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Deposition of TiO2 doped Ta2O5 thin films by photo-induced CVD method using 222nm excimer lamps Irving I. Liaw* and Ian W. Boyd
Electronic and Electrical Engineering, University College London, Torrington Place, London WC1E 7JE, UK * Corresponding author: Tel : +44-207-679-3196; fax: +44-207-388-9325 Email address: firstname.lastname@example.org (I.I. Liaw) Abstract Photochemical deposition using 222nm excimer lamps of TiO2 doped Ta2O5 thin films on heated silicon substrates at 400°C is described. Tantalum tetrathoxy
dimethylamenoethoxide and titanium isopropoxide compounds were used as precursors and introduced into a reacting chamber by flowing with an Ar carrier gas. Molar ratio mixtures of precursor compositions produced films of thicknesses around 5 - 45nm with refractive indices from 1.62 – 2.08 depend on the amount of precursor introduced during the deposition process and a subsequent UV annealing process. After metal evaporation of aluminum dots to form MOS capacitor test structures, leakage currents were measured, showing a reduction by 2 orders of magnitude after the annealing step. Subsequent measurement of the C-V relationship of the film also revealed the formation of an excellent interface with the underlying substrate. Keywords: Dielectric; Excimer lamp; Ta2O5 – TiO2 Introduction Replacement material systems are being researched to take over from the ubiquitous SiO2 which is perceived as reaching its practical limit as a consequence of miniaturization . For implementation as gate dielectric material in sub-0.1 µm applications in complementary metal-oxide-semiconductor (CMOS) technology, a range of material systems and deposition techniques have been considered . As thicknesses
The effect of post deposition low temperature UV annealing is also discussed. . a strong enhancement of κ by a factor of 4 has been achieved in Ta2O5 ceramic through the controlled addition of 8mol% of TiO2 in bulk was first reported by Cava et al. In particular. avoiding the damaging effects of ionic bombardment which plague other processes . The prospect of new devices using an established material with an easily incorporated doping step. The thermal and chemical stability of Ta2O5 allows the formation of good quality films under microelectronic processing conditions. direct tunnelling of electrons leads to an increase of leakage current densities and device reliability is impaired. Results presented clearly show that the dielectric properties are dependent on calcination of the films. an expected threefold area reduction for capacitive components might eliminate the need for complex three dimensional capacitor geometries for small-area components. Such a process prevents unwanted effects such as early film crystallization whilst providing good control of composition and microstructure.of this dielectric is reduced to barely a few molecules. Although this method of deposition requires post-deposition treatments to desorb the C and H contamination. may extend the use of Ta2O5 to even higher densities. Significant increases in dielectric constant (κ) when Ta2O5 is doped with other oxides such as Al2O3  and ZrO2  have been reported. . Experience from its usage in capacitors and its compatibility with other compounds used in microelectronics manufacturing make it one of the most attractive and widely researched replacement dielectric materials. Coupled with this. A novel low temperature process using an excimer lamp assisted ultraviolet injection liquid source chemical vapour deposition system (UVILS-CVD) utilising metal organic (MO) precursors is used. this reduces dielectric leakage.
Post deposition UV annealing by excimer lamps of an increased wavelength (172nm) is then carried out on some of the films for 2 and 10 minutes. 10. CV measurements were performed at 1Mhz . The precursor is introduced in vapour form into the processing chamber via a heated showerhead using Ar and N2O as a carrier gas and oxidising agent respectively. Details of the liquid injection source  and complete UV source photo-CVD [9. FSIB cleaned substrates of 1cm2 P-type Si (100) were cut and blown dry with N2 and loaded directly onto a substrate holder maintained at 400° C during deposition within the processing chamber which is evacuated by a single stage rotary pump to about 10-1 mbar maintained by a Pfeiffer automatic controller.Experimental details The process system comprises two stainless steel chambers with a MgF2 glass window transparent to UV light separating the top lamp chamber and lower processing chamber. titanium isopropoxide compounds and anhydrous cyclohexane solvent mixed using precision syringes is connected to the liquid injection system. Fourier Transform Infrared Spectra (FTIR) were taken by a Perkin Elmer Paragon 1000 Spectrometer providing an insight to the variation in the bonding configurations of the binary compound film. Narrow emission band UV at a central wavelenth of 222nm is generated by a dielectric barrier discharge in the lamp chamber. Thickness and refractive index measurements of the deposited films were measured using a Rudolph Auto Ellipsometer II (λ = 633nm). A metallization process by thermal evaporation of aluminium dots was done to form MIS test structures for electrical characterization. A sealed container carrying a molar weighted ratio of liquid metal organic precursor of tantalum tetrathoxy dimethylamenoethoxide. 11] have been described elsewhere. Films are deposited by the irradiation of the vapour within the chamber.
