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Surface & Coatings Technology 202 (2007) 121 125 www.elsevier.com/locate/surfcoat

An alternative micro-area X-ray diffraction method for residual stress measurement of Pb(Zr,Ti)O3 film
F. Yang a,b,, W.D. Fei b , Z.M. Gao c , J.Q. Jiang a
b

School of Materials Science and Engineering, Southeast University, NanJing 211189, P.R. China School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, P.R. China c School of Chemistry, Jilin University, Chang Chun 130012, P.R. China Received 25 March 2007; accepted in revised form 29 April 2007 Available online 10 May 2007

Abstract An alternative X-ray diffraction method for micro-area residual stress measurement was proposed by means of the analysis of a single diffraction ring, which was performed on a laboratory X-ray microdiffraction system equipped with a 2D planar detector. The microdiffraction experiments were employed to evaluate the residual stress in solgel-derived Pb(Zr,Ti)O3 film before and after Ag electrode deposition. The tensile stresses of about 2.3 GPa and 1.2 GPa were calculated in the micro-area of film without and with electrode, which was related to a top electrode stress relaxation effect. 2007 Elsevier B.V. All rights reserved.
Keywords: XRD2; Solgel; Residual stress; Ag electrode

1. Introduction Residual stress is one of the important features that determine the performance of structural and functional materials [1]. For solid films, residual stress is especially obvious due to great thermal mismatch and/or lattice mismatch between film and substrate. Excessively large residual stress in the films may cause delamination and/or cracking. Residual stress plays such a significant role in film behavior that many researches have been initiated to measure and modulate it in the films. In particular, the advantage of Pb(Zr,Ti)O3 (PZT) thin films in favorable piezoelectric and ferroelectric properties has made them good candidates for the Micro-electromechanical Systems (MEMs) and nonvolatile ferroelectric random access memories (FRAM). It has been pointed out that residual stress could have crucial influence on PZT films structure and properties. Shaw et al. reported that the degradation of permittivity and remanent

Corresponding author. School of Materials Science and Engineering, Southeast University, NanJing, 211189, P.R. China. Tel./fax: +86 25 52090630. E-mail address: yang_fan@seu.edu.cn (F. Yang). 0257-8972/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2007.04.125

polarization was ascribed to the presence of residual stress in PZT film [2]. Another example of the effect of residual stress on ferroelectric properties of solgel derived PZT film was discussed by Garino et al. [3], in which an increase of the dielectric constant (by 2%) and remanent polarization (by 11%) in film was observed, while the residual tensile stress was lowered by about 30%. Therefore, it is essential to understand the role of residual stress in PZT films in order to improve film performance. Indeed, the effect of the residual stress in micron scale on the resulting dielectric and ferroelectric properties of PZT films should also be considered in view of the reducing planar dimension in the microfabrication and FRAM applications. In recent years, there have been lots of researches on the residual stress in PZT films [4,5]. And a growing attention has fell into the category of micron scale structure and residual stress in the films, especially in the areas of top electrode. It has been found that the difference of stress state in micron scale area of PZT films led to the obvious discrepancy of ferroelectrics [6]. Moreover, the study of surface treatment effects on thickness dependence of Pb(Zr0.52Ti0.48)O3 capacitors has indicated that it is not intrinsic but extrinsic effect, such as interfacial or

