Precursors For Film Growth Research Articles

Volatile and thermally stable silver pyrazolate complexes containing N-heterocyclic carbene ligands

A series of monomeric, dimeric, and tetrameric silver(I) complexes containing pyrazolate and N-heterocyclic carbene ligands has been synthesized and characterized. These complexes combine good volatility and high thermal stability, and are promising candidates for the growth of silver metal films by atomic layer deposition. • Ag(I) complexes containing pyrazolate and N-heterocyclic carbene ligands were synthesized and characterized. • The complexes adopt monomeric, dimeric, or tetrameric structures. • Most of the complexes are volatile and have high thermal stabilities. • The new complexes are promising atomic layer deposition precursors for Ag metal films. Treatment of [Ag((CF 3 ) 2 pz)] 3 or [Ag(tBu,C 3 F 7 )pz)] 3 (pz = pyrazolate) with various stable N-heterocyclic carbenes (NHC) afforded silver(I) complexes containing pyrazolate and NHC ligands in 10–81% crystalline yields. These complexes were analyzed by spectral and analytical techniques and by X-ray crystal structure determinations. The solid state structures showed monomeric, dimeric, or tetrameric formulations, depending upon the pyrazolate and NHC substituents. To evaluate their potential as thin film growth precursors, [Ag((CF 3 ) 2 pz)] 3, [Ag(tBu,C 3 F 7 )pz)] 3 , and the new complexes were evaluated by thermogravimetric analyses, sublimation studies, thermal decomposition temperatures, and solution reduction experiments with potential reducing agents. The decomposition temperatures were higher for complexes containing (CF 3 ) 2 pz ligands (203 to 293 °C) than for those containing (tBu,C 3 F 7 )pz ligands (160 to 200 °C). The complexes sublimed between 110 and 140 °C at 0.2 Torr. Solution reactions of several complexes with aqueous hydrazine, 1,1-dimethylhydrazine, formic acid, and tBuNH 2 led to the formation of silver metal. Several of the new complexes have promising precursor properties for use in thin film growth by the atomic layer deposition and chemical vapor deposition techniques.

In Situ Investigation of the Thermal Decomposition of Cl4(CH3CN)W(NiPr) During Simulated Chemical Vapor Deposition

Design of precursors for thin film growth by chemical vapor deposition (CVD) can be informed by knowledge of the precursor decomposition mechanism. However, the vast majority of decomposition characterization is done by techniques that do not capture CVD conditions. This work used a custom CVD reactor with in situ Raman spectroscopy capabilities to investigate the gas phase thermal decomposition of the tungsten imido complex Cl4(CH3CN)WNiPr, a known precursor for the aerosol‐assisted (AA)CVD of tungsten carbonitride thin films. In combination with previous computational and ex situ data, we propose a decomposition mechanism for this precursor under CVD conditions, based on observation of gas phase products of N(imido)‐C bond homolysis and σ‐bond metathesis between the precursor W–Cl bond and H2.

Synthesis of Zirconium Diboride Films and ZrB2/BC x N y Heterostructures

Using mechanochemical synthesis, we have prepared zirconium borohydride, Zr(BH4)4, as a precursor for ZrB2 film growth by chemical vapor deposition. We have carried out the thermodynamic modeling of phase formation processes in the Zr–B–(N)–H and Zr–B–(N)–H–O systems in a wide temperature range, from 100 to 2500°C, at various p(H2)/p(Zr(BH4)4) and p(NH3)/p(Zr(BH4)4) partial pressure ratios in the starting gas mixtures. A process has been proposed for the growth of zirconium diboride films by Zr(BH4)4 decomposition using two techniques: chemical vapor deposition and plasma-enhanced chemical vapor deposition. We also developed a process for the growth of multilayer ZrB2-and BC x N y -based structures.

Absolute density of precursor SiH3 radicals and H atoms in H2-diluted SiH4 gas plasma for deposition of microcrystalline silicon films

Microcrystalline hydrogenated silicon films were produced at a high deposition rate of about 2 nm/s by using a capacitively coupled plasma under a practical pressure of around 1 kPa. The SiH4 source gas was almost fully dissociated when highly diluted with H2 gas, and the dominant species in the gas phase were found to be SiH3 radicals, which are film-growth precursors, and H atoms. The absolute density of these species was measured as the partial pressure of SiH4 gas was varied. With the increasing SiH4 gas flow rate, the SiH3 radical density, which was on the order of 1012 cm−3, increased linearly, while the H-atom density remained constant at about 1012 cm−3. The film growth mechanism was described in terms of precursors, based on the measured flux of SiH3 radicals and H atoms, and the relative fraction of higher-order radicals.

