- Nano Express
- Open Access
Nanocolumnar Preferentially Oriented PSZT Thin Films Deposited on Thermally Grown Silicon Dioxide
© to the authors 2008
- Received: 24 July 2008
- Accepted: 22 October 2008
- Published: 11 November 2008
We report the first instance of deposition of preferentially oriented, nanocrystalline, and nanocolumnar strontium-doped lead zirconate titanate (PSZT) ferroelectric thin films directly on thermal silicon dioxide. No intermediate seed or activation layers were used between PSZT and silicon dioxide. The deposited thin films have been characterised using a combination of diffraction and microscopy techniques.
- PSZT thin films
- Silicon dioxide
There is potential for harnessing the nonlinear properties of ferroelectric thin films for applications in photonics and integration with left-handed materials (metamaterials), as has been demonstrated for bulk ferroelectric crystals [1, 2]. These applications demand that ferroelectric thin films are deposited on dielectric and optically transparent material. One of the most suitable dielectric layers for the deposition of ferroelectrics is silicon dioxide (SiO2), considering its thermal stability and suitability for optical applications.
Lead zirconate titanate (PZT) is most commonly used ferroelectric material in commercial applications and results of characterisation of PZT thin films have been extensively reported (e.g. [3, 4]). While deposition of thin films on PZT on SiO2 has been investigated [5, 6], attaining perovskite structured c-axis (columnar) growth directly on SiO2 has proved to be a challenge. Excellent approaches using intermediate layers to seed or control the subsequent PZT deposition have been proposed [5, 6]. While these result in c-axis oriented PZT films, the use of seed layers demands additional deposition steps and access to materials. Most importantly, we have observed that an additional layer needs to be incorporated into models used to simulate nonlinear characteristics for thin films.
In this work, we demonstrate that we have overcome this need for intermediary seed layers, in the deposition of columnar PZT compounds on SiO2, using optimised deposition conditions. We report on the growth of perovskite structured nanocolumnar strontium-doped PZT (PSZT) thin films. We have used strontium-doped PZT, rather than undoped PZT, in order to capitalise on its enhanced ferroelectric and piezoelectric properties [7–9], which in turn will influence its electro-optic performance.
Deposition of PSZT Thin Films
PSZT thin film deposition conditions
Target to substrate distance
10% oxygen in argon
9.0 × 10−6 Torr
1.0 × 10−2 Torr
For obtaining films exhibiting suitable ferroelectric properties, thermal processing was carried out (either post-deposition or in situ). The aim of this processing was to enable crystal growth in the thin films and attainc-axis orientation.
PSZT thin films were deposited either at room temperature followed by an annealing process or at a substrate temperature of 700 °C. PSZT thin films deposited at room temperature were subject to post-deposition furnace annealing at 700 °C for 3 h in the presence of high purity argon. In the case of samples deposited at temperatures of 700 °C, the samples were heated to deposition substrate temperature at a ramp rate of 10 °C/min and cooled, subsequent to deposition, at 5 °C/min; previous work has shown that these conditions improve the degree of perovskite orientation in the thin films .
X-ray Diffraction Analysis
PSZT thin film samples were cleaned by rinsing in solvents (acetone and isopropyl alcohol) and deionised water. Glancing angle X-ray diffraction (XRD) analysis was carried out using a Scintag X-ray diffractometer with an X-ray incidence angle of 5°. The data presented correspond to radiation from copperK α wavelength.
Atomic Force Microscopy Analysis
The surface roughness and grain sizes of the PSZT thin films were studied using atomic force microscopy (AFM). AFM scans were carried out using a Digital Instruments Dimension 3100 scanning probe microscope with a Nanoscope IIIa controller. The scans were carried out in contact mode.
Electron Microscopy Analysis
Cross-section analysis of the thin films was carried out on a field emission gun scanning electron microscope (FEI Nova NanoSEM). Plan view specimens for transmission electron microscopy (TEM) analysis were prepared by mechanically grinding away the backing silicon from the film. The specimens were then ion milled to electron transparency at room temperature using 4 kV argon ions incident at 5°. The analysis was carried out at an accelerating voltage of 200 kV on a JEOL 2010F TEM with a Gatan Imaging Filter.
X-ray Diffraction Analysis
Figure 1b is representative of diffractograms obtained for PSZT thin films deposited at substrate temperature of 700 °C. Expected perovskite peaks at 2θ of 29.6° and 49.3°, for (104) and (108) orientations, for a rhombohedral PSZT unit cell  were observed. Smaller peaks obtained at 34.3° and 58.5° correspond to (006) and (300) orientations, respectively. The temperature at which these thin films were deposited was chosen to encourage thermally driven grain growth and the diffractogram (Fig. 1b) confirms that this resulted in uniform crystal growth, manifested as strong and sharp peaks in the diffractogram. These results, with strong c-axis preference, also promise strong columnar growth in the thin films (discussed in section “Electron Microscopy Analysis”).
These results indicate that though post-deposition annealing encouraged grain growth, only thin film deposition at high temperatures (in situ substrate heating) results in strong preferential orientation. The PSZT thin film samples deposited at 700 °C, with promising XRD results, were subject to further analyses.
