Applied Surface Science 409 (2017) 194–199

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Full Length Article

Direct observation of hopping induced spin polarization current in

oxygen deficient Co-doped ZnO by Andreev reflection technique
Kung-Shang Yang a , Tzu-Yu Huang a , G.D. Dwivedi a , Lu-Kuei Lin b , Shang-Fan Lee b ,
Shih-Jye Sun c , Hsiung Chou a,∗
a
Department of Physics, National Sun Yat-sen University, Kaohsiung, Taiwan
b
Institute of Physics, Academia Sinica, Taipei, Taiwan
c
Department of Applied Physics, National University of Kaohsiung, Kaohsiung, Taiwan

a r t i c l e i n f o a b s t r a c t

Article history: Oxygen vacancy induced ferromagnetic coupling in diluted magnetic oxide (DMO) semiconductors have
Received 18 August 2016 been reported in several studies, but technologically more crucial spin-polarized current (SPC) is still
Received in revised form 8 January 2017 under-developed in DMOs. Few studies have claimed that VRH mechanism can originate the SPC, but,
Accepted 27 February 2017
how VRH mechanism associated with percolation path, is not clearly understood. We used Point-contact
Available online 28 February 2017
Andreev reflection (PCAR) technique to probe the SPC in Co-doped ZnO (CZO) films. Since the high resis-
tance samples cause broadening in conductance(G)-voltage(V) curves, which may result in an unreliable
Keywords:
evaluation of spin polarization, we include two extra parameters, (i) effective temperature and (ii) spread-
Andreev reflection
Spin polarization
ing resistance, for the simulation to avoid the uncertainty in extracting spin polarization. The effective G-V
curves and higher spin polarization can be obtained above a certain oxygen vacancy concentration. The
number of completed and fragmentary percolation paths is proportional to the concentration of oxygen
vacancies. For low oxygen vacancy samples, the Pb-tip has a higher probability of covering fragmentary
percolation paths than the complete ones, due to its small contact size. The completed paths may remain
independent of one another and get polarized in different directions, resulting in lower spin-polarization
value. High oxygen vacancy samples provide a high density of completed path, most of them link to one
another by crossing over, and gives rise to high spin-polarization value.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
After metallic ferromagnets proved their potential applications
in spintronic devices [1], semiconductor-based ferromagnets, such
as dilute magnetic oxides (DMOs), began to gain attention over
the past few decades due to their ability for use at room tem-
perature [2,3]. Even though DMOs have been studied vigorously,
most studies have mainly focused on the origin of its ferromag-
netism. From an application point of view, the most important
issue is improving the performance of the current-driven spintronic
devices by increasing the spin polarization (P) of the transport
current. However, only very few studies have focused on direct
measurements of spin-polarized current (SPC) in DMOs [4–6].
There are few methods to determine P, such as spin-dependent
tunneling [7], spin-resolved photoemission [8] and the Andreev
reflection (AR) at the superconductor/ferromagnet interface [9,10].
∗ Corresponding author.
E-mail address: hchou@mail.nsysu.edu.tw (H. Chou).
Point contact (PC) Andreev reflection technique is the one can
directly measure SPC on the original format of the film without
undergoing a complicated fabrication process, but instead by only
using a sharp superconductor tip to make a point contact with
the magnetic films. Andreev reflection generates a hole current
when an incident normal current is converted to a supercurrent
at the normal-metal/superconductor interface. The process can be
described as an incident electron from one of the spin density of
states (DOS) at EF moving into the superconductor, where a super-
conducting pair is formed. To form the superconducting pair, the
other electron with opposite spin and momentum state must exist
inside the superconductor. To compensate for the newly-formed
electron pair, a hole must be generated at the normal metal site of
the interface which has an identical spin state as the newly formed
electron but moves in a direction opposite to the incident electron.
Since the majority and minority spin DOS at EF are equal (P = 0%)
for a normal metal, AR holes can transport through normal metal
and act as an extra channel for electric conduction, which doubles
the normal-state conductance (G) when the applied voltage < the
superconductor gap (). This process is called Andreev reflection

http://dx.doi.org/10.1016/j.apsusc.2017.02.230
0169-4332/© 2017 Elsevier B.V. All rights reserved.