Study on re-sputtering during CNx film deposition through spectroscopic diagnostics of plasma

A nitrogen-carbon plasma was generated during the deposition of carbon nitride (CNx) thin films by pulsed laser ablation of a graphite target in a discharge nitrogen plasma, and the optical emission of the generated nitrogen-carbon plasma was measured for the diagnostics of the plasma and the characterization of the process of CNx film deposition. The nitrogen-carbon plasma was recognized to contain various species including nitrogen molecules and molecular ions excited in the ambient N2 gas, carbon atoms and atomic ions ablated from the graphite target and CN radicals. The temporal evolution and spatial distribution of the CN emission and their dependence on the substrate bias voltage show two groups of CN radicals flying in opposite directions. One represents the CN radicals formed as the products of the reactions occurring in the nitrogen-carbon plasma, revealing the reactive deposition of CNx film due to the reactive expansion of the ablation carbon plasma in the discharge nitrogen plasma and the effective formation of gaseous CN radicals as precursors for CNx film growth. The other one represents the CN radicals re-sputtered from the growing CNx film by energetic plasma species, evidencing the re-sputtering of the growing film accompanying film growth. And, the re-sputtering presents ion-induced sputtering features.

Exploration for the potential precursors for zirconium carbide atomic layer deposition via comprehensive computational mechanistic study of the gas phase decomposition of neopentyl zirconium derivatives

We previously reported the probable gas phase decomposition mechanism of tetraneopentyl zirconium (ZrNp4) under typical MOCVD (metalorganic chemical vapor deposition) conditions (400 to 800 °C) using computational thermochemistry. By the same approach, we performed a mechanistic study of the gas phase decomposition of trineopentyl zirconium monochloride (ZrNp3Cl) to evaluate its possibility as a CVD precursor for ZrC film growth. It was demonstrated that strong Zr-Cl bonding would require much higher growth temperatures to drive the gas phase decomposition of ZrNp3Cl, compared to ZrNp4. The higher temperature growth would pose the problem of accelerated gas phase parasitic reactions, which potentially hamper ZrC deposition on the surface. However, strong Zr-Cl bonding offers the possibility of ZrC ALD (atomic layer deposition) using dineopentyl zirconium dichloride (ZrNp2Cl2), and a postulated scheme is presented based on the results from the gas phase decomposition study of ZrNp4 and/or ZrNp3Cl.

Control of growth process for obtaining high-quality a-SiO:H

Film-growth process of hydrogenated amorphous silicon–oxygen alloys (a-SiO:H) from CO2/(CO2 + SiH4) plasma has been investigated to control the optoelectronic properties in the resulting materials. Optical emission spectroscopy results and simple simulation results for steady-state density of chemical species in the plasma indicate that main film-growth precursors for a-SiO:H are SiH3, OH, and O. Si dangling-bond defect density is drastically increased in a-SiO:H when increasing the CO2 gas ratio in CO2/(CO2 + SiH4) plasma, being caused by the increase in the contribution ratio of Si-related short-lifetime species (SiHx, x < 2) to film growth owing to a severe SiH4-molecule depletion because of high-rate consumption reaction of SiH4 with O produced from CO2 in the plasma. Considering the primary electron impact dissociation reactions of source gas molecules and several secondary chemical reactions in the plasma, the guiding principle for obtaining high quality a-SiO:H has been proposed.

Synthesis, Structure, and Solution Reduction Reactions of Volatile and Thermally Stable Mid to Late First Row Transition Metal Complexes Containing Hydrazonate Ligands

