Thin Solid Films 416 (2002) 136144

Correlation between microstructure and barrier properties of TiN thin films used Cu interconnects
M. Moriyamaa,*, T. Kawazoeb, M. Tanakac, M. Murakamia
a

Department of Materials Science and Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan b Toyota Motor Corporation, Toyota, Japan c Kawasaki Heavy Industries, Ltd, Tokyo, Japan Received 24 April 2001; received in revised form 4 June 2002; accepted 9 July 2002

Abstract In order to develop a fabrication process to prepare thermally stable TiN thin films, the TiN films were prepared by the sputterdeposition technique with various process parameters. The barrier property of the TiN films which prevented the Cu diffusion into Si or SiO2 were found to be influenced by the radio-frequency power, AryN2 gas ratio, and substrate temperature of the sputtering system. By adjusting these process parameters, the 25-nm-thick TiN films with excellent thermal stability that prevented the Cu diffusion at 850 8C for 30 min were successfully prepared. Microstructural analysis by X-ray diffraction and transmission electron microscopy indicated that the microstructure of the TiN films was sensitive to the thermal stability and that the TiN films with strong fiber structure and large grain size had higher resistance to the Cu diffusion into Si. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Diffusion barrier; Copper interconnects; Grain boundary diffusion; Sputtering; Titanium nitride

1. Introduction Use of the Cu interconnects in Si-ULSI devices requires development of barrier layers which prevent Cu diffusion into the Si substrates and SiO2 insulators at elevated temperatures. For the conventional Si-devices with 0.25-mm wide line, the barriers are required to prevent the Cu diffusion at temperatures of approximately 400 8C and the barrier layer thickness is less than 40 nm to keep the advantage of the lower effective resistivity of Cu interconnects compared with Al interconnects. In order to prepare the barrier layers for the Cu interconnect, which satisfy these requirements, various barrier metals have been developed, such as W w1x, Ta w2x, WN w3x, TaN w4x, TiN w5x, TiSiN w6x, and TaSiN w7x, and these barrier layers prevented the Cu diffusion at temperatures below 600 8C. However, special devices are required to anneal at 700 8C for 30 min in order to activate implanted Bq
*Corresponding author. Tel.: q81-75-753-54752; fax: q81-75753-3579. E-mail address: moriyama@micro.mtl.kyoto-u.ac.jp (M. Moriyama). 0040-6090/02/$ - see front matter PII: S 0 0 4 0 - 6 0 9 0 0 2 . 0 0 6 0 2 - 8

ions prior to preparation of the interconnect materials. In order to apply Cu interconnects to these special devices, the barriers that prevent Cu diffusion into Si or SiO2 at such high temperature must be developed. To prepare the thermally stable barrier layers which will be applicable to these devices, we selected TiN films prepared by physical vapor deposition (PVD). PVD-TiN films have resistivity of an order of magnitude lower than those required for ULSI devices (-300 mV cm), and have extensive history in use for barrier layers for Al interconnects. There have been many previous studies which addressed the barrier properties of TiN films used in the Al interconnects w8,9x. The excellent barrier property of the TiN films for Cu diffusion was demonstrated by Wang et al. w5x and Park et al. w10x for the sputtered TiN films 100-nm thick. The physical properties of the TiN films were found to depend strongly upon the microstructure of the films. To improve the barrier properties of the TiN films, they pointed out that control of the microstructures of TiN films is essential. The investigations of the relationship between the film microstructure and the deposition