 K.-S. Yang et al. / Applied Surface Science 409 (2017) 194–199
[11]. In contrast, for a ferromagnet with P = 100% at EF , no other
spin states to the incident spin state are available for reflected holes
to transport, so the AR is blocked and the conductance is severely
suppressed [9,10].
Since the first experimental study was reported [9,10], this tech-
nique has mainly focused on low resistance samples. Coey et al. [10]
used PCAR to determine the spin polarization in CrO2 and obtained
90% spin polarization. Braden et al. [12] studied the SPC in GaM-
nAs film through fabricating a plane structure with a large area,
instead of cross-stripe geometry, to efficiently reduce the junction
resistance; they thus obtained 90% spin polarization. Yates et al. [5]
studied the spin-polarized current in Mn-doped ZnO films through
the PCAR technique. But the dilute magnetic oxides (DMOs) based
on ZnO (Zn1-X CoX O and Zn1-X MnX O) usually accompany large resis-
tances in the semiconducting state, which makes it more difficult
to probe spin polarization by PCAR. Therefore, Yates co-doped 1%
Al to bring the sample to a metallic state. The spin polarization was
only exhibited in Mn and Al co-doped ZnO films and the maximum
spin polarization was 55%, while no SPC was detected for Al-doped
ZnO films. This result suggests that Mn plays a key role in the origin
of ferromagnetic coupling and spin polarization.
As mentioned, DMO in the semiconducting state possesses rel-
atively high resistance; therefore, reports on direct probing of spin
polarization by PCAR are rare. Xu et al. [4] observed tunneling
magnetoresistance in a magnetic tunnel junction realized by using
Co-doped ZnO as the bottom layer and Co metal as the top fer-
romagnetic electrode. In addition, studies [13–15] have suggested
that doping single Co element without involving oxygen vacancies
into a ZnO system cannot effectively produce ferromagnetic cou-
pling. According to our previous study [16,17], the oxygen vacancy
(VO ) could produce localized states and even create many perco-
lation paths to enhance the SPC. Percolation paths of the present
samples have widths in the nanometer scale. Some percolation
paths run throughout a sample and some percolation paths are the
short forming fragmentary type of paths. To be able to probe spin
polarization current, it is crucial to identify the effects of contacts
that cover mostly completed or mostly fragmentary paths. Prob-
ing of various spots is necessary to collect all types of data curves
for various contacts and understand its effects. Among of these
contacts, the effective ones that reflect the intrinsic spin polar-
ization current must be identified for the next step to evaluate
the spin polarization value of the sample. The theory models, the
Mazin’s modified-BTK [18] model in ballistic and diffusive limits
(formula is shown in Table 1), must also be modified to meet the
high resistance property of the present samples. The high resis-
tance of samples could cause local Joule heating around the apex,
with extra resistance coming from current spreading in the film.
Hence, we incorporate two extra parameters, those of the spreading
resistance () [19] and the effective temperature (Teff ) [20], to the
Table 1
The total interface current in different regimes: BNM = ballistic nonmagnetic;
 nonmagnetic; DHM = diffusive half-
BHM = ballistic half-metallic; DNM = diffusive
   2
−1
metallic. Where F (S) = cosh 2Z 2 + s / 2Z 2 + s
E <
 
2 1+ˇ 2
BNM  2
ˇ2 + 1 + Z 2
BHM 0 contact fails and the measured G-V curves exhibit wide spectra
1+ˇ     
DNM Im F −iˇ − F iˇ
2ˇ
DHM 0 ˇF
195
modified-BTK model. Our results reveal that the ballistic limit data
spectra fitting are in better agreement than those of the diffusive
limit in terms of the fitting curves, as well as the ballistic limit pro-
ducing higher spin polarization. This suggests that our films have
neither oxidized surfaces due to exposure in atmosphere nor any
high barrier strengths at the contacts which result from a Fermi
velocity mismatch between the superconducting-tip/CZO-surface.
As the concentration of VO of CZO increases, the SPC is enhanced.
