumped to 1×10 −3 Pa and the deposition substrate was kept at 300℃. The samples were prepared as follows. First, the substrates were cleaned for 30 min by Ar + sputtering at a bias voltage of −800 V before Ti ion etching to smooth the substrate surface. Then, Ti interlayer was deposited to improve adhesion and reduce stress at the coating- substrate interface. Finally, TiBCN films were deposited on the Ti interlayer. The deposition parameters are listed in Table 1 Table 1 . To ascertain the film homogeneity, all the substrates were rotated at a speed of 4 rpm. We note that a low flux of Ar gas could be fed into the chamber to enhance the efficiency of glow discharge during the process of Ti-ion etching. Particularly, C 2 H 2 gas was set at a stable flow rate of 150 sccm at N 2 flow rates of 40–350 sccm during deposition using the TiB 2 target, while the Ti cathode was turned off. Ar gas was fed in to maintain work pressure at 0.59 Pa for depositing TiBCN films. The samples were allowed to cool down to room temperature. 1 1 Deposition step 1 1 Target current (A) 1 1 Bias voltage (V) 1 1 Temperature (℃) 1 1 Deposition time (min) 1 1 Ambient 1 1 Pressure (Pa) 1 1 Ar-ion etching 1 1 0 1 1 −800 1 1 300 1 1 30 1 1 Ar 1 1 2.0 1 1 Ti-ion etching 1 1 70 1 1 −800 1 1 300 1 1 10 1 1 Vacuum 1 1 2×10 −2 1 1 Ti interlayer 1 1 70 1 1 −200 1 1 300 1 1 10 1 1 Vacuum 1 1 2×10 −2 1 1 TiBCN 1 1 60 1 1 −200 1 1 300–350 1 1 30 1 1 C 2 H 2 +N 2 +Ar 1 1 0.59 The samples were measured by X-ray diffraction (XRD, D8 ADVANCE) with Cu Kα ray (λ=0.1541 nm). XPS(, XSAM800 KRATOS) using Al Kα ray (1253.6 eV) was employed to investigate the samples’ binding energy and elemental composition. The microstructure was examined by cross-view high-resolution transmission electron microscopy (HRTEM, JEOL JEM 2010). Field emission scanning electron microscopy (SEM, S4800) was used to measure the cross-section micrograph. The surface topography was probed on an atomic force microscope (AFM, Shimadzu SPM-9500J3) operated in the tapping mode with a probing area of 2 μm×2 μm. The samples were measured by RBS using 1.62 MeV proton beams, with a detection angle of 165° using a planar silicon detector with a resolution of 14 keV at FWHM. 3. Results and Discussion 1 XRD patterns of the TiBCN films grown on Si(100) substrate are shown in Fig.1. Fig.1. The main peak at 40.17° is attributed to hexagonal Ti(101) (JCPDS No. 5-0682) [ 9 9 ] from the interlayer. The peaks at 35.1° and 38.36° are from interlayer Ti(100) and (002) or from TiN 0.3 (100) and (002) in the TiBCN films. The two groups of peaks, which are very close (0.1° apart) to each other, are attributed to Ti and TiN 0.3 , respectively. The attribution to TiN is based on chemical bonding of N-Ti (397.1 eV) and TiN (455.8 eV). The grain size of Ti/TiN crystals is 24.5–32.7 nm, calculated by Scherer formula [ 10 10 ] using the peak (40.17°). Intensity of the main peak increased with the N 2 flow rate up to 250 sccm, where it began to decrease. Above N 2 flow rates of 250 sccm, the grain size was smaller. This can be attributed to the corporation of N 2 into the growing film, which leads to a lower surface mobility [ 11 11 ] . The peak at around 35° can also be ascribed to TiB 2 /Ti(B,C) (100) [ 7 7 ] and supported by Ti(B,C) (188.4 eV) from the following XPS B 1s spectra. Figure 2 Figure 2 shows RBS spectra for the films deposited at N 2 flow rate of 40–350 sccm, with the simulated spectra (solid line) by SIMNAR. The RBS results of Ti, B, C and N concentrations in the samples are given in Table 2 Table 2 . The Ti concentration of TiBCN films, which was separated by subtracting Ti interlayer, almost keeps at 11% with varying N 2 flow rates. The B and C contents decreased with increasing N 2 flow rate from 18.9% to 9.4% and from 65.6% to 