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strain effect related to electrode that provides a reasonable interpretation on the degradation of the remanent polarization [7]. As the top electrode would exert considerable effect on the micro-area stress state, the evaluation of stress state in top electrode areas would thereafter help to understand electrode effect on the properties of Metal/PZT/Metal structure. Many experimental techniques have been developed to measure the amount of stress/strain in thin films, amongst which X-ray diffraction (XRD) is a well-known non-destructive method that is routinely employed to determine the level of residual stress in the films [810]. But the conventional XRD technique can only allow determining the average stress throughout the entire film as the illuminated area is millimeter scale. The curvature method using Stoney's equation is also mentioned in the residual stress analysis of films [11]; nevertheless, it fails to evaluate the local stress in micro area. Additionally, due to the effects of both underlying layers and interdiffusion among layers, residual stress of the films deposited on the heterostructure substrate could not be determined from the wafer curvature. Recently, a bidimensional (2D) X-ray diffraction technique (XRD2) has developed and theoretically shed light on the socalled mesoscale (0.1 m100 m) stress analysis in thin film and coatings [12]. By combining the use of X-ray microdiffraction with the fast large-area two-dimensional-detector technology, this technique allows for the orientation and strain/stress mapping of polycrystalline thin films with micrometer/submicrometer spatial resolution. When the monochromatic beam is used, the resulting diffraction patterns recorded in 2D detector are Debye-Schereer ring patterns, resulting from the scattering of thousands of grains. Because the presence of residual stress in the film will result in the deformation of Debye rings, the strain/stress can be evaluated through the Debye ring analysis [13]. To obtain the stress/strain information, Debye ring is taken and analyzed at each point of map, in which each part of Debye ring has to be assigned to another orientation of the diffraction vector with respect to the sample reference system. In the research given by Gelfi et al. [14,15], X-ray diffraction Debye ring analysis for stress measurement (DRAST) based on XRD2 diffractometer was demonstrated, by combining a collimator with a diameter of 300 m with a cylindrical image plate(IP) detector, and the residual stresses in TiN and LaCoO3 films were well determined. In this article, an alternative micro-area residual stress measurement method is described based on the XRD2 diffractometer, equipped with a planar 2D detector instead of the cylindrical 2D detector mentioned in Ref. [14]. By using this method, the residual stress in PZT film prepared by the solgel route is explored, and the influence of top electrode on the micro-area residual stress is discussed as well. 2. Experimental procedure The Pb(Zr,Ti)O3 thin film of nominal morphotropic phase boundary (MPB) composition was prepared on Pt/Ti/SiO2/Si substrate by a modified solgel route, in which Zr/Ti ratio of 50/ 50 was verified by EDS analysis. The as-derived film with the

thickness of about 200 nm was crystallized at 650 C under ambient atmosphere. The elaborate procedure of fabricating PZT film has been previously published [16]. The Ag top electrode was deposited by DC sputtering on the condition of the sputtering pressure of 0.5 Pa and the sputtering current of 0.1 A, where the base pressure was 1.0 10E 3 Pa. The thickness of Ag electrode is 200 nm, with diameter of 0.3 mm. The XRD2 experiments with a fixed incidence angle of 18 and exposure time of 60 s were performed in a Bruker AXS D8 Diffractometer, operated at 40 kV and 35 mA using CuK radiation. The microbeam with illuminated spot size of 100 m was carried out through a long collimator, and meanwhile diffraction rings were collected as XRD2 images by a rectangular planar detector. For comparison, four micro-areas of PZT film were analyzed (see Fig. 1), hereafter denoted as A1, A2, A3 and A4, of which A1 and A2 referred to the illuminated areas with Ag electrode, while A3 and A4 represented the areas without Ag electrode. The Debye rings of the 111-diffraction in PZT film were taken into account in the residual stress measurement based on XRD2 images. 3. Results and discussion 3.1. XRD2 geometry definitions To describe the relationship between residual stress and XRD2 measurement, it is necessary to build two coordinate systems (O-XYZ and O-XYZ), the configuration is shown in Fig. 2. In the scattering geometry of XRD2 measurement (Fig. 2b), the point O represents the X-ray illuminated zone, O is the center of Debye rings. For convenience, O-XYZ coordinate is fixed on the sample, O -XYZ coordinate is fixed Y on the Debye ring. The direction of vector OO 0 is that of the Y incidence beam, with OZ axis direction is film normal diY Y Y Y rection, OY , OZ and OO 0 are in the same plane. O 0 Y 0 axis is Y0 Y0 Y Y0 OO , and O 0 X axis is parallel to OX axis. O 0 Z axis lays in Y Y the plane that is determined by OO 0 and OY axis. The vector Y Y O 0 P is parallel to ON which defines the normal direction of the Y Y diffraction plane. The angle between the vector ON and OZ is Y Y0 angle. The angle between the vector OY and OO is incidence Y Y angle (), and that between the vector OP and OO 0 is diffraction angle (2)(in O-XYZ coordinate), describing the Y rotation of O 0 P on the diffraction ring. The point P is the

Fig. 1. Top view of PZT sample, white dots show the areas illuminated by X-ray microbeam with diameter of 100 m, while black dots are Ag top electrode.

