3.2. Magnetic Properties with Deformable Substrates
The effects of various deformable substrates were investigated by comparing the magnetic properties of the Ta/CoFeB/MgO/Ta thin films sputtered onto the substrates. The magnetic properties were extracted from the M-H loop measured when an in-plane magnetic field was applied using the SQUID-VSM. As shown in
Figure 4, it was confirmed that all Ta/CoFeB/MgO/Ta thin films on various substrates exhibited in-plane magnetic anisotropy through having rectangular M-H loops in the case of in-plane, unlike the case of out-of-plane [
16].
We can derive various magnetic properties such as saturation magnetization, remanence, coercive field, magnetic anisotropy field (
Hk), and magnetic anisotropy constant (
K) from the M-H loop [
36]. In the case of the magnetic anisotropy constant,
K, it is one of the important elements in a sensor which detects the magnetic field angle, and indicator for evaluating the magnetic anisotropy. To know the value of
K, however, we must not only know the exact hard axis,
Ms, and
Hk, but also other various analysis [
37]. In magnetic anisotropy energy (
Ea) (see Equation (1)),
K0 is an isotropic term that is not affected by angle,
Ku is a uniaxial anisotropy constant, and
Kc is a magneto-crystalline anisotropy constant that contributes to four-fold symmetry (or biaxial characteristics) [
16,
37,
38]:
In magnetic thin films with in-plane magnetic anisotropy, hard axis is formed in the normal direction of most planes by shape anisotropy due to thin thickness and wide area [
16,
36]. So, analyzing the magnetic anisotropy of the plane’s normal direction is not appropriate for assessing sensors that sense the in-plane magnetic field angle. Instead, we obtained the magnetic anisotropy field between the in-plane magnetic anisotropy and the out-of-plane magnetic anisotropy for each sample, and did not calculate the magnetic anisotropy energy separately. The magnetic anisotropy fields are about 8.2 kOe (Si/SiO
2), 6.3 kOe (PDMS), 3.5 kOe (PI), and 13 kOe (PEN), respectively.
Even, we did not proceed with crystallization of the Ta/CoFeB/MgO/Ta thin films through annealing process. And, here, we focus on base studies for magnetic sensors and especially in-plane magnetic field angle sensors. Therefore, we only analyzed the angle dependence of
Hc and
Mr/Ms which can be quickly identified according to the substrates. In general, in the magnetic thin film research, the
Hc change indicates the presence or absence of pinning effects of the magnetic domain movements due to substrate roughness or impurities [
36], and
Mr/Ms change implies that multi-grains or magnetic domains are composed of magnetic anisotropies of various orientation [
39,
40]. These two values (
Hc and
Mr/Ms) are one of the practical elements for qualitatively evaluating the magnetic anisotropy of a sample [
38,
41,
42].
As depicted in
Figure 4 and
Figure 5a,c, all magnetizations (
M) were normalized into saturation magnetization (
Ms ~ 1100 emu/cc) of each sample with the substrate to compare the variation with magnetic field angle in each sample. So, we used
M/Ms as y-axis of M-H loop. In this article, we represented M/M
s-H loop as M-H loop for readability.
Figure 5a,c shows the case where the magnetic field is applied at 0° and 90°, respectively. When the magnetic field is applied at 0° (
Figure 5a), there is no significant difference in the shape of the M-H loop depending on the substrate, except for the sample in which the Ta/CoFeB/MgO/Ta thin film is grown on the Si/SiO
2 substrate. For the Si/SiO
2 sample, the rectangular shape of the loop was the most prominent among the four samples (Si/SiO
2, PDMS, PI, and PEN). The rectangular shape of the M-H loop means that the sample has good magnetic anisotropy and quick magnetic switching property. Whereas, in the case of 90° (
Figure 5b), the shapes of the M-H loops were clearly different depending on each substrate, and it can be seen that a large difference occurs in the value of the
Hc and
Mr/Ms (see
Table 1). The
Hc increased when the angle of the magnetic field changed from 0° to 90°. In the PEN sample with the largest change, the
Hc increased by about 4 times from
Hc,0° = 20.96 Oe to
Hc,90° = 84.35 Oe. This value (
Hc,90° = 84.35 Oe) is about 6.6 times larger than the 90° value of Si/SiO
2 sample (
Hc,90° = 12.65 Oe) (
Table 1). This result is related to the roughness of the substrate surface. As the roughness increases, the pinning effect intensifies, and eventually the
Hc increases in proportion to the roughness. As shown in
Figure 5c,d, Si/SiO
2 and PDMS samples with alike roughness have similar
Hc values, and PI and PEN samples with large roughness also tend to have large
Hc values. Looking at the y-axis scales in
Figure 5b,d, it can be seen that range of y-axis scale is much smaller when the angle of the magnetic field is 0° than 90°. Through curve fit, we can know that both angles show similar tendencies.
However, it is hard to explain that the
Hc change with magnetic field angle only by the pinning effect. Mostly, the
Mr/Ms changes by variation of magnetic anisotropy orientations of multi-grains, and the
Hc are affected by grain size of them [
43]. So, the effect is noticeable in case of deformable substrates which have rough and bumpy surfaces, because it is easy for rough and bumpy surfaces to make multi-grains of magnetic thin films by physically dividing areas. So, unlike the Si/SiO
2 and PDMS samples having smooth surfaces, the rough PI and PEN samples had a substantial variation in
Hc between the magnetic field angles 0° and 90°, which does not exist only between the two angles. Similarly, the
Mr/Ms became smaller at 90° than at 0° since the magnetic anisotropy of each grain is formed in many directions. The
Mr/Ms and
Hc continuously change from 0° to 360° of the magnetic field angles. We guessed that this influence of multi-grains is one of the causes of biaxial characteristics. Detailed its analysis is conducted in 3.3 with
Figure 7 and
Table 2.
3.3. Angular Dependence of Hc and Mr/Ms
Since we focus on research that will be based on the magnetic sensors to be used as the in-plane angle sensors, the M-H loops of all samples were measured in the in-plane directions at 30° intervals from 0° to 360° (see
Figure 6).
Figure 6.
Angle dependence of Hc and Mr/Ms of (a) Si/SiO2; (b) PDMS; (c) PI; and (d) PEN from 0° to 360° in polar coordinate system.
Figure 6.
Angle dependence of Hc and Mr/Ms of (a) Si/SiO2; (b) PDMS; (c) PI; and (d) PEN from 0° to 360° in polar coordinate system.
The in-plane easy axis of all the samples was formed by shape anisotropy, because the amorphous CoFeB thin film is very thin of 7 nm. For the same reason, the hard axis was formed in the direction perpendicular to the plane. So, the Si/SiO
2 sample showed isotropic properties for both
Hc and
Mr/Ms. However, it had not a perfect isotropic shape in a polar coordinate system. This impact is due to our sputtering system. Our sputter was equipped with the 45° (
φ = 45°,
Figure 2) tilted sputter gun, and the sample holder rotates at 10 rpm. So, when sputtering is progressing while the sample holder rotates, the energy applied to the substrate is different according to the direction of the sample, and consequently, the stress transferred to the thin film is different depending on the direction of the sample [
44].
Figure 7.
M-H loops with magnetic field angle from 0° to 150° of (a) PI sample; and (b) PEN sample.
Figure 7.
M-H loops with magnetic field angle from 0° to 150° of (a) PI sample; and (b) PEN sample.
Table 2.
Rq, Hc, and Mr/Ms with substrates at 0° and 90°.
Table 2.
Rq, Hc, and Mr/Ms with substrates at 0° and 90°.
Angle |
Hc, Oe |
Mr/Ms
|
PI |
PEN |
PI |
PEN |
0° |
0.259 |
0.239 |
0.533 |
0.691 |
30° |
0.258 |
0.227 |
0.420 |
0.290 |
60° |
0.349 |
0.194 |
0.162 |
0.243 |
90° |
0.866 |
0.937 |
0.413 |
0.690 |
120° |
0.496 |
0.016 |
0.546 |
0.034 |
150° |
0.389 |
0.083 |
0.345 |
0.141 |
This stress or strain is related to the magnetostriction effect. In particular, the CoFeB is one of the materials with a large magnetostriction constant (
λs = 31×10
-6) [
36,
45]. For this reason, the sample sputtered onto the Si/SiO
2 substrate did not have fully isotropic properties. In the sample of the PDMS substrate, which has a slightly rougher surface than the Si/SiO
2 sample, the
Mr/Ms was somewhat isotropic, but the
Hc wasn’t isotropic. In contrast, the PI and PEN samples exhibited either uniaxial or biaxial characteristics. As depicted in
Figure 6c, the
Hc of the PI sample had maximum values at 90° and 270°. It showed minimum values at 0° and 180° with the uniaxial property. The
Mr/Ms of PI sample had high values at 0°, 120°, 180°, and 300°. Its low values appeared at 60°, 150°, 240°, and 330°, so, it had four-fold symmetry (or biaxial characteristic). In
Figure 6d, the PEN sample also revealed biaxial characteristics for both
Hc and
Mr/Ms. The
Hc of the PEN sample has seemed almost uniaxial due to the large difference between the values of 90° (or 270°) and 0° (or 180°), whereas the
Mr/Ms had almost the same high values at 0°, 90°, 180°, and 270°. It had also the same low values at 60°, 120°, 240°, and 300°. The PEN sample had a complete biaxial characteristic in both
Hc and
Mr/Ms. The detailed M-H loops of the PI and PEN samples according to the angle of applied magnetic field were exhibited in
Figure 7a,b, respectively. For visibility, only the angles from 0° to 150° were inserted.
