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Thin Solid Films 380 (2000) 252-255

Raman spectra of TiN/AlN superlattices
M. Bernarda, A. Deneuville">*, 0. Thomasb,P. Gergaudb,P. Sandstrom", J. Birch"
aLEPES-CNRS,BP 166, 38042 Grenoble Cidex 9, France bMTOP-CNRS,Faculte' des Sciences et Techniques de Saint Erome, 13397Marseille Cidex 20, France 'Department of Physics, Linkoping University, S-58183 Linkoping, Sweden


TIN (4.5 nm)/AlN (3, 6, 22 nm) superlattices deposited by DC magnetron sputtering on MgO(001) at a temperature of 850°C exhibit Raman signals. They indicate N and Ti vacancies (as in thick TIN) in TIN,-, layers (x = 3 f 2%). x is higher for the sample with 3-nm thick AlN layers, which is ascribed to N diffusion from AlN (standing close to the TIN interfaces) to TIN. In comparison to Raman peaks of thick AlN, there are split signals of wurzite AlN phase, and a signal from another phase, which might be defective rocksalt AlN standing close to the TIN interfaces. The Raman signals clearly show interactions between A N and TIN layers. 0 2000 Elsevier Science B.V. All rights reserved.
Keywords: SC/metal superlattices; Nanometric layers; Raman; Vacancies; TiN, A1N

1. Introduction

2. Experimental details

For nm-size TiN/AIN superlattices grown on Mg0(001), the AIN phase transition from wurzite to rocksalt cubic was recently seen, when the AIN thick2 nm [1,2]. These results need to be ness became I confirmed and understood from the characteristics of the AIN and TiN layers. While the Raman signals of wurzite AIN are well known [3], the selection rules forbid first-order Raman signals from any cubic phase. In fact, rocksalt cubic TiN [4-6] and zinc-blende AIN [7] give Raman signals. On nm-size TiN (4.5 nm)/AlN (3, 6, 22 nm) superlattices, with a constant TiN thickness, we identify from Raman spectroscopy: (i) several AIN phases; and (ii) sub-stoichiometric TiN, -n layers containing N and Ti vacancies. The significance of these results will be discussed.
*Corresponding author. Tel.: + 33-476-881009; fax: + 33-476887988. E-mail address: (A. Deneuville).

The samples were deposited by DC magnetron sputtering on MgO(001) substrates at 850"C, beginning with the TiN deposition from elemental Ti (99.98%) and AI (99.999%) targets using N, of N 70 purity as a sputtering gas at a total pressure of 10 mtorr. The thickness of the layers was determined by fitting X-ray reflectivity curves with GIXA software. The TiN thickness was kept constant at 4.5 f 0.2 nm while the AIN thickness increased from 3 f 0.5 to 6 f 1 to 22 f 4 nm, with 22, 17 and 10 periods, respectively. The micro Raman spectra were recorded at room temperature in a backscattering geometry with a Dilor Labram apparatus. They were excited at energies E , of 1.96, 2.41, 2.71 and 3.4 eV (632,514,458 and 363 nm, respectively) by HeeNe and Ar lasers.
3. Results and discussion

All the properties of the samples vary systematically with their preparation conditions. The Raman signals

0040-6090/00/$ - see front matter 0 2000 Elsevier Science B.V. All rights reserved PII: S 0 0 4 0 - 6 0 9 O ( 0 0 ) 0 1 5 3 1- 5