This can be attributed to the increase in VO causing an increase in
completed percolation paths in the film for carrier hopping.
2. Experiment
Zn0.95 Co0.05 O (CZO) films with varying VO were grown on a
fused quartz substrate by using magnetron sputtering. Films were
grown in (H2 + Ar) atmosphere, where H2 :Ar ratios were varied
as 5%, 10%, 20% and 30%, to manipulate the concentration of the
VO . In other words, VO increases in the films with increasing H2 %
in the growth atmosphere. The existence of VO was confirmed
by optical transmittance and XPS measurements [16] CZO films
grown at a specific H2 % are denoted as CZO-#% throughout this
paper. Films were grown at room temperature, unlike other high-
temperature processing conditions, to reduce the possibility of
hydrogen doping into the films. The possible existence of Co clus-
ters and hydrogen incorporation into the films were excluded
by X-ray diffraction measurements [16]. Extended X-ray absorp-
tion fine spectra (EXAFS) and X-ray absorption near edge spectra
(XANES) at Co K-edge confirmed that Co substituted at the Zn-site
[16]. A superconducting Pb-tip was formed by sharpening a Pb wire
(purity 99.9% and diameter 2 mm) with scissors. The apex of the
sharpened tip was approximately a few microns or less. The tip
was fixed on a holder which moved towards the film surface by
0.04375 mm per revolution of the differential screw. The sample
was attached to a stage and immersed into liquid helium to set
the measurement temperature at 4.2 K. The contacts were made by
carefully rotating the differential screw until an electric conduc-
tion was observed. A three-step delta technique [21] was used to
measure the current (I) as a function of applied voltage on the point
contacts. Each I–V curve was taken first order differential to convert
to G and normalized by its high-bias value for further analysis.
3. Results and discussion
To distinguish fine differences of each initial contacts, we mea-
sured a G-V curve each time when the tip touched the film surface.
After obtaining effective contacts, a series of G-V curves were mea-
sured by pressing the Pb-tip further into the films. Generally, the
sharper Pb-tip provides a smaller contact size, and the smaller
contact area limits the transport channels, which result in larger
contact resistance. For a ballistic contact, the contact size must be
smaller than the mean free path of the carriers to reduce the possi-
bility of inelastic scattering and measurement noise at the contact
interface due to the inelastic scattering. Therefore, the effective
− 1.
contact is defined when the recorded G-V curves can be described
by two criteria: (1) a narrow G-V curve to meet the narrow energy
E <
gap, ∼1.35 eV, of the superconducting Pb-tip at 4.2 K; and (2) a rel-
2ˇ atively high contact resistance to fulfill the basic requirement of
1 + ˇ + 2Z 2 the ballistic tunneling limit. To illustrate various contacts, several
contact G-V curves of CZO-30% are shown in Fig. 1 If the initial
2ˇ
1 + ˇ + 2Z 2
  (green circle or the pink square curves) then raise the Pb-tip and
2ˇF ˇ
 2  move to another point to make another contact. If the contact is
1+ˇ good, such as that denoted by the red star curve where the contact
−1
2 resistance is as large as 1.93k, the suppression of G-V curve at
zero-bias will be the deepest and its width will be the narrowest of
196 K.-S. Yang et al. / Applied Surface Science 409 (2017) 194–199
Fig. 1. Experimental Conductance (G) – Bias (V) curves obtained from repeated con-
tacts between Pb-tip and CZO-30% film. The green circles, pink squares, and red stars
are the G-V curves for initial contacts. The green circle and pink square curves with
wider FWHH and lower contact resistances represent bad contact conditions. The
red star curve with narrow FWHH and large contact resistance represents good
contact condition. After obtaining good contact, many measurements were taken
by further pushing Pb-tip toward the film until broadening G-V curves (black trian-
gle and blue circle curves) were observed indicating over contact conditions. (For
interpretation of the references to colour in this figure legend, the reader is referred
to the web version of this article.)
Fig. 2. G-V spectra of CZO-5%, 10%, 20% and 30% show different conductivities.
Severe suppression of G(0) value and narrow spectra can be obtained by increasing
the number of oxygen vacancies. Inset plot shows the variation of FWHH of G-V
curves with oxygen vacancies.
the series of measurements. When a good contact is secured, the
Pb-tip is pushed down several times further into the film to collect
G-V curves. When the Pb-tip penetrates into the film to the state
where the Pb-tip is flattened, the contact resistance will decrease
and the G-V curves will become wider, shown as the black triangle
and blue circle curves, indicating a contact diameter larger than the
mean free path of carriers. The effective G-V curves of one sample
were collected from several measurements with effective contacts.
The present samples contain various oxygen vacancies and show
very different conductivities. The G-V curves of each sample, along
with their contact resistances, are shown in Fig. 2 Contact resis-
tances of CZO-5% and −10% samples, shown as the blue and green
triangles in Fig. 2, are as high as 46 k and 16 k, respectively.
As the result, those G-V curves have high contact resistance are
relatively wide. In contrast, the CZO-20% and −30% samples mani-
fest the narrowest dip in G-V curves. Their full width at half height,
FWHH, as a function of H2 %, are plotted in the inset of Fig. 2 The CZO-
5% sample shows FWHH of 25 mV, which drops quickly to nearly
5 meV for CZO-20% and −30% samples, moreover, CZO-5% and −10%
curves do not show flat features in high voltage range (higher than
15 mV) and the slopes of CZO-5% and −10% conductance curves
vary slower than CZO-20% and −30% curves. Both features exhibit
high resistance of CZO-5% and −10% samples, while applied exter-
nal electric field on CZO-5% and −10% samples could not provide
adequate electrons to convert into the supercurrent. This results
in even worst yield of Andreev reflection probability in the super-
conducting gap energy range, which can be easily canceled out by
the other electrons. Therefore, we can conclude the dip in the G-V
curve of CZO-5% and −10% is due to the relatively less change in
slope of I–V curve (high resistance) and could not provide reliable
P. Therefore, we exclude CZO-5% and −10% G-V curves and focus
on analysis of CZO-20% and −30% curves. A previous study [22] has
suggested that the G value at V = 0 (G(0)) is a guide toward the P
value. Severely decreasing G(0) values can lead to high spin polar-
ization. The suppression of G(0) of the CZO-30% sample in Fig. 2,
at about 0.82, is deeper than that of the CZO-20% sample, at about
0.95, which suggests the CZO-30% sample carries a higher percent-
age of spin polarization current than does the CZO-20% sample.
The mechanism responsible for this reinforcement in spin polar-
ization current will be explained in the following paragraphs for
the CZO-20% and CZO-30% samples.
The original Blonder-Tinkham-Klapwijk (BTK) [23]
model only considered electric tunneling at the normal-
metal/superconducting interface when the point contact size
was smaller than the mean free path of electrons, or the ballistic
limit. In order to interpret the spin polarization of a ferromagnetic
material in a point contact with a superconducting tip, Strijkers
et al. adopted the original BTK model and modified it for a fer-
romagnetic state [24] by considering the current which crosses
the interface as a sum of polarized and unpolarized spin currents;
this is termed as the modified BTK model (MBTK). As mentioned
earlier, DMO with high resistance introduces intensive scattering
which broadens and smears out the characteristics of G-V curves.
To consider the broadening effect, in addition to the conventional
MBTK parameters of spin polarization, P, superconducting gap, ,
and interface barrier strength, Z, we add two extra parameters:
the spreading resistance  [19] and the effective temperature Teff
[20] for both ballistic and diffusive limits [18].
More specifically, when the current tunnels through the small
contact area into a film with relatively high resistance, the Joule
heating effect will act as a spreading resistance sandwiched
between the superconducting tip and the film. The temperature of
the interface at the contact point will be altered due to this strong
Joule heating effect; therefore, an effective temperature is needed
as an extra parameter. Since the present samples exhibit large resis-
tance, the current in the film around the superconducting tip apex
will spread over a certain range before returning to the direction of
the current flow at the film’s surface. These additional resistances,
as suggested by Chen et al. [25], can be attributed to the spread-
ing resistance effect as well. Both the spreading resistance and the
effective temperature will broaden and reduce the depth of the G-V
curve.
