Integrated Ferroelectrics, 38 (2001) 211-220


F. Fitsilisa, S. Regnerya,b, P. Ehrharta, R. Wasera F. Schienleb, M. Schumacherb, H. Juergensenb

Institut für Festkörperforschung, Forschungszentrum Jülich GmbH, D52425 Jülich, Germany; bAIXTRON AG, Kackertstr. 15 - 17, D-52072 Aachen, Germany

We report on the properties of thin BST films which were grown in a planetary multi-wafer MOCVD reactor which handles 5 six inch wafers simultaneously. The reactor is combined with a liquid delivery system which mixes the liquid precursors from three different sources: 0.35 molar solutions of Ba(thd)2 and Sr(thd)2 and a 0.4 molar solution of Ti(O-i-Pr)2(thd)2. Film growth on strongly (111)-textured Pt substrates is investigated within a wide parameter field. We focus on the properties of films with the composition Ba0.7Sr0.3TiO3 and thickness between 10 and 130 nm. Topics to be discussed include: the change of the texture of the BST films, which is (100) for deposition temperatures above 600°C and changes to a random orientation at lower temperature, and a comparison of planar films with films on structured substrates. The electrical properties, e.g., permittivity and leakage current, are discussed in relation to the microstructure.

Keywords MOCVD; (Ba,Sr)TiO3; multi-wafer reactor, liquid delivery; leakage current; conformal deposition;

1. INTRODUCTION (BaxSr1-x)TiO3, (BST), is one of the prime candidates as a high-kdielectric in integrated high-density capacitors for future multi-GBit DRAM memory cells1 as well as for dielectric tunable devices and remarkable progress has been achieved in the metal-organic chemical vapor deposition (MOCVD) of thin BST films2-4. Most of the experimental reactors used for the development of mass production tools presently have a single wafer showerhead design3-5 and we report as a comparison on the performance of a planetary multi-wafer reactor offering extremely high throughput due to possible batch mode processing which results in low cost of ownership. The microstructure and the film stress were investigated by X-ray diffraction (XRD) and the composition of the films was routinely determined by X-ray fluorescence (XRF) analysis. In addition, the possible incorporation of carbonate phases was monitored by IRabsorption spectroscopy. Details of the microstructure were investigated by scanning electron microscopy (SEM) and by transmission electron microscopy (TEM). BST properties depend critically on the stoichiometry, the microstructure, as well as on the films thickness. For the present discussion we selected films of a composition around (Ba0.7Sr0.3)TiO3. We deposited BST thin films at susceptor temperatures ranging from 520°C to 655°C and also varied the film stoichiometry, i.e. different ratio of the Group-II/Ti content. We first discuss the thickness dependence of the permittivity based on the dead layer model. Secondly, we discuss the thickness dependence of the leakage current for the same films. The influence of the sample stoichiometry is discussed for the films grown at 595°C. Finally, the step coverage was examined, which is essential for the envisaged DRAM application. 2. REACTOR PERFORMANCE An AIXTRON 2600G3 Planetary Reactor® was used, which can handle five 6-inch wafers simultaneously. The gas inlet is in the center of the reactor providing a pure horizontal gas flow, which makes this reactor a radial flow system. A liquid precursor delivery system, ATMI-300B6, mixes the liquid precursors of three different sources: 0.35 molar solutions of Ba(thd)2 and Sr(thd)2 and a 0.4 molar solution of

Ti(O_iPr)2(thd)2. The liquid mixture is delivered by a micro-pump to the vaporizer on top of the reactor. The process conditions are summarized in Table 1. All temperatures referred in this paper are susceptor temperatures. The actual wafer surface temperatures are measured to be 20-50°C lower depending on the process temperature and pressure. Table 1: Typical deposition conditions Susceptor temperature 520 – 655°C Reactor pressure 2 mbar Liquid source feeding rate 0.08ml/s Vaporization temperature 225 – 245°C Film thickness 10-130 nm The efficiency of the precursor consumption, defined as the ratio of the quantity deposited on all 5 wafers and the amount of the individual precursor elements contained in the consumed liquid, is an important parameter for the costs of ownership. The observed values of 45% for Ti and 35-40% for Ba and Sr are extraordinarily high as compared to the values reported for conventional showerhead reactors2. Finally, due to the gas-foil rotation principle we obtained a good homogeneity of stoichiometry and film thickness over 6" wafers7. These results are supported by ellipsometry measurements, which yield, as an example, a thickness of 32,4 ± 0,4 nm and a stoichiometry variation of 53,8 ± 0,3 at% Ti. Similarly small differences were observed between the five simultaneously processed wafers (Fig.1).
40 30 20 10 0 -80 -60 -40 -20 0 20 40 60 80 Position on Wafer [mm]
40 30 20 10 0 0 1 2 3 4 5 Wafer No.

