Vacuum 66 (2002) 479485

Etching characteristics of magnetic materials (Co, Fe, Ni) using CO/NH3 gas plasma for hardening mask etching
N. Matsui*, K. Mashimo, A. Egami, A. Konishi, O. Okada, T. Tsukada
Anelva Corporation, 5-8-1 Yotsuya, Fuchu, Tokyo 183-8508, Japan

Abstract Etching of magnetic materials, NiFe, CoFe, and Fe, has been studied with a high-density helicon plasma source using non-corrosive CO/NH3 gas. High etch rates, ranging from 45 to 130 nm/min, were achieved. The etch rate strongly depended on both plasma density and ion energy. The main etching mechanism is interpreted as physical sputtering rather than as chemical reaction. A high selectivity of 616 was achieved by using hard masks of Ti or Ta. This is attributed to the hardening surface layer of the masks by nitradation, carbonization, or oxidation in CO/NH3 gas plasma. This etching process is named as hardening mask etching. This etching process was also applied for tunneling magneto-resistive (TMR) multi-layers that uses magnetic random access memory with a Ta mask. A high anisotropy of about 801 was obtained without residues, sidewall deposition, and corrosion. This process is potentially applicable to the etching of thin magnetic materials in TMR stacks, patterned media, and read/write head. r 2002 Published by Elsevier Science Ltd.
Keywords: Magnetic materials; NiFe; CO/NH3 high-density helicon plasma; HM-etching; Ti; Ta; Magnetic random access memory (MRAM); Tunneling magnet-resistive multi-layers (TMR)

1. Introduction Micro-fabrication process of magnetic materials have become increasingly important for magnetic random access memory (MRAM), and patterned media, read/write heads for data storage, etc. MRAM, as a fast and non-volatile memory with low power consumption, appears to be one of the suitable candidates for the next memory generation [13]. Ion milling [4] is widely used in micro-fabrication of magnetic materials involving multi-layer stacks such as MRAM [2,3]. However, there are many problems of sidewall deposition and lack of
*Corresponding author. E-mail address: matsuin@ccgw.anelva.co.jp (N. Matsui).

selectivity in this process. The conventional reactive ion etching using Cl2-based plasmas has also been used for the magnetic materials [58]. But this process also exhibits problems due to relatively non-volatile products and after corrosion caused by residual chlorine. Nakatani reported the use of noncorrosive CO/ NH3 gas in etching magnetic materials using parallel-plate RF plasma [9]. The etch rate increases with the addition of NH3 into CO. The maximum etch rate of 65 nm/min was achieved in the etching of NiFe. Therefore, etching with CO/ NH3 was recommended for ultra-micro-fabrication technique of magnetic materials. In this etching, a hard mask of Ti was used because a high etch rate was observed for photoresist. Jung et al. proposed SiO2 as the mask for CO/NH3

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etching. However, it was pointed out that faceting of the mask leads to sloped sidewalls in deep etching due to physical sputtering rather than due to chemical reaction [10,11]. In this study, etching of the magnetic materials, NiFe, CoFe, and Fe, was investigated in a highdensity helicon plasma using the noncorrosive CO/ NH3 gas. A high selectivity of 616 was achieved by using hard masks of Ti or Ta. In the etching of TMR multi-layer on MRAM using Ta hard mask, a high anisotropy of about 801 was obtained.

2. Experimental Etching of NiFe, CoFe, Fe, Ti, Ta single layer and TMR multi-layers of Ta(mask)/CoFe/Al2O3/ CoFe/PtMn/Ta/th-SiO2 on Si substrate was investigated in CO/NH3 gas plasma. Patterning of Ti and Ta masks was formed by using a photoresist mask. A schematic representation of the experimental apparatus is shown in Fig. 1. A helicon plasma source with an excitation frequency of 13.56 MHz and RF power up to 3000 W was selected as a high-density plasma source. The substrate holder was biased by the frequency of 1.6 MHz up to

2000 W so that an independent control of plasma density and ion energy could be achieved in the etching process. The wafer was electrically chucked with a He backside-cooled substrate holder. The temperature of the wafer was maintained at about 801C. The etching was carried out at a low pressure of 0.8 Pa. In the experiments, a single Langmuir probe (Fast ProbetPlasma Materials and Technology) was used for monitoring ion saturation current that is proportional to the plasma density during the etching. An analysis of XPS and TEM-EDX was used to study elements of samples surface and depth prole for the evaluation of modied surface in the etching process.

3. Results and discussion 3.1. NiFe etching in high-density CO/NH3 gas plasma Fig. 2 shows the etch rate of NiFe and ion saturation current (probe biased to 70 V) as a

Fig. 1. Schematic representation of helicon plasma source.

