J Mater Sci: Mater Electron (2007) 18:535539 DOI 10.

1007/s10854-006-9053-z

Wet etching of sputtered tantalum thin lms in NaOH and KOH based solutions
S. Sood R. Peelamedu K. B. Sundaram E. Dein R. M. Todi

Received: 25 May 2006 / Accepted: 2 October 2006 / Published online: 18 November 2006 Springer Science+Business Media, LLC 2006

Abstract In this paper, a wet chemical etching technique to selectively etch tantalum thin lm in sodium hydroxide and potassium hydroxide based solutions was developed. Tantalum thin lms were deposited by a DC-magnetron sputtering technique on silica and yttria-stabilized zirconia (YSZ) substrates. After deposition, the lms were etched in hot NaOH/ H2O2 and KOH/H2O2 based solutions with Au/Cr lm as a hard mask. The etch rate was studied as a function of temperature and concentration of the etchants.

1 Introduction As a highly stable refractory metal, Ta is chosen as a thin lm coating material in a variety of applications. It also has high melting point, low toxicity, and excellent chemical resistance to most chemicals [1, 2]. Tantalum is an excellent electrode material for thin lm capacitors and is one of the most promising barriers to prevent highly diffusing copper from reacting with underlying silicon [3, 4]. Tantalum-based capacitors

S. Sood R. Peelamedu K. B. Sundaram R. M. Todi (&) School of Electrical Engineering and Computer Science, University of Centeral Florida, 4000 Centeral Florida, Orlando, FL 32828, USA e-mail: rtodi@mail.ucf.edu S. Sood R. Peelamedu K. B. Sundaram E. Dein R. M. Todi Advanced Materials Processing and Analysis Center, University of Central Florida, Orlando, FL 32816, USA

provide higher volumetric capacitance with high-reliability characteristics over a wide range of temperatures from 55C to 125C.[1] Recently there has been much interest in the fabrication of MEMS devices where Ta lms exhibit superior properties over other metals. As such, selective etching of Ta lms is a technological issue in many applications. The most common technique used for etching Ta lms is dry etching in low pressure plasma reactors using a CF4/O2 mixture [5]. Etch rates of up to 6.0 lm/min have been achieved using this technique. However, the difculties with dry etching techniques are that specialized equipment is needed and some gases used in the process are very toxic and corrosive. In the past, HF and HNO3 based chemistries have been used to wet-etch Ta lms [6, 7]. However, a HNO3HF mixture cannot be used for silicon and ceramic substrates because it can result in damage to the unprotected surface of the substrate due to the presence of a relatively high amount of concentrated hydrouoric acid. Here for the rst time, we report on the wet etching studies of Ta thin lms using hot NaOH and KOH based solutions. This technique provides the desired etching selectivity between the Ta lm and the ceramic substrate to pattern Ta thin lms into useful electrode structures. The etching process was studied with different temperatures and etchant concentrations for both NaOHH2O2 and KOHH2O2 based solutions.

2 Tantalum lm deposition and etching studies For the etching studies, silicon and yttrium-stabilized zirconia (YSZ) substrates were used. Prior to

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deposition, the substrates were thoroughly cleaned to remove organic contaminants using the standard SC1 cleaning technique. The SC1 solution was prepared by heating the solution of NH4OH and H2O in 5:1 ratio to 80C. One part of H2O2 was then added to the solution just prior to immersing the substrates. The substrates were immersed in the solution and cleaned for 15 min. This was followed by a DI water rinse for 5 min. Tantalum thin lms were DC sputtered using a magnetron sputtering system at a xed power of 200 W, constant pressure of 5 mTorr at 20 sccm of Ar ow. The substrate temperature was maintained at 300C during deposition. The sputtering chamber was evacuated to a base pressure of 5 108 torr and backlled with Argon. Before the actual deposition, pre-sputtering was done for 10 min to equilibrate the target surface and remove any oxide and other potential contaminants present. Films having a thickness ranging from 150 nm to 5000 nm were successfully deposited. The deposited lms were then annealed in-situ using the substrate heater set at 500C to remove any stresses induced in the Ta lm during the

deposition. It was found that unannealed Ta lms tended to peel off the ceramic substrates due to residual stress in the lms. Before etching, the lms were patterned using a photolithographic procedure as shown in the process ow diagram (Fig. 1). Since both NaOH and KOH are highly reactive etchants; we used a Au layer (~50 nm) with an underlying seed layer of Cr (~30 nm) as a hard mask. The Cr layer was used to improve the adhesion of Au to the Ta lm. Both Cr and Au lms were evaporated on Ta using a conventional lament evaporation system. The lms were then patterned using Shipley 1813 positive photo resist to open up the windows for Ta etching. After etching, the Au was removed using potassium iodide and iodine solution while chrome was removed using a commercial chrome etchant (CR-7). No under-cutting of the Cr/Au mask layer was observed during etching. This is evident from the vertical prole of the etched pattern shown in Fig. 2 using a Veeco optical prolometer. The patterned Ta samples were etched using both NaOH and KOH based solutions with H2O2. Different