48.9%, respectively, while the N content increased with the N 2 flow rate from 3.9% to 29.3%. The atomic stoichiometry and depth profile of the films were obtained by fitting of the RBS data using SIMNRA. In Fig. 2(a) Fig. 2(a) , a small peak at the left side is assigned to B from TiB 2 layer, and the ratio B: Ti is about 2:1. A broad nearby peak (left) of low intensity is attributed to Ti x B y with the ratio of Ti:B ( x : y ) from 9:1 to 8:2, which alludes that the boron atoms diffuse from TiB 2 layer into Ti interlayer, forming a gradient layer. The results are in accordance with the cross-sectional SEM images ( Fig.3 Fig.3 ), which reveal the three layers of TiBCN, TiB 2 -Ti x B y , and Ti interlayer. Actually, high RBS cross-section is only available between 1.62 MeV proton and Ti atom; while the other target atoms have just high non-Rutherford cross-sections, with low resolution of mass difference for B, C and N with respect to incident proton, resulting in serious overlapping signals of these light elements. However, identifiable and prolific light elements in the sample can induce drastic non-Rutherford scattering cross-sections by colliding with incident proton at ~ MeV, which combined with SIMNRA fitting give their relative concentrations. 1 1 Sample No. 1 1 TiBCN-40 1 1 TiBCN-150 1 1 TiBCN-200 1 1 TiBCN-250 1 1 TiBCN-300 1 1 TiBCN-350 1 1 N 2 gas (sccm) 1 1 40 1 1 150 1 1 200 1 1 250 1 1 300 1 1 350 1 1 Ti (at%) 1 1 11.54 1 1 10.80 1 1 11.44 1 1 11.86 1 1 11.74 1 1 11.80 1 1 B (at%) 1 1 18.93 1 1 12.51 1 1 10.55 1 1 10.70 1 1 9.96 1 1 9.40 1 1 C (at%) 1 1 65.63 1 1 56.34 1 1 52.80 1 1 54.56 1 1 48.95 1 1 50.40 1 1 N (at%) 1 1 3.91 1 1 20.30 1 1 25.20 1 1 22.86 1 1 29.33 1 1 28.40 1 1 Average surface roughness, Ra(nm) 1 1   1 1 152.13 1 1 152.50 1 1 145.13 1 1 137.29 1 1 131.06 1 1 Sample thickness (μm) 1 1   1 1 2.20 1 1 2.04 1 1 1.91 1 1 2.10 1 1 1.86 1 1 Average grain size (nm) 1 1   1 1 27.50 1 1 24.50 1 1 30.10 1 1 28.90 1 1 32.70 Figure 3 Figure 3 shows the cross-section SEM image of the TiBCN films. Although the deposition pressure was kept at 0.59 Pa in deposition of all the films, the micro-particle density on the surface is different. The flux of material emitted by either explosion or evaporation is composed of ions, neutral atoms, electrons and micro-droplets of the material. In arc ion plating, metal ions and micro-droplets are the main species responsible for the mass loss of the cathode, and unavoidably the particles would be deposited on the substrates [ 12 12 ] . The number of holes and microparticles reduce with increasing nitrogen pressure up to 300 sccm, which could be attributed to the poison effect of TiB 2 targets surface. During arc evaporation, if successive reactive gas is present in the deposition chamber, then the cathode material can be poisoned by reactive gas resulting in formation TiN, which has a high melting point, covering the target surface. The surface became rougher and exhibited worse morphology with increasing nitrogen pressure up to 350 sccm. This could be attributed to the excessively reactive nitrogen gas weakening the ion bombardment [ 13 13 ] . Cross section SEM of TiBCN-150 demonstrates that there are three layers: Ti interlayer, TiB 2 -Ti x B y , and TiBCN, which are confirmed by the RBS spectra and their fitting. AFM images of the films are illustrated in Fig. 4 Fig. 4 . The root-mean-square (RMS) roughness decreases from 152.1 nm to 131.1 nm with increasing the N 2 flow rate, as summarized in Table 2 Table 2 . Instead of drastic jumps, there are some decreases of RMS roughness associated with larger N 2 fluxes, in agreement with nanocrystal size in the TiBCN films of XRD results. The selective area diffraction (SAD) patterns of Ti interlayer and TiBCN films are shown in Fig. 5. Fig. 5. The SAD