Fig. 2. The NiFe etch rate and ion saturation current as a function of source power CO/NH3: 10/30 SCCM, pressure: 0.8 Pa.

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Fig. 3. TEM-EDX image in deep etching of Ni75Fe19 alloy; source power: 2500 W, bias power: 2000 W, CO/NH3: 5.2/ 14.8 SCCM, pressure: 0.8 Pa, Ni67Fe31 (2 mm) mask/Ni75Fe19.

Fig. 4. The bias power inuence on the etch rates of NiFe, CoFe, Fe, SiO2, Ti, and Ta; source power: 3000 W, CO/NH3: 10/30 SCCM, pressure: 0.8 Pa. Table 1 Selectivity of each magnetic material Mask Material NiFe Ti Ta 11.5 16.2 CoFe 8.2 11.1 Fe 5.9 7.9

function of plasma source power. Both the etch rate and the ion saturation current increase with the source power. A similar phenomenon was observed when the bias power was increased. A maximum etch rate of 130 nm/min for NiFe was obtained at a source/bias power of 3000 W/ 2000 W. These results suggest that the etch rate strongly depends on ion energy and plasma density. Fig. 3 shows a cross-sectional TEM image of Ni75Fe19 alloy etching. There was a 2 mm Ni67Fe31 mask on the Ni75Fe19 layer and the etching depth was 1 mm. An inclined columnar sidewall structure is seen in Fig. 3. The composition of deposited lm on the sidewall was identied as Ni75Fe19 by TEMEDX analysis. This result indicates that the sputtered species is deposited on the sidewall. From the result of this deep etching experiment, CO/NH3 gas etching is conrmed to be of mainly physical sputtering rather than chemical reaction. 3.2. Mask material in CO/NH3 gas plasma In etching process, mask material is important for the control of the shape of sidewalls. As the etch rate of photoresist is very high in CO/NH3 gas

Source power 3000 W, bias power 1200 W, CO/NH3 10/ 30 sccm, and pressure 0.8 Pa.

plasma, a hard material should be used as the mask. Fig. 4 shows the etch rate dependence on the bias power for NiFe, CoFe, Fe, SiO2, Ti, and Ta. The etch rates of Ti and Ta were almost ten times lower than that of the magnetic materials. Selectivities of Ti and Ta to the magnetic materials are shown in Table 1. This shows that Ti and Ta are suitable as the mask material. More detailed investigation for Ti mask was performed in order to clarify the reason for high selectivity. Fig. 5 shows the NiFe etch rate and selectivity with Ti for CO/NH3, NH3, and N2 gas plasmas. The NiFe etch rate was not so much changed by the gas species. However, the selectivity was inuenced signicantly. The largest selectivity was 12 with CO/NH3 gas plasma. Fig. 6 shows the depth prole of the Ti layer deposited on the th-SiO2 lm before and after CO/NH3

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Fig. 5. NiFe etch rate and Ti selectivity using CO/NH3, NH3 or N2 gas plasma; source power: 3000 W, bias power: 1200 W, pressure: 0.8 Pa, CO/NH3: 10/30 SCCM, NH3: 40 SCCM, N2: 200 SCCM.

etching measured by XPS. The surface of Ti before etching was oxidized (see Fig. 6a). The O concentration reached 60 at% near the surface. However, the surface concentration of O was decreased to 35 at% when the Ti layer was exposed to CO/NH3 plasma as shown in Fig. 6b. Nitrogen and carbonrich layer was formed near the surface by exposing in CO/NH3 plasma. This modied layer suppressed the etching of Ti. Then, the high selectivity to the Ti mask was obtained. This etching process is named as hardening mask Etching (HM-etching). A similar phenomenon will happen in the case of Ta. 3.3. Effect of mask thickness The thickness of mask used in CO/NH3 gas plasma is important to prevent the sidewall deposition. Fig. 7 shows the cross-sectional view of the NiFe using Ti masks after etching with thicknesses of 0.5 and 1.5 mm, respectively. The etching depth was 1 mm in both cases. The sidewall deposition was not observed in the 0.5 mm mask case, although it was observed in the 1.5 mm mask case. In the case of a thinner mask, we believe that the deposited materials on the sidewall were

Fig. 6. XPS depth prole of Ti before (a) and after (b) etching Ti in CO/NH3 gas plasma; source power: 3000 W, bias power: 1200 W, CO/NH3: 10/30 SCCM, pressure: 0.8 Pa.

removed by ion bombardment. Therefore, a thin mask is recommended for the process. 3.4. Etching of thin TMR multi-layers of MRAM Etching was applied for the thin TMR multilayers of MRAM with a Ta hard mask of 0.02 mm thickness. Fig. 8 shows SEM images of TMR multi-layers (Ta/CoFe/Al2O3/CoFe/PtMn/Ta/thSiO2/Si-substrate) after etching, of which the pattern width is in the range of 0.52 mm. Fig. 9 shows the enlarged cross-sectional TEM image of etched TMR multi-layers in the pattern width of

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Fig. 7. Cross-sectional view of the NiFe using Ti mask after etching; source power: 2500 W, bias power: 2000 W, CO/NH3: 5.2/14.8 SCCM, pressure: 0.8 Pa.

