Surface Chemistry in the Initial Stages of Titanium Nitride Atomic Layer Deposition Using Operando Ambient Pressure X-ray Photoelectron Spectroscopy
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Surface Chemistry in the Initial Stages of Titanium Nitride Atomic Layer Deposition Using Operando Ambient Pressure X-ray Photoelectron Spectroscopy
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Chemistry of Materials

Cite this: Chem. Mater. 2026, 38, 4, 1902–1914
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https://doi.org/10.1021/acs.chemmater.5c02974
Published February 11, 2026

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Abstract

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Studies of the surface chemistry of the first few cycles of atomic layer deposition (ALD) using in situ and time-resolved operando techniques are attractive for realizing, understanding, and obtaining true mechanistic information during the deposition. However, the latter techniques are yet to be applied to ALD of metal nitrides. Here, we present a surface-chemistry investigation through a time-resolved ambient pressure X-ray photoelectron spectroscopy (APXPS) study of the initial growth of titanium nitride (TiN). The Ti 2p, O 1s, N 1s, C 1s, and Si 2p core-level spectra recorded at different stages during the deposition show that chemisorption occurs immediately on the silicon dioxide surface due to the interaction of tetrakis(dimethylamido)titanium(IV) (TDMAT) with the surface. A delay in nucleation on the TDMAT-terminated surface was observed during the NH3 pulse. The intensity of the Ti 2p and N 1s core levels began to increase after four ALD cycles, showing that the surface was coated with Ti and N atoms and no Si signals were observed with time. The results show that ligand exchange reactions take place before transamination reactions. This was verified using the periodic changes in the intensity and peak positions of the above-mentioned spectra and complemented by residual gas analysis using mass spectrometry. These results can provide insights into the ALD surface growth of not only TiN but also other metal nitrides.

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1. Introduction

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Atomic layer deposition (ALD) is a thin-film synthesis technique defined by a series of sequential, self-terminating surface reactions involving a precursor and a reactive gas. (1) Under optimal conditions, these reactions reach saturation, thereby providing numerous benefits for the film quality, including excellent conformality, repeatability, uniformity over large areas, and precise and straightforward film-thickness control. (2) ALD is suitable for depositing a range of materials, including metals, metal oxides, and metal nitrides.
Although there have been many studies of ALD process developments, the mechanistic details of the interaction, reactivity, nucleation, and growth chemistry are still not well understood in most cases, particularly in the initial stages. Understanding the early interaction behavior of specific precursors is not only crucial for ALD process optimization purposes (since these mechanisms will govern the growth of the material) (3) but also because nucleation impacts the entirety of the growth process, hence significantly affecting the material’s properties and its functionality. (4)
Many ALD processes typically initiate with a nucleation phase, which is characterized by the formation and growth of islands. (5) After a varying number of cycles, influenced by the chemistry of the precursor and substrate interface, these islands merge to form a continuous film. However, the initial stages, or first few ALD cycles, are challenging to characterize using conventional techniques due to the complexity of the nucleation process, which becomes significantly easier to analyze once the steady-state growth regime is established. Performing in situ and time-resolved or operando measurements during deposition is the only way to gain accurate mechanistic information. In the context of ALD, the term in situ generally denotes experiments in which film growth is monitored intermittently between cycles, typically under vacuum and within the same reactor, thus preventing exposure of the sample to air. By contrast, we use the term operando to describe time-resolved characterization performed concurrently with film growth under realistic or near-realistic pressure conditions, thereby distinguishing it from in situ approaches that do not provide temporal resolution. (6) For decades, in situ measurements (7) have been performed primarily using mass spectrometry, infrared spectroscopy, quartz crystal microbalance measurements, optical emission spectrometry, spectroscopic ellipsometry, and ultrahigh vacuum (UHV) XPS. Operando experiments, e.g., operando ambient pressure X-ray photoelectron spectroscopy (APXPS), provide dynamic insights into chemical reactions during film growth under realistic temperature and pressure regimes similar to those in a reactor. Operando APXPS, which has gained much attention for time-resolved measurements in recent years, is conducted concurrently with the dosing of the precursor, i.e., monitoring the chemical environment of the substrate and film surface while pulsing the ALD precursors. (8−10) As opposed to the more common in situ XPS experiments that are performed after ALD half-cycles and at times under nonrealistic conditions (e.g., high vacuum), operando APXPS closely mimics or replicates actual processing environments, such as atmospheric or near-pressurized conditions. (11)
Titanium nitride (TiN) is one of the more widely studied ALD systems due to its desirable properties for numerous applications in the protective hard coatings industry and in semiconductor device manufacturing. Applications of TiN films include aluminum diffusion barriers, seed layers for copper plating, and gate electrodes in metal-oxide-semiconductor (MOS) devices. (12−14) In addition to these uses, TiN is widely employed as a diffusion barrier for catalytic metals in the growth of carbon nanotubes and the deposition of self-organized metallic particles. (15−18) TiN films are also well-known for their appealing golden hue, making them suitable for decorative purposes. (19,20) These applications make use of TiN properties such as the high melting point (∼3000 °C) and hardness (28 GPa at 25 °C) in combination with high thermal and electrical conductivity (23 W/mK and 135 μΩ/cm respectively). (21,22)
So far, operando APXPS surface chemistry studies of initial ALD stages have been limited to metals, e.g., Pt (10) and oxides e.g., HfO2 (6,9,23,24) and TiO2. (8) No APXPS investigations on nitrides have been reported yet. In contrast, using other techniques, several studies on the ALD of nitrides such as TiN have previously been published. (25−29) Here we present, for the first time, a surface-chemistry investigation through a comprehensive time-resolved APXPS study of the initial stages of TiN ALD, during an ongoing thermal ALD process using tetrakis(dimethylamido)titanium(IV) (Ti(NMe2)4, TDMAT) and ammonia (NH3) on a natively oxidized Si surface. The Si 2p, C 1s, O 1s, N 1s, and Ti 2p core-level spectra recorded at different stages of deposition (before, during, and after) and the observed periodic changes of the above-mentioned spectra intensity and peak positions help us understand that during the TiN ALD surface reactions, TDMAT readily chemisorbs through a ligand exchange mechanism with surface hydroxyls (||−OH) and a possible insertion reaction, while NH3 takes time to initiate the transamination reaction. The Ti 2p and N 1s spectra exhibit clear signatures of successful nitridation, evidenced by the emergence of Ti–O–N and Ti–N bonding, which become most pronounced after at least four ALD cycles. These findings provide a pathway to understand the surface reactions happening during metal nitride deposition by ALD.

