J Mater Sci: Mater Electron (2006) 17: 483488 DOI 10.

1007/s10854-006-8222-4

Growth and morphology of c-axis oriented Nd1.85 Ce0.15 CuO4y thin lms prepared by pulsed laser deposition technique
B. Prijamboedi S. Kashiwaya

Received: 12 August 2005 / Accepted: 24 February 2006 C Springer Science + Business Media, LLC 2006

Abstract On the electron-doped superconductor of Nd2x Cex CuO4y (NCCO) thin lm, the presence of non-c-axis oriented grains, which are identied as (110) reection peak at 2 = 32.5 in the x-ray diffraction (XRD) spectrum is always observed. Meanwhile, high quality thin lms without having impurities are necessary for device applications. We study the growth of NCCO thin lm prepared by pulsed laser deposition technique and found that the volume fraction of (110) oriented grains depends on the laser uence. With the laser uence of around 2.2 J/cm2 , NCCO thin lm, which is free from the presence of non-c-axis oriented grains, could be obtained. The atomic force microscope images show that with the absence of (110) oriented grain the c-axis oriented grains grow into rectangular shape with a spiral growth mode. The rocking curve measurement for (004) peak give a full width at half maximum value of 0.12 , which conrms the superior quality of the lm and this lm has superconducting critical temperature (Tc ) at 21 K with a transition width ( Tc ) of 1 K.

1. Introduction The discovery of superconductivity in Nd2x Cex CuO4y (NCCO) has received much attention since this material has unique properties compared with the hole-doped cuprates superconductor [1]. The charge carrier type in this system as a

B. Prijamboedi ( ) S. Kashiwaya Nanoelectronics Research Institute of AIST Tsukuba Central 2, Umezono 1-1-1, Tsukuba, Ibaraki 305-8568, JAPAN e-mail: bambang-p@aist.go.jp

result of Ce4+ substitution is electron, which is conrmed by Hall measurement [2]. The other unique properties are the absent of apical oxygen atoms outside the CuO2 layer and T2 -like temperature dependence of resistivity in the normal state. It is believed that this material could provide useful information to elucidate the mechanism of superconductivity in the cuprates. Meanwhile, the NCCO has number of difculties and disadvantages for application such as a relatively low superconducting critical temperature (Tc = 23 K with x = 0.15), the presence of superconductivity within a narrow Ce concentration range [1] and the necessity to remove oxygen atom in order to obtain high Tc value. Despite these problems, NCCO has some advantages such as better surface stability compared to YBa2 Cu3 O7y (YBCO) mate [4], rial [3] and longer in-plane coherence length of 7080 A which make this material a potential candidate to be used as device. The superconductor material could open new possibility in the development of new electronic devices such as superconductor-semiconductor hybrid junction [5, 6], hybrid Josepshon eld effect transistor [7] and for NCCO; it is a potential candidate for the fabrication of p-n junction device from the hole- and electron-doped superconductors [8]. Thin lm is the most suitable form for device application. The common method to fabricate NCCO thin lms is by pulsed laser deposition (PLD) technique. This technique is simple, versatile and can reproduce the stoichiometric composition of deposited thin lm from the target material [9]. Meanwhile, the PLD technique also has some disadvantages, such as medium quality of the thin lm surface and many interdependent deposition parameters. Some NCCO thin lms with high critical superconducting transition temperature have been successfully fabricated by PLD methods [1012]. However, the presence of peaks at 2 = 32.5 and

