Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/04—Coating on selected surface areas, e.g. using masks
  • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
  • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
  • C23C16/34—Nitrides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
  • C23C16/45523—Pulsed gas flow or change of composition over time
  • C23C16/45525—Atomic layer deposition [ALD]
  • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
  • C23C16/45536—Use of plasma, radiation or electromagnetic fields
  • C23C16/45542—Plasma being used non-continuously during the ALD reactions

Definitions

• This invention is generally related to thin film deposition methods. More particularly, the invention is related to thin film deposition methods applied to the manufacture of magnetic heads.
• Modern thin film magnetic heads such as used on magnetic storage drives, include numerous steps in which magnetic material is plated in a patterned photoresist or other dielectric material to define magnetic poles of the head.
• the plating process includes the deposition of a thin and highly conformal metallic seed layer inside the walls of patterned openings.
• a typical opening and seed layer deposited in that opening is shown in Fig. 1 .
• a typical application such as a
• a chemical vapor deposition (CVD) process is used to deposit a Ruthenium (Ru) seed layer.
• a highly conformal metallic pre-seed layer such as of
• Titanium Nitride must be deposited as a precursor to the CVD Ru layer.
• approximately 50 to 100 A of preseed layer must be deposited at temperatures below approximately 200 °C, using a non-corrosive chemistry.
• Similar coatings are used as diffusion barriers in thin film electrical devices because of their high melting point, good chemical and thermal stability, low resistivity, impermability to diffusion of silicon, and other reasons.
• Pre-seed layers for Ru coating are typically deposited by physical vapor deposition (PVD) or ion beam deposition (IBD) processes.
• PVD physical vapor deposition
• IBD ion beam deposition
• One exemplary process and processing tool for pre-seed deposition is the cycled plasma annealing atomic layer deposition (ALD) process and tool described in U.S.
• Patent 7,037,574 Another exemplary process and processing tool is described in U.S. Patent 7,071 ,1 18; this tool performs an ALD process including repeated, cycled delivery of a series of precursor pulses and purging pulses across the surface of the substrate, using a laminar flow gas injector. Both patents are assigned to the same assignee as the present application, and incorporated by reference herein in their entirety.
• Highly conformal TiN layers may be deposited by regular CVD or thermal ALD processes, but these processes require high processing temperatures which are inconsistent with applications for forming magnetic devices, in which temperatures must be maintained below, for example, 200 °C.
• An alternative process for pre-seeding for Ru coating is thus needed to achieve the necessary manufacturing uniformity while remaining below the requisite temperature limit.
• RF power is applied to the showerhead using a commercial ASM Polygon platform with an EmerALD reactor (as a reference, see N. Kobayashi, "Scalability of Plasma- enhanced CVD and ALD towards 450mm,” 7th Annual SEMATECH Symposium Japan, June 22, 201 1 , available online at: h tp://www.sematech.org/meetings/archives/symposia/9237/Session%2Q3%2Q45Qmm/5 %20Nobuvuki Kobayashi ASM.pdf .
• TDMAT has a relatively high vapor pressure and reacts rapidly on the surface, and deposits at a relatively low temperature (less than 200 C°), and does not produce corrosive by products. Those by-products which are produced are purged by the purging gas flow.
• the above-noted paper describes a cyclic process lasting 4300 ms per cycle, seen in Fig. 2. Hydrogen continuously flows throughout the cycle. In the first 2300 msec of the cycle a 600 msec purge flow is followed by a 200 msec flow of TDMAT, which is followed by a 1500 msec purge flow. The final 2000 msec of the cycle is a plasma pulse.
• the paper indicates that the resistivity of the TiN layer plated on the substrate by this process diminishes with increasing plasma power until the plasma power reaches a threshold of about 600 W applied for at least 1200 msec, above which point the resistivity of the TiN layer stabilizes at about 250 ⁇ -cm.
• a rf biased showerhead is much more complex and expensive than a simple gas showerhead used for standard CVD and it requires a higher level of maintenance.
• the rf showerhead is a potential source of particle defects due to nucleation at the plasma source (e.g. at or inside the RF biased showerhead). Also it may contribute to thickness non-uniformity due to non-uniform distribution of gas and plasma across the substrate surface. This can be related to the shortcomings in the process described in the above-referenced paper including in-film defectivity (particle contamination) and within-wafer thickness uniformity.