Figure 1: Thickness variations: a) across a 6" wafer and b) between five simultaneously processed wafers

3. MICROSTUCTURE Figure 2 shows the XRD patterns of slightly Ti-rich films deposited at different temperatures on sputter deposited Pt-substrates with a strong (111)-texture. We observe a very strong (100)-texture for depositions above 595°C and a transition to more polycrystalline and finally poorly crystalline growth at lower temperatures. The (100)-oriented films observed at high deposition temperatures show a width of the rocking curves of only 2-3 degrees which is similar to that of the underlying Pt7. This agreement indicates a good alignment of the (100)-fiber axis with the Pt-(111) axis and is further documented by HRTEM, Fig. 3,
(200) (100) 1E+08 Intensity [arb.units] 1E+07 1E+06 1E+05 1E+04 1E+03 1E+02 1E+01 20 30 40 50 2 theta [degree] 60 655°C 625°C 595°C 580°C 565°C Pt (111) a


001 010




Figure 2: XRD-diagrams for Ti-rich films deposited at different temperatures (GrII/Ti = 0.95-0.97)

Figure 3: HRTEM micrograph showing the Pt-BST interface for a sample deposited at 655°C.

which directly demonstrates this (100)-orientation of the BST on (111)Pt and the clean and sharp interfaces. The absolute value of the lattice parameter, as measured normal to the film plane, is, however, smaller than the expected bulk value. This difference results from a tensile stress of the film, which is thermally induced during cooling down of the film due to the different thermal expansion coefficients of BST and of the Si-substrate. Detailed strain measurements8 yield a tetragonal distortion of the film with an increased in-plane lattice constant, a, and a reduced lattice parameter perpendicular to the film, c, and can be quantified by the c/a-ratio with values between 0.994 and 0.989. Film stresses between 500 and 900 MPa can be deduced from these distortions. The c/a-ratio is always smaller than 1, thus opposite to the ferroelectric phase, where the preferred c-axis is larger than the two

identical a-axis. The substrate induced opposite lattice distortion yields therefore a plausible argument for the suppression of the phase transition in these films. Figure 4 summarizes the lattice parameters for (100)-textured films; there is no change observed for the Ti-rich samples and a steady increase with a rising Gr-II-content as regards the Gr-II rich samples. Similar observations had been reported for SrTiO3 films9 and attributed to the incorporation of the excess Gr-II elements in the form of Ruddlesden-Popper phases. In addition, we observe a change of the peak profile along with the variation of the average lattice parameter, there is a broadening and a tail to the low angle side which indicates an inhomogeneous incorporation of the excess Gr-II elements. Remarkable is the fact, that these structures seem not very stable, as there is a rearrangement to a more homogeneous structure during annealing in oxygen at a temperature of 550°C which is necessary after deposition of the Pt-top electrodes. For the Ti-rich samples there is no
4.02 4.01 4.00 3.99 3.98 3.97 0.7 0.8 0.9 1 Gr-II / Ti 1.1 1.2 1.3

a [Angström]

Figure 4: Dependence of the average lattice parameter, a, on the stoichiometry.

indication for a change of the lattice parameter and also no change of the line profile. Such a behavior is compatible with the formation of stable precipitates of amorphous TiOx at the grain boundaries as it has been observed at very high Ti content10, and there is no indication for the incorporation of larger amounts of surplus Ti in the interior of the grains. For films deposited at low temperatures indications for carbonate phases were observed by XRD and FTIR was used for more detailed investigations of the temperature and stoichiometry dependence of the carbonate formation. Figure 5a shows FTIR measurements for stoichiometric samples grown at different temperatures (565°C-625°C). No indication of any carbonate phases can be detected for temperatures above 565°C and only the absorption bands which can be assigned to BST are visible around 470 cm-1 and 790 cm-1 respectively 6,11. Below

580°C FTIR plots reveal the formation of SrCO3&BaCO3 (sharp peak at 860cm-1 and broad band around 1450 cm-1) and the BST absorption band become broader. Figure 5b displays the changes after 20 min by rapid thermal annealing for an original GII-rich 565°C sample. The initially the strong carbonate phase becomes weaker and finally disappears after 20min at 750°C.
625°C 595°C Transmitance (arb. Units)
Transmitance (arb. Units)

original 550°C anneal 650°C anneal 750°C anneal

580°C 565°C


SrCO3 & BaCO3

450 650 850 1050 1250 1450 1650 1850 2050
450 650 850 1050 1250 1450 1650 1850 2050 Wavenumber (cm-1)

Wavenumber (cm -1)

Figure 5b: FTIR spectra of a 565°C sample after different post-anneal steps

Figure 5a: FTIR measurements on stoichiometric samples grown at different temperatures

4.ELECTRICAL PROPERTIES For the electrical characterisation Pt top electrodes were deposited by magnetron sputtering. Electrode sizes of a diameter between 0.1 to 1.13 mm were obtained by a lift-off process. An additional post-annealing was performed ex-situ. The standard characterisation included the dielectric permittivity, εr, measured at a frequency of 1 kHz and the dissipation loss, tanδ, and leakage current. All measurements were performed at room temperature. It is generally observed that the permittivity of thin films shows some thickness dependence, which can be described by a so-called dead layer or interface layer. This model consists of a bulk region and the two interfaces to the electrodes which can be described by two capacitors of a lower permittivity 12. The resulting reciprocal capacitance of the film is given by equation 1. Hence, in a plot of 1/C versus thickness the slope reveals the bulk permittivity, while the intercept presents the interface capacitance.
A 2⋅ A A 2 ⋅ ti (t − 2 ⋅ ti ) = + = + ε0 ⋅ε B C Ci CB ε 0 ⋅ ε i