2002 Elsevier Science B.V. All rights reserved.

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condition are very important to further improve the thermal stability of the TiN films. For the TiN films, the orientational crossover phenomena (the preferred orientation change from (1 0 0) to (1 1 1) with increasing film thickness) was recently observed in the sputtered films w11,12x. This experimental result implies that the microstructure of TiN films is influenced by the film thickness. There are few reports that studied the relationship among the TiN film microstructures, the deposition parameters, and the barrier properties for Cu diffusion using thin (-40 nm) films. The purposes of the present investigation are twofold. The first is to understand the diffusion mechanism of Cu in the TiN barriers by analyzing microstructure of the TiN films which were deposited at various conditions using X-ray diffraction (XRD) and transmission electron microscopy (TEM). These studies will provide us a guideline for developing the barrier layers, which would be used in the future ULSI devices. The second purpose is to challenge the development of a thermally stable thin TiN barrier layer (-40 nm) which withstands at temperatures above 700 8C to apply this barrier layer to the special devices with 0.25-mm wide line. 2. Experimental procedures (1 0 0)-oriented n-type Si wafers were used as the substrates in the present experiments. The wafers were dipped in 5% HF solution for 1 min, and rinsed in super clean water and isopropyl alcohol. After blowing with dry N2 gas, the wafers were mounted on the sample holder and immediately loaded into the vacuum chamber. The sputter-deposition chamber was evacuated to 3=10y8 Torr. The film depositions were carried out in the radio-frequency (r.f.) magnetron sputtering system. The TiN films were deposited at various r.f. powers by reactively sputtering a pure Ti (99.99 at.%) target in ArqN2 gas with various AryN2 gas ratios. The substrate temperatures were changed from room temperature (RT) to 600 8C. To study the thermal stability of the TiN layers for Cu diffusion, the Cu films 100-nm thick were deposited on the TiN layers without breaking vacuum. After the film depositions were completed, the samples were cooled to RT before transferring them to the loadlock chamber. The SiyTiN (25 nm)yCu (100 nm) samples were annealed at temperatures ranging from 600 to 900 8C for 30 min in 5% H2 yN2 mixed gas atmosphere. Microstructural analysis of the samples before and after annealing was carried out by XRD and TEM. TEM observations were performed in both cross-sectional and plan-views using a 400-kV electron microscope (JEM4000EX) equipped with a top-entry goniometer. Samples for plan-view TEM observations were prepared by depositing TiN films (25 nm) on Si3N4 films (;60 nm), which allowed us in situ TEM observation. The

Fig. 1. (a) A cross-sectional HREM image of SiyTiN (25 nm)yCu (100 nm) sample and (b) corresponding schematic illustration.

present microstructural analysis of each sample was repeated at least three times to reduce the scatter of the measurements. 3. Experimental results 3.1. Microstructural analysis Fig. 1a shows a typical cross-sectional high-resolution electron microscopy (HREM) image of the SiyTiN (25 nm)yCu (100 nm) sample. Cross-section of the TiN film structure, which was deduced from the contrast of lattice images in Fig. 1a, is schematically shown in Fig. 1b. As shown in these figures, the 25-nm TiN films are composed of two layers: columnar grains with lowindex preferred orientation (i.e. fiber structure) at the top, and small grains with rather random orientation at the bottom. The thickness of the fiber-grained layer is approximately 20 nm, and the mean grain size of the bottom layer is approximately 5 nm. To investigate the relationship between the film microstructure and the deposition condition, the TiN films were prepared with various deposition conditions (different AryN2 gas ratio, r.f. power, and substrate temperature (Ts)) and were analyzed by XRD and TEM. 3.1.1. Effect of AryN2 gas flow ratio The XRD profiles of 25- and 100-nm-thick TiN films deposited at various AryN2 gas flow ratios are shown in Fig. 2a and b, respectively. As shown in Fig. 2a, the peak intensity and sharpness of the (1 1 1) and the (2 0 0) TiN peaks slightly increase with increasing Ar gas flow ratio. This result implies that the vertical grain sizes increase with the Ar gas flow ratio. The intensity

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1, 70 mV cm for AryN2 s4y1, and 117 mV cm for Ary N2s1y1. 3.1.2. Effect of r.f. powers Fig. 4a and b are the plan-view TEM images of the 25-nm TiN films deposited with r.f. power of 40 and 195 W, respectively. These films were deposited at the AryN2 gas flow ratio of 10y1, keeping the substrate temperature at RT. As seen in Fig. 4a and b, the average grain sizes increase with increasing the r.f. power. However, there is no significant change in XRD profiles between these samples. Fig. 5 illustrates the relationship between the r.f. powers applied to the TiN films during film preparation and the electrical resistivities (r) of the TiN films. The resistivities of TiN films decrease with increasing the r.f. powers. This reduction of the r values

Fig. 2. XRD peak profiles obtained from SiyTiN samples that were deposited at different AryN2 gas ratios, (a) SiyTiN (25 nm) and (b) SiyTiN (100 nm).