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3.2. Residual stress measured by micro-area XRD2 method Firstly, the relationship between residual stress and XRD2 measurement parameters is provided as follows. If the in-plane stress possessed a symmetry so that 11 = 22 = ; assuming the presence of a biaxial stress state in PZT film, and the normal direction (33) as well as the shear stresses (ij) (for i or j = 1, 2, 3 where i j) are zero, we have e11 e33 r11 m 1 m r; r22 r33 E E E m 2m r11 r22 r; E E 5

where, ii and ii are the principal components of stress and strain, v and E are the Poisson's ratio and Young's modulus of the film. Thus, the lattice strain in direction ( ) can be written as ew e33 cos2 w e11 sin 2 w r 1 m cos 2 w 1 m E 6

Using differentiation of Bragg's equation, the following equation can be obtained for the strain in the direction of :
Fig. 2. Schematic diagram of XRD2 apparatus (a) panorama view; (b) scattering geometry.

1 ew cot h0 2h 2h0 ; 2

projection of P on the planar detector, in this case, the position P can be determined by the two parameters, and 2. The diffraction vector q is defined with respect to the O-XY Z system by 2 and angle. It is figured out from Fig. 2b that the principal cosines of q vector in this reference system are: cos v 0 sin v 1

where, 0 is the Bragg angle of (hkl) plane in stress-free sample. Subsequently, combining Eq. (6) with (7), the general equation for the residual stress calculation can be given as 2h 2 tan h0 r 1 m cos 2 w 1 m 2h0 E r r 1 m cos 2 x sin 2 v 2 tan h0 1 m 2h0 E E 8

2 tan h0

To determine the residual stresses, nevertheless, it is necessary to explore the deformation of interplanar spacing with respect to the OXYZ coordinate system (sample reference system). Based on the above coordinate system configuration, the coordinate Y change can be implemented by a clockwise rotation around O0 X 0 axis, in which the rotation angle equals to incidence angle . Then the resulting rotational matrix is 0 1 1 0 0 @0 cos x sin x A: 2 0 sin x cos x The principal cosines of diffraction vector q with respect to the O-XYZ coordinate system (sample reference system) can thereof be derived as cos v sin x sin v cos x sin v: 3

For brevity, the above equation can be rewritten as 2h m sin2 v D here, m 2 tan h0 r 1 v cos2 x E r 1 m 2h0 E 10 9

D 2 tan h0

11

2 versus sin2plot will be linear according to Eq. (8). The residual stress can be obtained by determining the slope of the linear fits between the fractional change in diffraction angle and the term sin2. 3.3. Micro-area residual stress in PZT film Fig. 3 displays a typical XRD2 image of the PZT film, and meanwhile the XRD pattern of film by integrating all Debye

Hereby, the inclination angle between the diffraction vector and the surface normal, angle can be given by the following equation: w arccos cos x sin v: 4

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Fig. 3. Typical XRD2 image of solgel-derived PZT film, the arrows represent the increasing direction of the angle and diffraction angle, meanwhile the XRD pattern of PZT film by integrating all Debye rings in XRD2 image is shown as well.

rings in XRD2 image is shown as well. Among the (100), (110) and (111) diffractions, the intensity of (111) diffraction is highest, thus the fact indicates that there would be moderate (111) preferred orientation in PZT film. Here, {111} diffraction ring of PZT film is adopted for the stress measurements according to the consideration in three perspectives. First, intensity of 111-diffraction is comparatively high to assure the precision. Second, the 111-diffraction is single peak without splitting effect when PZT film is in ferroelectric state. At last, the use of the (hhh) diffraction will be helpful to minimize the crystallographic texture effect on the linearity of 2sin2 curves [17,18]. To determine the 2 value corresponding to a certain angle ( value is automatically provided during the integrate operation in XRD2 analysis software, GADDs), the integration within the range of two degree is performed on XRD2 image, and the middle value of is chosen as value for the following analysis. To derive 2 sin2 plot of {111} diffraction, interspacing of 5 is adopted on integrating the {111} Debye ring. The resulting diffraction patterns of {111} diffraction in every angle are corrected for Lorentzian Polarization Absorption effects and then the (111) peaks are fitted by PseudoVoigt function. Consequently the residual stress is calculated by fitting the 2 versus sin2 plots. Fig. 4a shows the linear fits of 2sin2 in PZT film with Ag electrode, while the linear fits of 2sin2 in PZT film without Ag electrode are depicted in Fig. 4b. It can be seen that satisfactory linear fits are achieved and the simulations give the fitting slope (m) values of about 0.013 and 0.025, for the areas with and without Ag top electrode, respectively. Moreover, the fitting slopes of 2sin2 plots are coincident within error in different areas with identical circumstance, e.g., A1 and A2 spots, experimentally exhibiting that residual stress measure-

