This action might not be possible to undo. Are you sure you want to continue?
Interface Reaction between Titanium Thin Films and Sapphire Substrates
H. J. Kang, C. H. Kim and J. H. Kim
Department of Physics, Chungbuk National University, Cheongju 361-763
C. N. Whang
Department of Physics, Yonsei University, Seoul 120-749 (Received 10 January 1997) The microscopic properties of the interface reaction between titanium thin ﬁlms and sapphire substrates have been studied using X-ray photoelectron spectroscopy (XPS). The XPS measurements of the valence-band, and the Ti(2p) and the Al(2p) core-level peaks indicate that titanium does not react with sapphire at room temperature. At about 1073 K, the titanium begins to react with sapphire through the formation of TiO2 and metallic Al at the interface. On the other hand, the interface reaction due to ion-beam mixing during depth proﬁling is negligible compared with the thermal reaction.
I. INTRODUCTION Metal-ceramic bonding has been widely applied in aerospace, automobiles, industrial machines, etc. [1,2]. Furthermore, the successful application of metal-ceramic bonding is very important in semiconductor device packaging . Experimental studies of adherence strengths of metal and oxide ceramics show that the metal-oxgen bond at the interface enhances the intrinsic adhesive strength . Also, the reactions at the interface between the metal and sapphire are of importance in understanding the mechanisms of adhesion, etc. These interfacial reactions between the metal thin ﬁlm and the sapphire (α-Al2 O3 ) substrate have been studied in Refs. 5–9. Titanium is widely used in microelectronics technology, and titanium oxides are known to have large values for the heat of formation. Aluminum oxide (Al2 O3 ) is also one of the most important ceramic meterials in microelectronics packaging because of its superior physical and chemical properties. The Ti/sapphire system is an excellent choice in studying the interface reaction. Recently, an important concern is understanding the microscopic properties of the interface between Ti and a ceramic. Koyama et al.  indicated that there were no binding energy shifts of the Ti(2p) and the Al(2p) corelevel peaks below 1073 K. On the other hand, Selverian et al.  showed that Ti reacted with sapphire at room temperature. It is still inconclusive whether the interface reaction between titanium and sapphire occurs or not in the initial stage of deposition at room temperature. This problem is very important in that this chemical reaction at the interface enhances the adhesion between the
metal and the ceramic. On the other hand, in light of these conﬂicting observations, the interface reaction between titanium and sapphire merits futher study. In our previous paper , we reported the results for the interaction of either submonolayer titanium (Ti) or zirconium (Zr) with sapphire, which showed that neither sample reacted with the sapphire substrate at room temperature; however, Ti reacted more actively with sapphire than Zr did at high temperatures. Although the previous results have lead to signiﬁcant progress in understanding the bonding state between submonolayer Ti and sapphire, the process-related information during the growth of thin ﬁlm has not been obtained. In addition, the diﬀerence in the interface reaction between a submonolayer and a thin ﬁlm raises a question as to how well the submonolayer represents a thin metallic ﬁlm. The aim of this present study is to clarify the thickness and the temperature dependences of the interface reaction between Ti thin ﬁlms and sapphire substrate. For this, the bonding states between Ti and sapphire with increasing Ti coverage and substrate temperature were investigated using X-ray photoelectron spectroscopy (XPS).
II. EXPERIMENTAL PROCEDURE The substrates were single crystals of α-Al2 O3 (sapphire), 8 mm × 5 mm × 1 mm-thick. To obtain carboncontamination-free surfaces, the sapphire substrates were heat-treated for 48 h at 1273 K in a furnace. XPS was preformed using a VG-ESCALAB 210 system. The base pressure was 5×10−9 Pa. The XPS measurement was
an IRlamp was introduced in the prechamber . and Ti(2p) core-level peaks and the valence band peak were monitored as a function of the temperature and the thickness of the ﬁlm. RESULTS AND DISCUSSION 1. Figure 1 shows the full spectra from a clean sapphire substrate and submonolayer Ti-deposited samples. The Al(2p). 1. 1(b). -159- was transferred into the prechamber to heat it up. 1(a). done with a mono-Al X-ray source using the constant pass-energy mode (10 eV). Ti ﬁlms were prepared in situ by Ar+ beam sputter deposition. To see the interface reaction more in detail. J. and the Ti(2p) peaks were monitored as a function of temperature and are plotted in Fig. An electron ﬂood gun was used to neutralize the charge built up on sapphire. III. As can be seen in Fig. O(1s). . Then. From these methods. 2. the sapphire substrate surface was free of carbon contamination. the Al(2p). the specimen The phrase “metallic aluminium” or “metallic titanium” is used to refer to a metallic type of bonding. Figure 2(a) shows the valence band spectra from submonolayer Ti on sapphire. and (iii) 1073 K. (ii) 973 K. the specimen was transferred into the main chamber for XPS analysis. The high and low binding-energy peaks show the valence band of Al-O Fig.Interface Reaction between Titanium Thin Films and Sapphire Substrates – H. contamination-free thin ﬁlms were obtained. the valence-band. corresponds to a submonolayer. For heating the specimen. After Ti sputter deposition in the main chamber. The full spectra (a) before and (b) after submonolayer Ti deposition. which is diﬀerent from that of the Al or the Ti element. Fig. Temperatures were changed from 300 K to 1073 K. The Ti peak of the deposited sample. Kang et al. (a) Valence band and the (b) Al(2p) and the (c) Ti(2p) photoemission peaks obtained from submonolayer Ti deposition and heat treatment at (i) 300 K. 2. Reactions Between Submonolayer Titanium and Sapphire Fig.