2. Methods

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Employing time-resolved APXPS for surface and gas phase analysis, in conjunction with mass spectrometry as demonstrated in this study, offers an excellent approach for identifying reaction intermediates or metastable surface species that are challenging to detect using standard XPS techniques. Ultimately, we showcase the capability to monitor dynamic alterations in surface chemistry associated with nitride ALD, which could be highly beneficial for development and control in various applications.

2.1. APXPS

A specialized ALD reaction cell developed for the SPECIES beamline at the MAX IV synchrotron in Lund, Sweden was used for the experiments. (30,31) The ALD reaction cell is contained within a UHV chamber and can be filled to a pressure of up to 20 mbar while still maintaining high vacuum conditions in the outer chamber and allowing simultaneous XPS measurements. Specific details regarding the ALD setup can be found in the comprehensive description by Kokkonen et al., (32) while an overall description of the SPECIES beamline and the endstation is provided in earlier publications. (30,33) The APXPS measurements were conducted using either the snapshot or swept mode of the electron energy analyzer. In the snapshot mode, electron spectra with a limited energy range – defined by the pass energy of the analyzer – are acquired with high time resolution. The benefit of time resolution comes at a cost in that the varying efficiency across the detector is not averaged out and that, therefore, the spectrum is affected by incorrect relative intensities at different energies. In the swept mode a variation in efficiency is averaged out since each kinetic energy is measured in each channel of the detector. This renders the relative intensities accurate, but spectrum acquisition is relatively slow. During the half-cycles, the O 1s, Ti 2p, N 1s, C 1s, and Si 2p core-level spectra were measured in snapshot mode using a photon energy of 680 eV. The swept spectra were measured at different photon energies with each resulting in approximately the same electron kinetic energies, allowing us to probe each core level with the same probing depth. The overall spectral resolution, given by (ΔEA)2+(ΔEBL)2 (where ΔEA represents the analyzer resolution and ΔEBL is the beamline-dependent photon energy resolution), was approximately 250 and 350 meV for swept-mode and snapshot-mode measurements, respectively. To minimize the occurrence of X-ray induced effects in the spectra, the sample was continuously moved by automatically scanning it to new positions for each XPS measurement. This movement resulted in slight variations in the overall signal intensity due to minor drifts of the sample in and out of the optimal focus position of the electron energy analyzer.

2.2. Film Deposition

Crystalline Si(100) wafers, covered with a native oxide layer, served as substrates for the ALD process. Before being introduced into the APXPS system, the substrates underwent cleaning in an ultrasonic bath using deionized water, ethanol, and acetone. Subsequently, the sample was transferred into the UHV chamber of the AXPS system and into the ALD cell. A TDMAT container (acquired from Sigma-Aldrich) was attached to the gas system of the setup and heated to about 70 °C. The process temperature of the sample was set to around 250 °C, as monitored by a thermocouple attached to the sample holder close to the sample. A total pressure of approximately 0.8 mbar (being the sum of either the vapor pressure of the TDMAT precursor or its coreactant NH3 and the Ar carrier gas) was maintained in the ALD cell during deposition. For both half and full ALD cycles, 5 × 5 s pulses of TDMAT and 5 × 50 ms NH3 with 30 and 5 s purge times, respectively, were used. Purge times were made long enough to ensure adequate separation between the two precursor pulses and allow enough time to obtain adequate XPS signal statistics.

2.3. Data Analysis

The binding energy scale in all instances and in the first spectrum of the time-resolved series was calibrated using the Si 2p3/2 peak of bulk silicon, which is found at 99.3 eV, (34) aligning well with values reported in the literature. (35−37) The TDMAT signal was designated as the starting point of a cycle, for the back-to-back cycles. Intensity calibration of the time-resolved spectra was performed by dividing the swept spectrum by the corresponding snapshot spectrum to obtain channel-dependent calibration factors. All 200 data points in each snapshot scan were multiplied with the corresponding factor. Linear or polynomial backgrounds were removed from all spectra. For peak position evolution, a Voigt function was fitted to the region around the local maximum, and the resulting peak centers were plotted as a function of time. All data were acquired using SpecsLab Prodigy 4. The CasaXPS software was used to fit the swept XPS data with Gaussian–Lorentzian lineshapes and linear backgrounds. The fit parameters can be found in Tables S1–S4 in the Supporting Information. Origin 2019 was used for refined plotting.

2.4. Residual Gas Analysis

To support the APXPS data regarding the reactions occurring during TiN ALD, we used residual gas analysis (RGA) with a time-of-flight mass spectrometer (ToF-MS). The ToF-MS was located on the first differentially pumped section of the electron analyzer; thus, we assume that the ToF-MS data is rather sensitive to the gaseous products released from the sample during the half-cycle reactions. However, determining the exact contribution of observed data from the sample surface versus the chamber walls remains unknown.

3. Results

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First ALD Half-Cycle: TDMAT

Figure 1 shows the time-resolved O 1s, Ti 2p, N 1s, C 1s, and Si 2p ambient pressure X-ray photoelectron (APXP) spectra measured on the Si substrate surface in the first half-cycle, i.e., before, during, and after exposure to TDMAT at 250 °C. The dashed horizontal lines indicate the starting time of the Ar carrier gas flow followed by the 5 × 5 s TDMAT pulses.

Figure 1

Figure 1. Time-resolved a) O 1s, b) Ti 2p, c) N 1s, d) C 1s, and e) Si 2p APXP spectra measured during the TDMAT half-cycle at 250 °C while f) shows the peak position evolution of the main peak regions in C 1s and Ti 2p plots as a function of time during the TDMAT pulse. The spectra were measured using a photon energy of 680 eV. The color scale shows how the intensity of the indicated core levels changes with time. For ease of visibility, the Ti 2p, N 1s, and C 1s intensities were multiplied by factors, as indicated, relative to the Si 2p intensity.