were noticed in any of the films. The weak absorption band at 8001000cm-1 attributed to the presence of a suboxide layer . The deposition rates are approximately 18. The value range between 1. IV measurements were then performed using a HP4145B on these formed capacitor structures. The linear and rapid growth rate reflects the precise level of control which is afforded by the deposition technique employed.using a HP 4275A. It is noted that no C-H or OH peaks at 1600cm-1 and 3600cm-1. 14]. the actual deposition may not have resulted in 8mol% content of TiO2 within the deposited films. Results and discussion Fig.8nm/min and 25. The refractive indices of deposited films vary with thickness and length of post process annealing. It may then be prudent to conclude that the 8mol% referred to henceforth is the mol% in the vapour rather than the deposited film. a peak at about 1070cm-1 attributed to stretching vibration of the Si- . FTIR spectra of 400-1400 cm-1 range for a set of 8% 10nm thick film with varied annealing times are shown in Fig 2.3nm/min for 8% and 10% TiO2 doping respectively. as with other CVD processes. The peak at around 433cm-1 associated with TiO2 is seen to have some enhancement after 2min anneal. However.08 for varying thickness compare well with previous work . 1 shows a plot of deposition rates of Ta2O5-TiO2 thin films for 2 molar compositions.62 and 2. An enhancement in the Ta-OTa and Ta-O stretching vibrational modes at around 600-700cm-1 is noticed and intensifies after UV annealing [13. respectively. The growth rate is clearly more rapid at a higher concentration of TiO2. However. It is the opinion of the authors that despite mixing the liquid precursors in the exact mol%. the mechanics of deposition are not completely understood. is reduced after 10 minute annealing.
A 10 minute annealing step improves this to 2. Leakage current density as low as 9.0. Refractive indices of good quality between 1.29 x 10-8 A/cm2 at 1MV cm-1.92)/Si test capacitors fabricated using 10nm thick film layers for as deposited and 10 minute annealed film is shown in Fig. 3. Conclusion The growth of thin TiO2 doped Ta2O5 films at 400°C by UVILS-CVD with subsequent UV annealing has been demonstrated. This additional step has been shown to form stronger lattice structures by replacing impurities and defects by allowing stoichometric formation of suboxides within the dielectric film. The oxygen radicals formed in the UV annealing step promote oxygen diffusion and oxidation in the as deposited films which also causes formation of the SiO2 layer . 4 shows the Capacitance-voltage (C-V) characteristics at a frequency of 1MHz for the above described 10 minute annealed film.08) – Ta2O5(0. Fig. This low offset value seems to indicate good band forming structure at the interfaces. These values compare favourably to pure Ta2O5 films twice as thick .O bond in SiO2 is observed to form .1V indicating the presence of positive fixed charges near the film/substrate interface with little or no C-V hysteresis effects and therefore a reduction in positive surface charge .5 x 10-7 A/cm2 at 1MV cm-1 is achieved for the UV as-deposited films at 400°C without the need for any annealing step. in turn reducing leakage current. As mentioned above. The flat band volatage (VFB) which is a result of the work-function difference between the Al gate and the p-ype Si substrate via the deposited thin film was observed to be only slightly negative ~ . it is clear that the UV annealing step helps remove defects present in the film by the introduction of active oxygen species reacting with the suboxides present within the film.62 . The Current-voltage measurement (I-V) of Al/TiO2(0.