Treatment of MCl2 (M = Ni, Co, Fe, Mn, Cr) with 2 equiv of the hydrazonate salts K(tBuNNCHCtBuO), K(tBuNNCHCiPrO), or K(tBuNNCMeCMeO) afforded the complexes M(tBuNNCHCtBuO)2 (M = Ni, 65%; Co, 80%; Fe, 83%; Mn, 68%; Cr, 64%), M(tBuNNCHCiPrO)2 (M = Ni, 63%; Co, 86%; Fe, 75%), and M(tBuNNCMeCMeO)2 (M = Ni, 34%; Co, 29%; Fe, 27%). Crystal structure determinations of Co(tBuNNCHCtBuO)2, M(tBuNNCHCiPrO)2 (M = Ni, Co), and M(tBuNNCMeCMeO)2 (M = Ni, Co, Fe) revealed monomeric complexes with tetrahedral geometries about the metal centers. To evaluate the potential of these new complexes as film growth precursors, preparative sublimations, thermogravimetric analyses, solid state decomposition studies, and solution reactions with reducing coreagents were carried out. M(tBuNNCHCtBuO)2 sublime between 120 and 135 °C at 0.05 Torr, whereas M(tBuNNCHCiPrO)2 and M(tBuNNCMeCMeO)2 sublime between 100 and 105 °C at the same pressure. All complexes afforded ≥96% recovery of sublimed material, with ≤3% of nonvolatile residues. The solid state decomposition temperatures were highest for M(tBuNNCHCiPrO)2 (273-308 °C), intermediate for M(tBuNNCHCtBuO)2 (241-278 °C), and lowest for M(tBuNNCMeCMeO)2 (235-250 °C). Treatment of Co(tBuNNCHCtBuO)2 in tetrahydrofuran with hydrazine, BH3(L) (L = NHMe2, SMe2, THF), pinacol borane, and LiAlH4 led to rapid formation of cobalt metal, while analogous reductions of Mn(tBuNNCHCtBuO)2 with BH3(THF), pinacol borane, and LiAlH4 appeared to afford manganese metal. The new complexes M(tBuNNCHCtBuO)2, M(tBuNNCHCiPrO)2, and M(tBuNNCMeCMeO)2 have very promising properties for use as precursors for the growth of the respective metals in atomic layer deposition film growth processes.

Volatility and High Thermal Stability in Mid- to Late-First-Row Transition-Metal Diazadienyl Complexes

Treatment of MCl2 (M = Cr, Mn, Fe, Co, Ni) with 2 equiv of lithium metal and 1,4-di-tert-butyl-1,3-diazadiene (tBu2DAD) in tetrahydrofuran at ambient temperature afforded Cr(tBu2DAD)2 (38%), Mn(tBu2DAD)2 (81%), Fe(tBu2DAD)2 (47%), Co(tBu2DAD)2 (36%), and Ni(tBu2DAD)2 (41%). Crystal structure determinations revealed monomeric complexes that adopt tetrahedral coordination environments and were consistent with tBu2DAD radical anion ligands. To evaluate the viability of M(tBu2DAD)2 (M = Cr, Mn, Fe, Co, Ni) as potential film growth precursors, thermogravimetric analyses, preparative sublimations, and solid-state decomposition studies were performed. Mn(tBu2DAD)2 is the most thermally robust among the series, with a solid-state decomposition temperature of 325 °C, a sublimation temperature of 120 °C/0.05 Torr, and a nonvolatile residue of 4.3% in a preparative sublimation. Thermogravimetric traces of all complexes show weight loss regimes from 150 to 225 °C with final percent residues at 500 °C ranging from 1.5 to 3.6%. Thermolysis studies reveal that all complexes except Mn(tBu2DAD)2 decompose into their respective crystalline metal powders under an inert atmosphere. Mn(tBu2DAD)2 may afford amorphous manganese metal upon thermolysis.

Deposition of WNxCy from the Tungsten Piperidylhydrazido Complex Cl4(CH3CN)W(N-pip) as a Single-Source Precursor

The tungsten piperidylhydrazido complex Cl4(CH3CN)W(N-pip) (1) was used as a single-source precursor for film growth of tungsten carbonitride (WNxCy) by metal-organic chemical vapor deposition (CVD) in H2 carrier. Multiple spectroscopic techniques were used for preliminary evaluation of the suitability of 1 as a precursor and to suggest possible fragmentation pathways. The microstructure of films deposited below 500°C was X-ray amorphous, with the highest N content in the film occurring for growth at 400°C. The chemical bonding state of films deposited at 400°C was WNxCy, while tungsten oxide (WO3) was observed for films deposited at 300°C. Film growth rates varied from 2.7 Å/min (300°C) to 29.4 Å/min (700°C) with deposition temperature. The lowest measured resistivity value is 0.9 mΩ cm for a film grown at 550°C. The diffusion barrier properties were investigated using Cu/WNxCy/Si stacks consisting of Cu deposited by reactive sputtering on WNxCy films deposited at 400°C. The Cu/WNxCy/Si stacks annealed at 500°C for 30 min maintained the integrity of both Cu/WNxCy and WNxCy/Si interfaces as determined by x-ray diffraction measurement, detection of etch-pits, and the Auger electron spectroscopy depth profile. These results support the conclusion that WNxCy deposited from 1 is a viable barrier material to prevent diffusion of Cu in Si for Cu interconnect technology.