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68 in the X-ray diffraction (XRD) spectra are always reported even in the sample prepared by RF-sputtering method [13]. Those peaks indicate the presence of non-c-axis oriented grains and it could induce defects on the lm. There were reports that discussed the origin of these peaks. Some reported that these peaks come from the reection of (110) and (220) planes of NCCO crystal [14] and the other suggested that it comes from the reection of (400) and (800) plane of NdCeO3.5 (NCO) compound [15]. The same peaks were also observed in the Ce-free Pr2 CuO4y thin lms [16] and it raised a doubt that NCO compound is responsible for the origin of those peaks. We studied the growth of high quality c-axis oriented NCCO thin lms prepared by pulsed laser deposition technique, which do not show foreign peaks at 2 = 34.5 and 68 in the XRD spectrum. High quality NCCO thin lm with less defect and impurity is necessary for the device application since the cuprate based superconductor device is very sensitive to the disorder [17]. We focused the study on the effect of laser uence on the target surface to the growth and morphology of the NCCO thin lm. We used a method that has been reported before that the laser uence could be simply adjusted by shifting the distance between the waist of the focusing laser lens and the target surface, dwt [18]. We found that the intensity of the foreign peaks decreases with the decreasing of the laser uence. We could prepare high quality NCCO lm without the presence of (110) oriented grains as it was conrmed by XRD and atomic force measurement (AFM) and found different morphology of the NCCO thin lm affected by the presence of (110) oriented grains.

at 10 rpm so that the laser beam does not impinge on the same spot. The target-substrate distance was set at 32 mm. After deposition, the NCCO thin lm sample was subsequently annealed at 700 C in vacuum of 1.33 103 Pa for about 15 minutes. To study the effect of the laser uence on the growth of NCCO thin lms, some samples were prepared in different distance between the waist of the lens and the target surface, dwt ; sample A: 50 cm, sample B: 51.5 cm and sample C: 53 cm. The laser uence was estimated by measuring the size of the laser spot on the target for each different dwt value. With constant deposition time (45 minutes), the thickness of for sample A, 2200 A for sample B and the lms are 3300 A 1600 A for sample C. Thin lms sample then were characterized by an atomic force microscope (AFM) to analyze its surface morphology and it was performed in the air at room temperature. The x-ray spectrometer was used to study the NCCO thin lm crystal structure and resistivity and superconducting critical temperature were measured by a standard four-probe technique in the temperature range between 2 K and 300 K.

3. Results and discussions Figure 1 shows the x-ray diffraction spectra of NCCO thin lm sample prepared with different waist of the lens to target surface distance, dwt . The spectra show that it mainly consists of the peaks from c-axis oriented grains of (001) reection planes and SrTiO3 substrate. In sample A and B, peaks at 2 = 32.5 and 68 are clearly observed, indicating the presence of non-c-axis oriented grains. The same peaks are not observed in sample C. The ratio between the intensity of peak at 2 = 32.5 (I110 ) and the intensity of peak from the (002) reection (I002 ) is shown in Table 1 as well as the deposition rate and the laser uence on the target. It shows that by increasing the waist of lens to the target surface distance or decreasing the laser uence, the deposition rate decreases and it will reduce the volume fraction of non-c-axis oriented grain on the NCCO lm. The rocking curve measurement ( scan) was carried out for the (004) reection plane of the NCCO thin lms. In Figure 2, the results of the rocking curve scan for (004) peak from all samples are shown. The rocking curve measurement gives full width at half maximum (FWHM) values of 0.9 for sample A, 0.6 for sample B and 0.12 for sample C. The small FWHM value obtained for sample C indicates a highly oriented epitaxial growth of NCCO thin lms characterized by a narrow mosaic spread distribution. In Figure 3(a) and 3(b), AFM images from sample A, scanned from a 5 5 m2 and 0.5 0.5 m2 areas are shown. On this lm, we can clearly observed two different types of grain. We notice some large and at grains with size

