The role of ionization fraction on the surface roughness, density and interface mixing of the films deposited by thermal evaporation, dc magnetron sputtering and HiPIMS: An atomistic simulation
Movaffaq Kateb, Hamidreza Hajihoseini, Jon Tomas Gudmundsson, Snorri Ingvarsson
We explore the effect of ionization fraction on the epitaxial growth of Cu film on Cu (111) substrate at room temperature. We compare thermal evaporation, dc magnetron sputtering (dcMS) and high power impulse magnetron sputtering (HiPIMS). Three deposition conditions i.e. fully neutral, 50% ionized and 100% ionized flux were considered as thermal evaporation, dcMS and HiPIMS, respectively, for ~20000 adatoms. It is shown that higher ionization fraction of the deposition flux leads to smoother surfaces by two major mechanisms i.e. decreasing clustering in the vapor phase and bi-collision of high energy ions at the film surface. The bi-collision event consists of local amorphization which fills the gaps between islands followed by crystallization due to secondary collisions. We found bi-collision events to be very important to prevent island growth to become dominant and increase the surface roughness. Regardless of the deposition method, epitaxial Cu thin films suffer from stacking fault areas (twin boundaries) in agreement with recent experimental results. In addition, HiPIMS deposition presents considerable interface mixing while it is negligible in thermal evaporation and dcMS deposition, those present less adhesion accordingly.
The growth rate during reactive high power pulsed magnetron sputtering (HIPIMS) of titanium nitride is measured with a temporal resolution of up to 25 us using a rotating shutter concept. According to that concept a 200 um slit is rotated in front of the substrate synchronous with the HIPIMS pulses. Thereby, the growth flux is laterally distributed over the substrate. By measuring the resulting deposition profile with profilometry and with x-ray photoelectron spectroscopy, the temporal variation of the titanium and nitrogen growth flux per pulse is deduced. The analysis reveals that film growt…
In this work, we studied phase formation, structural and magnetic properties of iron-nitride (Fe-N) thin films deposited using high power impulse magnetron sputtering (HiPIMS) and direct current magnetron sputtering (dc-MS). The nitrogen partial pressure during deposition was systematically varied both in HiPIMS and dc-MS. Resulting Fe-N films were characterized for their microstructure, magnetic properties and nitrogen concentration. We found that HiPIMS deposited Fe-N films show a globular nanocrystalline microstructure and improved soft magnetic properties. In addition, it was found that th…
On Tailoring Structural and Optoelectronic Properties of TiO2 Thin Films Synthesized via 'Room' Temperature High Power Impulse Magnetron Sputtering (HiPIMS)
The effect of applying a positive voltage pulse (Urev = 10 - 150 V) directly after the negative high power impulse magnetron sputtering (HiPIMS) pulse (bipolar HiPIMS) is investigated for the reactive sputter deposition of TiN thin films. Energy-resolved mass spectroscopy analyses are performed to gain insight in the effect on the ion energy distribution function of the various ions. It is demonstrated that the energy of a large fraction of the ions can be tuned by a reverse target potential and gain energy corresponding to the applied Urev. Microscopy observations and x-ray reflectometry reve…
We explore combination of high power impulse magnetron sputtering (HiPIMS) and substrate bias for the epitaxial growth of Cu film on Cu (111) substrate by molecular dynamics simulation. A fully ionized deposition flux was used to represent the high ionization fraction in the HiPIMS process. To mimic different substrate bias, we assumed the deposition flux with a flat energy distribution in the low, moderate and high energy ranges. We also compared the results of fully ionized flux with results assuming a completely neutral flux, in analogy with thermal evaporation. It is confirmed that in the …
A beam experiment is presented to study heterogeneous reactions relevant to plasma-surface interactions. Atom and ion beams are focused onto the sample to expose it to quantified beams of oxygen, nitrogen, hydrogen, noble gas ions and metal vapor. The heterogeneous surface processes are monitored in-situ and in real time by means of a quartz crystal microbalance (QCM) and Fourier transform infrared spectroscopy (FTIR). Two examples illustrate the capabilities of the particle beam setup: oxidation and nitriding of aluminum as a model of target poisoning during reactive magnetron sputtering, and…