Growth and microstructure properties of microcrystalline silicon films deposited using jet-ICPCVD

Microcrystalline silicon films were deposited at a high rate and low temperature using jet-type inductively coupled plasma chemical vapor deposition (jet-ICPCVD). An investigation into the deposition rate and microstructure properties of the deposited films showed that a high deposition rate of over 20 nm/s can be achieved while maintaining reasonable material quality. The deposition rate can be controlled by regulating the generation rate and transport of film growth precursors. The film with high crystallinity deposited at low temperature could principally result from hydrogen-induced chemical annealing.

Mid-frequency deposition of a-C:H films using five different precursors

Mid-frequency deposition of a-C:H films using five different precursors

Growth and stability of CVD Ni 3N and ALD NiO dual layers

Abstract Multilayers of combinations of NiO, Ni3N and Ni have been grown by ALD and CVD techniques at 250 °C. Layers of low thermodynamical stability have been modified to reach the target structures. The Ni layers have been formed by decomposition of metastable Ni3N layers, i.e., the Ni3N layers act as precursor for Ni film growth. This new reaction route enables production of Ni/NiO layer structures by chemical means for the first time. By choosing suitable low temperature annealing conditions like 180 °C in a 1 Torr hydrogen atmosphere, good control of the interfaces is obtained. It has also been shown that it is possible to grow multilayers which are ordered both with respect to each other, the substrate and the Ni films. For instance the following structure Ni (111)/NiO (111)/α-Al2O3 (00l) has been grown. Moreover, another new reaction route is deposition of thin epitaxial seed layers of NiO (111) for subsequent growth of Ni3N at a high rate. Single phase Ni (111) films could then be obtained by decomposition at 350 °C of the Ni3N layers. The demonstrated reaction routes for film growth in the Ni–O–N system can also be applied in several similar systems.

Mid-frequency deposition of a-C:H films using five different precursors

Abstract The plasma-enhanced chemical vapour deposition (PECVD) of amorphous hydrogenated carbon films from pulsed discharges with frequencies in the range from 50 kHz to 250 kHz was investigated. Five different hydrocarbons (acetylene C2H2, isobutene C4H8, cyclopentene C5H8, toluene C7H8 and cycloheptatriene C7H8) were probed as film growth precursors. In addition, two types of pulse-generators with somewhat different waveforms were used to power the discharges in the so called mid-frequency range. The a-C:H films deposited in a parallel-plate reactor were characterised for their thickness/deposition rate, hardness and hydrogen content. The hydrogen concentration in the films varied between 19 at.-% and 37 at.-%. With the substrate temperature held constant, it is roughly in inverse proportion to the hardness. The film with the highest hardness of 25 GPa was formed at a deposition rate of 0.8 μm/h in the C2H2 discharge at the lowest investigated pressure of 2 Pa. With increasing molecular mass of the precursor mostly weaker films were deposited. Relatively high values of both deposition rate and hardness were achieved using the precursor isobutene: a hardness of 21 GPa combined with a deposition rate of 4.1 μm/h. From the probed precursors, isobutene is also most advantageous for a-C:H deposition at higher pressures (up to 50 Pa investigated). But, as an over-all trend, the a-C:H hardness decreases with increasing deposition rate.

Uniform Coating of TiO<SUB>2</SUB> Thin Films on Particles by Rotating Cylindrical PCVD Reactor

We analyzed TiO2 thin film growth on glass particles in a rotating cylindrical plasma chemical vapor deposition (PCVD) reactor and numerically investigated the effects of several process variables on the film growth. An increase in titanium tetra-isopropoxide (TTIP) or O2 partial pressure can enhance the film growth rate on the particles because the concentration of TiO(x), which is the main precursor for thin film growth, becomes higher in the reactor. As the particle diameter decreases, the TiO(x) concentration increases and the thin film on the particles grows more quickly. The neutral-radical reaction between TTIP and O radicals for TiO(x) generation in TTIP + O2 plasmas can be important to enhance the thin film growth rate on the particles. The growth rate of TiO2 film predicted in this study was 1 approximately 20 nm/min, which is in good agreement with the published experimental results. This study suggests that a uniform TiO2 thin film on particles can be obtained by using a rotating cylindrical PCVD reactor.

