phys. stat. sol. (c) 4, No. 4, 1481 1484 (2007) / DOI 10.1002/pssc.

200674157

Optical and electrical characterization of SiO2 films obtained by atmospheric pressure chemical vapor deposition
H. Jurez*1, T. Daz1, M. Pacio2, G. Garca S.1, E. Rosendo1, M. Rubin1, G. Romero2, A. Garca2, and C. Morales2
1

Universidad Autnoma de Puebla, CIDS-ICUAP, 14 Sur and Av. San Claudio, San Manuel, 7200 Puebla, Mxico Centro de Investigacin y Estudios Avanzados del I. P. N., Av. Instituto Politcnico Nacional 2508, 07360, Mxico, D. F.

Received 12 July 2006, revised 23 September 2006, accepted 11 October 2006 Published online 30 March 2007 PACS 73.40.Ns, 78.30.Ly, 78.66.Jg, 81.05.Gc, 81.15.Gh SiO2 films by atmospheric pressure chemical vapor deposition (APCVD) process, using tetraethoxysilane (TEOS) and ozone (O3) as reactant were obtained. The films were deposited on silicon substrates at various temperatures 125, 150, 175, 200, 225 and 250 C Fourier transforms infrared (FTIR) spectroscopy was used to characterize the SiO2 films. Absorbance spectrums show the vibration modes corresponding to SiO2 films. Additional absorption bands due to residual groups were also observed, but they were found to be dependent on the deposition temperature. The observed current flowing through the oxide could be related to these residual groups, mainly to hydroxyl groups.
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1 Introduction
CVD is a method in which precursor molecules in gas phase, react chemically to become a solid material in film form, on the substrate surface. The advantages of CVD technique on other methods are; the relative easiness to get materials of a wide range, controllable in the stoichiometry composition and in the layer structure which is difficult or impossible of achieving by other techniques. Organosilicon materials such tetraethoxysilane (TEOS), Si[OCH2CH3]4 have increasingly been used as a silicon source because it provides better film quality and excellent step coverage compared to the conventional method where organosilicon materials are not used [1, 2]. Desirable aspects of TEOS as a silicon source are safety, easy of handling, and chemical stability. However, conventional thermal CVD TEOS processes require prohibitively high temperatures which exclude their application in forming dielectric layer in multilevel metal structures. Recent works have shown that TEOS/Ozone chemistries for oxide films fulfill the low thermal budget requirements of ULSI multilevel metal processing retain many of the desirable properties of others TEOS-based processes and exhibit self-planarizing superior characteristics to all other oxide deposition processes. The CVD reaction of TEOS with ozone yields silicon dioxide thin films with excellent planar fill characteristics at unusually low process temperatures (300 C to 400 C) [38]. In this work we report the deposition of SiO2 films by APCVD using TEOS and O3, where one of the main contributions was the deposit of these films in the range of temperatures from 125 to 250C. We show that the incorporation grade of residual products in the SiO2 films depends on the deposition temperature, finding that, a correlation exists between its existence and the current flowing through the film.
*

Corresponding author: hjuarez@cs.buap.mx, Phone: +(222)2295500 ext. 7855, Fax: +(222)2295500 ext. 7876

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H. Jurez et al.: Optical and electrical characterization of SiO2 films