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The O 1s and Si 2p spectra of the initial substrate surface indicate that the SiO2 surface is possibly hydroxylated, (36,38) while the intensities decrease when Ar carrier gas starts to flow and further decreases during the TDMAT pulses. Contrary to common assumptions, SiO2 surfaces are rarely fully hydroxylated, and the true extent of hydroxylation remains difficult to quantify with XPS. While defects readily undergo hydroxylation, the inherent resistance of silica to full hydroxylation (40,41) challenges the conventional view of a uniformly hydroxylated surface. High O 1s and Si 2p intensities alone are insufficient to infer hydroxyl coverage, as oxide and hydroxide contributions are difficult to disentangle spectroscopically. (40) Careful comparison to reference studies such as Miyaji et al., (42) which differentiates oxide and hydroxyl peaks, and Namiki et al., (39) which positions the O 1s oxide peak relative to Si 2p, provides a framework for a more rigorous assessment of surface hydroxylation in initial ALD cycles.
The apparent shift of the entire O 1s spectrum to lower binding energy after the TDMAT pulses is due to a new peak that is in agreement with the formation of titanium oxide. (43,44) As expected, no signal is seen in the Ti 2p spectrum of the initial surface. It appears gradually during the 5 × 5 s TDMAT pulses before it increases after the pulsing is completed. A clear correlation is observed between the Ti 2p signal and the N 1s and C 1s signals, accompanied by a 0.1 eV shift in the Si 2p peak. As no spectral calibration was applied beyond the one based on the Si 2p position in the first spectrum of the time-resolved measurement (cf. Methods), this shift is attributed to band bending effects rather than to calibration artifacts. Low N 1s and C 1s intensities are shown to appear on the initial surface as adsorbed species, which reduce in intensity when Ar carrier gas flows. Increased intensities are seen with a C 1s displacement toward higher binding energy by approximately 1.3 eV during the TDMAT pulses. These signals decrease again when the first half-cycle is completed. An interesting point is that the reaction is not immediate; instead a clear delay in Ti incorporation is observed. This is evidenced by the change in Ti 2p signal intensity between the period during the TDMAT pulses and the period following the TDMAT pulses. The initial N 1s binding energy (∼399 eV) during TDMAT pulses agrees with that of the amide ligand. (45) The increase in the observed N 1s peak (∼399 eV) (46) and C 1s peak (∼286 eV) (47) intensities during the pulses indicates the adsorption of surface complex species from the methylamido precursor. (48) The Ti 2p peak looks different (during and after TDMAT pulses) which could be a sign of different oxidation states that coalesce into the titanium oxide-like features creating an apparent increase of intensity. More likely, the signal is characteristic of the intact surface-adsorbed precursor prior to ligand removal. It might also be due to the TDMAT gas phase signal. Afterward, the decrease of these two peak intensities seems to be correlated with the increase of the Ti 2p peak intensity (∼459 eV) (49) after the TDMAT pulses are completed. A plausible explanation for this is the removal of amido ligands (which contain both N and C) during purging, leaving behind Ti bonded to the initial substrate surface oxide species. (50) In other words, the increase in Ti 2p is due to the removal of the DMA– ligands, and so the titanium signal becomes less attenuated.

Second ALD Half-Cycle: NH3

Figure 2 displays the time-resolved O 1s, Ti 2p, N 1s, C 1s, and Si 2p APXPS signal intensities measured during the second half-cycle of ALD of TiN, i.e., the NH3 pulsing. The horizontal lines indicate the starting times for two NH3 pulse trains. The first pulse train consisted of one set of 5 × 50 ms NH3 pulses. The second pulse train comprised 10 sets of 5 × 50 ms NH3 pulses.

Figure 2

Figure 2. Time-resolved a) O 1s, b) Ti 2p, c) N 1s, d) C 1s, and e) Si 2p APXPS spectra measured during the NH3 half-cycle at 250 °C while f) shows the center of gravity plot as a function of time during the first and second NH3 pulse trains to visualize the dynamic changes. The spectra were measured using a photon energy of 680 eV. The color scale shows how the intensity of the indicated core levels changes with time. For ease of visibility, the Ti 2p, N 1s, and C 1s intensities were multiplied by factors, as indicated, relative to the Si 2p intensity.

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The evolution of the spectral signals can be followed the same way as in the first half-cycle, both in terms of the intensity and binding energy. The intensities do not show any apparent trends from the beginning to the end of the NH3 half-cycle pulses. From Figure 2, it is clear that prior to the Ar carrier gas and the two NH3 pulses, the surface had titanium adsorbed from the TDMAT pulse in the first half-cycle as shown by the Ti 2p intensity map. While changes are observed in the C 1s region, the O 1s signal remains largely unchanged. The variation in C 1s is therefore more plausibly attributed to the accumulation of unreacted (“free”) ligands from the gas phase on the surface. In addition, the carrier gas was turned off between the two half-cycles shown in Figures 1 and 2, which may also influence the observed signals. The C 1s peak position appears to be constant before and after the NH3 exposure, shown by the stability of the C 1s center of gravity (Figure 2f), which accounts for the absence of a measurable decrease or increase during the NH3 pulses. To resolve this more clearly, intensity evolution extracted at defined time points from the image plots would allow a more direct comparison of the temporal evolution indicating that no ligand removal is evident in the second half-cycle through NH3-assisted ligand exchange surface reactions. This is shown in Figure 3.

Figure 3

Figure 3. a) N 1s and b) C 1s intensity evolutions extracted at defined time points from the image plots in Figure 2c) and d), respectively, allowing a more direct comparison of the temporal evolution indicating that no ligand removal is evident in the second half-cycle through NH3-assisted ligand exchange surface reactions.

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Interestingly, the failure to remove precursor ligands in the second half-cycle deviates from observations in our other SiO2 experiments (even though for oxides), suggesting that variations in the initial surface state (e.g., differences in surface hydroxyl density and defect concentration) may have altered the reaction. (9) Such differences could reflect modified ligand desorption kinetics or alternative reaction pathways, potentially influencing the nucleation behavior and early growth mode of the TiN film. It is worthwhile noting that carbon-containing species are detected at the onset of the second half-cycle, despite their low intensity at the end of the first half-cycle. The observed binding energy is too low to correspond to nitrogen-bonded amido ligands, suggesting the presence of aliphatic carbon likely originating from residual chamber gases. No nitrogen is detected in the snapshot spectra, which rules out an assignment to methyl–methylenimine or other N-containing species. (6,51) The appearance of such adventitious carbon between half-cycles may influence the initial surface chemistry by transiently passivating reactive sites, and this possibility will be further examined in the context of the swept spectra. The Ti 2p signal is strong from the beginning, after the first half-cycle (TDMAT exposure), consistent with the presence of Ti on the surface. The relatively constant binding energy and intensity suggest Ti 2p (∼459 eV) (49,52) remains in a stable Ti–O environment and is not significantly altered during NH3 exposure. N 1s shows a noisy background signal at lower binding energy regions indicating that there is no direct evidence of nitrogen incorporation occurring, i.e., NH3 may not strongly chemisorb or decompose on the surface in just one-half-cycle.
An important consideration is the time interval between ALD half-cycles. In our experiments, the waiting time was 41 min between the initial TDMAT half-cycle and the subsequent NH3 half-cycle and 44 min between completion of the NH3 half-cycle and the initiation of additional ALD cycles. Longer delays between half-cycles increase the likelihood of impurity incorporation, whereas shorter intervals reduce this risk.

