Wet Etching of Bi2Te3 Thin Films Compatible with Microelectronic Fabrication Processes

T. Ngai and U. Ghoshal Nanocoolers, Inc., 5307 Industrial Oaks Blvd. Suite 100, Austin, Texas 78735, USA tngai@nanocoolers.com Abstract A major limitation in fabricating a monolithic Bi2Te3based thermoelectric thin film device is patterning poorly adhesive Bi2Te3 and Bi0.5Sb1.5Te3 thin films. In this paper, we present a simple wet etching process that can prevent the delamination of thermoelectric thin films. This process is compatible with standard IC fabrication technology and can pattern Bi2Te3 thin films down to micrometer scale dimensions. We use an etching solution of HNO3:CH3COOH:H2O2:H2O, and a single-layer photoresist etch mask. Etch rate of ~ 100 nm/min has been measured. Inclusion of H2O2 changes the etching mechanism, where H2O2 replaces HNO3 as the oxidizer. Etching uniformity and controllability can be achieved by incorporating H2O2. With this etching process, the fabrication of a monolithic thin film thermoelectric cooling device using wet chemistry becomes feasible. In recent years, driven by the need to handle higher cooling power densities, there is growing interest in the research of high efficiency thin films thermoelectric coolers for miniaturized thermoelectric applications in the microelectronics industry. Telluride compounds are the best thermoelectric materials known to date because of high Seebeck coefficient, low resistivity, and low thermal conductivity. Much effort has been focused on the development of high quality telluride thin films. Several promising approaches exploiting the size effects of thin thermoelectric films have been proposed. Thermoelectric figure of merit (ZT) enhancement through the use of quantumconfinement effects [1], phonon-blocking/electrontransmitting superlattices [2], or thermionic effects in heterostructures [3], which are all associated with lowdimensional thin film structures, had been theoretically predicted and experimental confirmed; Bi2Te3-based and PbTe-based superlattices have shown unprecedented high ZT values at near room temperature. Nevertheless, compared with material research, research on the fabrication of thermoelectric thin film coolers and the on-chip integration of thermoelectric thin films are seriously lagging behind. Etching of telluride thin films is an essential technology for the fabrication of thermoelectric cooler, but little has done on the development of etching techniques of these films. Most of telluride thin film patterns reported in literature was defined by physical bombardment of argon ions instead of reactive ion etching (RIE). This technique offers very little selectivity of telluride over photoresist and bottom metal electrode and surface damage of bottom electrode can ensue. Moreover, photoresist masks are very likely carbonized due to a long time exposure to high energy ion beams. Removal of harden 978-1-4244-2263-0/08/$25.00 2008 IEEE. photoresist further increases the process complexity. Monolithic fabrication of thermoelectric thin film coolers becomes very challenging using this dry etching technique. Compared with dry etching, wet etching is an effective alternative due to its high etching rate, low cost and high selectivity. The most common wet etchant for bulk tellurides is a solution of HNO3 and HCl mixture. However, this highly corrosive solution could cause a vigorous uncontrollable reaction with telluride, resulting in severe edge undercutting and even pattern disappearance. Furthermore, HNO3 and HCl mixture could trigger the delamination of weakly adhering telluride films from bottom substrates in our experiment. In this paper, we propose a novel approach for telluride thin film wet etching using HNO3:CH3COOH:H2O2:H2O solution as the etchant. The same etching technique can be extended to the etching of other telluride films. The samples used in this experiment were ~1 m thick Bi2Te3 films grown on TiW/SiO2/Si substrates using DC magnetron sputtering, where TiW was the intermediate layer applied to enhance the adherence between telluride films and substrates. Etch patterns were predefined by conventional lithography (AZ 5209 photoresist). The thickness of the etched films was measured by a surface profilometer (ALPHA 500, TENCOR). Optical microscopy and scanning electron microscopy (SEM) were employed to investigate the obtained patterns. HNO3 was believed to be a basic component of any Bi2Te3 wet etchant. At relatively high concentrated nitric acid, etching of Bi2Te3 proceeded by converting Bi2Te3 to soluble nitrates. Three etchants were used in this study: HNO3:H2O, HNO3:CH3COOH:H2O and HNO3:CH3COOH:H2O2:H2O.
300 250 Etch time (second) 200 150 100 50 0 1:1 1:2 1:3 1:4

Figure 1: Plot of etch time for 1 m B2Te3 films vs. volume ratio of HNO3:H2O. Fig. 1 shows the etch time for ~1 m Bi2Te3 films as a function of HNO3 concentration. The dependence of 2007 International Conference on Thermoelectrics

70% HNO3 : H2O

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oxidizing power of nitric acid on HNO3 concentration is well known. Several studies claimed that the oxidizing power of nitric acid in concentrated solution was determined by undissociated HNO3 [4]. No etching was observed at the solutions with a volume ratio of HNO3:H2O below 1:4. It seemed that controllable etch rates desirable for thin film patterning could be obtained by carefully adjusting the acid concentration. Nevertheless, Fig. 2 indicates a non-linear time dependence of etch depth in 1HNO3:3H2O solution. It was observed that a more violent reaction occurred in the last few seconds of etching, accompanied with a large amount of bubble release. Most of films were etched at this final period. The actual reaction mechanism between Bi2Te3 and nitric acid is not well understood. Robbins and Schwartz [5] proposed that the chemical reaction in nitric acid was initiated by undissociated species, resulting in a gradual build up of catalyst such as NO2 at the film surface that triggers an avalanche reaction in last few seconds etching. These etching characteristics of HNO3:H2O solution can ensure an unmanageable etching of Bi2Te3 films and a heavy undercutting of patterns. Fig. 3 demonstrates a typical undercutting, as high as 6:1, found at the edges of the patterns. This degree of undercutting is unacceptable for thermoelectric cooler device fabrication application and needed to be reduced.