This model was applied on the permittivity values of Ti-rich films with different thickness for three growth temperatures (565°C, 595°C and 655°C). In addition a series of GrII-rich samples grown at 595°C was examined. Figure 6 shows the plots for the different thickness series and table 2 summarizes the results.
100 80 A/C [m²/F] 60 40 20 0 0 20 40 60 80 100 thickness [nm] 120 140 565°C Ti-rich 595°C Ti-rich 595°C GII-rich 655°C Ti-rich

Figure 6: Thickness dependence of the reciprocal permittivity and extrapolation from the linear fit

Growth Temp (°C) 565 595 595 655

GII/Ti ratio 0.90-0-98 0.93-0.96 1.00-1.11 0.91-0.95

Interface cap. Bulk Permittivity (fF/µm²) 70 282 94 869 152 666 122 777

Table 2 The bulk permittivity, shows a strong increase from 565 to 595°C and seems constant within the uncertainties at higher temperatures. The interface capacitance shows a slight but more systematic increase with deposition temperature for the Ti-rich samples. In spite of the scatter of the data there is an indication for a higher capacity of the Gr-II-rich samples deposited at 595°C. For the samples discussed above we recorded the leakage current as a function of the applied field, since we want to compare films of different thickness, Figure 7 a)-d). All diagrams show a clear dependency of the leakage current on the film thickness; the thinner the film, the lower the leakage current for a given applied field. This behavior indicates that the current is not simply controlled by the bulk and details are under investigation. Remarkable are the rather low currents of <10-10A/cm² especially for the 15 and 30 nm films and the

655°C GII/Ti=0.92-0.95

1E-02 1E-04

565°C GII/Ti=0.97-0.98

1E-02 1E-04

J [A/cm²]

J [A/cm²]

1E-06 1E-08 1E-10 1E-12 -500 0 71nm 46nm 30nm 24nm -1500 -1000 500 1000 1500

1E-06 1E-08 1E-10 1E-12 -500 0

60nm 45nm 30nm 15nm 500 1000 1500



Applied Field [kV/cm]

Applied Field [kV/cm]

595°C GII/Ti=0.93-0.94

1E-02 1E-04

595°C GII/Ti=1.00-1.02 J [A/cm²]

1E-02 1E-04 1E-06 1E-08 1E-10 111 nm 56 nm 33 nm 14 nm 500 1000 1500

J [A/cm²]

1E-06 1E-08 1E-10 1E-12 -1500 -1000 -500 0

109 nm 55 nm 31 nm 20 nm

500 1000 1500

1E-12 -1500 -1000 -500 0

Field [KV/cm]

Field [KV/cm]

Figure 7: Leakage current for a)-b) samples deposited at different temperatures and c)-d) samples of different stoichiometry at 595°C

prominent difference in the field dependence of the current for films of different thickness. In summary, we observe a dependence of epsilon on the deposition temperature only between Tdep = 565 and 595°C and these changes might be related to the improved crystalline quality of the films. The lower quality at 565°C might additionally be affected by carbonate formation as evidenced through FTIR measurements especially for high Gr-II contents. However, also an increasing surface roughness which affect the top electrode must be considered. The leakage current in the region of low fields is always <10-10 A/cm² and seems less effected by the deposition temperature of the films, however, the differences increase at higher fields. Similarly, the 595°C samples of different stoichiometry differ mainly by the field dependence and this fact makes comparisons to other related work very problematic.

5. CONFORMAL DEPOSITION We examined the MOCVD deposition of BST films on structured platinized wafers at three different deposition temperatures (595°C, 565°C and 520°C). The film microstructure at these temperatures varies from (100)-oriented @ 595°C, polycrystalline @ 565°C and finally at @ 520°C partly crystalline as revealed by the SEM figures and the weak XRD lines. The conformal deposition of the film was determined from SEM pictures. The step coverage is quantified by the ratio of the film thickness at the side to the film thickness at the top of the structure and increases with sinking temperature as displayed in Fig. 8 a-c.


BST Pt SiO 2



Figure 8: Step coverage for 3 different susceptor temperatures: a) 520°C b) 565°C and c) 595°C

For the 595°C sample the step coverage is about 0.55 and becomes 0.66 for the 565°C one. Finally, the 520°C sample reaches a step coverage around 0.81. This improvement of the step coverage is observed along with the transition from the transport limited growth to a kinetically controlled growth rate as evidenced by a reduction of the deposition rate below 565°C. Additionally, crystallinity worsens with reduced temperature, so that it seems inevitable to include additional processing

steps. Although there are major corrections in thickness necessary due to the non-ideal step coverage and the increased total area the structured wafers deposited at 565°C show similar electrical properties as the planar films. Acknowledgments The authors greatly acknowledge the help of W. Krumpen in the course of XRF analyses. References
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