In reality, it is hard to judge whether the contact is closer to the
ballistic or to the diffusive limit. Woods et al. found that the data
curve generated by a diffusive model can be fitted by the ballistic
model with a different Z value [26]. Based on this observation, we
used both models to fit our data to confirm which model better
fits our data. To reduce the uncertainty of fitting parameters and to
consider samples with large resistances and a Joule heating effect,
we fixed the superconducting band-gap of Pb at 1.35 meV instead
of fitting all the parameters simultaneously. In addition, as men-
tioned, G(0) is a guide leading to the P value. Therefore, the various
kinds of refinements introduced should at least show a good fit
to the experimental G(0) value to avoid an unreasonable P value.
Under this constraint, we illustrate how the effective temperature
and the spreading resistance affect the G-V spectra in ballistic and
diffusive limits, as shown in Fig. 3 One of the CZO-30% G-V spectra,
for example, is fitted by three different combinations of Teff and .
The black curve involves only a Teff parameter and does not fit the
width of the G-V curve well. The blue curve shows an approach with
fixed experimental temperature of 4.2 K, which can only reproduce
the G(0) value but fails to fit the turning points and the width of
 K.-S. Yang et al. / Applied Surface Science 409 (2017) 194–199 197

Fig. 3. Fitting results of an experimental curve when added one parameter of Teff ,
the black dash-dotted line, or (, the blue dashed line, and both Teff ,  parameters,
the red solid curve, as variables in the ballistic limit (a) and in the diffusive limit
(b). (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

the experimental curve. The red curve in Fig. 3(a) is the best fit
in the ballistic limit, including both Teff and  parameters. A simi-
lar result can be found in the diffusive limit, as shown in Fig. 3(b).
The blue curve shows an approach involving only the  parameter.
The fitting results show worse fitting at the turning points and the
width of the curve; as a result, the obtained P value is severely sup-
pressed. From Fig. 3, we can clearly see that including both Teff and
 parameters are crucial for a good data fit. However, the P value
may be overestimated when its calculation involves both Teff and 
parameters. To avoid this inaccuracy, smaller Teff and  values were
chosen in order to increase the accuracy of the P value that can be
obtained. Fortunately, we collected several G-V curves that exhibit Fig. 4. Fitting results of experimental PCAR curves of CZO-30%, with a hump (a) or
narrow and deep features to ensure a good fit and reasonable P without hump (b), and CZO-20% (c) in ballistic and diffusive limits.
values.
Among all G-V curves for the CZO-30% sample, two kinds of G-V
curves were observed. One shows two humps at the turning points, Following the fitting processes and considerations as aforemen-
as marked by two red triangles in Fig. 4(a), and the other shows two tioned, the two types of G-V curves of the CZO 30% sample were
plateaus in the high voltage regions, as shown in Fig. 4(b). These fitted with both ballistic and diffusive limits and are shown in
humps may be caused by the large interface barrier strength or by Fig. 4(a) and (b). Accordingly, both limits exhibit a similar good fit in
the mismatch between the Fermi velocities of the superconduct- the −/e < V < /e region. The key feature of the diffusive model is
ing tip and the ferromagnetic film across the contact point [27]. two humps at around ±/e, even when the Z value is small. How-
Since the latter is an intrinsic property of the film, it should affect ever, most of our data curves did not contain humps; therefore,
all measurements. The fact that there are two types of G-V curves we conclude that our measured G-V curves have a good agreement
suggest that the former, that of a large interface barrier strength, with the ballistic limit [in Fig. 4(b)], which indicates most of the
is the reason for the observed humps, especially when the contact present contact points are free from oxidation and the extracted Z
situation varies with different Pb-tips. values are approximately zero. In addition, we have also obtained
198 K.-S. Yang et al. / Applied Surface Science 409 (2017) 194–199
0.8
CZO-30%-Ballistic
CZO-30%-Diffusive
0.7
CZO-20%-Ballistic
CZO-20%-Diffusive
0.6
Pol a r i za t i o n
0.5
0.4
0.3
0.2
0.1
0.0
0.0 0.2 0.4 0.6 0.8 1.0
Z
Fig. 5. P versus Z results collected from a simulation of PCAR spectra in ballistic
and diffusive limits. For CZO-30%, linear extrapolations to Z = 0 give 73% and 65%
in ballistic and diffusive limits, respectively. For CZO-20%, all of the points are very
close to Z = 0 and give 62% and 43% in ballistic and diffusive limits, respectively.