Volatility and High Thermal Stability in Tantalum Complexes Containing Imido, Amidinate, and Halide or Dialkylamide Ligands

Treatment of Ta(NtBu)Cl(3)(py)(2) with 2 equiv of Li(iPrNCMeNiPr) or Li(tBuNCMeNtBu) afforded Ta(NtBu)(iPrNCMeNiPr)(2)Cl and Ta(NtBu)(tBuNCMeNtBu)(2)Cl in 63% and 61% yields, respectively. Treatment of Ta(NtBu)(iPrNCMeNiPr)(2)Cl or Ta(NtBu)(tBuNCMeNtBu)(2)Cl with LiNRR' afforded Ta(NtBu)(iPrNCMeNiPr)(2)(NRR') and Ta(NtBu)(tBuNCMeNtBu)(2)(NRR') in 79-92% yields (R, R' = Me, Et). Treatment of Ta(NtBu)(tBuNCMeNtBu)(2)Cl with AgBF(4) afforded Ta(NtBu)(tBuNCMeNtBu)(2)F in 54% yield, while treatment of Ta(NtBu)(tBuNCMeNtBu)(2)Cl with BBr(3) afforded Ta(NtBu)(tBuNCMe-NtBu)(2)Br in 68% yield. X-ray crystal structures of Ta(NtBu)(tBuNCMeNtBu)(2)F and Ta(NtBu)(tBuNCMeNtBu)(2)Br revealed that the amidinate ligands exhibit eta(2)-coordination, and that the imido and halide ligands are cis to each other within the distorted octahedral structures. NMR studies indicated that the other complexes have analogous structures. Additionally, variable temperature NMR studies revealed that some of the complexes undergo amidinate rearrangement. The enthalpies, entropies, and free energies of activation for these rearrangements were calculated for Ta(NtBu)(tBuNCMeNtBu)(2)X (X = F, Cl, Br). When X = F, DeltaH(double dagger) = 9.1 +/- 0.4 kcal/mol, DeltaS(double dagger) = -20.5 +/- 1.6 cal/mol x K, and DeltaG(double dagger)(298 K) = 15.3 +/- 0.7 kcal/mol. For X = Cl, DeltaH(double dagger) = 12.4 +/- 0.3 kcal/mol, DeltaS(double dagger) = -20.2 +/- 0.8 cal/mol x K, and DeltaG(double dagger)(298 K) = 18.4 +/- 0.3 kcal/mol. When X = Br, DeltaH(double dagger) = 12.5 +/- 0.5 kcal/mol, DeltaS(double dagger) = -21.7 +/- 1.5 cal/mol x K, and DeltaG(double dagger)(298 K) = 19.0 +/- 0.7 kcal/mol. All of the complexes are volatile, and they sublime between 120 and 203 degrees C. In addition, Ta(NtBu)(iPrNCMeNiPr)(2)NMe(2) has a decomposition point that is 65-160 degrees C higher than widely used film growth precursors and is therefore a promising candidate for use in chemical vapor deposition and atomic layer deposition film growth techniques.

Mechanisms of adsorption and decomposition of metal alkylamide precursors for ultrathin film growth

Atomic layer deposition film growth is usually characterized by the presence of a transient (nonlinear) regime, where surface reactions of precursors take place on the substrate, resembling the first stages of chemical vapor deposition and affecting the composition of the forming interface. Here, the adsorption and decomposition of tetrakis(dimethylamido)titanium, Ti[N(CH3)2]4, tetrakis(dimethylamido)zirconium, Zr[N(CH3)2]4, tetrakis(dimethylamido)hafnium, Hf[N(CH3)2]4, pentakis(dimethylamido)tantalum, Ta[N(CH3)2]5, and bis(t-butylimido)-bis(dimethylamido)tungsten, [(CH3)3CN]2W[N(CH3)2]2, on a silicon substrate are investigated using density functional methods. These alkylamides are widely used for deposition of both diffusion barriers and high-permittivity (high-κ) materials. Adsorption is found to be dissociative, with scission of metal-ligand bonds being more feasible than scission of N–C bonds, suggesting that decomposition of ligands is not favored at low temperatures. However, decomposition through C–H bond scission may ultimately lead to the formation of Si–C bonds, without significant kinetic requirements and producing highly stable structures. The overall feasibility of the adsorption/decomposition pathway outlined here explains the presence of carbon at the interface in alkylamide-based deposition schemes.