• the present invention forms a TiN layer by a Plasma Enhanced Atomic Layer Deposition (PE-ALD) process that differs in significant ways from the prior art processes discussed in the background.
• PE-ALD Plasma Enhanced Atomic Layer Deposition
• the present invention overcomes the shortcomings of the prior art in part by taking advantage of the fact that a substrate-side RF bias can be used to generate a relatively dense plasma above the substrate.
• a conventional, electrically grounded, CVD showerhead is used.
• the plasma is localized to the substrate surface which can actually improve the uniformity of reactant generation at this surface, while reducing the sources of potential particle generation which are associated with the external plasma generator.
• Substrate-side RF bias is not normally used in PE-ALD; it has been used to provide an induced DC substrate bias for film modification (controlling ion bombardment energy e.g. for stress control or modification of the film
• substrate-side RF bias is not used as the sole plasma source as is proposed in the present application.
• substrate rf bias above some rf power level in thin film deposition processes is typically
• a cyclic PE-ALD process consists of four steps in two phases; in a first phase, a TDMAT pulse is performed followed by an inert gas purge, and in a second phase, a H 2 gas pulse and RF power pulse to the substrate fixture (plasma) are concurrently performed, followed by another inert gas purge. Cycles of this process build a TiN film on the substrate that is highly conformal and provides film properties that meet or exceed those obtained by the background process. It is believed that this improvement is attributable to the exclusion of H 2 flow during the TDMAT and purge steps.
• the Veeco NEXUS® CVD tool available from the assignee of this application and in wide use in the industry, is used as the chamber for the implementation of the inventive process described above, as particularly optimized and adapted for that platform as explained herein.
• the NEXUS® CVD system features a showerhead type gas delivery system and a dual-zone resistive heated chuck with +/- 2°C temperature control to a 250 °C maximum temperature.
• the substrate is biased for in-situ plasma generation for nucleation, densification and PEALD (13.56 MHz).
• the system is fitted with dual, 3.6 liter ampoules coated for ToRuS and TDMAT. Load cell sensors are used to accurately measure the precursor level.
• Fig. 1 illustrates a seed layer and Ru coating in a deep feature in the surface of a substrate
• Fig. 2 illustrates the sequencing of a PE-ALD TiN deposition cycle in accordance with the prior art discussed in the background;
• Fig. 3 illustrates a cycle of one embodiment of a PE-ALD process in accordance with the present invention, as presently envisioned after experimentation with the relative duration of TDMAT and H 2 flow durations and purge durations.
• TDMAT flows for 1 .5 seconds (1500msec) followed by 1 seconds (1000msec) of purge;
• H 2 flows in concert with the application of RF plasma energy for 2.5 seconds (2500msec) followed by 1 seconds (1000msec) of purge
• the resulting total cycle time is 6 seconds;
• Fig. 4a illustrates the growth rate achieved by the process of the present invention as a function of the duration of TDMAT flow, showing that the growth rate improves steadily until the TDMAT flow duration reaches approximately 1 .5-2 seconds, which is the duration used in the process illustrated in Fig. 3. It can be seen from this figure that the surface deposition per cycle is self-limiting as even much longer flow rates do not increase deposition rate;
• Fig. 4b illustrates the deposited film thickness as a function of the number of cycles in accordance with the cycle conditions shown in Fig.3.
• the growth rate is approximately 100 A for each -230 cycles, greater than 250A/hr, which is similar to the growth rate of 100 A for -300 cycles accomplished by the paper described in the background;
• Fig. 5a illustrates a depth profile for a TiN film grown according to principles of the present invention
• Fig. 5b illustrates a depth survey of the Ti 2p peaks
• Fig. 5c illustrates C1 s peaks.
• Fig. 6 illustrates film resistivity as a function of temperature and plasma power.
• Fig. 7 a illustrates the resistivity of the deposited film as a function of the TDMAT pulse time, showing that film resistivity reduces with increasing pulse time, but levels off at relatively short pulse times, illustrating that fairly short pulses of TDMAT are sufficient to saturate the surface for reaction and achieve resistivity similar to the 250 ⁇ -cm measured in the paper discussed in the background
• Fig. 7b illustrates the resistivity of the deposited film as a function of the applied plasma power, showing the higher plasma power acts to introduce greater resistivity;
• Fig. 8 illustrates the dependence of growth rate (A per cycle) and DC bias voltage applied to the substrate, as a function of plasma power applied.
• a threshold minimum plasma power is required for significant growth, but above that threshold power, the growth rate declines, as a result of etching due to substrate DC bias.
• the optimal plasma power can be selected to be just above the threshold required to induce high deposition rates;
• Fig. 9 illustrates the dependence of growth rate upon plasma/H 2 pulse time, suggesting that there is limited dependence of growth rate on plasma/H 2 pulse time;
• Fig. 10 illustrates the dependence of resistivity upon plasma/H 2 pulse time, similarly suggesting that there is limited dependence of growth rate on plasma/H 2 pulse time once the pulse time exceeds approximately 1 second;
• Figs. 1 1 a, 1 1 b and 1 1 c illustrate the results of density and ordering measurements on deposited films using glancing angle x ray diffraction (XRD) analysis.
• XRD x ray diffraction
• Fig. 12 illustrates the stoichiometry of an approximately 270 A film developed in accordance with principles of the present invention, atop a Silicon Oxide substrate, as measured by Rutherford backscattering spectrometry (RBS).
• the TiN film measures as Ti 47.0 at% and N 53.0 at%, and below the film the substrate measures trace levels of N included in the Si and O of the substrate. C inclusion is below the RBS detection limit;
• Fig. 13 illustrates the dependence of film density upon applied plasma power, showing the decrease in film density with increasing plasma power
• Fig. 14 illustrates the dependence of surface roughness with plasma power, showing increased roughness with increasing plasma power.
• Fig. 15a is a micrograph of a cross section of a TiN film (dark black) formed in accordance with the principles of the present invention, showing good step coverage and uniformity
• Fig. 15c and 15d are selected area electron diffraction patterns of the film
• Fig. 15d is a plan view showing the grains of this film which are characteristic of a relatively amorphous TiN matrix with some nano-grains;
• Fig. 16 is a cross sectional SEM view of an approximately 70 A PEALD based TiN film, overcoated with approximately 100 A of CVD deposited Ru. The resulting deposition conformality is similar for features of various sizes as shown in the close-up views. Although the SEM does not easily distinguish TiN film from Ru, the good conformality of the combined TiN / Ru coating indicates that the TiN pre-seed layer was conformal;
• Fig. 17 shows stress of a film grown according to principles of the present invention, as a function of plasma power
• Fig. 18 illustrates a comparison of etch rates of films deposited under varying plasma power
• Fig. 19 illustrates the densities (XRR) of TiN films deposited at different plasma powers are plotted and compared with the densities of films grown in rf-biased shower head plasma;
• Fig. 20 illustrates an optical characterization of TiN film grown according to principles of the present invention, using a variable angle spectroscopic ellipsometer.
• Fig. 21 shows wafer-to-wafer (WtW) repeatability and within wafer (WiW) uniformity accomplished in repetition of the process of the present invention.
• a two phase process for PE-ALD TiN deposition using the process sequence shown in Fig. 3, achieves a thruput of greater than 250 A coating per hour of processing time, at deposition temperatures below 200 °C. Film densities of 4.3 - 5.3 gm/cm 3 and resistivities of 100-300 ⁇ -cm have been demonstrated, at surface roughnesses of less than 6 A. Virtually no incubation period is required for the process.
• a Veeco Instruments NEXUSTM CVD system was used for this research. This system uses a grounded vertical-flow gas shower head with plasma generation provided by 13.56 MHz RF bias at the substrate. TDMAT was supplied through a bubbler at room temperature using ultra high purity Ar as the carrier gas. H 2 gas was used as reactant. Substrate heat is provided by the wafer chuck, equipped with conductive heaters and backside Helium gas. 150 mm Si wafers with thermal SiO2 of 5000 A were used in these experiments.
• Deposited films were characterized by glancing angle x-ray diffraction and x-ray reflectivity using a PANalytical X'pert PRO MRD x-ray analysis system.
• Fig. 3 shows a schematic of an exemplary sequence of pulse and purge of gases.
• a wide range of pulse and purge steps was investigated to optimize the process, with a total cycle time from 5 to 19 seconds.
• TDMAT pulse times in the range from 0.5 - 5s, H2 pulse times of 0.75 - 8s, and purge times of 1 -3s were investigated. Effects of key process parameters for the substrate-biased configuration are described below.
• the TDMAT pulse time was varied to deposit TiN films while keeping other parameters the same as shown in Fig. 3. As indicated in Fig.
• the deposition rate increases with the TDMAT pulse time and saturates at around 1 second, clearly indicating self-limiting surface chemisorption process of the TDMAT on SiO 2 .
• the bulk TiN lattice parameter of 4.2 A and the growth rate around 0.41 A cycle it is reasonable to believe that approximately one tenth of the SiO 2 surface is covered with TDMAT molecules in one cycle.
• Similar experiments were performed by varying H 2 pulse and plasma time. It was found that the growth rate saturates at ⁇ 1 second, which means that a minimum of 1 sec of H 2 pulse/plasma is needed to fully reduce the TDMAT in to TiN during each cycle.
• film thickness was measured as a function of the number of deposition cycles and plotted in Fig. 4b. It can be seen that the thickness is linearly related to the number of cycles, showing that the process is complimentary.
• Fig. 5a for a TiN film grown at 250 W, 200°C and the corresponding depth survey of the Ti 2p peaks is illustrated in Fig. 5b.
• Fig. 5c shows C1 s peaks.
• the first 100 A of the film surface was oxidized by post-deposition exposure to ambient air to form TiO2. It was removed by sputtering, and the results below describe the remaining 750 A of the deposited film.
• This film was found to be primarily composed of TiN with approximately 5% of oxygen and 8-9% of carbon.
• the Ti 2p peaks and C1 s survey indicate that Ti is predominantly bonded to N.
• the film resistivity as a function of temperature and plasma power is shown in Fig. 6. It can be seen that the resistivity of the as-grown TiN films at 250 W significantly varies with substrate temperature: as the temperature increases from 150 °C to 200 °C, the volume resistivity decreases from 950 ⁇ -cm to 185 ⁇ -cm. Over the range from 250 W to 350 W at 200 °C, the measured resistivity is -200 ⁇ -cm. As the plasma power increases further to 550 W, the film resistivity gradually increases to -300 ⁇ -cm.
• Fig. 7a the effect of varying the TDMAT and H 2 /plasma pulse times are shown.
• the resistivity of the films gradually lowers with pulse time of TDMAT to saturate at above 1 second.
• the resistivity of the films gradually lowers with H 2 pulse to saturate at above 1 second. Slight gradual increase in resistivity above 3 seconds of H 2 pulse may be attributed to more dis-ordered structure in the film due to increased ion-bombardment.
• the ratio of peak intensities of the (1 1 1 ) to (200) and (220) are significantly higher than that of powder diffraction, which indicates that the film is textured with the [1 1 1 ] preferentially pointing out-of-plane.
• the peaks of the films deposited at 150 °C and 175 °C processes have an obvious shift to higher value of 2-theta, which is not observed for films deposited at 200 °C and 250 W. As discussed in reference to Fig. 5, this could be due to different or incomplete chemical reaction, possibly due to formation of carbide with different lattice parameters.
• Nominal thicknesses of 400 A of TiN films were deposited on standard patterned Si wafers with line-spacing trenches of S1O2 on SiO2/SiNx Si stack with trench depth of ⁇ 1 micron.
• Cross-sectional TEM characterization of the samples deposited using 200 °C, 450 W and 200 °C, 250 W processes was carried out.
• a low magnification bright field image is shown in Fig. 15a for the film deposited at 200 °C and 450 W. It can be seen that the step coverage of the TiN film is ⁇ 100 % for the features with aspect ratio of 4:1 .
• Step coverage in a 10:1 AR TSV structure (not shown here) with a 20 micron trench width is seen to be more than 85 %.
• the selected area electron diffraction patterns (SAEDP) of the films are shown in Fig. 15b and 15c.
• the SAEDP of 250 W process shows an uneven bright spot-on-ring character. These bright spots are consistent with the fact that the film is textured with preferential [1 1 1 ] pointing out-of- plane direction, as indicated by the XRD results discussed earlier.
• the 450 W process SAEDP is more ring like with diffraction spots more evenly distributed and diffused. This clearly indicates that the film structure is more disordered and less textured as we increase the plasma power.
• High resolution TEM which is not shown here, indicates that the film structure of the 200 °C 450 W has nano-sized grains buried in an amorphous phase matrix.
• FIG. 16 shows a cross-sectional SEM image of a trench structure with an aspect ratio of 6:1 .
• the step coverage of the Ru and the TiN is nearly 100% within the error of measurement. From scratch and peel test, both Ru/TiN and TiN/SiO2 interfaces show good adhesion between these layers. No delamination of Ru was observed on peel test until the Ru thickness increases up to 1200 A. Good step coverage and adhesive properties of the TiN and Ru layers make TiN a good material to serve as pre-seed for Ru in DS applications.
• Fig. 17 shows stress in a 100 A TiN film as a function of plasma power.
• the residual stress in the film is compressive and decreases with plasma power.
• the stress can be introduced from the difference of thermal expansion coefficients (TEC) of materials during sample cooling, ion bombardment, and to some extent, mismatch of lattices.
• TEC thermal expansion coefficients
• the bombardment of the ions results in knocking-out of some atomic species from the growing film in addition to disordering the lattice structure of nano-crystallites.
• the removal of the atoms and disordering of lattice relaxes the film and thus lowers the residual compressive stress of the film.
• the stress can be lowered to under -200 MPa.
• etch rate of PEALD based TiN film (-180 A/min) is lowest among all the films. This confirms a highly structural quality of the film in terms of etch resistance.
• the etch rate of the films investigated in this paper in SC1 etchant was found to be ⁇ 7, 8 and 12 A/min for 250, 350 and 450 W plasma processes respectively, which shows that the etch rate increases with the plasma power. This could be attributed to marginal decrease in density of the films with plasma power, as shown in Fig. 19.
• the inventors believe that the much higher etch-resistance of our films is due to energetic ion bombardment in our substrate biased plasma process.
• the films are believed to be less textured and are denser compared to films grown under shower head biased plasma configuration.
• the latter is shown in Fig. 19, where the densities (XRR) of our TiN films deposited at different plasma powers are plotted and compared with the densities of films grown in rf-biased shower head plasma.
• the mass densities of films grown by the process of the present invention are higher and approach that of bulk TiN (5.4 g/cm3) reported in the literature.
• Fig. 20 shows optical characterization of our TiN film by a variable angle spectroscopic ellipsometer.
• the TiN films were grown on the Si (1 1 1 ) substrate using standard 450 W PEALD process.
• the dielectric functions of the polycrystalline PVD TiN film available from literature are also plotted in Fig. 20.
• the imaginary part of the permittivity ( ⁇ ") which signifies propagation loss in the film, is comparable in visible and near IR region of wavelength.
• the loss in our PEALD film gets significantly higher compared to the PVD TiN, an indication of the near-amorphous nature of the PEALD film grown in accordance with the present invention.
• the differences in the optical losses at different wavelength range for amorphous and polycrystalline TiN films are primarily due to their differences in the absorption mechanism. At shorter wavelength, i.e. visible and near IR, the damping in the dielectric function is caused by collision of electrons with electrons and phonons. But at longer wavelength, i.e.
• Fig. 21 shows wafer-to-wafer (WtW) repeatability and within wafer (WiW) uniformity.
• WtW wafer-to-wafer
• WiW wafer-to-wafer
• Typical 3-sigma over mean WtW repeatability and WiW uniformity in sheet resistance are seen to be below 3 % and 6 % respectively.
• Typical growth rate is seen to be 0.4 A cycle.
• the method described above is directed specifically to deposition of TiN, the same method may be advantageously used for PEALD of other similar metal compounds, e.g. nitrides, oxides, or carbides of other transition metals, particularly the refractory metal compounds, including technologically important materials such as CrN, TaN, TiO 2 , ZrO 2 , Cr 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , TiC, CrC, WC, MoC, and also including alloys of these metals, such as TiAIN, TiCN, NiCrBSi, and cobalt chromium aluminum yttrium [CoCrAIY].
• nitrides, oxides, or carbides of other transition metals particularly the refractory metal compounds, including technologically important materials such as CrN, TaN, TiO 2 , ZrO 2 , Cr 2 O 3 , Nb 2 O 5 , Ta 2 O 5 , TiC, CrC, WC, MoC, and also including alloys of these
• the PEALD process would use a precursor corresponding to the above-described TDMAT for TiN deposition, i.e. some compound of the metal species to be deposited which is thermally and chemically stable but readily reacts with a reactant species corresponding to H 2 for TiN deposition, e.g.
• PEALD precursors and plasma reactants for these materials e.g. as tabulated in the following reference H. B. Profijt, et al, "Plasma- Assisted Atomic Layer Deposition: Basics, Opportunities, and Challenges," J. Vac. Sci. Technol. A, Vol. 29, No. 5, Sep/Oct 201 1 , p. 050801 -1 , may be used.

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