and (c) Ti(2p) spectra for increasing coverage of the Ti overlayer on sapphire at 300 K. . at 1073 K. 2. These ﬁgures show that Ti reacted with sapphire at 1073 K and that metallic Al was formed. This can be explained by the Ti reacting with the oxygen in the sapphire and not with the Al. no bindingenergy shifts for either peak were observed. the Al(2p). 2(c)(iii) is found to be due to the formation of TiO2 and is interpreted in terms of charge transfer from Ti to oxygen . (b) Al(2p). 1. Therefore. the Al(2p) core-level peak does not change until 973 K. Figure 3 shows XPS full spectra obtained from a clean sapphire substrate by increasing the coverage of the Ti overlayer up to 5 nm. 2(b). The full spectra with increasing coverage of the Ti overlayer on sapphire at 300 K. July 1997 Fig. During deposition of the Ti thin ﬁlm. As can be seen in Fig. These results led to the conclusion that the Ti reacts with sapphire at temperatures over 1073 K. and the Ti(2p) peaks were monitored to Fig. These results clearly show that there is no The same experiments were carried out by increasing the Ti overlayer on sapphire. 2(b)(iii)]. 4. metallic Al is formed due to the interface reaction (Ti-O). The binding energy shift of the Ti core level relative to the metallic state in Fig.13]. the valence-band. 2(a)(iii) at high temperature. Reactions Between Titanium Thin Film and Sapphire bonding and O(2p) of sapphire. the two main peaks are from the Ti(2p3/2 ) and Ti(2p1/2 ) core levels of pure metal Ti. Until 973 K. Vol.-160- Journal of the Korean Physical Society. 2(b)(ii)] to metallic Al [Fig. interfacial reaction at 300 K. However. 31. 3. 2(c). respectively [7. while the peak observed on the high binding-energy side at 1073 K is due to titanium oxide. After submonolayer Ti deposition. but it shows a change at 1073 K. Again. the shape of the peaks does not change at room temperature. (a) Valence-band. In Fig. the binding energy of the aluminum core level relative to that of the oxide state shifts from the oxide state of Al [Fig. the interface reaction can be seen clearly from the valence band region in Fig. No.
Selverian’s experimental procedure was as follows: the sapphire substrate was cleaned by Ar+ ion bombardment and heated before Ti deposition. Figure 5(c) shows the Ti(2p) spectra obtained from the thin ﬁlm during depth proﬁling. which may be due to the interface reaction of ion-beam mixing during sputter-depth proﬁling. the electronic structure of titanium was metallic Ti and/or an intermediate oxidation state of titanium: TiOx (x < 2). and (c) Ti(2p) spectra for depth proﬁling of the Ti overlayer on sapphire at 300 K. These results clearly show that interface reaction due to ion-beam mixing is negligible compared with the thermal reaction at the interface. As can be seen in Fig. 5(c). whereas the Al(2p) peak decreases and the metal Ti peak increases. 5. as plotted in Fig. the Al(2p) spectrum includes a small contribution from the Al metallic peak and a large contribution from the Al3+ peak. At the interface. The annealing and cleaning procedures mentioned above were repeated prior to each experiment. this phenomena was due not to the eﬀect of temperature but to the effect of interfacial mixing by ion bombardment. the valence band. the shapes of the peaks do not change. The peak shape of Al and Ti does not change as the coverage of Ti on sapphire increases. Ti atoms were mixed with the sapphire surface. and the Al(2p) and the Ti(2p) peaks were measured during depth proﬁl- ing and are plotted in Fig. Selverian et al. the titanium was removed from the sapphire substrate by Ar+ ion sputtering. see the thickness dependence of the interface reaction at room temperature. In this experiment. the valence band. (b) Al(2p). These spectra have similar peak shapes. but the low binding-energy peaks are slightly decreased. To see the eﬀect of ion-beam mixing in the interface reaction more in detail. This phenomena can be observed from the Al(2p) peaks. 4. The valence band was absolutely different from the sapphire or the Ti metal valence bands. 5(b)(iii). Mainly the Al3+ photoemission peak from Al2 O3 was detected. After Ti deposition up to 5 nm. These results clearly show that there was no interfacial reaction at 300 K. which indicates TiO2 . We might conclude that the interfacial reaction at 300 K took place due to the ion-bombardment procedure. -161- Fig. the Ti(2p) spectra do not clearly exhibit the eﬀect of ion-beam mixing at the interface. Al(2p). Comparing with Fig. The shapes of the valence band peaks change from metal Ti to Al2 O3 during depth proﬁling. whereas tiny metallic Al peaks were observed. the sample was heated at 1073 K in situ. According to tight-binding theory . The Ti+4 peak. As can be seen in Fig. then. (a) Valence-band.  published a contradicting report that the metallic Al peak slowly grew with increasing coverage of Ti at 300 K. Ti was oxidized and a part of the Al in the sapphire was changed into metallic Al. 5. even in thin Ti ﬁlms. during the substrate cleaning by ion bombardment. On the other hand. the shapes of the valence-band peaks change from Al2 O3 to metal Ti as Ti coverage increases. These metallic Al peaks are due to ion-beam mixing. Al-O bonding is . After one experimental run. J. that is. no metallic alumium and no Ti+4 peaks were observed. and Ti(2p) peaks were obtained during depth proﬁling. From this point of view. Kang et al. cannot be seen in Fig. 6. 4(a).Interface Reaction between Titanium Thin Films and Sapphire Substrates – H.