Three Additional ALD Cycles: 3 × (TDMAT + NH3)

The time-resolved APXPS data recorded during three subsequent ALD cycles at 250 °C are displayed in Figure 4, illustrating the evolution of the O 1s, Ti 2p, N 1s, C 1s ,and Si 2p APXP spectra as the deposition progresses. The Ar carrier gas flow was kept open after the second half-cycle, and we continued to initiate three additional full ALD cycles, meaning that we studied four full ALD cycles in total in this investigation.

Figure 4

Figure 4. Time-resolved a) O 1s, b) Ti 2p, c) N 1s, d) C 1s, and e) Si 2p APXP spectra measured during three additional cycles at 250 °C, while f) and g) show the peak position evolution of the main peak regions in Ti 2p and C 1s plots as a function of time during the ALD cycles. The color scale shows how the intensity of the indicated core levels changes over time. The spectra were measured using a photon energy of 680 eV. The time at which each ALD half-cycle starts is marked by horizontal dashed lines and denoted TDMAT or NH3 to symbolize when each corresponding half-cycle starts and ends. Note that this is a continuation of Figures 1 and 2, hence precursor pulsing starts at TDMAT (2). We can clearly see the five short pulses of TDMAT in each of the TDMAT pulse trains as drops in Ti 2p intensity (this is superimposed on the raster-induced intensity changes). The dotted red line on the Ti 2p map shows the shift toward lower binding energies during the three ALD cycles with time, indicating a shift from oxide toward nitride character in the films. The oscillating behavior shown on the maps has nothing to do with the ALD process itself but emanates from the continuous movement of the sample during analysis as mentioned in the Methods section. For ease of visibility, the O 1s intensity was multiplied by a factor of 2 relative to the Si 2p intensity.

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Most notably, the Ti 2p spectra indicate approximately a 1.3 eV shift toward lower binding energy after the second TDMAT pulse compared to after the first TDMAT pulse. Here we need to be aware that the deposited TDMAT (see Figure 1 and Figure 5b) has a similar Ti 2p binding energy as TiN, from the adsorbed Ti–N(CH3)2 species. (53) The Ti 2p peak center of gravity is stable after the second TDMAT pulse, with negligible shift in the peak position after the third cycle, suggesting a new chemical state of Ti at this stage of the deposition, i.e., the Ti–N increases while the Ti–O decreases.

Figure 5

Figure 5. APXPS core level scans of the a) O 1s, b) Ti 2p, c) N 1s, and d) C 1s lines at 250 °C from an initial substrate surface until after the three additional ALD cycles. The spectra were measured using photon energies of 680 eV for the O 1s and Ti 2p lines, while 550 and 410 eV were used in the measurement of the N 1s and C 1s spectra, respectively. To make incorporation of N and Ti more visible and easier to follow, the corresponding survey spectrum for each of the four conditions is available in the Supporting Information. For ease of identification of minor components, the relevant spectra were multiplied by corresponding factors as shown.

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The N 1s and the C 1s both show spectra with increased intensities during the TDMAT pulse showing that both N and C emanate from the precursor ligands. Following TDMAT exposure, distinct spectral signatures corresponding to adsorbed amido ligands are evident. Subsequent pulsing of NH3 results in the systematic disappearance of these signals, consistent with the reactive removal of the amido species - likely via transamination and hydrogenation pathways. However, experimental artifacts, most notably the intensity fluctuations due to sample rastering, complicate the precise quantification of these transformations. A major component which could be attributed to carbon-containing groups (ligands, -NMe2) is observed during a TDMAT pulse, while in the N 1s signal the lower binding energy at ∼397 eV (54) associated with Ti–N was observed as more TDMAT and NH3 pulses were made. This suggests that the NH3 reacts with TDMAT to form TiN with the ligand removed intact. Notably, there is also a 0.3 eV shift toward lower binding energy for O 1s when more cycles are executed, indicating a transition from silicon oxide to titanium oxide and finally to an oxynitride, i.e., that the process is incorporating N. This can be followed more clearly in Figure 5 on the fitted high-resolution core level spectra collected after each of the depositions shown in Figures 1–4.
Combining Figures 1–4 with Figure 5, from TDMAT pulse 2 to NH3 pulse 4, the time-resolved APXPS data shows clear signatures of the ALD growth mechanism for TiN. During each TDMAT pulse, there is a noticeable increase in the Ti 2p and C 1s signals, indicating adsorption of TDMAT along with its organic ligands. The Ti 2p peak appears shifted from 459 eV to a lower binding energy of 458.5 eV, consistent with a reduced Ti environment. Upon introduction of NH3, the N 1s signal increases, providing direct evidence of nitrogen incorporation. Notably, the N 1s peak not only increases in intensity but also stabilizes in position near 396.7 eV, (54) which is characteristic of metal-nitride bonding, confirming the formation of Ti–N bonds rather than weakly bound or physisorbed nitrogen species. During the subsequent NH3 half-cycle, the C 1s signal decreases, reflecting the removal of ligands, while the Ti 2p peak shifts slightly to lower binding energy. This cycle-dependent evolution is consistent with progressive ligand elimination and reduction of the Ti species, ultimately leading to TiN formation. Within the ALD cycle, TDMAT exposure introduces Ti–N(CH3)2 surface species, whereas the subsequent NH3 half-cycle promotes ligand removal, evidenced by a decrease in the C 1s signal. Concurrently, the Ti 2p peak shifts to lower binding energy, indicating progressive reduction of the Ti center. This cyclic sequence of ligand adsorption and removal is consistent with the stepwise evolution toward TiN formation. The O 1s intensity tends to decrease during NH3 exposure, suggesting the elimination of oxygen contamination on the surface. Throughout these cycles, the gradual attenuation of the Si 2p signal confirms the progressive buildup of the TiN film on the Si substrate.
Figure 5 shows the deconvoluted O 1s, Ti 2p, N 1s, and C 1s core-level spectra, illustrating how the chemical environment changes from the initial surface before pulsing any precursors, to the half-cycles of TDMAT and NH3, before three full additional ALD cycles were initiated. The peak shifts, positions, and intensities speak to the transition toward TiN formation. All measurements were taken with substrate at 250 °C.