1.6 mm. A Ta lm existed in the upper layer of the TMR multi-layer, which was used as a hard mask in the etching. In all pattern widths, there was no sidewall deposition and a good anisotropy was observed. The taper angle of TMR multi-layer was about 801 (see Fig. 9). Using the HM-etching, the TMR multi-layers could be etched with good prole. Fig. 10 shows TEM-EDX spectra of TMR multi-layer after etching. After the TMR multilayer was etched off, the bottom layer SiO2 appeared as shown in Fig. 10d. This result indicates that the upper Ta layer was remained even after the lower Ta layers etched off. The surface of the Ta mask layer was natively oxidized. This oxide layer seemed to suppress the Ta mask layer etching. On the other hand, the lower layer of the Ta was not natively oxidized. Then, the etch rate of the lower layer may be higher than that of the mask layer. The etch rate of the oxidized layer will be lower than that of the unoxidized layer when the oxidized layer was remained on the etched surface, because the oxidized layer is formed also during etching and the etching is prevented by this oxidized layer. The uncovered thin Ta was etched immediately just before the surface reacted with CO/NH3 gas plasma.

Fig. 8. SEM image of TMR multi-layer after CO/NH3 etching; source power: 3000 W, bias power: 1200 W, CO/NH3: 50/ 150 SCCM, pressure: 0.8 Pa Ta/CoFe/Al2O3/CoFe/PtMn/Ta/ th-SiO2 on Si substrate.

Small Ta on the SiO2 layer remained in the corner of TMR multi-layer (Figs. 9 and 10c). It was identied by EDX analysis that the remained Ta was oxidized during the etching due to the use of CO gas (Fig. 10c). This might be due to the neutral activated species arriving at the corner. Here, the effect of ion bombardment is relatively small. The oxidation, which makes Ta harder, is responsible for the remaining Ta.

4. Conclusion Etching of magnetic materials in CO/NH3 plasma was studied. High etch rates in the range

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Fig. 9. Cross-sectional TEM image of TMR multi-layer after CO/NH3 etching; source power: 3000 W, bias power: 1200 W, CO/NH3: 50/150 SCCM, pressure: 0.8 Pa Ta/CoFe/Al2O3/ CoFe/PtMn/Ta/th-SiO2 on Si substrate.

of 45130 nm/min were obtained for NiFe, CoFe, and Fe. The etch rate depended on plasma density and ion energy. The etching properties are mainly dominated by the physical sputtering rather than chemical reaction. Ti and Ta were used as the mask materials due to their high selectivity with respect to the magnetic materials. A selectivity of 616 was obtained, which is attributed to the hardening surface of the mask layer during the etching. Therefore, this etching is named as hardening mask etching (HM-etching). In the etching of TMR multi-layers using thin Ta hard mask, a high anisotropy of about 801 was obtained without residues, sidewall deposition, and corrosion. This process is useful for the etching of thin magnetic materials in TMR stacks
" Fig. 10. TEM-EDX spectra of various positions of the TMR multi-layer after etching; source power: 3000 W, bias power: 1200 W, CO/NH3: 50/150 SCCM, pressure: 0.8 Pa; (a) the upper half of the upper layer Ta; (b) the lower half of the upper layer Ta; (c) the small Ta near the corner of TMR; and (d) surface completely etched off of metal layers; (*) Ga came from the ion source of FIB.

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with a scale of about 0.5 mm. Other potential application is fabrication of patterned media and read/write heads.

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Acknowledgements The authors are grateful to Dr. I. Nakatani of National Institute for Materials Science Nano Material Laboratory for useful discussion and encouragement. Many thanks are expressed to T. Yoshida, T. Akiyama, N. Suzuki, Y. Miura, M. Suzuki, ANELVA Corp. for their help with the experimental setup, N. Watanabe, K. Tsunekawa, D. Nakajima, ANELVA Corp. for their help with sample preparation, and J. Kudera, ANELVA Corp., for his discussion. This study was partly supported by the Japan Science and Technology Corporation.