Magnesium complexes containing β-ketiminate and β-diketiminate ligands with dimethylamino substituents on the ligand core nitrogen atoms

Abstract Treatment of dibutylmagnesium with two equivalents of 4-(2,2-dimethylhydrazino)dimethylhydrazone-3-penten-2-one (L1H) in diethyl ether afforded Mg(L1)2 (76%), which contains η2-L1 ligands with tetrahedral coordination at the magnesium ion. Similar treatment of dibutylmagnesium with 4-(2,2-dimethylhydrazino)-3-penten-2-one (L2H) or 5-(2,2-dimethylhydrazino)-2,6-dimethyl-4-hepten-3-one (L3H) and 4-tert-butylpyridine (4-tBupy) in diethyl ether afforded the octahedral complexes Mg(L2)2(4-tBupy)2 (85%) and Mg(L3)2(4-tBupy)2 (79%). Treatment of dibutylmagnesium with two equivalents of L2H or L3H in the absence of 4-tBupy afforded [Mg(L2)2]2 and Mg(L3)2, however, these complexes were difficult to isolate due to the sticky nature of the crude products. A better synthetic approach entailed sublimation of Mg(L2)2(4-tBupy)2 or Mg(L3)2(4-tBupy)2 at 95–100 °C/0.05 Torr, which afforded [Mg(L2)2]2 (94%) and Mg(L3)2 (80%) as colorless crystalline solids that were easily isolated. Treatment of [MgCp(CH3)(OEt2)]2 with two equivalents each of 4-tBupy and L1H afforded MgCp(L1)(4-tBupy) (65%). Similar treatment of [MgCp(CH3)(OEt2)]2 with two equivalents of L2H or L3H afforded the dimeric complexes [MgCp(L2)]2 (81%) and [MgCp(L3)]2 (84%), respectively. [MgCp(L2)]2 and [MgCp(L3)]2 decompose upon attempted sublimation at 125–130 °C/0.05 Torr to afford Cp2Mg (47–53%) and [Mg(L2)2]2 (67%) or Mg(L3)2 (74%). The X-ray crystal structures of Mg(L1)2, Mg(L3)2(4-tBupy)2, [Mg(L2)2]2, Mg(L3)2, MgCp(L1)(4-tBupy), [MgCp(L2)]2, and [MgCp(L3)]2 are described. The thermal stability and volatility of the complexes were determined through preparative sublimation experiments. Many of the complexes sublime without decomposition at moderate temperatures and low pressures, and thus represent new potential precursors for thin film growth using chemical vapor deposition and related techniques.

Mechanistic Details of Atomic Layer Deposition (ALD) Processes

Several examples are provided where the reaction mechanisms of atomic layer deposition (ALD) processes have been characterized by a combination of surface-sensitive techniques. In the first, a proposal is advanced for the layer-by-layer growth of metal films using metal carbonyl precursors and hydrogen as a carbon monoxide displacement agent. For copper film growth, the use of amidinate complexes has being characterized. A third example comprises the deposition of TiN films from TiCl4 and ammonia. Finally, the use of Zr(EtMe)4 as a precursor for zirconium nitride ALD film growth on high surface-area silica is briefly explored.

A study on the flexibility of the hot-filament configuration and its implementation for diamond, boron carbide and ternary alloys deposition

Abstract This paper presents an experimental report on the conditions to grow films with variable composition in the Ta–B–C triangle using the hot-filament (HF) configuration. The HF-Chemical Vapor Deposition (HFCVD) mode is when the precursors for film growth are obtained exclusively from the gas-phase species. Diamond films were produced by feeding the growth system with hydrogen-diluted methane, β-boron films by substituting the methane fraction with diborane, and boron carbide using mixtures of both gases. A second operational mode is achieved when filament sublimation is allowed. In this HF-Physical Vapor Deposition (HFPVD) mode the species stemming from filament and reacting with the gas-atmosphere are the precursors for film growth. The deposition of TaC and TaBC films by means of Ta filaments is reported. A very versatile mode was found when the conditions are adapted during the period of the deposition, switching from PVD to CVD to grow diamond on in-situ deposited TaC.