Journal of the Korean Physical Society, Vol. 40, No. 2, February 2002, pp.

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Electrical Properties of Sputtered Ni-Cr-Al-Cu Thin Film Resistors with Ni and Cr Contents
Boong-Joo Lee and Duck-Chool Lee
Functional Thin lms Laboratory, Electrical Engineering, Inha University, Incheon 402-751

Chul-Soo Kim
Sentrotek Co., Ltd. #192-3, Anyang-7Dong, Manan-Gu, Anyang 430-817 (Received 30 July 2001, in nal form 15 November 2001) In this work, we fabricated thin lm resistors using three dierent Ni-Cr-Al-Cu target compositions by using DC/RF magnetron sputter. The electrical properties, such as the sheet resistance and the TCR (temperature coecient of resistance) of the Ni-Cr-Al-Cu thin lms and the eects of annealing in air up to 400 C were examined. In general, the TCR was increased as the annealing temperature was increased. Transmission electon microscopy (TEM) and X-ray diraction (XRD) analysis of a thin lm with a composition of 74 : 18 : 4 : 4 wt% (Ni : Cr : Al : Cu) conrmed that the sharp increase in both the sheet resistance and the TCR of the lm annealed at 400 C in air was due to the formation of the rhombohedral NiO phase in the lm. The TCR of Ni-Cr-Al-Cu thin lms decreased as the Ni/Cr ratio was decreased at constant Al and Cu. Above 38 wt% of Cr, the TCR became negative. XRD analysis revealed that the decrease in the TCR of Ni-Cr-Al-Cu thin lms with decreasing Ni/Cr ratio was due to microcrystalline structures in these thin lms. The optimal composition was determined to be 51 : 41 : 4 : 4 wt% (Ni : Cr : Al : Cu) and the TCR of the as-deposited thin lms was 27 ppm/ C. Through heat treatment, we obtained thin lm resistors with low values of the TCR below 10 ppm/ C.
PACS numbers: 73.61.At, 72.15.-V Keywords: Thin lm resister, TCR(temperature coecient of resistance), Annealing

I. INTRODUCTION

Rapid technological advancements in many electronics industries, such as in the information and telecommunication, the aerospace, and the precision measurement sectors of industry, require the continuous development of electronic components to achieve higher precision, reliability, and integration. Among these components, the resistor is one of the fundamental components and is primarily used in electronic circuits. In this respect, the demands for thin lm resistors with low temperature coecients of resistance (TCRs) and high precision have been increasing dramatically in recent years [112]. NiCr is one of the most commonly used resistive materials for fabricating precision thin lm resistors. This alloy exhibits a wide range of resistivities, a low TCR and highly stable electrical properties. Thus, much research on the fabrication process, the material compositions, and the electrical and the physical characteristics of NiCr resistor thin lms have been undertaken [27]. In earlier research on NiCr, the evaporation method
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was used to fabricate the thin lms, but it proved difcult to control the composition of such lms because of the large dierences in the vapor pressures of Ni and Cr. For this reason, research on NiCr thin lms made by sputtering [15], in order to obtain better compositional repeatability, have been reported in recent years. Changes in electrical properties such as the TCR, the resistivity, and the sheet resistance have been studied for various compositions of NiCr - based alloys made by adding Al, Cu, Si, Mn, Mo, etc. to binary Ni-Cr alloys. Heat treatment not only improves long-term stability but also improves the consistency of the TCR values. Eects of annealing treatments on NiCr resistor thin lms have also reported [712]. The used bulk alloy target is called as the Evanohms alloy and is known to have very low TCR characteristics. This study was undertaken to investigate both the eects of compositions and annealing treatments on the electrical properties of sputtered NiCr-Al-Cu thin lm resistors and the fabricational aspects of thin lm resistors with low values of the TCR.

boongjoolee@hotmail.com; Fax : 032-863-5822

II. EXPERIMENTAL
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-340Table 1. Sputtering condition. DC power [W] Pressure [mTorr] Ar ow rate [sccm] Annealing

Journal of the Korean Physical Society, Vol. 40, No. 2, February 2002

250 5, 15, 25 50 150-400 C/Air, 15 hr.

Table 2. Target content(wt%). Ni 74 56 51 Cr 18 36 41 Al 4 4 4 Cu 4 4 4 Ni/Cr 4.11 1.56 1.24 Fig. 1. BSE image of a Ni-Cr-Al-Cu target(#1).