2. Experimental Polished single crystal SrTiO3 (001) with thickness of 0.5 mm was used as substrate and it was glued on a stainless steel block heater with silver paste. The deposition chamber then was evacuated into a typical pressure of 1.33 104 Pa and the heater temperature was raised to 820 C. The temperature was measured by a sheathed thermocouple inserted into the block heater. During deposition, oxygen pressure was maintained at 93.3 Pa by ooding the oxygen gas with ow rate of 17.5 sccm into the chamber. An ArF excimer laser (Compex 205 from LambdaPhysik, = 193 nm) with a repetition rate of 2 Hz was used as excitation source. A mask with an opening with size of 2 1 cm2 was put on the laser beam output window. The laser energy measured after it passed the mask is about 100 mJ. The laser beam is focused by a lens with focal length of 50 cm onto the surface of NCCO ceramic target prepared by a conventional solid-state reaction method. The purity of the NCCO target (Dowa Co. Ltd.) is 99.9% (3N) and with density of 90%. During deposition, target is rotated
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Fig. 2 Graph of rocking curve measurement result for the (004) reection peak for Nd1.85 Ce0.15 CuO4y thin lms prepared with different waist lens to target surface distance

Fig. 1 Plots of intensity vs. 2 of x-ray diffraction spectra for Nd1.85 Ce0.15 CuO4y thin lm grown on SrTiO3 with different distance between the waist of lens and target surface (dwt ): a). Sample A; dwt = 50 cm. b). Sample B; dwt = 51.5 cm. c). Sample C; dwt = 53 cm

around 80 200 nm2 . The other grains have smaller size and round shape with diameter around 60 nm2 and these grains are higher than the previous mentioned one. The size of the small grains is very homogenous and well distributed on the thin lm surface. The small grains observed on sample A seem to be different with those of the spherical particulate or droplet, which are commonly observed on the lm prepared by laser deposition technique since the particulates has inhomogenous size. In sample B (Figure 3(c)), larger grains or islands were observed compared to the previous lm. These

grains are not regularly shaped. Detail scan on sample B (Figure 3(d)) reveals the presence of nano-sized grains grow between the large grains as well as on the top ones. The AFM micrographs of sample C are shown in Figure 3(e) and 3(f). On the sample C, we can clearly see grains grow with rectangular shape. The grain is characterized by hillock growth with a clearly seen terracing structure. Some screw dislocations can be observed and it indicates the spiral growth mode of the NCCO grains. The step height of the terrace is around which was determined from a cross section analysis 10 A, and it is close to one unit cell c-axis length of NCCO of 12 A. We can mention here that few nano-sized grains or particles can still be observed on some of NCCO grains. By comparing the AFM micrographs from these samples, we realize that the population and size of small and spherical grains decreases as the intensity of (110) peak in the XRD spectra decreases. It would indicate that these grains are responsible for the (110) and (220) peaks observed in the XRD spectra. In sample A, the (110) oriented grains are dominant compared with the c-axis oriented ones, where the c-axis oriented grains are seen as at grains and it is conrm with the high value of I(110) /I(002) . Meanwhile, in the sample B, we should expect that the volume fraction of c-axis oriented grains increases and it grows as large irregular shape islands. As we saw on the AFM micrograph of sample A and B, the non-c-axis grains hinder the growth of the large at c-axis

Table 1 Values of some deposition parameters (waist of lens to target distance and laser uence), NCCO growth rate and ratio between the intensity of (110) and (002) reection peaks of NCCO. The waist of lens to target distance, dwt (cm) 50 51.5 53 Laser uence (J/cm2 ) 4.2 2.8 2.2 NCCO growth rate (A/pulse) 0.6 0.4 0.3

Sample Name A B C

I110 /I002 4.75 1 0

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(a)

(b)

(c)

(d)

(e)

(f)

Fig. 3 AFM images of Nd1.85 Ce0.15 CuO4y thin lm grown on SrTiO3 . a). Sample A, scanned on 5 5 m2 surface area. b). Sample A, scanned on 0.5 0.5 m2 surface area. c). Sample B, scanned on

5 5 m2 surface area. d). Sample B, scanned on 1 1 m2 surface area. d). Sample C, scanned on 5 5 m2 surface area. e). Sample C, scanned on 1 1 m2 surface area

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oriented grains and as the result, we have very small c-axis oriented grains in sample A and irregular shape of c-axis oriented grains in sample B. The AFM image of sample C give a detail image of defects caused by the small (110) oriented grains on the c-axis oriented ones (Figure 3(f )) but since the number of (110) oriented grains is so small, we could not see the peaks at the XRD spectrum. The AFM analysis shows that by reducing the laser uence on the target surface would give a favorable condition for c-axis oriented grains to grow as large rectangular grains. A slow growth rate as the result of low laser uence on target surface could be the factor for growing high quality c-axis oriented NCCO thin lm. In the case of YBCO thin lm prepared by PLD method, the a-axis and c-axis oriented grains both can grow on the lms at a certain condition [19]. According to the adatom migration model, the adatom of each element would migrate in a relatively long distance and climb steps before residing at the stable site if they are forming c-axis oriented grains. Meanwhile, short distance movement would be needed for a-axis oriented growth [20]. The same mechanism could be considered for the growth of NCCO thin lm and in this case, the growth of (110) oriented grains seems to be similar with the growth of a-axis oriented grain in YBCO. Since all three NCCO samples were prepared only with different laser uence on the target surface, it could be assumed that the most relevant factor to be considered in the NCCO case is the density of evaporated atoms that impinge the substrate surface. In the condition of low evaporated atoms density, we could expect a lower probability of inter collision and early reaction between atoms and therefore, the mobility of the adatoms on the surface would increase and it would give more opportunity for the adatoms to nd a stable position and to form c-axis oriented grains. The kinetic model might explain that the observed (110) oriented grains are smaller and higher than for c-axis oriented ones since for this growth, the adatoms only need to move in very short distance. The result from resistivity measurement is shown in Figure 4. Sample A shows the highest resistivity compared with other samples and has a minimum at temperature around 75 K. The onset of superconducting critical temperature (Tc, onset ) is at T = 18 K but the zero resistivity (Tc0 ) was observed below 11 K. The resistivity was found to be lower for sample B than for sample A with a minimum at temperature around 50 K. Tc0 for sample B is at 15 K. The resistivity data of the two samples (A and B) show a characteristic of the underdoped NCCO, which has a resistivity minimum above Tc . However, as we have seen on the AFM micrographs, both samples have poor inter-grain connection and dislocation defect due to the presence of (110) oriented grains and it would give high electrical resistance value. For sample C, Tc,onset was observed at around 22 K with Tc0 at 21 K as it is shown in the insert of Figure 4. The resistivity results again conrm the

Fig. 4 Graph of electrical resistivity vs. temperature of Nd1.85 Ce0.15 CuO4y thin lm grown on SrTiO3 . The insert graph shows the resistivity of sample C around its superconducting critical temperature

quality of the NCCO thin lm grown with low laser uence on the target surface. 4. Summary High quality NCCO thin lm has been fabricated by pulsed laser deposition technique. The sample that did not show (110) reection peak in the XRD spectrum was fabricated with low laser uence on the target surface of 2.2 J/cm2 and the fraction of the non-c-axis oriented grains on the NCCO lm can be controlled by changing the laser uence on the target surface. The rocking curve measurement of this NCCO thin lm gave a FHMW value of 0.12 and resistivity measurement showed a Tc0 value of 21 K with Tc = 1 K, which conrm the high quality of the sample. The non-c-axis oriented grains would induce some defects and change the morphology on the c-axis oriented ones and the c-axis oriented grains grew into rectangular shaped grains with a clear view of the terracing structure.
Acknowledgements We would like to thank H. Yamasaki, Y. Nakagawa, and J. C. Nie for allowing us using some equipments and help during measurement and deposition. B. P would thank M. Murugesan for suggestion and discussion. This work was supported by the Japan Society for the Promotion of Science (JSPS).

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