Al2O3 thin films have been deposited at substrate temperatures between 500°C to 600°C by reactive magnetron sputtering using an additional arbitrary substrate bias to tailor the energy distribution of the incident ions. The films were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The film structure being amorphous, nanocrystalline, or crystalline was correlated with characteristic ion energy distributions. The evolving crystalline structure is connected with different levels of displacements per atom (dpa) in the growing film as being derived from…
The investigations of the reactive magnetron depositing of the stoichiometric coatings metal-metalloid were done. The dependences between sputtering parameters of a target and processes of plasmochemical formation on the surface of sample metal-metalloid and formations of coatings of the appropriate structure were investigated. Experimental data on stoichiometric coatings AlN, Al2O3, TiN, TiO2 is given. Features of reactive magnetron deposition and investigation results for obtaining of coatings with pregiven properties in particular for providing stability and controllability of coating depos…
The microstructure, mechanical properties and thermal stability of AlTiN and AlTiBN coatings grown by reactive high-power impulse magnetron sputtering (HiPIMS) have been analyzed as a function of Al/(Al+Ti) ratio, x, between 0.5 and 0.8. The coatings were predominantly formed by a face-centered cubic Ti(Al)N crystalline phase, both with and without B, even for x ratios as high as 0.6, which is higher than the ratio typically encountered for AlTiN coatings deposited by reactive magnetron sputtering. B doping, in combination with the highly energetic deposition conditions offered by HiPIMS, resu…
We present results of carbon coatings on metal substrates in cylindrical hollow cathode (CHC) direct current magnetron sputtering. This is a new technique of making amorphous carbon film in CHC magnetron sputtering from regenerative sooting discharge. The carbon films are deposited on Cu and Al substrates in Ne atmosphere and compared with the films of carbon soot on the same materials produced from conventional arc discharge between graphite electrodes at 80 Angstrom in He background. The films are characterized using online emission, Raman, and Fourier transform infrared spectroscopy; X-ray …
Titanium (Ti), due to its excellent properties, is widely exploited in thin film technology that usually leads to the production of α-phase (hcp) Ti films. In this work, we investigate the phase evolution of Ti films deposited by varying type and energy of the film-forming species. To investigate different plasma species environments, films with different thicknesses are grown by using conventional Direct Current Magnetron Sputtering (DCMS) and High Power Impulse Magnetron Sputtering (HiPIMS). Furthermore, HiPIMS depositions with different substrate bias voltage US (0 V, -300 V and -500 V) are…
A simple and cost effective approach to stabilize the sputtering process in the transition zone during reactive high-power impulse magnetron sputtering (HiPIMS) is proposed. The method is based on real-time monitoring and control of the discharge current waveforms. To stabilize the process conditions at a given set point, a feedback control system was implemented that automatically regulates the pulse frequency, and thereby the average sputtering power, to maintain a constant maximum discharge current. In the present study, the variation of the pulse current waveforms over a wide range of reac…
Epitaxial Fe4N thin films grown on lattice-matched LaAlO3 (LAO) substrate using sputtering and molecular beam epitaxy techniques have been studied in this work. Within the sputtering process, films were grown with conventional direct current magnetron sputtering (dcMS) and for the first time, using a high power impulse magnetron sputtering (HiPIMS) process. Surface morphology and depth profile reveal that HiPIMS deposited film has the lowest roughness, the highest packing density and the sharpest interface. La from the LAO substrate and Fe from the film interdiffuse and forms an undesired inte…
We investigate the effect of atomic ordering on the magnetic anisotropy of Ni80Fe20 at.% (Py). To this end, Py films were grown epitaxially on MgO (001) using dc magnetron sputtering (dcMS) and high power impulse magnetron sputtering (HiPIMS). Aside from twin boundaries observed in the latter case, both methods present high quality single crystals with cube-on-cube epitaxial relationship as verified by the polar mapping of important crystal planes. However, X-ray diffraction results indicate higher order for the dcMS deposited film towards L12 Ni3Fe superlattice. This difference can be underst…