some spectra containing humps [Fig. 4(a)], which indicates that
spectra with different tip conditions could introduce different lev-
els of scattering or barriers at the interface, causing these humps
to appear at around ±/e. On the other hand, none of our CZO-20%
G-V curves exhibit a hump, which can be attributed to the good sur-
face conditions. But the probability of obtaining an effective contact
is less than in CZO-30% due to fewer percolation paths; therefore, no
curves with humps were obtained. Fig. 4(C) shows the one CZO-20%
curve fitting result. The ballistic approach shows better agreement
as well. The turning point range for the diffusive approach, how-
ever, does not fit well, which suggests that the diffusive approach
is a poor choice for CZO-20%.
All of our present spectra have shown a broadening effect,
which makes extracting a reliable spin polarization more diffi-
cult. However, in Barden’s experiments [12], they used a trilayer
heterostructure with a large area to reduce the measurement resis-
tance. Even the Fermi velocity mismatch between the Ga layer and
the Ga1-x Mnx As layer is large. G-V spectra with no hump still can
be obtained. This suggests that the highly suppressed G value can-
not attribute to the barrier strength or Fermi velocity mismatch,
but rather to the high spin polarization of the Ga1-x Mnx As layer. In
contrast, the FWHH of T. W. Chiang’s [25] G-V are around 5 mV and
G(0) is around 0.87. The FWHH of Barden’s G-V spectra is around
1 mV and G(0) is around 0.25. This huge difference is due to the
sample resistance and experimental temperature. Even though the
G-V spectra exhibit such large differences, their simulations pro-
vide nearly the same P values, which suggests that AR is not only
very sensitive to interface condition and simple resistance but also
to the spin polarization of the ferromagnet. A similar situation can
be seen in our study. Therefore, even for our sample with large resis-
tance which causes the broadening effect, we still rely on the MBTK
model in the ballistic limit to provide the optimal interpretation of
our AR measurements.
The extracted P values versus Z values of CZO-30% and 20%
are plotted in Fig. 5. Currently, there are no absolute extrapola-
tion processes, either quadratic [27], linear [23] or spin flip [29]
dependent approaches, which describe the P-Z relationship for all
systems. Some papers have found that the high resistance con-
tact increases the difficulty in estimating correct spin polarization
[21,28,30]. Regardless of which extrapolation approach is used, the
guiding concept is to set the polarization value, when Z = 0, to be
the spin polarization value of the sample. For CZO-30% G-V spectra,
many data points are very close to zero, with only a few having a
Fig. 6. Schematic diagram of percolation paths in CZO-20%, formed by oxygen
vacancies (a) and CZO-30% (b). Red cones demonstrate the Pb-tip that has an effec-
tive contact area as a circle. Pink dashed cone demonstrates that the contact area
poorly covered percolation paths, which reduces the spin polarization. (For inter-
pretation of the references to colour in this figure legend, the reader is referred to
the web version of this article.)
larger Z value. Therefore, we use dashed lines as visual guidelines
to extrapolate the Z-P relationship. The ballistic limit gives rise to a
polarization of 73%, higher than that of the diffusive limit of 65%. For
CZO-20% curves, the large Z value data points are not available, and
the ballistic limit and the diffusive limit give polarization of 62% and
43%, respectively. As mentioned, the ballistic limit approach can
consistently fit CZO-30% and CZO-20% G-V spectra, but the diffu-
sive limit approach shows a worse fitting result with CZO-20% G-V
spectra. Thus, we can reasonably take the spin polarization values of
the ballistic limits as the measured values for the present samples.
The analysis shows that the spin polarization increases from 62% to
73% for the CZO-20% and the CZO-30% samples, respectively. The
higher the concentration of oxygen vacancies, the larger the spin
polarization.
