Journal of the Korean Physical Society, Vol. 55, No. 2, August 2009, pp.

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Electric Properties of PVDF-TrFE (75/25) Thin Films with a Lanthanum Zirconium Oxide Buer Layer for FeRAM
Hui-Seong Han, Ho-Seung Jeon, Gwang-Geun Lee, Kwi-Jung Kim and Byung-Eun Park
School of Electrical and Computer Engineering, University of Seoul, Seoul 130-743 (Received 26 August 2008) Metal-ferroelectric-insulator-semiconductor capacitors, using polyvinylidene uoride triuoroethylene (P(VDF-TrFE)) as a ferroelectric layer and lanthanum zirconium oxide (LaZrOx ) as an insulator layer, were fabricated on a p-type Si (100) substrate. We prepared the lms by using a spin-coating method. From the C-V characteristics of the LaZrOx /Si structure, we observed negligible hysteresis. The equivalent oxide thickness (EOT) was about 7.9 nm. We, then, spin-coated the P(VDF-TrFE) lms on the LaZrOx /Si structure by using various solutions with dierent concentrations (1, 3, and 5 wt%). The P(VDF-TrFE) was crystallized at 165 C for 30 minutes. The memory window width in the C-V (capacitance-voltage) curve of the Au/P(VDF-TrFE)/LaZrOx /Si structure was about 2 V for a voltage sweep of 5 V. The memory window width increased as the thickness of the P(VDF-TrFE) lm increased. The value of the leakage current density at 5 V was about 3.5 108 A/cm2 for the thick lm from the 5-wt% solution. From these results, we expect the combination of P(VDF-TrFE) and a LaZrOx thin lm to be both useful and promising for a ferroelectric random access memory operating at a low voltage.
PACS numbers: 77.84.Jd, 77.84.-s Keywords: MFIS, ferroelectric, PVDF-TrFE, LaZrOx , FeRAM

I. INTRODUCTION Researchers and developers have shown great interest in the development of nonvolatile memories based on ferroelectric materials. For nondestructive read-out ferroelectric random access memory a ferroelectric gate structure is required. However, it is still dicult to obtain a good quality ferroelectric thin lm on a Si surface. Thus, a buer layer with a high dielectric constant is often inserted between the ferroelectric lm and the Si substrate [1,2]. There has been much research on a buer insulator that has good electrical properties, such as low leakage current and high dielectric constant, for a metalferroelectric-insulator (MFIS) structure. Representative buer insulators include HfO2 , LaAlO3 , SrTa2 O6 , ZrO2 , and Dy2 O3 . They have high dielectric constants (10 50) with low leakage currents (below 106 A/cm2 ) and have good interface characteristics [37]. Good switching and memory characteristics have been obtained in MFIS structures by Kodama et al. [8]. The LaZrOx system is attractive as a buer insulating layer. Because of both the lanthanum and zirconium atoms, the constituents of the LaZrOx thin lm are considered to be thermally stable in contact with Si [9]. For this reason, we expected
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the LaZrOx thin lm to be the most advantageous buer insulator to investigate because a ferroelectric layer usually requires high-temperature annealing. The ferroelectric polymer polyvinylidene uoridetriuoroethylene (P(VDF-TrFE)) lm has an unique mechanism of ferroelectricity. There have been some eorts to apply a P(VDF-TrFE) thin lm to a ferroelectric random access memory (FeRAM) [10]. In particular, a P(VDF-TrFE) thin lm is a promising candidate for a FeRAM due to its low processing temperature. This temperature is much lower than that of inorganic ferroelectrics such as Pb(Zr,Ti)O3 (PZT), SrBi2 Ta2 O9 (SBT), and (Bi,La)4 Ti3 O12 (BLT) [11 16]. In this study, we fabricated a LaZrOx /Si metalinsulator-semiconductor (MIS) structure and a P(VDFTrFE)/LaZrOx /Si MFIS structure by combining an organic ferroelectric gate layer with an inorganic buer layer.

II. EXPERIMENTS To fabricate the MFIS structure, we prepared a LaZrOx thin lm and a P(VDF-TrFE) lm by using a sol-gel method. The LaZrOx thin lm was deposited on a Si substrate by using a spin-coating method at a rota-898-

pbe@uos.ac.kr; Fax: +82-2-2249-6802

Electric Properties of PVDF-TrFE (75/25) Thin Films Hui-Seong Han et al.

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Fig. 1. High-frequency C-V characteristic curve of the Au/LaZrOx /Si structure.

tion speed of 3000 rpm for 20 seconds. Then, the lm was thermally treated using a two-step heat treatment composed of baking at 400 C for 10 minutes and annealing at 750 C for 30 minutes in an oxygen atmosphere. The typical lm thickness was about 30 nm. We used a P(VDF-TrFE) polymer containing VDF (75%) and TrFE (25%) that was dissolved in a dimethylformamide (DMF) solvent. We prepared three types of P(VDFTrFE) solutions with dierent concentrations (1, 3, and 5 wt%), what were used to control the lm thickness. Each P(VDF-TrFE) solution was spin-coated on an annealed LaZrOx lm at 2500 rpm for 10 seconds. Then, to remove residual solvents on the P(VDF-TrFE) lm and improve the crystallinity, we annealed the P(VDF-TrFE) lm at 165 C for an hour. Finally, Au dot electrodes with a 100 m diameter were thermally evaporated onto the P(VDF-TrFE) lms surface. We investigated the capacitance-voltage (C-V) and current density-voltage (J-V) characteristics by using an HP4280A C-V meter and an HP4155C semiconductor parameter analyzer, respectively.

III. RESULTS AND DISCUSSION Figure 1 shows the high-frequency (1MHz) C-V characteristic curve of the Au/LaZrOx /Si structure for a bias sweeping range of 5 V. We observed negligible hysteresis, meaning that the structure had little chance to trap charge. Large capacitance or small equivalent oxide thickness (EOT) for a buer insulator is required to distribute enough bias voltage to the ferroelectric layer; also, that is why high-k materials are generally investigated as buer insulators. We found, as indicated in Fig. 1, that the accumulation capacitance value was about 440 nF/cm2 , identical with a 7.9 nm of EOT. The calculated dielectric constant was 14.8 for the structure. This constant is being expected might be attributed to the
Fig. 2. C-V curves of Au/P(VDF-TrFE)/LaZrOx /Si structures. P(VDF-TrFE) lms were deposited using various solutions with dierent concentration: (a) 1-, (b) 3-, and (c) 5-wt%.

formation of a low-k interface oxide layer during the annealing processing. Figure 2 illustrates the C-V characteristic curves of the Au/P(VDF-TrFE)/LaZrOx /Si MFIS structure formed using P(VDF-TrFE) solutions with dierent concentrations (1, 3, and 5 wt%). A thicker P(VDF-TrFE) lm

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Journal of the Korean Physical Society, Vol. 55, No. 2, August 2009

Fig. 3. Memory window widths for three P(VDF-TrFE) lm thicknesses as a function of the bias voltage. The lm thickness was controlled by using its sol-gel solution concentration.

Fig. 4. J-V characteristic curves of Au/P(VDF-TrFE)/Si and Au/P(VDF-TrFE)/LaZrOx /Si structures. The LaZrOx buer insulator dramatically improves the leakage property.

was formed from a solution with a higher concentration. Regardless of the weight fraction of the solution, all C-V curves showed hysteresis loops with a clockwise trace, as indicated by the arrows. The accumulation capacitance of the 1-wt% P(VDF-TrFE) lm on LaZrOx was 230 nF/cm2 for a bias voltage sweep of 5 V. As the concentration of the solution was increased, as can be seen from Fig. 2, the accumulation capacitance decreased to 90 and 42 nF/cm2 for the same bias voltage sweep. The memory window width of the Au/P(VDFTrFE)/LaZrOx /Si, measured for a voltage sweep of 5 V, was about 0.7, 2.2, and 3 V for 1-, 3-, and 5-wt% P(VDF-TrFE) lms on LaZrOx /Si structures, respectively. Contrary to the accumulation capacitance, the memory window width increased as the concentration of the solution increased, meaning that a large portion of the applied voltage could be distributed to the P(VDFTrFE) lm in the MFIS structure. This happened as the lm thickness increased, resulting in the decrease in a capacitance of the P(VDF-TrFE) thin lm. The large voltage distribution to the P(VDF-TrFE) lm leads to an increase of the remnant polarization in the lm. In a FeRAM, a reduction of the remnant polarization in the ferroelectric lm results in a reduction of the programmable memory window. Therefore, a larger memory window width is better than a small one for this memory device. We also demonstrated that the memory window width and the threshold voltage shift gradually increased with increasing voltage. Figure 3 illustrates the variations in the memory window width with the bias voltage. The lines for 3- and 5-wt% P(VDF-TrFE) lms in Fig. 3 show a rapid increase as compared with the one for 1 wt%-P(VDF-TrFE). From the above results, the P(VDF-TrFE) lms, except for the 1-wt% lm, are suitable to apply to a FeRAM from the point of view of the memory window width.

Fig. 5. AFM surface images for P(VDF-TrFE) lms from (a) 3 and (b) 5 wt%.

Figure 4 shows the J-V characteristics of the same samples as those used in Fig. 2. The current densities for the P(VDF-TrFE) lms obtained from the 1-, 3-, and 5-wt% solution, were lower than 106 , 107 , and 107 A/cm2 , respectively. With the MFIS structure, we also made a MFS structure capacitor. As the weight

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fraction of the P(VDF-TrFE) in the solution increased, the current density decreased. This observation might be related to the thickness. We observed the surface morphology of the P(VDF-TrFE) by using AFM. Figure 5 shows the surface AFM images of P(VDF-TrFE) lms. We were not able to nd the lamella structure at a 1-wt% solution, but we were able to nd it at the 3- and 5-wt% solutions. The ferroelectric polymer basically consists of two-phase structures, amorphous and crystalline lamella. Thus the ferroelectricity of P(VDFTrFE) originates from the lamella structure in the lm [17,18]. These AFM images agree with the C-V measurements. As mentioned above, the memory window width from the C-V curves for 3- and 5-wt% P(VDF-TrFE) is much larger than that of 1-wt% P(VDF-TrFE). We measured the root-mean-square roughnesses (Rrms) as 4.136 and 9.560 nm at 3- and 5-wt%, respectively. These values indicate that the P(VDF-TrFE) lm has a good surface morphology, especially at 3-wt%.

ACKNOWLEDGMENTS This work was supported by a Korea Science and Engineering Foundation (KOSEF) grant funded by the Korea government Ministry of Education, Science, and Technology (MEST), (No. R01-2007-000-11985-0).

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IV. CONCLUSION In this work, we applied a LaZrOx thin lm as a buer layer and a P(VDF-TrFE) lm as a ferroelectric-gate layer. The C-V characteristics of the Au/LaZrOx /Si MIS structure revealed that the LaZrOx thin lm had good electrical properties and was suitable for a buer layer in a MFIS structure. We estimated the EOT value of the LaZrOx lm as about 7.9 nm. For the Au/P(VDFTrFE)/LaZrOx /Si MFIS structures, the memory window width increased with increasing applied bias voltage and with increasing thickness of the P(VDF-TrFE) lm. The 3- and 5-wt% P(VDF-TrFE) lms, deposited on the LaZrOx /Si structure showed a memory window width of over 2 V at a bias sweep range of 5 V. The value of the leakage current density was about 3.5 108 A/cm2 for a 5-wt% thick lm. The good ferroelectricity of the 3- and 5-wt% P(VDF-TrFE) lms was caused by the lamellae structure shown in the AFM images. From these results, we expect a combination of P(VDF-TrFE) and LaZrOx thin lms to be useful and promising for a 1T-type FeRAM at a low voltage; however, more properties in term of parameters such as the retention time and the endurance should be veried.