Structural, interfacial, optical, and transport properties of large-area MoS2 ultra-thin films on BN-buffered silicon substrates fabricated using magnetron sputtering are investigated. A relatively simple growth strategy is demonstrated here that simultaneously promotes superior interfacial and bulk MoS2 properties. Few layers of MoS2 are established using X-ray reflectivity, diffraction, ellipsometry, and Raman spectroscopy measurements. Layer-specific modeling of optical constants shows very good agreement with first-principles calculations. Conductivity measurements reveal that few-layer Mo…
Optimized DC magnetron sputtering system for the deposition of transparent conductive oxides (TCOs), such indium tin oxide (ITO) on glass substrate has been applied in order to achieve low-emitting (low-e) transparent coatings. To obtain the concerned electrical resistance and high infrared reflection, first the effect of applied sputtering power then oxygen flow on the properties of films have been investigated. The other depositions parameters are kept constant. Film deposition at at temperature 400 degree of Celsius in oxygen flow of 3 Standard Cubic Centimeters per Minute results in transp…
In this work, amorphous thin films in Mg-Si-O-N system were prepared in order to investigate the dependence of optical and mechanical properties on Mg composition. Reactive RF magnetron co-sputtering from magnesium and silicon targets were used for the deposition of Mg-Si-O-N thin films. Films were deposited on float glass, silica wafers and sapphire substrates in an Ar, N2 and O2 gas mixture. X-ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, spectroscopic ellipsometry, and nanoindentation were employed to characterize the composition, surface morphology,…
Nanocrystalline n-AlN:Er thin films were deposited on (001) Silicon substrates by r. f. magnetron sputtering at room temperature to study the correlation between 1.54 $μ$m IR photoluminescence (PL) intensity, AlN crystalline structure and Er concentration rate. This study first presents how Energy-Dispersive Spectroscopy of X-rays (EDSX) Er Cliff Lorimer sensitivity factor alpha = 5 is obtained by combining EDSX and electron probe micro analysis (EPMA) results on reference samples. It secondly presents the relative PL intensities of nanocrystallized samples prepared with identical sputtering p…
We study the microstructure and magnetic properties of Ni80Fe20 thin films grown by high power impulse magnetron sputtering (HiPIMS), and compare with films grown by dc magnetron sputtering (dcMS). The films were grown under a tilt angle of 35° to identical thickness of 37 nm using both techniques, at different pressure (0.13-0.73 Pa) and substrate temperature (room temperature and 100 °C). All of our films display effective in-plane uniaxial anisotropy with square easy axis and linear hard axis magnetization traces. X-ray diffraction reveals that there is very little change in grain size with…
Thin films of phase pure pyrochlore Gd2Ti2O7 have been synthesized by RF magnetron sputtering. The films were prepared from oxide targets in 50%O2/Ar atmosphere and deposited on 111 YSZ substrates at a temperature of 800C. The pyrochlore structure was confirmed via grazing angle x-ray diffraction and selected area electron diffraction (SAED). TEM analysis also showed that the films were dense and of uniform thickness with surface roughness of approximately 8nm. The total conductivity measured with AC impedance spectroscopy was found to be independent of thickness and comparable in magnitude to…
In order to obtain Ni-Mn-Ga epitaxial films crystallized in martensite structures showing Magnetic-Induced Rearrangement (MIR) of martensite variants, a fine control of the composition is required. Here we present how the co-sputtering process might be helpful in the development of Ni-Mn-Ga epitaxial films. A batch of epitaxial Ni-Mn-Ga films deposited by co-sputtering of a Ni-Mn-Ga ternary target and a pure manganese target has been studied. The co-sputtering process allows a precise control of the film compositions and enables keeping the epitaxial growth of Ni-Mn-Ga austenite during deposit…
ITO thin films were deposited on glass substrates by d.c. magnetron sputtering with varied oxygen flow rates. It was found that the optical absorption decreases and optical absorption edge has blue shifts with the increasing oxygen flow rate. Oxygen vacancy concentration was characterized and analyzed by XPS. It is shown that the oxygen vacancy concentration increases with oxygen flow rates, which is a different observation from the current understanding. The energy band structures associated with different vacancy concentrations of ITO were calculated using the first-principle based on densit…