O 1s

Fitted peaks in Figure 5a confirm the presence of a native silicon oxide layer on the initial substrate surface, with a peak located at 532.3 eV, (55,56) which disappears after four full ALD cycles and subsequently the appearance of the oxynitride component. It is also important to mention that the peak at approximately 532.0 eV can also be assigned to surface hydroxyl (Si–OH) (49,57−59) groups; as discussed previously, the degree of hydroxylation cannot be determined in an easy and straightforward manner since it depends on the exact state of the surface. After the first TDMAT pulse, two environments are observed: the higher binding energy component for Si–O as already mentioned and a new lower-energy component peak appearing at ∼530.6 eV (49,60) that is attributed to lattice oxygen coordinated to a metal in a manner similar to that found in TiO2. (58,59,61) After the TDMAT and NH3 pulses on the third ALD cycle, the higher-energy component of TiO2 is still visible; however a new higher binding energy feature located at 531.1 eV emerges and corresponds to Ti–O–N oxynitride type of bonding from nitrogen incorporation into the films. (62) This peak assignment is based on the electronegativity differences among O (3.4), N (3.0), and Ti (1.5). However, other studies on the O 1s XPS features attributed to oxide versus oxynitride components in TiN films exhibit substantial inconsistency. For instance, one investigation attributes features at binding energies of 530.4 ± 0.2 eV and 531.5 ± 0.2 eV to Ti–N–O and Ti–O species, respectively, (62) while Cherono et al. assigned the oxide (O–Ti) peak at ∼529.97 eV, the oxynitride (O–Ti–N) feature at ∼531.20 eV, and adsorbed oxygen species such as hydroxyls at ∼533.65 eV, highlighting how peak positions shift depending on film composition and processing conditions. (64) These discrepancies underscore the lack of consensus and the sensitivity of peak assignments to film stoichiometry and analytical approach. (65)

Ti 2p

In the Ti 2p region (Figure 5b), a clear stepwise chemical evolution is observed across the initial ALD cycles. During the first and second half-cycles, the Ti 2p peak is centered at ∼459.0 eV, characteristic of Ti–O bonding environments typical of oxidized species, and by the third ALD cycle, this feature shifts toward lower binding energies, with distinct contributions at approximately 458.3 eV (Ti–O–N) and 456.5 eV (Ti–N). (66) This progression indicates a gradual transformation of the interfacial chemistry from oxygen-rich, oxidized titanium species toward a more nitrogen-rich TiN-like environment as the film nucleates and grows. Such a stepwise evolution suggests that the initial cycles involve ligand exchange reactions with residual surface oxygen/hydroxyl species (67) (which are expected to persist even under high-vacuum conditions due to the ubiquitous presence of trace water and its strong tendency to adsorb on surfaces), while subsequent cycles increasingly favor the formation of stoichiometric Ti–N bonding environments. The binding energy of titanium during the first half-cycle in adsorbed TDMAT (in which Ti is still bonded to amido ligands) has been reported and can be assigned at around 457 eV. (53,68) The Ti 2p spectral deconvolution after four full ALD cycles reveals additional features. A secondary peak at approximately 456.5 eV, attributed to TiN bonding, is labeled Ti–N. (69,70) The appearance of the Ti 2p peak associated with TiN at such lower binding energy signifies the presence of nitrogen in the bonding environment, suggesting a Ti–N interaction. Meanwhile, the peak near 458.3 eV is associated with titanium oxynitride (TiOxNy) and is designated as Ti–O–N. (70−72) This additional intermediate peak indicates a mixed bonding scenario where both nitrogen and oxygen are present around titanium atoms. This component emerges when oxygen is incorporated during the film growth, leading to a substitution of nitrogen by oxygen. (52) Even after four ALD cycles, a minor Ti component may remain bonded to residual amido species (e.g., Ti–DMA or Ti–MMI), as evidenced by distinct features in the N 1s spectrum indicating the presence of such nitrogen-containing ligands.

N 1s

Peak fittings for the N part are shown in Figure 5c. The initial surface exhibits two peaks, one at ∼401 eV and another one at ∼399 eV. The small peak at 401.3 eV is possibly residual dimethylamine (45) in the chamber from prior experiments done with TDMAT, while the peak at 398.5 eV can be assigned to chemisorbed N surface species designated as Si–O–N. (73) Upon pulsing TDMAT on the first half-cycle, amine, imine, and adsorbed TDMAT species features at 400.4 eV, 397.5, and 396.7 eV, respectively, are observed. When NH3 is dosed, the N 1s binding energy with three contributions is observed at ∼401 eV, 398, and 397 eV. Of these binding energies, 401.4 eV can be attributed to hydrogen bonded/protonated amines. (74,75) The other peak at 399 eV is from NHx termination, (76) and lastly, 397.5 eV is assigned to an imine. (45) As the film grows, features of Ti–N and Ti–O–N at 396.7 eV (77) and 398.4 eV, (63) respectively, become apparent. After four ALD cycles, deconvolution of the N 1s region reveals four distinct components within the binding energy range of approximately 396–401 eV. Consistently, the final spectra acquired in snapshot mode display an almost similar set of features. This agreement supports their assignment, as measurements performed in swept mode could be affected by adventitious adsorption of residual TDMAT-related species during the temporal delay preceding spectral acquisition. The highest binding energy feature at 400.4 eV is designated as the amine species. (45,75) This peak is associated with the presence of amine precursor ligands as nitrogen-containing contaminant surface species. (78) The remaining three peaks are linked to Ti–O–N, imine, and Ti–N bonding. The peaks at 398.9 and 397.2 eV are attributed to Ti–O–N (79) and imine respectively, while the lower binding energy peak near 396.7 eV corresponds to Ti–N. (52,63,80) However, the exact positions of these peaks can vary depending on the chemical environment and the stoichiometry of the oxynitride. (65) The peak assignments in the Ti 2p, N 1s, and O 1s regions are consistent and align well: indicating the presence of amounts of Ti–O–N, a significant concentration of Ti–N bonding, and suppressed amounts of Ti–O after four ALD cycles.

C 1s

With reference to a similar ligand system study using tetrakis(dimethylamino)hafnium(IV) (TDMAHf), (6) the carbon configuration observed during the dosing of TDMAT possibly corresponds to two organic ligand components: methyl methylenimine (MMI, N(CH3)(CH2)) and dimethylamine (DMA, HN(CH3)2). MMI features carbon atoms in two environments: CH3 and CH2 (typically either a three-membered ring or between adjacent surface complexes). (45) In contrast, both carbon atoms in DMA are present only as CH3 groups. C 1s signal starts by revealing two components, with the higher binding energy peak position assigned to DMA remaining constant over time; possibly a result of both preceding experiments in the same experimental setup and ligand exchange or transamination reactions. The C peak assigned to C contamination disappears during the TDMAT pulse and reappears during the NH3 pulse, while the C peak assigned to DMA decreases during the NH3 pulse. Notably NH3 then seems to ‘‘clean’’ the reaction surface as well as removing ligands from the TDMAT. We can attribute the lower binding energy peak (285.3 eV) in Figure 5d, during the TDMAT pulse, to the presence of MMI from an insertion reaction (81) in which a β-hydrogen from one dimethylamido ligand on TDMAT transfers to the titanium center and then inserts into another dimethylamido ligand’s N–C bond, releasing dimethylamine as a byproduct. (82) This process necessitates two different carbon species and, consequently, two peaks at varying binding energies that should change over time. Therefore, we assign the higher binding energy peak (286.4 eV) component to DMA, indicating the presence of either the intact TDMAT molecule, a ligand reaction, and insertion reaction or a transamination product on the surface.

Mass Spectrometry

We conducted time-of-flight mass-spectral analysis of residual gases during the pulsing of precursors into the APXPS chamber, focusing on the evolution of specific masses over time to emphasize the significance of the different chemical reactions to provide excellent complementary information to the time-resolved XPS data, shedding light on the gaseous byproducts during each ALD cycle. Figure 6 displays specific mass trends which are used to illustrate changes in reaction byproducts during TiN deposition using TDMAT and NH3. Alternating green and purple shaded regions denote the TDMAT and NH3 pulse windows, respectively. The intensity traces of key gas-phase species – including DMA, MMI, NH3, and minor byproducts such as CH4 and N2 are shown as a function of time. Clear periodic peaks of DMA and MMI (which can be an ionized version of the protonated ligand) coincide with each TDMAT pulse, consistent with ligand desorption and precursor decomposition. In contrast, sharp NH3 spikes and transient increases in CH4 and N2 follow NH3 pulses, indicating nitrogen delivery and ligand cleanup. This figure complements the APXPS data by capturing the volatile chemical dynamics of the ALD process. The introduction of NH3 results in a clear increase in signals at m/z 17 (NH3), 16 (CH4), and 28 (N2), along with very minor contributions from CH3 (partly from CH4) at m/z 15 and O2 at m/z 32.

Figure 6

Figure 6. Time-of-flight mass spectrometric behavior of detected species during TiN ALD from TDMAT and NH3.

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It is, however, important to note that the mass resolution is generally moderate, resulting in spectral crosstalk, with overlapping signals that complicate accurate quantification of individual masses in the trend plots.

4. Discussion

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Neither the Ti 2p nor N 1s spectra show any Ti–N bonding peaks during the first and second half-cycles. However, TiN is observed after four full ALD cycles where the N 1s spectrum indicates nitrogen bound to titanium at 396.6 eV and the Ti 2p spectrum showing titanium to nitrogen bonding at 456.6 eV.
Nitrides from various other X[N(CH3)2)]n references, where X represents a metal and n the oxidation number of the metal, found in the NIST database (83) have been shown to have nitrogen peaks between 398 and 401 eV. The N 1s peak at 400.4 eV during the TDMAT half-cycle can be assigned to HN(CH3)2 species. (84) While DMA species would not be expected to persist at elevated temperatures ─ consistent with our previous observations showing no DMA-related signals at 280 °C (6) ─ literature reports indicate that such species can remain stable even up to approximately 250 °C under certain conditions. (68) When combined with Fourier transform infrared spectroscopy (FTIR), evidence of incorporated imine, N(CH3–CH2) in TiN deposited in another study (85) of the TDMAT/NH3 process was found, where the second N 1s peak at 397.5 eV corresponds to the imine from an insertion reaction involving two amide ligands. (45) Additionally, the intensity of the nitrogen peak associated with incorporated protonated ligands (HN(CH3)2) gets lower during the NH3 pulse, suggesting that this half-cycle is effective in removing precursor ligands from the surface. However, during the first NH3 half-cycle, there is no evidence of either a ligand exchange or transamination reaction toward nitridation because the titanium spectrum still shows bonding to lattice oxygen. It is important to note, though, that the bonding of titanium to lattice oxygen (TiO2) at 458.9 eV (86,87) during the first half-cycle is possibly a result of ligand exchange between the substrate surface hydroxyl (−OH) groups when exposed to TDMAT. Clearly, there is also the insertion reaction toward MMI (see C 1s spectrum), which also allows for Ti–O bonds to be formed. Thereafter, transamination of *TiN(CH3)2 surface species occurs when exposed to NH3, releasing protonated ligands as dimethyl amine shown at 400.4 eV (45,74) This is still not enough to cause Ti–N bond formation at this point. However, after four ALD cycles, the presence of a N 1s peak at 396.7 eV (84) confirms nitrogen bound to titanium.

Reaction Mechanisms

From our results above, we formulate a suggested surface chemical mechanism for the ALD process of TiN from TDMAT and NH3. Reactions occur immediately on silicon native oxide due to the ready interaction of TDMAT with the surface hydroxyl (−OH) groups, which means that the initial TDMAT ligand exchange reactivity is governed by the available surface −OH groups. These hydroxyl groups are replaced by dimethylamino ligands, releasing dimethylamine as a byproduct.
‐xOH*+Ti(NMe2)4→‐Ox‐Ti‐(NMe2)4‐x*+xHNMe2(g)
(1)
However, the detection of MMI during the first half-cycle provides strong evidence that a parallel reaction pathway is active, proceeding independently of surface hydroxyl groups. This observation implies that the density of surface hydroxyls is insufficient to fully react with all adsorbed TDMAT species. Instead, a fraction of TDMAT appears to undergo insertion or decomposition reactions (illustrated later in reactions 5 and 6) directly on nonhydroxylated surface sites, resulting in MMI formation, likely through a bimolecular reaction pathway. (6) This challenges the often-assumed hydroxyl-saturation model for initial ALD nucleation and highlights the need to consider alternative surface reaction pathways that become accessible when hydroxyl coverage is limited.
The kinetics of the reaction is lower during the NH3 pulse. The reaction between TDMAT and NH3 is known to be ‘rapid even at room temperature’; (88) however, these rapid reactions were not observed in the early ALD stages studied in this work. There is a delay in nucleation or bonding on the TDMAT-terminated surface, after which the growth rate or the Ti–N bonding character is expected to increase as the surface becomes coated with both Ti and N atoms. Nucleation delay is commonly attributed to factors such as the density of reactive surface sites, exchange reactions, and the presence of persistent ligands. (89) These effects are expected to diminish with increasing ALD cycles, leading to a gradual increase in the growth per cycle (GPC) until a steady state is reached. (5) In the second half-cycle, more dimethylamine is released upon reaction with NH3 ligands, leaving behind an -NH2-terminated ‘oxynitride’ surface.
‐Ox‐Ti‐(NMe2)4‐x*+(4‐x)NH3→‐Ox‐Ti‐(NH2)4‐x+(4‐x)HNMe2(g)
(2)
This can be supported by the N 1s peak at ∼400.4 eV, shown in Figure 5c, which is consistent with amine species. (74,75) Release of amine species happens in both the first and second half-cycles and is observed in the nitrogen spectra throughout the cycles. A simplified illustration of this mechanism is shown in Figure 7.

Figure 7

Figure 7. A simplified illustration of the early stages of TiN ALD showing TDMAT reacting with an OH-terminated surface, emitting the protonated ligand, dimethylamine, leaving the surface terminated in titanium dimethylamide, completing the first half of the reaction. In the second half, the introduced ammonia removes the surface bound dimethylamide as dimethylamine, resulting in an NH2-terminated surface.

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In our previous study, (90) we have shown that dimethylamido metal precursors such as TDMAT follow more complex reaction pathways other than the common and expected ligand exchange reactions including ligand decomposition, disproportionation, and hydrogenation. Other byproducts from a ‘partial’ ligand exchange combined with protonation of the methyl part of the ligand, as confirmed by mass spectrometry shown in Figure 6, include CH4 (methane) upon interaction with NH3. The result of this reaction leaves behind an amino group bonded to the Ti and possibly an unreacted methyl reaction site.
‐Ox‐Ti‐(NMe2)4‐x*+xNH3→‐Ox‐Ti‐(NMex)(NH2)4‐2x+xCH4(g)
(3)
As more precursor pulses are initiated, the amino-terminated N part may act as an additional reaction site, which would release more CH4 with more NH3 exposure.
Referring to Figure 4, the C 1s signal is markedly more intense during the first half-cycle than during the second half-cycle, suggesting a higher surface coverage of carbon-containing species during the initial precursor exposure compared to the subsequent coreactant step. A plausible explanation for this is the possible partial decomposition of the precursor, at temperatures higher than 200 °C (28,91,92) as well as 80–85% dissociation of the adsorbed TDMAT, releasing different fragments, as verified by previous XPS studies. (68)
Ti[N(Me)2]4→‐NMe2+CH4+(Me2N)2Ti=NMe
(4)
Another possible source of carbon is MeN=CH2 (MMI) in the films through a β-hydride elimination process or an insertion reaction which leads to a three-membered ring or dimer. (81,93)
Ti[N(Me)2]4→H‐Ti[N(Me)2]3+MeN=CH2
(5)
Ti[N(Me)2]4→Ti(NMeCH2)(NMe2)2+HNMe2→HTi(NMeCH2)(NMe2)+MeN=CH2
(6)
Spectroscopically, distinguishing between the source of MMI as a β-hydride elimination or an insertion reaction pathway is likely challenging. A more detailed consideration of the possible reaction products is therefore warranted to enable reliable interpretation of the observed signals.
The decrease in the C 1s signal after the pulse of NH3, which alters the chemistry involved, is seen to eliminate carbon contamination from the resulting TiN thin film, through formation of HNMe2 from transamination and amine elimination reactions. (94)
3Ti(NMe2)4+4NH3→3TiN+12HNMe2+12N2
(7)
Mass spectrometry results (Figure 6) indicate that when NH3 is pulsed there is a noticeable increase in DMA– and DMA signals, along with a significant rise in the m/z 43 (MMI) signal, as confirmed by DFT that insertion reactions are viable involving amido complexes via the β-hydride insertion pathway. (6) During the NH3 pulse, β-hydride transfer from one dimethylamido ligand on TDMAT to the titanium center can be followed by hydride insertion into the N–C bond of another dimethylamido ligand, leading to the release of dimethylamine (DMA); NH3 facilitates this insertion-driven decomposition by protonating the departing amido fragments, thereby accelerating ligand elimination as amines. This observation aligns well with the APXPS results (Figure 5c and 5d), which reveal their adsorption onto the sample surface and possible presence of these species in the gas phase.
The increase in CH4 at m/z 16, during the NH3 pulse, suggests another reactive pathway for methane removal from the surface, reaction 4. However, it is important to note that, in processes that use NH3 as a coreactant, m/z 16 can either be CH4, NH2, or a combination of both. (95) Distinguishing between these two species can be challenging. Although we could only detect volatile species using residual gas analysis, there is clear evidence of release of different species that corroborate the interactions and reactions stimulated by this TiN ALD process on a silicon surface. It is important to consider the pumping efficiency and sticking probability of each gas, as NH3 typically takes a long time to evacuate since it adheres more readily to the walls. Thus, we may be overestimating the concentration of heavier or less polar organics (carbonaceous species from the precursor) in the analysis relative to the amount of NH3 released, since it adheres more readily to the walls when the pressure equilibrium shifts. As a result, relatively less of NH3 is measured in the gas phase, even though it might be present in larger quantities. On the other hand, the carbonaceous species may remain ‘artificially’ in the gas phase, skewing measurements.
ToF-MS results seem to support the APXPS results quite well. The mass spectrometry data provides clear evidence of surface reactions through the detection of volatile byproducts. However, it is noteworthy to take extra caution with interpretation of these results. For example, m/z 16, 17, and 18 probably all contain each other’s masses. So, when we talk about an increase of CH4 (16) during NH3 (17) pulses, that could suggest different reaction pathways than the ones already mentioned. We do not really know how much of the m/z 16 signal actually contains CH4. All this points to the difficulty in distinguishing between different species, especially those with closely linked mass-to-charge ratios. Each TDMAT pulse is marked by prominent signals from DMA, its deprotonated form (DMA–), and (MMI), indicating ligand desorption and possible precursor fragmentation. These species appear consistently across the TDMAT pulses, confirming the delivery of TDMAT and associated organics to the surface. In contrast, during the NH3 pulses, the signals for DMA and MMI drop significantly, while NH3 peaks rise sharply, indicating successful introduction of the nitrogen source. A moderate rise in N2 and CH4 during this step suggests additional gas-phase reactions, possibly from the breakdown of residual ligands. This pattern strongly supports and aligns well with APXPS observations of ligand removal and nitrogen incorporation.

5. Conclusions

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TiN deposition by ALD on silicon with a native oxide layer was investigated during the initial cycles by APXPS. The reactivity on the silicon oxide surface is higher during the first half-cycle (TDMAT), likely due to the presence of hydroxyl groups on the surface which serve as reactive sites for TiN nucleation, forming a layer of Si–O–Ti bonding at the SiO2/TiN interface. Furthermore, the observed MMI during TDMAT pulses indicated the possibility of an insertion reaction. In contrast, during the second half-cycle (NH3), the presence of NHx species is inferred from the XPS results, confirming that an NHx termination occurs during this stage of the ALD process. After four ALD cycles, the TiN bond formation becomes evident. The first visible incorporation of the nitride character in the form of TiN/TiON bonds was found after the fourth ALD cycle. Signals of carbonaceous species DMA, MMI, and CH4 among other reaction products were observed from both APXS and mass spectrometry. These results have shown that there are other significant reaction mechanisms and pathways that take place during the formation of nitrides from alkylamido precursors other than the more generalized and expected ligand exchange reactions. We find these results to be a useful indicator of how time-resolved APXPS is a remarkable tool to fundamentally understand how reactions occur during TiN ALD, in real time and without exposure to external environments. On top of providing important mechanistic insights, the use of time-resolved APXPS during ALD from dimethylamido precursors may provide a simple method to control their reaction with NH3 to improve the properties of TiN and related nitride materials.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.5c02974.