ratios of the (1 1 1) and (2 0 0) peaks obtained from the 25-nm TiN films were similar to that of the TiN film with random orientation. The XRD profiles of 100nm TiN films show that the (1 1 1) peak intensity drastically increases with increasing Ar gas flow. The (1 1 1) peak intensity increases with the film thickness, suggesting that grains at the top layer (as shown in Fig. 1) have the (1 1 1) preferred orientation for the films deposited at AryN2 of 10y1. The plan-view TEM images of the 25-nm TiN films deposited at AryN2 of 1y1 and 10y1 are shown in Fig. 3a and b, respectively. These images show that the TiN films have a polycrystalline structure and that the grain sizes are in the range of 5 20 nm for various Ar gas flow ratios. The film compositions, which were determined by Rutherford backscattering spectrometry, were not dependent on the AryN2 gas ratio, and the TiyN ratios of the film was close to 46y54. The electrical resistivities of these TiN films were measured to be 54 mV cm for AryN2s10y

Fig. 3. Plan-view TEM images of the TiN films deposited at different AryN2 gas flow ratios, (a) AryN2s1y1 and (b) AryN2s10y1.

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Fig. 5. Electrical resistivity of TiN (25 nm) films deposited at various r.f. powers.

Fig. 4. Plan-view TEM images of the TiN films deposited at different r.f. powers, (a) 40 W and (b) 195 W.

could be due to reduction of the grain boundary (GB) densities in the films. 3.1.3. Effect of substrate temperature The effect of the substrate temperature on the film microstructure was studied by depositing the TiN films at various substrate temperatures. These films were deposited with the r.f. power of 80 W and AryN2 gas flow ratio of 10y1. Fig. 6a and b show the XRD profiles for the TiN films with various thicknesses deposited at RT and 400 8C, respectively. The peak intensities from the (1 1 1) and (2 0 0) TiN are observed to increase with film thickness. However, the microstructures of the films deposited at 400 8C and RT are quite different. No preferred orientation is observed for the TiN films deposited at RT even for the TiN film with thickness of 100 nm. However, the TiN films deposited at 400 8C have strong (1 0 0) texture at the initial stages of the film growth (film thickness -30 nm). These results indicate that the increase of the substrate temperature

Fig. 6. XRD peak profiles obtained from SiyTiN samples that were deposited at different film thickness, (a) TssRT and (b) Tss400 8C.

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Fig. 7. Plan-view TEM images of the TiN films deposited at different substrate temperatures, (a) TssRT and (b) Tss400 8C.

(Ts) during films deposition enhances (1 0 0) preferred orientation (i.e. decreases the mosaic-spread angle). Fig. 7a and b show the plan-view TEM micrographs of the 25-nm TiN films deposited with r.f. power of 80 W keeping Ts at RT and 400 8C, respectively. As shown in Fig. 7, the grain size distribution of the film deposited at TssRT is similar to that of deposited at 400 8C. Weak (1 1 1) diffraction ring and strong (2 0 0) and (2 2 0) rings are observed in the electron diffraction pattern shown in Fig. 7b. This result shows a strong preferential (1 0 0) orientation of the TiN films deposited at 400 8C, in contrast with the randomly oriented grains in the films deposited at RT. 3.2. Thermal stability of TiN barrier layers In order to study a relationship between the TiN film microstructure and the thermal stability, SiyTiN (25 nm)yCu (100 nm) samples, which were prepared by various deposition conditions and annealed at temperatures in the range of 600900 8C for 30 min, were analyzed by XRD. Fig. 8 shows an example of XRD profiles of the SiyTiN (25 nm)yCu (100 nm) sample (prepared with AryN2s10y1, r.f. powers195 W, and TssRT) before and after annealing. Cu (1 1 1), Cu (2 0 0), and weak TiN (1 1 1) peaks are observed in the as-deposited and annealed samples. After annealing at 900 8C for 30 min, the peak from Cu silicide (Cu3Si) is observed, which indicates intermixing of Cu and Si through the TiN barrier layer. No Cu3Si forms at temperatures of 850 8C, indicating the upper limit of the thermal stability of this TiN barrier is 850 8C. Fig. 9a, b and c show the thermal stabilities of the 25-nm TiN barrier layers which were deposited with different r.f. powers, AryN2 gas ratios, and substrate temperatures. As seen in Fig. 9, the thermal stability of

the TiN barrier layer increases with increasing these parameters. The highest temperature which the TiN layers prevent the Cu diffusion is 850 8C for 30 min. The sheet resistivity of the 25-nm-thick TiN film was measured to be 46 mV cm. These results satisfy the requirements for the barrier layer used in the special devices, which must withstand the thermal stability of 700 8C for 30 min. 4. Discussion 4.1. The diffusion mechanism of Cu in TiN barrier The diffusion coefficients of Cu in the TiN barrier were determined by analyzing the XRD peak profiles.