Our previous finding [16,17] that temperature dependence of
conductivity could be fully explained by a combinational model of
VRH and the thermal excitation mechanisms. Our results show that
the VRH channel is the major electric conduction over the thermal
excited channel at low temperature. The present PCAR experiment
was done at low temperate, which is probing the channel just the
same as the VRH channel. For the thermal excited channel, the
electron transport in conduction band is a normal current with-
out spin preference for the Zeeman splitting of the conduction
band is negligible comparing to the hopping channel. Therefore, the
VRH mechanism is definitely the major channel for spin polarized
current. Those studies support the concentric bounded magnetic
polaron model [31], in which the shallow oxygen vacancies act
as localization sites that allow localized carriers to hop from site
to site via a variable range hopping mechanism. Since the shal-
low oxygen vacancy states overlap with the narrow Co 3d-t2g↓
empty subband, the spin of those hopping carriers is polarized.
The hopping conduction then becomes a spin polarized current.
This mechanism is illustrated in Fig. 6. For the CZO-20% sample, the
density of oxygen vacancies acts as shallow localized sites are suf-
 K.-S. Yang et al. / Applied Surface Science 409 (2017) 194–199
ficiently over the percolation limits such that there are chances for
the localized sites to locate within the hopping range and form a
percolation path across the samples, shown as the long percolation
path in Fig. 6(a). The carriers can hop by the variable range hop-
ping mechanism along this path to mediate spin coupling and to
form spin polarization current. Fragmentary localized paths, such
as the short percolation path in Fig. 6(a), cannot contribute fer-
romagnetic coupling and spin current. The polarization direction
of isolated paths may be different. Since the density of percola-
tion paths are very diluted and the width of percolation paths
are very narrow (a few nm in scale), a large Pb contact, repre-
sented as cones with flat bottom surfaces in Fig. 6, may contact
at a point lacking completed percolation paths or containing only
fragmentary percolation paths, as the dashed purple cone shows.
As a result of this situation, the initial contact is poor and the elec-
tric conductivity is mainly contributed by the leakage currents or
a combination of several fragmentary percolation paths, as shown
in bad contact G-V curves (Fig. 1). When the contact point moves
to an effective point, as the red cones, it covers a complete perco-
lation path, perhaps together with some other short paths; then
the electric conductivity is mainly contributed by the VRH hop-
ping off the long-percolating path. Therefore, the spin polarization
is 61% for the CZO-20% sample. By increasing oxygen vacancies, the
CZO-30% sample contains a higher concentration of shallow oxygen
vacancies states and therefore higher number of concentrated BMP
spheres and completed percolation paths, as shown in Fig. 6(b). The
completed percolation paths have the very high possibility to cross
over each other and are polarized in the same direction. Therefore,
the effective contact may cover a higher density of crossed com-
pleted percolation paths and very few fragmentary paths, and the
spin polarization shows very high value (73%).
In summary, some oxygen vacancies introduced intentionally
during growth behave as localization sites for carriers to hop on
them. However, the localization sites distribute unevenly. When
the localization sites are slightly more than the percolation limit,
a combination of completed and fragmentary percolation paths is
formed. The completed percolation path mediates spin polarization
current while those fragmentary ones along with current leakage
can also carry part of current with no polarization preference. At
this stage, the use of PCAR to measure the spin polarization value
needs special care in order to extract the intrinsic spin polarization
value of the sample. For samples with very high oxygen vacancies
or localization sites, high density of completed percolation paths
may cover most of the surface area and has very high possibility
to cross over one another. Those paths may couple to one another
via crossover points and align their spin polarization to the same
direction to promote the spin polarization value of the sample. This
study reveals that the PCAR is a sensitive tool to investigate the spin
polarization current. With very careful analysis of the G-V curves
upon each contact, we were able to identify an effective contact
by means of G-V curve width. Including the spreading resistance
and the effective temperature as two extra parameters for simula-
tion are crucial, especially for the present samples with very high
199
resistance. The present results indicate that a higher spin polariza-
tion can be obtained by increasing oxygen vacancy concentration,
which equivalent to increasing the number of completed percola-
tion paths.
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