Figure 4: SEM image of the Bi2Te3 pattern after etching in 1HNO3: 2CH3COOH:3H2O. To improve the pattern quality and reduce undercutting, acetic acid was considered as an additive to the nitric acid solution. SEM image of the etched Bi2Te3 pattern is shown in Fig. 4. Although the pattern edges were chipped, the undercutting was significantly decreased. The primary role of acetic acid in the etchant is the same as that of H2O, functioning as a diluent. It had been found that lesser ionization of nitric acid in acetic acid than in water allows a much higher tolerance for the diluent in the acetic acid diluted etchant than the water diluted etchant. Consequently better etching control became possible in the acetic acid diluted solution by reducing nitric acid concentration. Thus the aggressive etching happened in the final etch period could be suppressed by decreasing the concentration of the reactants, without diminishing the oxidizing power of the etchant. But the etching in the acetic acid diluted etchant is still governed by the same mechanism that operates in the water diluted etchant. The variation of the etch rate throughout the etching process is predetermined by this mechanism, resulting in the unavoidable severe undercutting and the edge chipping. This HNO3:CH3COOH:H2O etchant is also unsatisfactory to meet the requirements of the etching uniformity and controllability for the device fabrication.
300 250 Etch Depth (nm) 200 150 100 50 0

1000 800 Etch Depth (nm) 600 400 200 0 20 30 40 50 60 70 80 90 100

Figure 2: Plot of etched thickness of Bi2Te3 films vs. etching time at 1HNO3:3H2O solution.

Etch time (second)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

Figure 3: Optical microscope image of 12 m wide patterns etched by HNO3:H2O solution before photoresist mask removal.

Figure 5: Plot of etched thickness of Bi2Te3 films vs. etching time in 1HNO3:2CH3COOH:0.2H2O2:4H2O solution. The other etchant used in this experiment was HNO3:CH3COOH:H2O2:H2O. Fig. 5 shows a constant etch rate throughout the etching process in this etchant, indicating

Etching time (min)

a rate-controlled etch reaction. This etching consistency can be explained by a change of etching mechanism, where HNO3 no longer serves as the oxidizing agent. H2O2 replaces HNO3 as the oxidizer in the low concentration of HNO3, while the role of HNO3 is downgraded to providing hydrogen ions. The etching reaction can be written as
6H + + 3H 2 O 2 + 6e 12H 2 O

and
2 4+ Te Bi Te Te Te O HNO + 6e . 2 3 2 4 3

The reaction rate depended on the etchant concentration. No increment of the reaction intensity was observed. This reaction could also be conducted in a mix of H2O2 and other acid such as sulfuric acid. Fig. 6 shows the SEM pictures of pattern etched in the the Bi2Te3 solution. The 1HNO3:2CH3COOH:0.2H2O2:4H2O undercutting is minimized to ~1:1. Although this etchant shows good selectivity over p-type Bi0.5Sb1.5Te3 and bottom metal electrode, the high concentration of H2O2 and HNO3 would deteriorate the photoresist mask, causing pattern distortion. The low concentration of the etchant is preferred.

3. Mahan, G. D. and Woods, L. M., Multilayer Thermionic Refrigeration, Phy. Rev. Lett., Vol. 80 (1998), pp. 40164019. 4. Cretella, M. and Gatos, The Reaction of Germanium with Nitric Acid Solutions, J. Electrochem. Soc., Vol. 105 (1958), pp. 487-492. 5. Robbins, H. and Schwartz, B., Chemical Etching of Silicon, J. Electrochem. Soc., Vol. 107, No. 2 (1960), pp. 108-111. 6. Ngai, T. and Ghoshal, U., Novel wet etching of Bi0.5Sb1.5Te3 thin films, to be published.

Figure 6: SEM image of the 12 m Bi2Te3 pattern after etching in 1HNO3:2CH3COOH:0.2H2O2:4H2O. In conclusion, we have developed a wet etching technique that allows the fabrication of Bi2Te3 structures with micron resolution and yields convenient etch rates. This etching technique is compatible with microelectronic manufacturing technologies, simplifying the thermoelectric device fabrication process. Its use can be extended to other telluride thin films such as PbTe or Bi2-xSexTe3. We have also developed a novel etching technique for p-type Bi0.5Sb1.5Te3 thin films [6]. Thus technologies for fabricating a monolithic Bi2Te3-based thermoelectric thin film device are all in place. References 1. L. D. Hicks and M. D. Dresselhaus, Effect of Quantumwell Structures on the Thermoelectric Figure of Merit, Phys. Rev. B, Vol. 47 (1993), pp. 12727-12731. 2. R. Venkatasubramanian, E. Sivola, T. Colpitts, and B. OQuinn, Thin-Film Thermoelectrics Devices with High Room-temperature Figure-of-Merit, Nature, vol. 413, pp. 597-602, October 2001.