Appl. R. J.P. Appl.Cava. R. 83 (1998) 1613-1616.K.D. (1998) 269.M. C.J. P. O’Bryan.B. 45 (2001) 1413-1431.Balland.I. References        S. Wallace.Y. J. Cava. Peck Jr & J. Anthony. Mater. J. J. R. J. Boyd. Excellent leakage characteristics comparable to pure Ta2O5 films twice the thickness suggests that the doping of TiO2 promises use at much higher current densities.. Lett.F. I.L. Phys.F. W. Gammel.and 2. The deposition rates of the film are significantly higher than other work using the same technique and considerations will be made in future work to consider more controlled flow rates and pressures on the final stoichometry of the formed film. B. Electrically. the films demonstrate low levels of leakage current due to the annealing step removing OH peaks and the formation of a good interface between the deposited film and the substrate as shown by the CV characteristics. .) acknowledges receipt of an Overseas Research Students (ORS) Award and the University of London’s Thomas Smythe Hughes Studentship. Kingon. Peck Jr. 89 (2001) 5243. Eng. R. G. 22. R. Considerations will also be made to study the molecular concentration of TiO2 in the deposited film. J.L.F. Autran. Wilk.08 were obtained in various growths with improving electrical characteristics after post deposition annealing. Devine & D..I.M. 70 (1997) 1396.L. Phys.J. Appl. This might well be the crux in considering the dielectric enhancement in films deposited by such a process.A.W. Zhang. Barber..L. Krajewski. Solid State Electron. Acknowledgements This work is partially funded by the European Commision under IST Research Project No.M. H. Chaneliere . Nature 377 (1995) 215. 10541 – Tantalum Pentoxide Photodeposition on Silicon (TOPS). J. Phys.J. One of us (I. W. Cava. Nature 377 (1995) 194. Sci. Streiffer & A. Krajewski. Krajewski.J. G. R. Roberts.
Y. 45 (2001) 1413-1431.T. Zhang. Solid State Electron. Williams. C. Zhang. D. Mooney. J. Zhang. Electrochem. Q. Mooney.M.T. D: Appl. Symp. 168 (2000) 307. Sci. Crean. Boyd. C. Yu.Fang. M. A. Boyd & J. J. O’Sullivan.T. Phys.Y. 139 (1992) 1956. Boyd. Soc. Process 70 (2000) 647.V. Appl. Phys. Fang.   F.Y. 567 (1999) 473.S. V.Y.A. Son. Roberts. W.  J.J. B. Sénateur.W. Jiminez. Ahn.W. C. G. Zhang. O.S. 567 (1999) 397. Appl. Z.K.M. F.M. Kelly. Beechinor. Crean.H. Hurley. Res. Microelect. Felten. Surf. Sénateur. Phy. P. J. Kaliwoh. Res.M. Beechinor. J. B.Y.L. Kelly. Weiss. Soc. Zhang. Sci. Phys. 19 (1999) 91-95. Surf. 66 24(1995) 1435. Sugimoto. Sci 186 (2002) 246-250.. J. Paillous.J. Kim.W. Zhang. Vrtis. J. Hurley. Kim. D. Chun.S.M. Senateur.A. I. G. J.Y.Boyd. G.P.K. M. Boyd. J.P. D.Y. Madar & A. I. (2003) 621-630. Jiminez. Appl. R. Electron. O’Sullivan.P. K. Paillous. M. Kwon. K. IV C5 (1995) I. Abrutis.        N. . Lee.B. He.V. J. I. J. I. Symp Proc. J. J. Mater.J. 1079.W.L. J. 32 No Q. P. Engg.Y. J. J. Proc.Boyd.Boyd. W. Zhang. P. A: Mater. Mater. Soc. I. Kwong. Dusatre. I. White. Mao. R. I. J. Wang. M. J.B. P. S. An. J.E. Mater.W.W.
Figures 50 45 40 Growth rate of Ti doped Ta thin films Thickness (nm) 35 30 25 20 15 10 5 0 0 20 40 60 80 100 120 8% TiO2 10% TiO2 Deposition Time (s) Fig. Growth rate of Ti doped Ta thin films for 8% and 10% TiO2. 1. .
U. 2 FTIR Spectra of as-deposited and UV–annealed films (10nm). .) 99 As-Deposited TaO 97 2 min anneal 10 min anneal 95 SiO 93 1400 1300 1200 1100 1000 900 800 700 600 500 400 Wavenumber Fig.Absolute Transmittance (A.
Current-voltage characteristics of Al/TiO2(0.E-09 0 1 2 3 Electric Field (MV/cm) 4 5 6 Fig. 3.08)-Ta2O5(0.E-03 Leakage current density (A/cm ) 1.E-08 As-deposited 10min 1.E-06 1.E-04 2 1.E-07 1.1.E-05 1. .92)/Si MIS test capacitors fabricated using 10nm thick dielectric layers.
.2 0.7 0. 4 Capacitance-voltage characteristics of MIS test capacitor at 1MHz.1 0.1 0 -3 -2 -1 0 V 1 2 3 T = 400°C P = ~100mbar Thickness = 10nm Fig.3 0.5 0. Note the flat band voltage which is a result of the Al gate to p-type Si workfunction difference through the thin film.4 0.6 Ti doped Ta2O5 thin film by UVILS-CVD C/Co 0.9 0.8 0.
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