2 Experimental procedures
SiO2 films were deposited on n-type (100) silicon substrates of 5 -cm. The silicon substrates were cleaned by a standard process (RCA) to eliminate organic and inorganic moistures on the silicon surface. The films were deposited by using an APCVD system, which was implemented in the laboratory at Centro de Investigaciones en Dispositivos Semiconductores [9]. It consisted of a cold walls vertical reactor which was made of quartz. The susceptor was manufactured of graphite and heated by an AC signal (10 Vp, 60 Hz). A type K thermocouple and an Eurotherm 2416 temperature controller were used, for the experiments TEOS was added to the system by passing a N2 flow (1.0 slm) through a bubbler that contained the precursor at room temperature. Additionally an O3/O2 flow was introduced into the reactor (0.5 slm). The partial pressure of the TEOS was 1.1 Torr and the ozone concentration by volume in oxygen was controlled to 5%. The SiO2 films were deposited from 125 to 250 C having deposition time between 3 min to 15 min. Film microstructure was examined by FTIR spectroscopy using a Bruker vector 22 spectrometer. The thickness and refraction index were measure with a Rudolph 439L633P ellipsometer. Metal-Oxide-Semiconductor capacitors (MOS-C) were manufactured to characterize the oxide electrically. Aluminum dots were deposited through a metal mask by thermal evaporation on the oxide films to get the top electrode. Aluminum was also deposited on the back silicon surface. The final area of the MOS structures was of 3.8 x103 cm2. High-frequency (hf) capacitance voltage (C-V) and current density voltage (J-V) characteristic of the MOS-C structures were obtained by using a C-V MDC automatic system. A voltage ramp rate of 1 V/s was used to drawn the J-V curves.

3 Results
Literature reports three absorption bands due to the optical vibration modes, stretching (1075 cm1), bending (800 cm1) and rocking (460 cm1) when thermal SiO2 material is characterized by FTIR technique [10]. SiO2 films obtained in APCVD TEOS-Ozone systems exhibited other additional bands corresponding to residual groups : C-H (2936-2978 cm1), ethoxy (OC2H5 at 1380-1470 cm1), acetic acid (642 and 3581 cm1), formic acid (1105 and 1776 cm1), acetaldehyde (1745 cm1), formaldehyde (29002642 and 1745 cm1) hydroxyl groups (920 and 3300 cm1); adsorbed water (1400-1600 and 3400-3600 cm1), CO2 ( 667 and 2300 cm1) and CO bonds (2140 cm1) [1114]. Figure 1 shows a series of absorbance spectra from SiO2 films obtained at different temperatures.
250 C

Table 1 Parameters from the SiO2 films obtained by APCVD. Deposition Temperature (C) 125 150 175 200 225 250 Deposition rate (nm/min) 6 11 21 19 15 8 Refraction Index 1.452 1.456 1.460 1.459 1.461 1.460

225 C
Absorbance (u. a.)

200 C A C F 175 C 150 C D 125 C

4000 3500 3000 2500 2000
-1

E B

1500

1000

500

Wavenumber (cm )

Fig. 1 (a) Absorbance spectrum of SiO2 films obtained by APCVD at different temperatures.

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phys. stat. sol. (c) 4, No. 4 (2007)

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In all cases the absorption bands corresponding to the vibration modes stretching (label A), bending (label B) and rocking (label C) of the SiO2 film are observed. This means it is possible the deposition of SiO2 films below 200 C in our APCVD system. Literature reports APCVD SiO2 films obtained at deposition temperatures higher than 250 C [48]. From the Fig. 1 it can be seen as the deposition temperature increases the quantity of residual groups reduces. For example, a reduction in the intensity on the absorption peaks in the OH and ethoxy groups (label D and E), H20 bonds (label F ) are observed if the deposition temperature is increased from 125 to 175 C, and its elimination starting around down 200 C. Some authors have been reported the reduction of residual products in APCVD systems at temperatures bigger than 300C and in PECVD systems at temperatures bigger than 200 C [5, 7, 17]. Deposition rate and the refraction index of the films as function of the deposition temperature are shown in Table 1. The values for the refraction index measured from the SiO2 films are around the value reported for the thermal SiO2 (1.46). The deposition rate has a maximum around 175 C and it decreased as the deposition temperature increases, due probably, to an enhance in the reactions in gas phase [9, 15]. Figure 2 shows the C-V (hf) characteristic for MOS-C with oxide obtained by APCVD at 200C, 175 C and 150C. In all the cases the curves from accumulation to depletion are observed, however MOS-C with SiO2 films obtained at 150 (Fig. 2(c)) and 175 C (Fig. 2(b)) the capacitor does not reach the equilibrium (inversion region) This behavior, according to some authors [9, 16] could be related with leakage current flowing through the oxide originated by the existence of residual groups, specially hydroxyl groups, into the SiO2 film [12, 17, 18], also, for the case of Fig. 2(c) hysteresis is observed, the one which is related with the existence of trapping charge into the oxide. MOS-C with SiO2 film obtained at 200 C and higher temperatures (Fig. 2a) exhibited similar characteristics to that MOS-C with thermal oxide (accumulationdepletion and inversion) reason why the quality of SiO2 films deposited by APCVD is good.