Fig. 4. Linear fits of 2 sin2 in solgel-derived PZT film (a) with Ag electrode; (b) without Ag electrode.

ment with the alternative micro-area XRD2 method proposed above is reliable. According to Eq. (10), the residual stresses in micro-areas of PZT film were obtained and shown in Fig. 5, where the isotropic Young's modulus of EPZT = 75.5 GPa and Poisson's ratio v = 0.3 are used for PZT with a composition close to the morphotropic phase boundary [19]. It is clear from Fig. 5 that there is significant difference in the residual stress of PZT film with and without Ag electrode. The area without Ag electrode exhibits larger residual tensile stress (2.3 0.1 GPa), while for the area with Ag electrode, there is lower residual tensile stress (1.2

Fig. 5. Residual stresses of solgel-derived PZT film with and without Ag electrode.

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0.1 GPa). The calculated residual stress might be overestimated, but the variation trend of stress between the PZT film with and without Ag electrode should be credible, that is, a Ag-electroderelated stress relaxation effect exhibits in the film. It can be inferred from the value of residual stress that the top electrode is tensile, partially sharing the residual tensile stress in PZT film. 4. Discussion According to previous analysis, the linear fits of 2sin2 in PZT film, measured by the alternative micro-area residual stress measurement method, are considerably satisfactory. The stress measurement on the different zones with identical circumstance gives the consistent results within error; and the stress measurement errors are below 15%, both of which suggest that the proposed method is credible and valuable in the micro-area residual stress measurement. Furthermore, the method needs only one exposure and the analysis of single Debye ring in combination of the use of microbeam, which makes it beneficial to measure the residual stress on the surface with complex geometry. It is worthwhile noting that an obvious residual stress relaxation effect takes place in PZT film after Ag top electrode is deposited on the surface. The Ag top electrode is deposited at room temperature with a low pressure, so the microstructures of micro-areas of PZT film with and without Ag electrode should be identical, namely, the evolution of microstructure in PZT film should not be the key reason for stress relaxation. Two factors are assumed to explain the residual stress relaxation in PZT film with Ag top electrode. First, it is related to the stress evolution during the growth of Ag electrode. The growth stress in Ag electrode during sputtering would affect the underlying PZT layer due to constraint effect, which may reduce the residual stress in PZT film. Second, it is supposed that residual stress relaxation in PZT film could be ascribed to the effect of mechanical boundary condition [20]. Other than the free surface case in PZT film without Ag electrode, the deposition of Ag electrode accounts for the variation of mechanical boundary condition of PZT film and thereof results in the stress redistribution in the heterostructure, i.e., Ag/PZT/Pt. As a result, residual tensile stress in PZT film decreases by means of partial balance between electrode and film. It has to be figured that there is still blemish in the proposed micro-area residual stress measurement method, since some experimental data are a little away from the linear regression fits, and the sin2 ranging from 0.82 to 1 is not adequately broad compared with the traditional sin2 method. It should be whereas considered that the shortcoming results from the usage of the rectangular planar detector with limited size. Unlike the cylindrical 2D detector that is able to record the full Debye ring, planar 2D detector can only collect parts of the Debye ring in limited range, where 2 ranges from 18 to 50 and angle is restricted within 65 to 90. To obtain better precision of stress measurement, alternative ways could be considered. Debye ring in higher 2 would better be used in the analysis for better accuracy and wider range. In the case of (111) Debye ring, using radiation with longer

wavelength, for instance, FeK radiation, would shift the diffraction line to a higher angle. In addition, it is beneficial to reconfigure the set-up of 2D detector to obtain broader 2 and range. The above mentioned improving approaches are under investigation. In summary, the exploration of electrode effect is necessary for a better understanding on stress state of ferroelectric films. Additionally, it is of importance to take top electrode effect into consideration when discussing the residual stress of piezoelectric or ferroelectric film, as top electrode is almost always present in practical application of the film. 5. Conclusions Based on the XRD2 diffractometer, an alternative X-ray diffraction method is proposed and performed in the micro-area residual stress measurement of solgel-derived PZT film. The mentioned technique can implement the evaluation of the micro-area residual stresses within short time, as only one exposure and the analysis of single Debye ring are needed. The effect of Ag top electrode on the residual stress of PZT film is also investigated and the XRD2 results indicate that the residual tensile stress of 1.2 GPa in PZT film with Ag electrode is much lower than that of 2.3 GPa in the film without Ag electrode, which suggests that top electrode has effect on the relaxation of micro-area residual stress. References
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