pattern of Ti interlayer in Fig. 5(a) Fig. 5(a) was indexed in terms of Ti hexagonal structure, which is consistent with the XRD results, showing the strongest Bragg reflection {101} and weak reflections of {100} and {200}. In the SAD of the TiBCN coating ( Fig. 5b Fig. 5b ), a diffused halo was observed, indicating the amorphous properties of TiBCN films. The high-resolution TEM images of TiBCN films are shown in Fig. 6. Fig. 6. Clearly there are some nanocrystals embedded in the amorphous matrix, corresponding to TiB(211), Ti 0.68 N 0.22 B 0.1 (102), TiB 2 (101), BN (012), and TiN (101) and (200) in Figs. 6(a)–6(d) Figs. 6(a)–6(d) , respectively. The size of the particles is 2–10 nm and the distance between two nanoparticles is about 10 nm. Due to the limited content of nanocrystals embedded into a large fraction of the amorphous phase, it is difficult to find evidence by XRD, though it is clear in HRTEM. XPS spectra of the TiBCN films at different N 2 flow rates are shown in Fig.7. Fig.7. The XPS peaks were de-convoluted to provide further information about the films. Gaussian fitting was performed to evaluate the contribution of various factors in the spectra, and the fitted curves are shown in color lines. The Gaussian curves contributing to the fitting are represented by a dashed line. The B 1s spectrum of TiB 2 in Fig. 7(a) Fig. 7(a) is ascribed to two peaks which correspond to TiB 2 (187.59 eV) [ 14 14 ] and B 2 O 3 (192.6 eV), respectively. The B 1s of TiBCN-40 shows three peaks at 188.4, 189.7 and 191.6 eV, corresponding to Ti (B,C), BN and BNO, respectively. The peak at 188.4 eV indicates that the environment around the boron atom in the TiB 2 structure is modified with increasing C content [ 15 15 ] . BN is amorphous in nature, as proved by XRD. In the Ti 2p spectrum of TiB 2 ( Fig.7b Fig.7b ), the peaks at around 454.3, 455.2, 457.6 and 458.7 eV are attributed to TiB 2 [ 14 14 ] , TiO, Ti 2 O 3 [ 16 16 ] and TiO 2 [ 17 17 ] , respectively. In the Ti 2p spectrum of TiBCN-40, the peaks at 454.9, 455.8 and 458.9 eV are of TiC [ 5 5 , 18 18 ] , TiN [ 19 19 ] andTiO 2 . After the Gaussian fitting, C 1s line is decomposed into two peaks which arise due to sp 2 C-C (284.5 eV) [ 15 15 , 21 21 ] and sp 3 C-C (285.4 eV) [ 22 22 ] ( Fig 7c Fig 7c ). In Fig.7(d) Fig.7(d) , two peaks of N 1s spectrum of TiBCN-40 are ascribed to the amorphous N-C (399.3 eV) [ 6 6 ] and Ti-N (397.5 eV) [ 20 20 ] . The comparative study of B 1s, Ti 2p, C 1s and N 1s spectra for TiB 2 and TiBCN-40 films indicates that adding of C 2 H 2 and N 2 influence the content of elements to a great extent, which leads to the sharp dropping of Ti and B content and increasing C and N contents. The films composition varied greatly, after adding N 2 and C 2 H 2 , the TiB 2 became Ti(B,C), TiN and TiC, forming amorphous phases, like BN, CN x , sp 2 C-C and sp 3 C-C. Figure 8(a) Figure 8(a) shows the B 1s spectra at the N 2 flow rate of 40–350 sccm. The peak at 190.3 eV is BN [ 5 5 , 23 23 ] , and 189.2 eV is pure B [ 14 14 ] . It can be seen that the B-N peak increases with the N 2 flow rate, while the B content decreases with increasing N 2 flow rate. The peaks at 284.5 and 285.4 eV in Fig. 8(b) Fig. 8(b) are related to sp 2 C-C and sp 3 C-C, respectively. Fig. 8(c) Fig. 8(c) shows the N 1s spectra of TiBCN at the N 2 rate flow of 40–350 sccm. At the low N 2 flow rates, the two peaks can be assigned to N-C (399.3 eV) and Ti-N (397.5 eV). At higher flow rates of N 2 , BN (398.2 eV) [ 5 5 , 17 17 ] appears and N-Ti shifts to 397.1 eV. The B-N and N-C peaks increase with the flow rate of N 2 , while TiN (397.1 eV) shows different trends. Ti 2p spectra at the N 2 flow rate of 40–350 sccm are shown in Fig.8(d) Fig.8(d) . The peak at 456.7 eV, corresponding to Ti(C, N) [ 5 5 , 24 24 ] , increases with the N 2 flow rate. The TiN position shifts to 455.6 eV [ 24 24 ] . The peak position at 458.5 eV is TiO 2 2p 3/2 , due to oxidation of the surface of the TiBCN layer. With increasing flow rate of N 2 , the phases of TiN, Ti(C,N), amorphous carbon, amorphous BN and pure B changed differently. The content of sp 3 C-C (285.4 eV) and TiN (397.1 eV) are plotted in Fig. 9 Fig. 9 , as a function of the N 2 flow rate. The sp 3 content decreased to a minimum at 150 sccm, where it began to increase; whereas the TiN content increased to a maximum at 200 sccm and then decreased, being the same changing trend as that of TiN (455.6 eV) in Ti 2p spectra. Amorphous phase BN, observed first at 150 sccm, increased with the N 2 flow rate; while pure boron, observed at 150 sccm, decreased with increasing N 2 flow rates. It can be seen that the growth of TiBCN films is affected significantly by the gas flow rate. At 40 sccm, the Ti atoms mainly bond with B and C atoms, just a small fraction of them bond with N atoms. At 150 sccm, Ti atoms become to bond with N atoms, resulting in excess B being present in single-element phase and in less C-Ti bonds, which leads to free C atoms becoming hybridized. At maximum amount of TiN at 200 sccm, amorphous BN and CN x are formed while pure B becomes less. With even more N 2 in the growing procedure, the large amount of C 2 H 2 and N 2 gases in the chamber favors Ti atoms to bond with N atoms [ 4 4 ] and form TiN on the surfaces, but the collisions between C, N, B and Ti atoms never stop, thus, excess C and N atoms will collide with TiN crystallites on the surface and incorporate into TiN, resulting in Ti(C,N) at the expense of TiN. There are two steps influencing sp 3 content at different N 2 fluxes: (1) at low fluxes of N 2 , Ti atoms bond with B and C atoms, and sp 2 C-C bonding is disordered due to incorporation of Ti and B, hence the large sp 3 content; while at higher fluxes of N 2 , Ti atoms become to bond with N atoms, then sp 2 C-C is recovered and sp 3 C-C content decreases; (2) at fluxes over 200 sccm, there are less Ti atoms to bond with N atoms, excess N atoms will incorporate with sp 2 C-C, leading to increase of sp 3 C-C containment. 4. Conclusion 1 TiBCN films deposited by multi-cathodic arc ion plating were characterized by RBS, XPS, XRD, SEM and AFM measurements. It was found that the TiBCN films consisted of nanocrystals including TiN, TiB 2 , TiB, and Ti 0.68 N 0.22 B 0.1 , with sizes less than 10 nm and amorphous matrix including BN, a-C, and CN x . XRD showed main peaks from Ti interlayer and TiN 0.3 of the TiBCN films, with weak peaks from TiN 0.7 C 0.3 (200) and TiB(100). 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Technol . 206 , 3777 - 3787 ( 2012 ). doi: 10.1016/j.surfcoat.2012.03.041 http://doi.org/10.1016/j.surfcoat.2012.03.041 Influence of carbon content on the microstructure and tribological properties of TiN(C) films in water lubrication 10.1007/s41365-017-0212-0 This work was supported by the National Natural Science Foundation of China (Nos. 11375135 and 11275141), International Cooperation Program of the Ministry of Science and Technology of China (No. 2015DFR00720), and Fundamental Research Funds for the Central Universities. 2016-07-05 2016-10-13 2016-11-02 2017-03-28 2017-05-01 2021-04-11 © China Science Publishing & Media Ltd. (Science Press), Shanghai Institute of Applied Physics, the Chinese Academy of Sciences, ChineseNuclear Society and Springer Nature Singapore Pte Ltd. 2017 This is a post-peer-review, pre-copyedit version of an article published in Nuclear Science and Techniques. The final authenticated version is available online at: http://dx.doi.org/10.1007/s41365-017-0212-0 http://dx.doi.org/10.1007/s41365-017-0212-0 . 2017 Nuclear Science and Techniques 05 28