#1 #2 #3

Thin lms were deposited using a DC/RF magnetron sputter system (model APEX EOS-310). The processing conditions and the target alloy compositions are summarized in Tables 1 and 2, respectively. Thin lm resistors were deposited on polished alumina (Al2 O3 ) substrates, which were scribed for the TCR measurement into 24 mm cell sizes with a laser. Glass and Si wafers were used as substrates for the thin-lm thickness and sheet-resistance measurements. Substrates were cleaned by the standard wet-cleaning procedure and were dried in nitrogen before they were loaded into the sputtering chamber. Microstructural, SAD (selected area diraction) patterns and EDS (energy dispersive spectroscopy) analysis of the thin lms were performed using a TEM (transmission electron microscope, Phillips CM30) at an accelerating voltage of 200 kV. The samples for the TEM were prepared by grinding to a thickness of about 20 mm using a dimple grinder, and the thinned samples were perforated using Ar-ion milling (Gatan dual ionmill) equipment. XRD (X-ray diractometer, Phillips XPERT-MPD) and EPMA (electron probe micro analyzer, CAMECA SX-51) were used to determine the crystalline phases and the compositions of the thin lms, respectively [16,17]. The sheet resistance and the thickness of the thin lms were measured using a 4-point probe (MILLER FPP5000) and a surface proler meter (Dektak3), respectively. For the TCR measurements, the sputtered thin lm was patterned as follows : Positive PR (AZ1512) was coated onto the thin lm by using a spin coater (WS400, Laurel) at 500 rpm/10 sec (step 1) and 5000 rpm/30 sec (step 2). The PR-coated samples were soft baked at 100 C for 60 sec on a hot plate. After UV exposure for 40 sec, the samples were hard baked at 110 C for 80 sec, using a mask aligner (MA-6, Karl-suss). Finally, the thin-lm resistor patterns were developed and etched using an etching solution, and the etched thin-lm samples were observed under an optical microscope (Leica Wild M3Z) to establish the optimum patterning conditions.

The resistance of the thin lm resistor sample was measured using a digital multimeter (HP 34401A) with a temperature chamber (4220A, S&A) between 25 C and 125 C. The samples were soaked for 10 minutes at the set temperatures before measuring their resistances, and the TCR values of the samples were calculated using Eq. (1) with the resistance R25 at 25 C and the resistance R85 at 85 C : T CR[ppm/ C] = 1 R[] R25 [] T [ C ] (1)

Here, TCR is the temperature coecient of resistance, R is the dierence in the resistances measured between 25 C and 85 C, and T is the temperature dierence between 25 C and 85 C.

III. RESULTS AND DISCUSSION

1. Characteristics of the Target (74Ni-18Cr4Al-4Cu : #1) and the Thin Films

The alloy content of the #1 target is shown in Table 2. It was tested by EPMA, and the microstructure was determined by the BSE (back scattered electron) image of the SEM. The result is shown in Fig. 1 and Table 3. In Fig. 1, the Ni-Cr-Al-Cu target does not contain a single phase and largely contains a Ni-rich and a Cr-rich phase. The bright-eld area in Fig. 1 represents the Nirich phase and the dark area the Cr-rich phase. As shown by Table 3, the Ni/Cr ratio of the Ni-rich phase is similar to the manufactures specication in Table 2 while that of Cr-rich phase was markedly dierent from that with a Ni/Cr ratio of 0.24. In the Cr-rich phases, the contents of Al and Cu were lower than the specication. A thin-lm resistor was deposited at a power of 250 W (DC), a pressure of 5 mTorr, and an Ar ow of 50 sccm. The EPMA showed that the sputtered thin lm

Electrical Properties of Sputtered Ni-Cr-Al-Cu Thin Film Resistors Boong-Joo Lee et al.

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Fig. 2. Variation of the TCR with sputtering pressure.

was 74.7 : 17.3 : 4 : 4 wt% (Ni-Cr-Al-Cu) as shown by Table 3, which matches the manufacturing specication within the error of the EPMA analysis. Fig. 2 shows the TCR of the thin lm sputtered using the #1 target, which was manufactured at 250 W (DC), and 50 sccm of Ar at various pressures, namely, 25 mTorr, 15 mTorr and 5 mTorr. As the pressure decreases, the TCR greatly decreases, taking on values of 138 ppm/ C, 114 ppm/ C and 77 ppm/ C, respectively. This result is believed to be the reason for the oxygen decrease in the thin lm and suggests that the oxygen in a thin lm inuences the TCR. From such results, we chose 5 mtorr as an optimum pressure. Thereafter, the standard process condition is at a power of 250 W (DC), a pressure of 5 mTorr, and an Ar ow of 50sccm. Thin lm annealing is essential for resistor stability. Fig. 3 shows X-ray diraction patterns of non-annealed and annealed thin lms, which were deposited on Al2 O3 substrates. Annealing was performed in air up to 400 C. In this gure, the non-annealed sample has a cubic structure, but the annealed sample (at 400 C in an air atmosphere) has a NiO rhombohedral structure. This is believed to be due to the oxidation of the thin lm during annealing. To reconrm the oxidation eect of the annealing

Fig. 3. XRD for various annealing temperatures (#1 target, annealing time:1hr).

treatment, we show in Fig. 4 the TEM and the SAD patterns of an annealed lm made from the #1 target in Table 2, which was annealed in an air atmosphere at 400 C for 1 hr [9,10]. In this gure, a columnar crystal structure can be seen in (a) and an oxidation layer in (b). From the EDS analysis, the Ni content of (a) was higher than that of (b). Also, from the SAD patterns, (a) had a cubic structure and (b) a NiO rhombohedral

Table 3. get(#1).