Fig. 1 Photolithography process ow for fabricating a Ta electrode pattern using KOH/NaOH based solutions

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J Mater Sci: Mater Electron (2007) 18:535539 Fig. 2 Optical prolometer measurements for a 200 lm diameter Ta dot using Au/Cr mask gave less than 1% overall undercut

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weight percent solutions of NaOH and KOH were prepared by mixing NaOH and KOH pellets in H2O. The weight percent of a solution is calculated using the following formula: w/v% = mass of solute (g) 100% volume of solution (ml) 1

For each run, the prepared solution was carefully pipetted into a Pyrex beaker and heated to the desired

etching temperature. H2O2 was then added to the solution just before immersing the sample. Etching studies were performed by changing temperature, percentage of H2O2 in solution, and the mass percent of NaOH/KOH in water. The solution temperature was varied from 65C to 105C for both NaOH and KOH etchants. In each case, the temperature was kept constant within 2C. The etch rates were measured using stylus prolometer (Alpha Step). The etched lms were further

Fig. 3 Average surface roughness (Ra) of the deposited Ta lm was 0.76 nm and peak-to-peak roughness (Rt) was 9.28 nm

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characterized using a Veeco Wyko NT3300 optical prolometer.

3 Results and discussion The average surface roughness (Ra) measurements of the deposited Ta lms were of the order of 0.76 nm, while the peak-to-peak roughness (Rt) measurements were less than 9.28 nm as shown in Fig. 3 using the optical prolometer. Figure 4 shows the etch rate of Ta as a function of temperature using a 30% NaOH and KOH with 10% H2O2 solution. Tantalum is etched by the peroxide to form its mineral acid, in this case tantalic acid (H2Ta2O6). This process is accelerated at higher pH and elevated temperatures. A strong base like KOH or NaOH speeds up the dissolution. The NaOH based solutions had a higher

etch rate than KOH based solutions for same percentage of H2O2 and at same temperature. The etch rate exhibits an exponential increase with temperature for NaOH and KOH based solutions as shown in Fig. 4. The Ta etch rate as a function of volume percentage of H2O2 in 30% NaOH and KOH solution at 80C is shown in Fig. 5. The etch rate has a linear relation with H2O2 concentration in both NaOH and KOH based solutions, with NaOH based solutions showing higher etching rates. Figure 6 shows the etch rate as a function of weight percentage of NaOH or KOH in water at 85C with 10% H2O2. Figure 7 is a 3-D image of 50 lm wide Ta electrode structures etched using NaOH and H2O2 that conrms negligible undercutting using this technique. The vertical walls of the etched Ta lm in this example exhibit the desirable smooth and straight etch characteristics.

Etch Rate using NaOH (A/sec)

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Fig. 5 Ta etch rate as a function of volume percentage of H2O2 in 30% NaOH and KOH solutions at 80C

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Fig. 4 Ta etch rate as a function of temperature (using 30% NaOH and KOH with 10% H2O2 in solution)

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J Mater Sci: Mater Electron (2007) 18:535539 Fig. 6 Ta etch rate as a function of change in weight percentage of NaOH and KOH in water (at 85 C with 10% H2O2)
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Fig. 7 Optical prolometer 3-D image of 50 lm wide Ta electrodes patterned using NaOH and H2O2 solution

4 Conclusion Wet etching studies of Ta lms on ceramic and silica substrates have been performed with less than 2% overall undercut having been achieved. The NaOHbased solutions showed higher etch rates than KOH based solutions with H2O2 as the reactive reagent. Deep Ta lm trenches with widths ranging from 10 lm to 200 lm for use in MEMS components were successfully fabricated using this technique.

References
1. W.D. Westwood, et al., Tantalum Thin Films (Academic Press, London, 1975). 2. P. N. Baker, Invited Review. Thin Solid Films 14, 325 (1972) 3. D. Ernur, et al., Microelectron. Eng. 64, 117124 (2002). 4. S. Kondo, et al., Jpn. J. Appl. Phys. 39 (Pt 1, No.11), 6216 (2000). 5. R. Hsiao, et al., Thin Solid Films 304(12), 381 (1997). 6. B. Wu, et al., United States Patent 6,329,299 (2001). 7. H. Endo, et al., United States Patent. 4,446,115 (1984).

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