VIII Contrasting grain types in a ceramic thick film HKL Technology 2001

VIII

Contrasting grain types in a ceramic thick film

Q:

What are the growth mechanisms of different grain populations in a PZT ceramic thick film?

Background
In the electronics and optics industries there are widespread applications of materials that have piezoelectric and ferroelectric properties. Piezoelectric materials are crystalline materials, often ceramics, that develop an electrical charge when subjected to mechanical stresses; ferroelectric materials are a subgroup of these that demonstrate spontaneous electrical polarisation, the direction of which can be altered by an external electrical field. The value of ferroelectric ceramics is clearly illustrated by their use in the semiconductor industry. Semiconductor memories such as dynamic random access memories (DRAMs) and static random access memories (SRAMs) currently dominate the market. However, the main problem with these memories is that they are "volatile" - in other words if the power fails, the stored information is lost. Ferroelectric random access memories (FRAMs), on the other hand, are non-volatile and have the added benefits of greater radiation hardness and higher speed. FRAMs made from ferroelectric thin films store data by altering (with an external electrical field) the magnitude and direction of electrical polarization. Their non-volatility is because the polarization remains in the same state after the voltage is removed, and their radiation hardness allows devices containing these memories to be used in harsh environments, such as outer space. One of the problems with ferroelectric memories is their tendency to lose the ability to store data after a certain number of read/write cycles. This phenomenon is called fatigue. At the moment the fatigue resistance of FRAMs is not sufficient for them to replace completely semiconductor memories, but this can be improved with further optimisation of both composition and microstructure. Lead zirconate titanate (PZT) is a ceramic material that exhibits excellent ferroelectric properties. PZT thin films are commonly used to make FRAM devices and the prospects are very bright for such devices to replace semiconductor memories in the near future. This application note focuses on the microstructure of a commercial PZT thick film deposited on a single crystal silicon wafer. The sample has been extensively thermally cycled, and automated EBSD analyses are used to characterise the microstructural properties of two contrasting grain populations. The resulting data may have important implications for the application of this PZT in FRAM devices.

Analysis
Experimental Set-Up
Sample Preparation SEM type EBSD System Acc. V. Probe Current Raw materials with 200 carbon coating W- filament HKL CHANNEL 5 30 kV ~10 nA

EBSD Details
Total grid dimensions Grid spacing Number of points Scanning speed Noise filtering level Large grain mapping (typical) 200 x 100 3 m 20,000 9 patterns/second Low Matrix mapping (typical) 139 x 104 1 m 14,456 8 patterns/second Low

VIII Contrasting grain types in a ceramic thick film HKL Technology 2001

Results
Figure 1: Secondary electron image
This secondary electron micrograph shows the general microstructure of the PZT thin film. Large grains, often with regular forms (e.g. star shaped), are isolated in a matrix of much smaller grains. These shapes may be explained by interpenetrative twinning, resulting in regular twin domains.

Figure 2: EBSPs from within a single large grain

The CHANNEL 5 acquisition software, Flamenco, has been used to view diffraction patterns collected from the individual domains in one of the large star-shaped PZT grains in figure 1. It is clear that the EBSPs 1 and 3 are identical, as are the EBSPs 2 and 4. Indexing these EBSPs as tetragonal (pseudo-cubic) PZT confirms that the orientation pairs are twin related, with a 60 rotation about a <111> axis.

VIII Contrasting grain types in a ceramic thick film HKL Technology 2001

Figure 3: Orientation maps of large grains

Small orientation maps were collected of individual large grains or clusters of large grains. A number of these are shown in figure 3, along with the EBSP quality maps. In all images the grain boundaries (>10) are marked in black, with subgrains (2-10) in grey. Twin boundaries (60 about <111>) are marked in red. It is clear that all the large grains are twinned. The twinning characteristics vary from grain to grain, but typically they have 2-fold or 3-fold structures.

Figure 4: Fine-grained matrix characteristics

The microstructure of the matrix was characterised using automated EBSD mapping. These images show the results of a typical EBSD analysis.
a. b.

Figure 4 (a): EBSP quality map, with grain boundaries (>10) shown in black and twin boundaries in red. The scale bar = 50 m. Figure 4 (b): Orientation map of the same area, with colours corresponding to the Euler angles. The wide range of colours indicates that there is almost no texture in this sample. Once again, grain boundaries (black) and twin boundaries (red) are marked.

VIII Contrasting grain types in a ceramic thick film HKL Technology 2001

Figure 4 (c): Grain size histogram for the matrix area. The mean grain size is 7.5 m.

Conclusions
Several PZT thick film specimens have been studied using both manual and automated EBSD. Two contrasting grain types have been identified on the surface of the silicon single crystal wafer: A matrix population of small grains (mean < 8 m), with no texture and very few twin boundaries. Isolated large grains, typically 100-250 m diameter, all characterised by distinctive twinning. These twins typically form two-fold or three-fold domains. It is likely that some form of abnormal grain growth has occurred in order to produce these large twinned grains. The EBSD data show that they do not have any preferred orientation with respect to the thick film: it is therefore possible that such grains have grown at isolated nucleation sites, although further EBSD analyses are required to confirm this interpretation. In summary, EBSD analyses have identified contrasting microstructural characteristics of two grain populations in these samples: this could have a damaging effect on the electrical properties of the PZT film.
Acknowledgements The National Institute of Standards and Technology, USA, is thanked for providing the sample and for allowing presentation of these data.