Composition analysis of a thin lm and tarNi 74 74.8 18.4 74.7 Cr 18 17.8 76.5 17.3 Al 4 3.9 2.1 4 Cu 4 3.1 3.0 4 Ni/Cr 4.11 4.20 0.24 4.31

(wt%) Manuf. Spec. target Ni-rich Cr-rich Thin lm

Fig. 4. TEM and SAD of a thin lm annealed at 400 C : (a) TEM, (b) SAD pattern of A, and (c) SAD pattern of B.

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Journal of the Korean Physical Society, Vol. 40, No. 2, February 2002

Fig. 7. Variation of the resistivity of a thin lm with Cr content.

Fig. 5. XRD of various target contents.

structure. Therefore, the thin lm annealed at 400 C has a cubic alloy structure in the thin lm and a NiO oxidation layer on surface, which agrees with the XRD results [12].

2. Electrical Properties with Variable Ni and Cr Contents

Fig. 5 presents the results of an XRD analysis of the thin lm which was fabricated using the #2 and the #3 targets in Table 2. The thin lm was deposited on a glass substrate and made under the standard process condition. As shown in the gure, the thin lm had a cubic structure with a (111) preferred orientation, regardless of composition. Also, the gure a peak broadening and a peak intensity decrease with decreasing Ni/Cr ratio.

This phenomenon implies that the crystalline structure is ne. Fig. 6 presents the values of the TCR of the thin lms made using the #1, #2, and #3 targets. As the Cr content increases, the TCR rapidly decreases. Above 38 wt% of Cr, the TCR of the as-deposited lm is negative. Fig. 7 presents the resistivities of thin lms versus Cr content. As the Cr content increases, the resistivity increases. This is believed to be due to better crystallinity and impurities with increasing Cr content [13,14]. This result is same as that from XRD (Fig. 6), where the crystal size decreased as the Cr content was increased. Fig. 8 shows the TCR as a function of the annealing treatment for the 3 kinds of target. The thin lms were fabricated using the standard condition. The annealing treatment is an important factor for the stability of the resistor [11]. The TCR was measured in an air atmosphere for 1 hr as a function of the annealing

Fig. 6. Variation of the TCR with the Cr content.

Fig. 8. Variation of the TCR with annealing temperature for three targets.

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1. As the process pressure decreased, the TCR decreased. The selected process condition was a power of 250 W (DC), a pressure of 5 mTorr, and an Ar ow of 50 sccm. 2. At constant Al and Cu, as the Cr content increased, so the TCR of the thin lm decreased. This was attributed to the microcrystalline structure. Above 38 wt% of Cr, the TCR became negative. 3. The TCR increased as the annealing temperature increased. The sharp increase in both the sheet resistance and the TCR for thin lms annealed at temperature over 300 C in air was due to the formation of a rhombohedral NiO phase in the lm.
Fig. 9. Variation of the TCR with annealing time (#3 target).

temperature. As shown in the gure, as the annealing temperature was increased, the TCR increased, which was attributed to oxidation [7,9]. The values of the TCR of the as-deposited thin lms made using the #1 and #2 targets were positive, but that made using the #3 target was negative. Above 300 C, the TCR rapidly increased, which was caused by NiO formation on the surface. Therefore, the TCR of the as-deposited thin lms should be negative for low TCR because the annealing treatment is essential and TCR increases with annealing. From these results, we selected the appropriate target, namely, 51 : 41 : 4 : 4 wt% (Ni : Cr : Al : Cu) which is the #3 target as shown in Table 2. Fig. 9 show the TCR as a function of the annealing time, the thin lms were fabricated using the selected #3 target. The sputtered thin lm was treated at 250 C and 275 C for dierent annealing times. As the annealing time was increased, the TCR increased. When thin lms were annealed at 250 C, the TCR was -10 0 ppm/ C at an annealing time of 25 hr, and when thin lms were annealed at 275 C, the TCR was 10 ppm/ C for an annealing time of 0.53.5 hr. Therefore, we selected an annealing condition of 250 C/3.5 hr.

4. The appropriate composition was selected as 51 wt%Ni-41 wt%Cr-4 wt%Al-4 wt%Cu. With the selected target, the TCR of the as-deposited thin lm was 27 ppm/ C. Through heat treatment, thin-lm resistors with TCR values of less than 10 ppm/ C were obtained.

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IV. CONCLUSION In this work, we fabricated thin lms for the purpose of fabricating low-TCR thin lm resistors, and we studied the dependenies of the electrical properties of Ni-Cr-AlCu thin lms on the process parameters and the target compositions. We found the following: