ICMAT 2003, Singapore Meeting

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: i.liaw@ee.ucl.ac.uk (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 [1]. 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 [2]. As thicknesses
of this dielectric is reduced to barely a few molecules, direct tunnelling of electrons leads

to an increase of leakage current densities and device reliability is impaired.

The thermal and chemical stability of Ta2O5 allows the formation of good quality films

under microelectronic processing conditions[3]. 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.

Significant increases in dielectric constant (κ) when Ta2O5 is doped with other oxides

such as Al2O3 [4] and ZrO2 [5] have been reported. In particular, 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. [6]. The prospect of new

devices using an established material with an easily incorporated doping step, may extend

the use of Ta2O5 to even higher densities. Coupled with this, an expected threefold area

reduction for capacitive components might eliminate the need for complex three

dimensional capacitor geometries for small-area components.

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. Such a process prevents unwanted effects such as early film

crystallization whilst providing good control of composition and microstructure, avoiding

the damaging effects of ionic bombardment which plague other processes [7]. Although

this method of deposition requires post-deposition treatments to desorb the C and H

contamination, this reduces dielectric leakage. The effect of post deposition low

temperature UV annealing is also discussed. Results presented clearly show that the

dielectric properties are dependent on calcination of the films.

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.

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. Narrow emission band UV at a central

wavelenth of 222nm is generated by a dielectric barrier discharge in the lamp chamber.

A sealed container carrying a molar weighted ratio of liquid metal organic precursor of

tantalum tetrathoxy dimethylamenoethoxide, titanium isopropoxide compounds and

anhydrous cyclohexane solvent mixed using precision syringes is connected to the liquid

injection system. 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. Films are deposited by the irradiation of the vapour within the chamber.

Details of the liquid injection source [8] and complete UV source photo-CVD [9, 10, 11]

have been described elsewhere. 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.

Thickness and refractive index measurements of the deposited films were measured using

a Rudolph Auto Ellipsometer II (λ = 633nm). 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.

A metallization process by thermal evaporation of aluminium dots was done to form MIS

test structures for electrical characterization. CV measurements were performed at 1Mhz

using a HP 4275A. IV measurements were then performed using a HP4145B on these

formed capacitor structures.

Results and discussion

Fig. 1 shows a plot of deposition rates of Ta2O5-TiO2 thin films for 2 molar compositions.

The deposition rates are approximately 18.8nm/min and 25.3nm/min for 8% and 10%

TiO2 doping respectively. The linear and rapid growth rate reflects the precise level of

control which is afforded by the deposition technique employed. The growth rate is

clearly more rapid at a higher concentration of TiO2. However, as with other CVD

processes, the mechanics of deposition are not completely understood. It is the opinion

of the authors that despite mixing the liquid precursors in the exact mol%, the actual

deposition may not have resulted in 8mol% content of TiO2 within the deposited films. It

may then be prudent to conclude that the 8mol% referred to henceforth is the mol% in the

vapour rather than the deposited film.

The refractive indices of deposited films vary with thickness and length of post process

annealing. The value range between 1.62 and 2.08 for varying thickness compare well

with previous work [12].

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. It is noted that no C-H or OH peaks at 1600cm-1 and

3600cm-1, respectively, were noticed in any of the films. An enhancement in the Ta-O-

Ta and Ta-O stretching vibrational modes at around 600-700cm-1 is noticed and

intensifies after UV annealing [13, 14]. The peak at around 433cm-1 associated with TiO2

is seen to have some enhancement after 2min anneal. The weak absorption band at 800-

1000cm-1 attributed to the presence of a suboxide layer [15], is reduced after 10 minute

annealing. However, a peak at about 1070cm-1 attributed to stretching vibration of the Si-
O bond in SiO2 is observed to form [16]. 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 [17].

The Current-voltage measurement (I-V) of Al/TiO2(0.08) – Ta2O5(0.92)/Si test capacitors

fabricated using 10nm thick film layers for as deposited and 10 minute annealed film is

shown in Fig. 3. Leakage current density as low as 9.5 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.

A 10 minute annealing step improves this to 2.29 x 10-8 A/cm2 at 1MV cm-1. As

mentioned above, 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, in turn reducing leakage current. These values compare favourably to

pure Ta2O5 films twice as thick [18].

Fig. 4 shows the Capacitance-voltage (C-V) characteristics at a frequency of 1MHz for

the above described 10 minute annealed film. 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 ~ - 0.1V 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 [9]. This low offset

value seems to indicate good band forming structure at the interfaces.

Conclusion

The growth of thin TiO2 doped Ta2O5 films at 400°C by UVILS-CVD with subsequent

UV annealing has been demonstrated. Refractive indices of good quality between 1.62
and 2.08 were obtained in various growths with improving electrical characteristics after

post deposition annealing. 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. 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. Excellent leakage

characteristics comparable to pure Ta2O5 films twice the thickness suggests that the

doping of TiO2 promises use at much higher current densities. Considerations will also

be made to study the molecular concentration of TiO2 in the deposited film. This might

well be the crux in considering the dielectric enhancement in films deposited by such a

process.

Acknowledgements

This work is partially funded by the European Commision under IST Research Project

No. 10541 – Tantalum Pentoxide Photodeposition on Silicon (TOPS). One of us (I.I.L.)

acknowledges receipt of an Overseas Research Students (ORS) Award and the University

of London’s Thomas Smythe Hughes Studentship.

References

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(1998) 269.
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P.L. Gammel, Appl. Phys. Lett. 70 (1997) 1396.
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[6] R.F. Cava, W.F. Peck Jr & J.J. Krajewski, Nature 377 (1995) 215.
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Figures

50
Growth rate of Ti doped Ta thin films
45

40

35
Thickness (nm)

30

25

20

15

10 8% TiO2
5 10% TiO2

0
0 20 40 60 80 100 120
Deposition Time (s)

Fig. 1. Growth rate of Ti doped Ta thin films for 8% and 10% TiO2.
Absolute Transmittance (A.U.)
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. 2 FTIR Spectra of as-deposited and UV–annealed films (10nm).
 1.E-03

Leakage current density (A/cm )

1.E-04

1.E-05

1.E-06

1.E-07

1.E-08
As-deposited
10min
1.E-09
0 1 2 3 4 5 6
Electric Field (MV/cm)

Fig. 3. Current-voltage characteristics of Al/TiO2(0.08)-Ta2O5(0.92)/Si MIS test

capacitors fabricated using 10nm thick dielectric layers.
 1
Ti doped Ta2O5 thin
0.9 film by UVILS-CVD
0.8
0.7
0.6
C/Co

0.5
0.4
0.3 T = 400°C
0.2 P = ~100mbar
Thickness = 10nm
0.1
0
-3 -2 -1 0 1 2 3
V
Fig. 4 Capacitance-voltage characteristics of MIS test capacitor at 1MHz. Note the
flat band voltage which is a result of the Al gate to p-type Si workfunction difference
through the thin film.