/Thin Solid Films 380 (2000)252-255 253 are highly reproducible. The Raman contributions from the different layers of a sample are cumulative. Its acoustical phonon signal is more + Y . respectively. the solid and the mixed curve are the A1N contribution to the Raman spectra for the samples with 22 and 6 nm of A N .and triangular-like signals are defect-induced first-order Raman scattering. normalized at 555 and 700 cm-'. Fig.8]. 3. While (except for the second-order contribution from 400 to 470 cm-') the curves are identical on the low wavenumber (TO) side. 1 shows the Raman spectra of the three samples excited by the 458-nm laser light. After shifting the curve of the sample with 3-nm AIN ) . In the inset. these 4. the concentration of N vacancies has to be higher in this last sample.1. when the ratio of N/Ti vacancy concentrations (and therefore x) increases: (i) the intensities of these second order signals decrease rapidly. and (iii) the signal from the acoustical phonons increases. The square-like (acoustical phonons with TA and LA modes. The small 414 cm-' (2 TA) structure and the wide maxima around 810 (LA + TO) and 1110 (2 TO) cm-' originate from overtones. at approx. The optical phonon signal from the sample with the 3-nm AIN layers is nearly identical to those of the two other samples. Therefore.) from wurzite AIN [3] is at approximately 660 cm-'.2. the firstorder Raman spectrum of TiN has to spread up to 620 cm-' 181. 3. the structures at a wavenumber of approximately 658 cm-' in Fig. R a m a n signal j?om the TiN layers Fig. Bernard et al. the AIN contribution to the Raman spectrum will be obtained by subtracting the TiN contribution to this Raman spectrum from the whole Raman signal of the sample. From the comparison of our spectra to these previous spectra.5-nm TiN films contain Ti and N vacancies. The inset of Fig. 200 and 306 cm-'1 and the triangular (TO modes up to a maximum at 555 cm-' and weak contribution of the LO modes up to 620 cm-'1 signals originate from Ti atoms surrounding N vacancies and N atoms surrounding Ti vacancies. the overall N sub-stoichiometry in our samples can be estimated as x=3f2%. We suggest a diffusion of N from AIN (standing at a distance < 6 nm from the TiN interfaces) to TiN. All spectra have the same square-like shape at 190-350 cm. Raman spectra of the three samples excited by the 458-nm laser light. because. the common component at 680-700 cm-' has to be ascribed to second-order TiN 200 400 600 800 1000 Wavenumber (cm-1) Fig. Hereafter. The more intense Raman signal (E. systematic variations appear on the high wavenumber side.61. R a m a n signal f r o m the AIN layers From coherent-inelastic neutron-scattering experiments and the calculated dispersion curves. 2. From previous works [6]. which partially fills the N vacancies in the TiN layers up to a saturated value. 1. the Raman by . respectively [5. like thicker TiN films [4] and TiN crystals [5. hereafter for each sample. The same structures are found in thin films and crystals of cubic rocksalt TiN [4-61.M. according to [6]. 1. respectively. 2 shows the two differential Raman spectra (which are expected to contain first-order AIN and secondorder TiN contributions) obtained by subtracting the normalized spectrum of the sample with 3-nm AIN from those of the two samples with thicker AIN layers s the penetration depth between 620 and 700 cm-'. Therefore. The signals from the acoustical and optical phonons are nearly identical for the samples with 6 and 22 nm AIN thickness.8 cm-' (to correct for its higher x signals of all samples were normalized at 555 and 700 cm-'. (ii) the first order signals shift rapidly to higher wavenumbers. reached here in the samples with AIN thickness 2 6 nm. in the differential spectra. we will separate the contributions of the AIN and TiN layers in the Raman signal of the samples. Raman spectra of Fig.and a triangular-like shape at approximately 555 cm-'. and finally wide maxima centered at approximately 810 and 1110 cm-'. From these features. but shifted to approximately 563 cm-'. Therefore. 2. A of the light is limited by the absorption of the TiN layers. The square. 1 for the samples with AIN thickness 2 6 nm originate from AIN.c i fn S S (R K B C E 400 440 480 520 560 600 640 680 Wavenumber (cm-1) ' Fig. intense and the mean wavenumber of its TA phonons appears at a higher (212 instead of 200 cm-'1 wavenumber. the same thickness of TiN.6. . is probed. but increasing thickness of AIN as the thickness of the AIN layers increases in the different samples.