Atomic layer deposition (ALD) provides a promising approach for deposition of ultrathin low-defect-density tunnel barriers, and it has been implemented in a high-vacuum magnetron sputtering system for in situ deposition of ALD-Al2O3 tunnel barriers in superconductor-insulator-superconductor (SIS) Josephson junctions. A smooth ALD-Al2O3 barrier layer was grown on a Al-wetted Nb bottom electrode and was followed with a top Nb electrode growth using sputtering. Preliminary low temperature measurements of current-voltage characteristics (IVC) of the Josephson junctions made from these trilayers co…
In this work we have synthesised thin films of MgyNi1-y(Hx) metal and metal hydride with y between 0 and 1. The films are deposited by magnetron co-sputtering of metallic targets of Mg and Ni. Metallic MgyNi1-y films were deposited with pure Ar plasma while MgyNi1-yHx hydride films were deposited reactively with 30% H2 in the Ar plasma. The depositions were done with a fixed substrate carrier, producing films with a spatial gradient in the Mg and Ni composition. The combinatorial method of co-sputtering gives an insight into the phase diagram of MgyNi1-y and MgyNi1-yHx, and allows us to invest…
We present deposition and characterization of multilayers consisting of 20 repetitions of 15 $Å$ thick permalloy Ni$_{80}$Fe$_{20}$ at. \% (Py) and 5 $Å$ Pt. The samples were prepared by two different sputter deposition methods, namely dc magnetron sputtering (dcMS) and high power impulse magnetron sputtering (HiPIMS), that represent low and moderate ionized flux fraction of the film forming material, respectively, for deposition of the Py layers. The effect of substrate roughness, working gas pressure and sputter power on the in-plane uniaxial magnetic anisotropy of the films are studied. The…
The transition metal ions doped with TiO2 films are of magnetic properties at room temperatures and have stimulated many scientists to study other properties. The Co-TiO2 sandwich composite films have been recently grown on glass and silicon substrates by using alternately radio frequency reactive and direct current magnetron sputtering. The microstructural properties of these films were characterized with Raman spectra and X-ray photoemission spectra (XPS). It shows an anatase TiO2 containing Co nano-layer. Optical absorption spectra have red shift with Co nano-layer increasing, which origina…
Copper deposition has been carried out at various time span on glass slide and silicon substrate by using indigenously developed unbalanced type DC magnetron sputtering system. The main objective of this work is to study the crystalline structure of the deposited materials and also to calculate the crystallite grain size. As a transition metal, Copper nano-particles and structures have several utilities in the field of photo-catalytic and sensor applications. Such structures are utilized to provide free electrons that enhance optical and electrical properties of the photo-catalytic sensor mate…
We studied the growth behavior, structural, electronic, and magnetic properties of cobalt nitride (Co-N) thin films deposited using direct current (dc) and high power impulse magnetron sputtering (HiPIMS) processes. The N$_2$ partial gas flow (\pn) was varied in close intervals to achieve the optimum conditions for the growth of tetra cobalt nitride (\tcn) phase. We found that Co-N films grown using HiPIMS process adopt (111) orientation as compared to the growth taking place along the (100) direction in the dcMS process. It was observed that HiPIMS grown Co-N~films were superior in terms of c…
The results of characterization of TiAlSiON hard coatings deposited on ferric-chromium AISI 430 stainless steel by plasma enhanced magnetron sputtering are presented. The coating with maximum hardness (of 45 GPa) was obtained at the following optimal values of elemental concentrations: Si ~5 at.%, Al ~15 at.%, and Ti ~27 at.%. The elastic modulus of the coating was 590 GPa. The reading of gaseous mixture (Ar-N2) pressure was 1*10-3 Torr and the reading of partial pressure of oxygen (O2) was 1*10-5 Torr. The X-ray diffraction (XRD) measurements showed the presence of Ti(Al)N. High-energy resolv…
Recently was reported a novel compound between rhenium and nitrogen, announced with ReN2 composition. This compound was synthesized by the high temperature and high pressure method. We found that the diffraction peaks of this compound are in agreement with the x-ray pattern of a rhenium-nitrogen film, under the assumption that the film is oriented on the substrate. The film was prepared by reactive magnetron sputtering, at room temperature, and deposited on a silicon wafer. From the analysis of the diffractograms it could be concluded that both materials share the same structure. By density fu…
Inverse Heusler alloy Mn2CoAl thin films, known as a spin-gapless semiconductor (SGS), grown by three different methods: ultra-high vacuum magnetron spattering, Ar-ion beam assisted sputtering, and molecular beam epitaxy, are investigated by comparing their electric transport properties, microstructures and atomic-level structures. Of the samples, the Mn2CoAl thin film grown by MBE consists of Mn- and Co-rich phases, the structures of which are determined to be the L21B-type and disordered L21-type, respectively, according to anomalous XRD analysis. None of them forms the XA-type structure exp…
We report the reduction in residual stress of AlN thin films and also the crystal structure, surface morphology and nanomechanical properties of magnetron sputtered as a function of substrate temperature (Ts, 35 - 600 ?C). The residual stress of these films was calculated by sin2 technique and found that they are varying from tensile to compression with temperature (Ts). Evolution of crystalline growth of AlN films was studied by GIXRD and transmission electron microscopy (TEM) and a preferred a-axis orientation was observed at 400 ?C. The cross-sectional TEM micrograph and selected area elect…
Er-doped aluminum nitride films, containing different Er concentrations, were obtained at room temperature by reactive radio frequency magnetron sputtering. The prepared samples show a nano-columnar microstructure and the size of the columns is dependent on the magnetron power. The Er-related photoluminescence (PL) was studied in relation with the temperature, the Er content and the microstructure. Steady-state PL, PL excitation spectroscopy and time-resolved PL were performed. Both visible and near infrared PL were obtained at room temperature for the as-deposited samples. It is demonstrated …
The superconducting nominal "non-doped" $La_{1.85}Y_{0.15}CuO_4$ (LYCO) thin films are successfully prepared by dc magnetron-sputtering and in situ post-annealing in vacuum. The best $T_{C0}$ more than 13K is achieved in the optimal LYCO films with highly pure c-axis oriented T'-type structure. In the normal state, the quasi-quadratic temperature dependence of resistivity, the negative Hall coefficient and effect of oxygen content in the films are quite similar to the typical Ce-doped T'-214 cuprates, suggesting that T'-LYCO shows the electron-doping nature like known n-type cuprates, and is n…
Raman studies of nanocomposite SiCN thin film by sputtering showed that with an increase of substrate temperature from room temperature to 500oC, a transition from mostly sp2 graphitic phase to sp3 carbon took place which was observed from the variation of ID/IG ratio and the peak shifts. This process resulted in the growth of C3N4 and Si3N4 crystallites in the amorphous matrix which led to an increase in hardness and modulus obtained through nanoindentation. However, at a further higher temperature of 600oC, again an increase of sp2 C concentration in the film was observed and the H and E val…
TiZrV film is mainly applied in the ultra-high vacuum pipe of storage ring. Thin film coatings of palladium which was added onto the TiZrV film to increase the service life of nonevaporable getters and enhance pumping speed for H2, was deposited on the inner face of stainless steel pipes by dc magnetron sputtering using argon gas as the sputtering gas. The TiZrV-Pd film properties were investigated by atomic force microscope (AFM), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and X-Ray Diffraction (XRD). The grain size of TiZrV and Pd film were about 0.42~1.3 nm a…
Bulk rhenium trioxide (ReO3) has an unusually high electrical conductivity and, being nanosized, has promising catalytic properties. However, the production of pure ReO3 thin films is challenging due to the difficulty to stabilize rhenium in a 6+ oxidation state. Here we present a novel approach for the deposition of ReOx (x = 1.6-2.9) thin films using reactive high power impulse magnetron sputtering (r-HiPIMS) from a metallic rhenium target in a mixed Ar/O2 atmosphere. The thin films were deposited in the gas-sustained self-sputtering regime, observed during r-HiPIMS process according to curr…
A transfer-rod-mounted rotatable sample holder enabling a compact modular vacuum system for ion-beam milling, oblique magnetron sputtering, and co-sputtering
Two dimensional materials are an emerging class of materials which is transforming the present day research activity on a phenomenal scale. Hexagonal boron nitride is a wide band gap 2D material which is an excellent substrate for graphene based electronics. To achieve the full potential of hBN scalable and high yield growth procedures are required. Here, we demonstrate the synthesis of hBN by reactive R.F magnetron sputtering over copper foil. Copper foil preparation conditions determines the phase selectivity of BN films. Deposition of hBN on non-electropolished Cu foils with predominant (10…
The step-wise growth of epitaxial Fe on Cu(001)/Si(001), investigated by in-situ polarized neutron reflectometry is presented. A sputter deposition system was integrated into the neutron reflectometer AMOR at the Swiss neutron spallation source SINQ, which enables the analysis of the microstructure and magnetic moments during all deposition steps of the Fe layer. We report on the progressive evolution of the accessible parameters describing the microstructure and the magnetic properties of the Fe film, which reproduce known features and extend our knowledge on the behavior of ultrathin iron fi…
Effect of annealing in the formation of well crystallized and textured SrFe$_{12}$O$_{19}$ films grown by RF magnetron sputtering
Instituto de Química Física “Rocasolano”, CSIC（罗卡索拉诺物理化学研究所，西班牙国家研究委员会）；Instituto de Cerámica y Vidrio, CSIC（陶瓷与玻璃研究所，西班牙国家研究委员会）；Alba Synchrotron Light Facility, CELLS（阿尔巴同步辐射光源，加泰罗尼亚高等研究理事会）
In this work, we studied cobalt nitride (Co-N) thin films deposited using a dc magnetron sputtering method at a substrate temperature (\Ts) of 523\,K. We find that independent of the reactive gas flow (\pn) used during sputtering, the phases of Co-N formed at this temperature seems to be identical having N \pat~$\sim$5. This is contrary to Co-N phases formed at lower \Ts. For \Ts$\sim$300\,K, an evolution of Co-N phases starting from Co(N)$\rightarrow$\tcn$\rightarrow$Co$_3$N$\rightarrow$CoN can be seen as \pn increases to 100\p, whereas when the substrate temperature increases to 523\,K, the …
As2S3 film doped with erbium is prepared using multi-layer magnetron sputtering. The optical properties were measured by reflectance spectroscopy, and its chemical composition is examined by x-ray photoelectron, Rutherford backscattering, and Raman spectroscopy. The results show that the refractive index and absorption coefficient follow closely to a sputtered As2S3 film, and there are no detectable Er-S clusters and photo-induced As2O3 in the film. Rutherford backscattering spectroscopy shows that the film is homogeneous, and revealed the concentration level of erbium, and the stoichiometry o…
An Automated Magnetron Sputtering Chamber for Ferroelectric Thin Film Deposition
Materials Research Institute, The Pennsylvania State University（宾夕法尼亚州立大学材料研究所）；Materials Science and Engineering, The Pennsylvania State University（宾夕法尼亚州立大学材料科学与工程系）
In this work, the results of fabricating ultra thin VO$_2$ films on the technologically relevant amorphous SiO$_2$ surface using reactive DC magnetron sputtering are presented. Results indicate that a post deposition anneal in low partial pressures of oxygen is an effective way at stabilizing the VO$_2$(M$_{1}$) phase on the SiO$_2$ surface. VO$_2$ films with a thickness of 42nm show a continuous microstructure, and undergo a resistivity change of more than a factor of 200 as the temperature of the film increases above 72$^{o}C$. The film shows hysteresis in the metal-insulator transition temp…
The effect of magnetron power on the room temperature 1.54 $μ$m infra-red photoluminescence intensity of erbium doped AlN films grown by r. f. magnetron sputtering, has been studied. The AlN:Er thin films were deposited on (001) Silicon substrates. The study presents relative photoluminescence intensities of nanocrystallized samples prepared with identical sputtering parameters for two erbium doping levels (0.5 and 1.5 atomic %). The structural evolution of the crystallites as a function of the power is followed by transmission electron microscopy. Copyright line will be provided by the publis…
Low-temperature epitaxial growth of refractory transition-metal nitride thin films by means of physical vapor deposition has been a recurring theme in advanced thin-film technology for several years. In the present study, 150-nm-thick epitaxial HfN layers are grown on MgO(001) by reactive high-impulse magnetron sputtering (HiPIMS) with no external substrate heating. Maximum film growth temperatures Ts due to plasma heating range from 70-150 °C, corresponding to Ts/Tm = 0.10-0.12 (in which Tm is the HfN melting point in K). During HiPIMS, gas and sputtered-metal ion fluxes incident at the growi…