These phenomena occur because Ti atoms diﬀuse into the sapphire due to heat treatment. These peaks indicate that oxide Ti and metallic Al coexist in this area. been studied using XPS. R. by the Korea Science and Engineering Foundation through the Atomic-Scale Surface Science Research Center at Yonsei University. Project No. Nicholas and D. (a) Valence-band. the chemical reaction between Ti thin ﬁlms and sapphire substrates occurs near the interface. IV. Kinsman. The metal Ti peak at 454 eV is dominant in the surface (Fig. Ceramic Bull.  M. E. The XPS results provided a fairly complete picture of the interface reaction between Ti thin ﬁlm and sapphire in the temperature range of 300 K to 1073 K. BSRI-96-2426. Vol. From this experiment. 1. and metallic Al is Al0 . Ministry of Education. 6. CONCLUSIONS The microscopic properties of the interface reaction between titanium thin ﬁlms and sapphire substrates have . As can be seen in Fig. Ohio. the interface reaction layer between the titanium thin ﬁlm and the sapphire substrate can be assessed to be about 2 nm after heat treatment at about 1073 K.  K. Mortimer. It was found that the Ti thin ﬁlm actively reacts with the sapphire over 1073 K. 657 (1985). as shown in Fig. Then. 1. The Ti(2p) peaks show the same results. Mat. Oyama. 6(c)(i)) and the oxide Ti peak at 458 eV grows in interface. and by the Basic Science Research Institute Program. These results lead to the conclusions that the Ti thin ﬁlm reacts with sapphire at 1073 K and that the interface reaction due to ion-beam mixing during depth proﬁling is negligible compared with the thermal reaction. 6(c). Sci. 1987). Titanium reacted with the sapphire only above a critical temperature of 1073 K. 68. Ti is more exactly Ti+4 . Tech. Huebel and T. 31. This result indicates that the reaction between Ti and sapphire occurs at the interface of the Ti thin ﬁlm on sapphire. G. 6(a). the Al(2p) core-level peak changes from a metallic Al(2p) peak to the Al(2p) peak in sapphire during the depth proﬁling. No.-162- Journal of the Korean Physical Society. (b) Al(2p). in Electronic Packaging and Corrosion in Microelectronics (American Society for Metals. 1591 (1989). and (c) Ti(2p) spectra for depth proﬁling of the Ti overlayer on sapphire at 1073 K. A. Mizuhara. and oxide Ti and metallic Al were formed at the interface. July 1997 Fig. ACKNOWLEDGMENTS This research was ﬁnancially supported by the Korea Science and Engineering Foundation (KOSEF-941-0200004-2). broken and then new peaks appear near a binding energy of 10 eV as shown in Fig. 6(b). REFERENCES  H.
Sci. J. J. S. 53. 2054 (1988). 64. B32. Notis. 74. H. C. Williams and S. Kolawa and M. Nicolet. J. H. Technol. Johnson and S. 6634 (1982). Appl. 6300 (1991). Ohuchi and M. Selverian. H. Mega and R.  H. P. A5. Kim. 1237 (1985). Kowalezyk. Appl. J. Ceram. Phys. V. Vac.  W. -163-  J. Kohyama. A. Vac. Kang et al. Phys.Interface Reaction between Titanium Thin Films and Sapphire Substrates – H. 137 (1994). 1288 (1987). M. W. Soc.  K. Ohuchi. Appl. Sci. Ohuchi.  M. Bortz and F. N. P. Sci. Cignac. J. Kim. Mat. Bortz and M. Mat. Sci. J. 26. Microbeam Analysis 3. J. 160 (1996).  Y. . S. F. Park and M. 3139 (1986). Sci. N. S. Arai. A. Phys. 830 (1993). J.  X. Nakahashi. Kang. E. Surf. Suenaga and M. Shimizu. J. J. Chou and Y. S. Pepper. J. Technol. R. 100/101. 28.  F. Chaug. 1163 (1991). Am. A4.  T. S. 15. Kim. S.  M. S. S. Koyama. H. Zhao. Rev.
This action might not be possible to undo. Are you sure you want to continue?