Fig. 8. XRD profiles of SiyTiN (25 nm)yCu (100 nm) sample before and after annealing.

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Fig. 9. Dependence of thermal stability of 25-nm-thick TiN barrier layers on different deposition parameters, (a) r.f. power; (b) AryN2 gas flow ratio; and (c) substrate temperature. The sign m indicates the temperature of barrier breakdown.

When the diffusion occurs following on the Ficks 1st and 2nd laws, the average diffusion length (L) of atoms is approximated by 2(Dt)1y2, where D is the diffusion coefficient of Cu in TiN films and t is the diffusion time. The D value of Cu in the barrier layer at elevated temperatures can be determined by substituting L for the barrier layer thickness. To determine the diffusion time (t) of Cu in the TiN, onset times for Cu3Si formation in the SiyTiN (25 nm)yCu (100 nm) sample were measured by XRD. The Arrhenius plots of the D values for the TiN barriers with r.f. powers150 W, Ary N2 gas flow ratios10y1 and TssRT are shown in Fig. 10 as a function of annealing temperatures in the range of 600900 8C. The temperature dependence of the diffusion coefficients is expressed by the Arrhenius relationship of DsD0 exp(yQykT), where D0 is the pre-exponential factor, Q is the activation energy for diffusion, k is Boltzmann constant, and T is temperature. The Q (eV) and D0 (cm2 sy1) values calculated from these plots are indicated in Fig. 10. The activation energies of Cu diffusion in TiN in the temperature ranges of 600800 8C and 800900 8C are 1.4 and 2.7 eV, respectively. The Q value in the temperature range of 800900 8C is a factor of ;2 larger than that in the temperature range of 600800 8C. The activation energy of the GB diffusion is about half of that of the lattice diffusion. Therefore, it is believed that the diffusion of Cu in the TiN layer in the temperature range of 600 800 8C and 800900 8C would be controlled by the GB and lattice diffusion mechanisms, respectively. It is also noted that no voids (or low-density regions) were observed around the GBs in the TiN films and is believed that the (GBs) act as fast diffusion paths in the low-temperature region. This suggests that reduction of GB diffusion is very important in improving the thermal stability of the TiN diffusion barriers.

4.2. Film microstructure and thermal stability of TiN barriers The atomic diffusivities through GBs depend on the atomic structures of the GBs. Thus, the diffusion coefficients along the GBs (Db) are dependent on misorientation between the neighboring grains. Extensive Db measurements have been carried out through the GBs with various misorientation angles w13x. Turnbull and Hoffman w14x measured the dDb values, where d is a width of the GB, as a function of the misorientation angles for Ag bicrystals. The geometrical configuration of the bicrystal is schematically shown in Fig. 11. The two grains (grains A and B) have the common w1 0 0x

Fig. 10. Diffusion coefficients of Cu in the TiN barrier layer at temperatures ranging from 600 to 900 8C.

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Fig. 11. Geometrical configuration of the bicrystal with w1 0 0x tiltGB.

axis within the GB plane. This axis is used as the rotation axis, and the angle f around the common w1 0 0x axis is used as a parameter of the misorientation between the two crystals. These GBs are conventionally called as w1 0 0x tilt grain boundaries (tilt-GBs). In these Ag tilt-GBs, the dDb values increased monotonically with increasing misorientation angle f (for f-168). In addition, the dDb values along the tilt axis (dDb) were found to be different from the dDbH values measured along the direction perpendicular to the tilt axis (Fig. 11) w15x. They explained those experimental results using the GB dislocation model proposed by Read and Shockley w16x. This theory predicts that when the misorientation angle between the adjacent grains is small, the tilt-GB is comprised of a periodic edge dislocation array as shown in Fig. 11 and that the interspacing between the dislocations decreases with increasing the angle f. The GB diffusion along the direction parallel to the tilt axis occurs along the dislocation pipes. As the angle f increases, the density of the diffusional paths in the GB plane increases, leading to an increase in the atomic flux. Since these dislocations have little contribution to the GB diffusion along the direction perpendicular to the tilt axis, the typical dDbH value is much smaller than the dDb value. Hoffman w15x and Biscondi w17x showed that this anisotropic diffusion occurred even in the tilt-GBs with large f, indicating that the dislocation model may be justified to all the tilt-GBs. Applying the GB dislocation model to the present results, the diffusion mechanism of Cu in the TiN barrier layers is discussed below. As shown in Fig. 2, the geometrical configuration of most of the GBs in the fiber structural TiN layer is similar to w1 0 0x or w1 1 1x tilt-GB. The deviation of these GBs from the pure tilt-