The known AIN phonon modes in this wavenumber range are E. Conclusion Some characteristics of the TiN and AIN layers in nm-size TiN (4. the chemical composition of the TiN and AIN layers depends on the thickness of the AIN layers. In particular. Raman spectra of the 22-nm sample at different excitation energies.41. increases. The 659 and 672 cm-' components are ascribed to a nearly relaxed wurzite phase. 4. Besides signals ascribed to a nearly relaxed wurzite AIN phase and another wurzite AIN phase. The existence of N vacancies in AIN near the TiN interface was shown in Section 3. Tanaka. Nomura. After normalizing each spectrum at 550 and 700 cm-' at each value of E. due to a resonant effect. 655. which have neighboring structures. The wide component at approximately 645 cm-' is too wide and too far away from the modes of the relaxed wurzite or zinc-blende phases to be ascribed to either of these phases. and the central 650-680 cm-' and the 620-650 cm-' parts (which vary with the AIN thickness) to AIN. increases.1. 3 at the corresponding E. 659. It is shown in the inset of Fig. Between 650 and 680 cm-'.. but with a higher x in the sample with the lowest AIN thickness (3 nm). (660 cm-' and EITO (673 cm-' for the (relaxed) wurzite phase [3] and TO (655 cm. The AIN Raman signals are different to those of thicker films. M. Setoyama. in this thickness range. Kitagawa. As the defect-induced first-order Raman signals look like the total distribution of phonons [4-61. and poor wavenumber resolution when E.254 M. the AIN contribution to the Raman spectra increases when E. x = 3 f 2%. The 645 cm-' signal obtained here presents all the characteristics of a defect-induced first-order Raman signal from a defective rocksalt AIN phase near the TiN interface. Actually.5 nm)/AIN (3. the same wavenumbers (645. Technol. In our superlattices.4 eV. 666 and 672 cm-' appear for the Lorentzian components in all the fits of the AIN contributions to the Raman spectra of the samples. 2. the subtraction of the (shifted) spectra from the sample with the 3-nm AIN layers from those shown in Fig. the central part 650-680 cm-' is too wide to be fitted by a single Lorentzian function. 4. the 645 cm-' signal might be ascribed to a defective AIN rocksalt phase standing near the TiN interfaces. 2.96.appear more and more clearly as E.. In addition to the predominant signals from TiN. with an overall N sub-stoichiometry TiN. 22 nm) superlattices were derived from Raman measurements. The origin of the shift remains unclear. of 1. T. this defective AIN rocksalt phase might exhibit a Raman signal at approximately 645 cm-'. 3 shows spectra obtained for the sample with the thicker (22 nm) AIN layers. Bernard et al. 4. because of the neighboring ratios of the intensities of the 666/655 cm-' and 672/659 cm-' components. gives the AIN contributions to the Raman spectra of Fig. such a defective AIN rocksalt phase would exhibit a defect-induced fist-order Raman scattering. exhibit Raman signals in the same wavenumber range [7].-. the existence and the wavenumbers of these components can be trusted. As the wurzite and cubic phases. .4 eV. we also ascribed the 655-666 cm-' pair to wurzite. 86/87 (1996) 225. Therefore.. Fig. 6. Surf.'1 for the zinc-blende phase [7]. 2. our TiN layers contain both N and Ti vacancies. References [l] M. 2 that the relative ratio of the 645 cm-' signal increases as the AIN thickness decreases. This difference is ascribed to N diffusion from the AIN standing in the vicinity of the TiN interfaces to the TiN layers. As in the inset of Fig. Coat. as in all other known rocksalt TiN materials. ' While the 655 cm-' signal might be ascribed to an AIN zinc-blende phase.71 and 3. N. Although there is some noise in the AlN contributions to the Raman spectra. Only the rocksalt AIN phase was otherwise reported [1. a signal from another phase appears. 3.21. /Thin Solid Films 380 (2000)252-255 Wavenumber (cm-1) Fig. As the defective TiN rocksalt phase. = 3. A1N contribution to the Raman spectra of the sample with 22-nm AIN layers at different light excitation energies. Therefore. 630 650 670 690 Fig. The Raman spectra of the same samples were recorded with light excitation E. they have to be wide. structures at a wavenumber of approximately 658 cm.. It could possibly be ascribed to a defect-induced first-order Raman signal from a defective rocksalt cubic phase of AIN near the TiN interfaces. Nakayama. A.

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