Fig. 2 Experimental C-V Curve for MOS-C with SiO2 obtained by APCVD at (a) 200 C, (b) 175 C and (c) 150 C.

The values of the current for MOS-C with oxide obtained to temperatures of 200 C or bigger were from 107 to 109 amperes, however for MOS-C with oxide obtained to temperatures of 175 or smaller, the current is increased notably. The J-V characteristic from MOS-C fabricated using SiO2 films obtained at 175 C is shown in Fig. 3a. The current density increases as the negative bias voltage is raised on the gate. Several current mechanisms are attributed to be responsible for the leakage current in this type of devices, Schottky emission, Poole-Frenkel (P-F) effect and Fowler-Nordheim tunneling are some of them. Our results were analyzed in terms of the two field lowering mechanism whose current J-V expressions are given by; - V 1/ 2 V 1/ 2 (1) J = A**T 2 exp b exp S 1/ 2 , J = J 0 exp PF 1/ 2 , kT kTd kTd for Schottky and P-F effect respectively. In these expressions A** is the Richardson constant, T the absolute temperature, S the Schottky barrier at injecting electrode interface, k the Boltzmann constant, d the film thickness, J0 is the low-field current, S and PF are the Schottky and P-F lowering coefficients. Figure 3b shows the log(J) V1/2 plot obtained from Fig. 3a. Two nearly linear regions can be observed and according to Eqs. (1), from the slope of that lines, it is possible calculate the field lowering coefficients. The calculated values were found to be S = 5.47 x104 eV cm1/2 V1/2 for Schottky coefficient and

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H. Jurez et al.: Optical and electrical characterization of SiO2 films

PF = 2.1 x104 eV cm1/2 V1/2 for P-F. Theoretically and experimentally PF > S is expected. The low P-F coefficient value calculated suggests us the observed current in the high voltage region in Fig. 3b is not dominated by P-F mechanism. It is thought that as the electrons are injected from the gate, some electrons are trapped into the bulk traps creating a space charge. At a suitably high current the increase in the internal field of trapped electrons reduces or cancels the current due to the voltage ramp causing the change in the slope [19]. The density of that traps could be related to the observed residual groups into the oxide.
-3

8.0x10
-2

10
-3

7.0x10
-3

-3

6.0x10
-3

10

J (A/cm )

5.0x10

J (A/cm )

-4

10

-3

4.0x10
-3

3.0x10
-3

-5

10

2.0x10
-6
-3

10

1.0x10

-7

10 0.5 1.0 1.5

1/2

2.0

2.5

BIAS GATE (-V)

BIAS GATE (V )

Fig. 3 (a) Characteristic J-V and (b) Schottky plot, Log (J)-V1/2, from MOS-C manufactured with SiO2 film obtained by APCVD at 175 C.

Conclusions

It was shown that it is possible the get of SiO2 films at temperatures from 125 to 250 C by APCVD technique using TEOS and ozone as precursor. Deposition rate from 6 to 21 nm/min were obtained. The quantity of residual groups was found to be dependent on the deposition temperature as it was shown from FTIR spectroscopy. Deposition temperatures bigger or around 200 C the residual groups were eliminated almost completely. The existence of residual groups in the film especially hydroxyl groups, might be related with the current transport in the SiO2 film.

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