Atomic Force Microscopy Analysis
Electron Microscopy Analysis
The thin region of the specimen gives us valuable information regarding the nanostructure of the thin films. Figure 4b shows that the grains vary in size from 80 to 100 nm, with well defined crystalline and polygonal structure. Strong Bragg diffraction from many grains in Fig. 4indicates that they share the same orientation. These nanocrystals extend all the way through the thickness of the specimen forming the columnar structure observed in the cross-sectional analysis. Selected area electron diffraction of the plan view specimen showed that the nanocrystals exhibited the expected perovskite structure, but were randomly distributed—there was no preferential orientation along the substrate surface (XRD indicated preferential orientation perpendicular to the substrate).
This article presents results from the first instance of deposition of preferentially oriented, nanocrystalline, and nanocolumnar PSZT thin films directly on thermal silicon dioxide. No intermediate seed or activation layers were used between PSZT and SiO2. A substrate temperature of 700 °C was found to be suitable for obtaining the desired perovskite structure, resulting in films which will exhibit ferroelectric properties suitable for investigation of nonlinear properties for photonics and integrated metamaterials applications.
This research was supported by the Australian Institute of Nuclear Science and Engineering and the CASS Foundation.
- Trull J, Cojocaru C, Fischer R, Saltiel SM, Staliunas K, Herrero R, Vilaseca R, Neshev DN, Krolikowski W, Kivshar YS: Opt. Express. 2007, 15: 15868. COI number [1:CAS:528:DC%2BD1cXitlemuw%3D%3D]; Bibcode number [2007OExpr..1515868T] COI number [1:CAS:528:DC%2BD1cXitlemuw%3D%3D]; Bibcode number [2007OExpr..1515868T] 10.1364/OE.15.015868View ArticleGoogle Scholar
- Fischer R, Saltiel SM, Neshev DN, Krolikowski W, Kivshar YS: Cent. Eur. J. Phys.. 2008, 6: 569. COI number [1:CAS:528:DC%2BD1cXhtVOrs7fE] COI number [1:CAS:528:DC%2BD1cXhtVOrs7fE] 10.2478/s11534-008-0073-6Google Scholar
- Muralt P, Kohli M, Maeder T, Kholkin A, Brooks K, Setter N, Luthier R: Sens. Actuators A. 1995, 48: 157. 10.1016/0924-4247(95)00994-9View ArticleGoogle Scholar
- Bi Z, Zhang Z, Fan P: J. Phys. Conf. Ser.. 2007, 61: 120. COI number [1:CAS:528:DC%2BD2sXot1amtbs%3D]; Bibcode number [2007JPhCS..61..120B] COI number [1:CAS:528:DC%2BD2sXot1amtbs%3D]; Bibcode number [2007JPhCS..61..120B] 10.1088/1742-6596/61/1/025View ArticleGoogle Scholar
- Zhao J, Lu L, Thompson CV, Lu Y, Song WD: Proc. SPIE. 2002, 4426: 221. COI number [1:CAS:528:DC%2BD38XivF2msL8%3D]; Bibcode number [2002SPIE.4426..221Z] COI number [1:CAS:528:DC%2BD38XivF2msL8%3D]; Bibcode number [2002SPIE.4426..221Z] 10.1117/12.456840View ArticleGoogle Scholar
- R. Ramesh, International Patent WO/1994/013471. Available online at http://www.wipo.int/pctdb/en/wo.jsp?IA=US1993010387
- Bedoya C, Muller C, Baudour J-L, Madigou V, Anne M, Roubin M: Mater. Sci. Eng. B. 2000, 75: 43. 10.1016/S0921-5107(00)00383-4View ArticleGoogle Scholar
- Zheng H, Reaney IM, Lee WE, Jones N, Thomas H: J. Am. Ceram. Soc.. 2002, 85: 207. COI number [1:CAS:528:DC%2BD38XmvVWqtg%3D%3D] COI number [1:CAS:528:DC%2BD38XmvVWqtg%3D%3D] 10.1111/j.1151-2916.2002.tb00457.xView ArticleGoogle Scholar
- Sriram S, Bhaskaran M, Holland AS, Short KT, Latella BA: J. Appl. Phys.. 2007, 101: 104910. Bibcode number [2007JAP...101j4910S] Bibcode number [2007JAP...101j4910S] 10.1063/1.2735407View ArticleGoogle Scholar
- S. Sriram, M. Bhaskaran, J. du Plessis, K.T. Short, V.P. Sivan, A.S. Holland, Micron 40, 104 (2009). doi:10.1016/j.micron.2007. 12.009Google Scholar
- Sriram S, Bhaskaran M, Holland AS: Semicond. Sci. Technol.. 2006, 21: 1236. COI number [1:CAS:528:DC%2BD28XhtFSisb7L]; Bibcode number [2006SeScT..21.1236S] COI number [1:CAS:528:DC%2BD28XhtFSisb7L]; Bibcode number [2006SeScT..21.1236S] 10.1088/0268-1242/21/9/005View ArticleGoogle Scholar
- Bhaskaran M, Sriram S, Mitchell DRG, Short KT, Holland AS: Thin Solid Films. 2008, 516: 8101. COI number [1:CAS:528:DC%2BD1cXhtVygtL7I] COI number [1:CAS:528:DC%2BD1cXhtVygtL7I] 10.1016/j.tsf.2008.04.041View ArticleGoogle Scholar