GB would be expressed by the mosaic-spread angle u as shown in Fig. 12a. These double-tilted GBs generate the dislocation network. TEM observation performed by Vystavel et al. w18x revealed that these dislocations consist of an array of parallel edge dislocations and a dislocation network which is composed of edge and screw dislocation. The density of these network dislocations will increase with increasing the angle u as shown in Fig. 12b. These dislocations contribute to the additional paths for atomic diffusion and increase the diffusion flux along the GBs. Therefore, the Cu diffusivity through the GBs in the fiber structural layer increases with increasing the mosaic spread angle u. If uis small enough, dDb in the fiber structural layer is smaller than that in the layer with randomly oriented grains. The ability of the barrier layer to prevent the Cu diffusion is considered to be larger in the layer with strong fiber structure. This is consistent with the experimental result reported by Murakami and deFontaine w19x in which Ag polycrystalline thin films with small mosaic-spread angle had very low diffusivity (same as bulk diffusivity) to Cu films. As already mentioned, the rotation angle f have strong effects on dDb values. If the TiN films which have perfect fiber structure and are composed of the tiltGBs with small f, excellent thermal stability will be expected. However, it is very difficult to control the rotation angle f in the TiN film, while the mosaicspread angle u in the film is controllable. Thus, we discussed only the effects of u on the thermal stability of the TiN barrier layers. Although there are no systematic experiments to correlate the dDb value with the angle u, Budke et al. w20x reported that the small deviation from the ideal tilt-GB, especially twist components, strongly enhanced the GB diffusion through tilt-GBs. We believed that this investigation supports qualitatively our present model. In the present study, the thermal stability was evaluated by formation of Cu silicides detected by XRD. Thus, the decreasing diffusional flux of Cu atoms through the TiN barrier layers is very important to prepare the barriers with high thermal stability. Large grains decrease the density of GBs in the film and the flux of Cu atoms that diffuse along the GBs. Therefore, we conclude that the TiN films with large Lfiber yLrandom ratio (Fig. 12a), small mosaic-spread angle, and large grain sizes are desirable as the barrier layers for Cu diffusion. 4.3. Film microstructures and deposition parameters Improving Ti and N adatom mobilities on the substrate surfaces during the film deposition would help to prepare TiN films with (1 0 0) preferred texture and large grain sizes. For the sputter-deposited films, the mobilities might increase by increasing the incident

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Fig. 12. (a) Geometrical configuration of GBs in the fiber structural TiN film. (b) Schematic representations of GB dislocation structure and corresponding diffusional flux of the fiber structural TiN layer, (i) pure tilt boundary; (ii) small u; and (iii) large u.

power of the sputtering system, the Ar gas ratio, and the substrate temperature. Preparation of TiN films by optimizing these deposition parameters would be essential to improve thermal stability of the barrier layers. As shown in Fig. 2, the Ar gas flow ratio effected the vertical grain sizes. The TiN film deposited at Ary N2 gas flow ratio of 10y1 had the (1 1 1) fiber grains at the top layer (Fig. 1), while the TiN deposited at Ary N2 gas flow ratio of 1y1 had the small granular structure and no preferred orientations. Poor thermal stability of the TiN (AryN2s1y1) films can be explained in terms of high density of fast diffusion paths. Increasing the r.f. power enhanced grain growth of TiN films during film deposition (Fig. 4) and reduced the density of fast diffusion paths. High substrate temperature enhanced

the (1 0 0) preferred orientation of the TiN films during the early stages of deposition in the bottom layer (Lrandom). 5. Conclusion The thermal stability and the film microstructures were correlated by analyzing the microstructure of the 25-nm-thick TiN barrier layers deposited at various conditions. It was found that the thermal stability was strongly correlated with the film microstructure, and the mosaic-spread angle of the films and grain sizes were found to be the key factors to control the thermally stability of the TiN barrier layers. The 25-nm-thick TiN films with low-index preferred texture and large grain

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