The biaxial characteristics of the PI and PEN samples were also analyzed due to the influence of our sputtering method. Because our samples were not annealed, it is difficult to see the effect of magneto-crystalline anisotropy. Even, they were not patterned to have shape anisotropy characteristics. The same large Hc and Mr/Ms at 90° and 270° in the PEN sample can’t be explained simply by the effect of the large roughness of the substrate. Unlike rigid Si/SiO2 substrates, the PDMS, PI, and PEN substrates are deformable substrates which have soft and bumpy surface and have a large interaction with thin films on its when it is being strained. So, the influence due to the stress between the substrate and the thin film acts more strongly than the case of the Si/SiO2 sample, and each substrate has different characteristics. However, the Ta/CoFeB/MgO/Ta thin film may have been formed in a directional shape to be able to have shape anisotropy on the deformable substrate because of the stress as well as the non-rigid surface of the deformable substrates. Therefore, we analyzed that the Ta/CoFeB/MgO/Ta thin film may have the biaxial anisotropy by shape anisotropy owing to the directional shape. It’s just that the size of the shape might have been formed with a micrometer scale or much smaller than that.
If the cause of all these phenomena is more clearly identified and applied, it is expected that various applications will be possible as deformable magnetic sensors. The magnetoresistance depends on the magnetic anisotropy, and it is related to
Hc and
Mr/
Ms [
29,
46,
47,
48]. So, for example, controlling magneto-crystalline anisotropy through annealing or forming shape anisotropy by patterning a magnetic thin film will enable effective magnetic sensors or in-plane angle sensors to be fabricated.
3.4. Strain Effects in the CoFeB Thin Film Sputtered on the PDMS Substrate
The effects of physical deformation (tensile strain in one direction) of the Ta/CoFeB/MgO/Ta thin film sputtered on the PDMS substrate was investigated at the macroscopic and microscopic scales using the SQUID-VSM and MFM, respectively. For each measurement, all stretched samples were placed on 4 mm × 4 mm glass substrates with 5% strain. This method is necessary for accurate measurement of stretchable samples. However, in the case of SQUID-VSM measurement, the magnitude of the detected magnetic moment may vary due to the change in the position of the Ta/CoFeB/MgO/Ta thin film on the sample holder, so it is recommended to apply a normalization operation. In addition, due to the characteristics of SQUID-VSM measurement in which the sample is shaken with rapid vibration of about 80 Hz, the sample must be firmly attached to the glass substrate to prevent separation due to rapid vibration transmitted to the sample. Hence, measuring the change in the properties by bending of the sample was difficult to implement, so it was not carried out. Moreover, even in MFM measurement, the distance between the sample and the tip of the MFM probe must be constant, but it is very difficult to maintain the bent sample at a constant distance.
The overall M–H loops are shown in
Figure 8a with before, with, and after 5% strain. The
Hc of the PDMS sample before and after strain were not significantly different. However, with tensile strain, the
Hc of the sample slightly increased, suggesting that a few grains formed anisotropy in a direction away from the applied direction of the magnetic field. Also, for the same reason, we ensured that strain tends to stabilize in-plane magnetization owing to the induced tensile stress [
49] by confirming that histogram of with strain was firmed high and narrow around 0° phase (
Figure 8b). Only with strain did the magnetic phase deviate from 0 degrees and shifted by 0.04°. It explains that the orientation of magnetic anisotropy has changed.
Table 3.
The Hc and Mr/Ms values with before, with, and after strain of the PDMS sample.
Table 3.
The Hc and Mr/Ms values with before, with, and after strain of the PDMS sample.
Condition |
Hc |
Mr/Ms |
Before strain |
16.12 |
0.645 |
With strain |
29.07 |
0.625 |
After strain |
12.41 |
0.485 |
The histogram of the after strain sample was wide. It was interpreted that the orientation of magnetic anisotropy was affected as the surface of the magnetic thin film became more uneven due to the fine scratches that occurred after stretching the sample. Thus, in order to use this sample as a mechanical strain sensor, it is recommended to artificially damage the sample by repeating the tensile operation several times and use it after the magnetic anisotropy orientation is stabilized. We anticipate that more precise measurement will be possible if a mechanical strain sensor based on spintronic devices is used together with the existing mechanical strain sensor.
The
Hc,
Mr/Ms, and magnetic phase were tuned by the tensile stress applied to the magnetic thin film, indicating that magnetic anisotropy orientation can be tuned by strain. Controlling the magnetic anisotropy is essential for adjusting the performance of the magnetic sensors or mechanical strain sensors [
1,
3].