  • Additional details from the APXPS measurements (PDF)

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Author Information

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  • Corresponding Authors
  • Authors
    • Peggy Bagherzadeh Tabrizi - Department of Physics, Chemistry and Biology, Linköping University, 581 83 Linköping, Sweden
    • Houyem Hafdi - Department of Physics, Chemistry and Biology, Linköping University, 581 83 Linköping, Sweden
    • Premrudee Promdet - Department of Physics, Chemistry and Biology, Linköping University, 581 83 Linköping, Sweden
    • Jonas Lauridsen - Seco Tools AB, 737 82 Fagersta, Sweden
    • Oscar Alm - Seco Tools AB, 737 82 Fagersta, Sweden
    • Tommy Larsson - Seco Tools AB, 737 82 Fagersta, Sweden
    • Rosemary Jones - MAX IV Laboratory, Lund University, Box 118, 221 00 Lund, Sweden;  Division of Synchrotron Radiation Research, Department of Physics, Lund University, Box 118, 221 00 Lund, Sweden;  Orcidhttps://orcid.org/0000-0001-6273-4243
    • Esko Kokkonen - MAX IV Laboratory, Lund University, Box 118, 221 00 Lund, Sweden;  Orcidhttps://orcid.org/0000-0002-3674-7486
    • Joachim Schnadt - MAX IV Laboratory, Lund University, Box 118, 221 00 Lund, Sweden;  Division of Synchrotron Radiation Research, Department of Physics, Lund University, Box 118, 221 00 Lund, Sweden;  NanoLund, Lund University, Box 118, 221 00 Lund, Sweden;  Orcidhttps://orcid.org/0000-0001-9375-831X
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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We gratefully acknowledge financial support by Seco Tools, by Vinnova, through the project “Surface chemical mechanisms during atomic layer deposition of hard nitrides” (2023-02815) and by the Stiftelsen för Strategisk Forskning (Swedish foundation for Strategic Research, SSF) through the project ‘‘Time-resolved low temperature CVD for III-nitrides’’ (SSF-RMA 15-0018). H.P. acknowledge financial support from the Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU No. 2009-00971). P.M. is grateful to Marcus Lorentzon for supplying the MIST code. J.S. acknowledges support by Vetenskapsrådet (Swedish Research Council, VR) under project grant no. 2023-03492. We acknowledge the MAX IV Laboratory for beamtime on the SPECIES beamline under proposal 20231261. Research conducted at MAX IV, a Swedish national user facility, is supported by VR under contract 2018-07152, Vinnova (Swedish Governmental Agency for Innovation Systems) under contract 2018-04969 and Formas under contract 2019-02496.

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  • Abstract

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    Figure 1

    Figure 1. Time-resolved a) O 1s, b) Ti 2p, c) N 1s, d) C 1s, and e) Si 2p APXP spectra measured during the TDMAT half-cycle at 250 °C while f) shows the peak position evolution of the main peak regions in C 1s and Ti 2p plots as a function of time during the TDMAT pulse. The spectra were measured using a photon energy of 680 eV. The color scale shows how the intensity of the indicated core levels changes with time. For ease of visibility, the Ti 2p, N 1s, and C 1s intensities were multiplied by factors, as indicated, relative to the Si 2p intensity.

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    Figure 2

    Figure 2. Time-resolved a) O 1s, b) Ti 2p, c) N 1s, d) C 1s, and e) Si 2p APXPS spectra measured during the NH3 half-cycle at 250 °C while f) shows the center of gravity plot as a function of time during the first and second NH3 pulse trains to visualize the dynamic changes. The spectra were measured using a photon energy of 680 eV. The color scale shows how the intensity of the indicated core levels changes with time. For ease of visibility, the Ti 2p, N 1s, and C 1s intensities were multiplied by factors, as indicated, relative to the Si 2p intensity.

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    Figure 3

    Figure 3. a) N 1s and b) C 1s intensity evolutions extracted at defined time points from the image plots in Figure 2c) and d), respectively, allowing a more direct comparison of the temporal evolution indicating that no ligand removal is evident in the second half-cycle through NH3-assisted ligand exchange surface reactions.

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    Figure 4

    Figure 4. Time-resolved a) O 1s, b) Ti 2p, c) N 1s, d) C 1s, and e) Si 2p APXP spectra measured during three additional cycles at 250 °C, while f) and g) show the peak position evolution of the main peak regions in Ti 2p and C 1s plots as a function of time during the ALD cycles. The color scale shows how the intensity of the indicated core levels changes over time. The spectra were measured using a photon energy of 680 eV. The time at which each ALD half-cycle starts is marked by horizontal dashed lines and denoted TDMAT or NH3 to symbolize when each corresponding half-cycle starts and ends. Note that this is a continuation of Figures 1 and 2, hence precursor pulsing starts at TDMAT (2). We can clearly see the five short pulses of TDMAT in each of the TDMAT pulse trains as drops in Ti 2p intensity (this is superimposed on the raster-induced intensity changes). The dotted red line on the Ti 2p map shows the shift toward lower binding energies during the three ALD cycles with time, indicating a shift from oxide toward nitride character in the films. The oscillating behavior shown on the maps has nothing to do with the ALD process itself but emanates from the continuous movement of the sample during analysis as mentioned in the Methods section. For ease of visibility, the O 1s intensity was multiplied by a factor of 2 relative to the Si 2p intensity.

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    Figure 5

    Figure 5. APXPS core level scans of the a) O 1s, b) Ti 2p, c) N 1s, and d) C 1s lines at 250 °C from an initial substrate surface until after the three additional ALD cycles. The spectra were measured using photon energies of 680 eV for the O 1s and Ti 2p lines, while 550 and 410 eV were used in the measurement of the N 1s and C 1s spectra, respectively. To make incorporation of N and Ti more visible and easier to follow, the corresponding survey spectrum for each of the four conditions is available in the Supporting Information. For ease of identification of minor components, the relevant spectra were multiplied by corresponding factors as shown.

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    Figure 6

    Figure 6. Time-of-flight mass spectrometric behavior of detected species during TiN ALD from TDMAT and NH3.

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    Figure 7

    Figure 7. A simplified illustration of the early stages of TiN ALD showing TDMAT reacting with an OH-terminated surface, emitting the protonated ligand, dimethylamine, leaving the surface terminated in titanium dimethylamide, completing the first half of the reaction. In the second half, the introduced ammonia removes the surface bound dimethylamide as dimethylamine, resulting in an NH2-terminated surface.

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