Application of the double relaxation oscillation superconducting quantum interference

device sensor to micro-tesla 1H nuclear magnetic resonance experiments

Chan Seok Kang, Kiwoong Kim, Seong-Joo Lee, Seong-min Hwang, Jin-Mok Kim, Kwon Kyu Yu, Hyukchan
Kwon, Sang Kil Lee, and Yong-Ho Lee

Citation: Journal of Applied Physics 110, 053906 (2011); doi: 10.1063/1.3626826

View online: http://dx.doi.org/10.1063/1.3626826
View Table of Contents: http://scitation.aip.org/content/aip/journal/jap/110/5?ver=pdfcov
Published by the AIP Publishing

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 JOURNAL OF APPLIED PHYSICS 110, 053906 (2011)

Application of the double relaxation oscillation superconducting quantum

interference device sensor to micro-tesla 1H nuclear magnetic resonance
experiments
Chan Seok Kang, Kiwoong Kim,a) Seong-Joo Lee, Seong-min Hwang, Jin-Mok Kim,
Kwon Kyu Yu, Hyukchan Kwon, Sang Kil Lee, and Yong-Ho Lee
Brain and Cognition Measurement Lab, Korea Research Institute of Standards and Science,
Deajeon 305-340, South Korea
(Received 15 June 2011; accepted 22 July 2011; published online 8 September 2011)
We developed an ultra-low field (ULF)-nuclear magnetic resonance (NMR) measurement system
capable of working with a measurement field (Bm) of several micro-tesla and performed basic
NMR studies with a double relaxation oscillation superconducting quantum interference device
(DROS) instead of conventional dc-SQUIDs. DROS is a SQUID sensor utilizing a relaxation
oscillation between a dc-SQUID and a relaxation circuit; the new unit consists of an inductor and a
resistor, and is connected in parallel with the SQUID. DROS has a 10 times larger flux-to-voltage
transfer coefficient (mV/u0) than that of the dc-SQUID, and this large transfer coefficient enables
the acquisition of the SQUID signal with a simple flux-locked-loop (FLL) circuit using room
temperature pre-amplifiers. The DROS second-order gradiometer showed average field noise of 9.2
lu0/HHz in a magnetically shielded room (MSR). In addition, a current limiter formed of a
Josephson junction array was put in a flux-transformer of DROS to prevent excessive currents that
can be generated from the high pre-polarization field (Bp). Using this system, we measured an 1H
NMR signal in water under 2.8 lT Bm field and reconstructed a one-dimensional MR image from
the 1H NMR signal under a gradient field BG of 4.09 nT/mm. In addition, we confirmed that the
ULF-NMR system can measure the NMR signal in the presence of metal without any distortion by
measuring the NMR signal of a sample wrapped with metal. Lastly, we have measured the scalar
J-coupling of trimethylphosphate and were able to confirm a clear doublet NMR signal with the
coupling strength J3[P,H] ¼ 10.4 6 0.8 Hz. Finally, because the existing ULF-NMR/MRI studies
were almost all performed with dc-SQUID based systems, we constructed a dc-SQUID-based
ULF-NMR system in addition to the DROS based system and compared the characteristics of
the two different systems by operating the two systems under identical experimental conditions.
C 2011 American Institute of Physics. [doi:10.1063/1.3626826]
V

I. INTRODUCTION To overcome these shortcomings and also to reduce pro-

duction and maintenance costs, low-field MRI systems oper-
A magnetic resonance imaging (MRI) system is a device
ating with millitesla to sub-millitesla level B0 fields using
capable of three-dimensional imaging of certain atomic
resistive magnet coils or permanent magnets in place of the
nuclei, usually hydrogen, in a target object. Due to its ability
expensive superconducting magnet coil of the conventional
to provide detailed images from deep inside the human body
high-field MRI have been consistently proposed,4–7 and,
in a completely noninvasive manner, the MRI system
recently, ultra-low field MRI (ULF-MRI) systems with
became an important part of standard medical diagnosis
microtesla B0 field have been introduced.8–13
tools. The sensitivity of the conventional MRI system, which
The most important aspect of these ULF-MRI systems is
picks up nuclear magnetic resonance signals with an RF
their ability to produce strong magnetic resonance (MR) sig-
receiver coil, is proportional to the magnetization of the
nals from samples while keeping B0 low, down to the several
object as well as its resonance frequency. Therefore, most
microtesla level. The pre-polarization method4,7 achieves this
conventional MRI systems employ a superconductor magnet
by separating the main magnetic field into two parts, one pro-
coil capable of producing the B0 field of up to a few tesla to
viding a micro-tesla level measurement field (hereafter
increase the magnetization. This superconductor magnet
denoted as Bm field) that induces nuclear spin precession, and
constitutes the major part of the production and maintenance
the other providing a much stronger (up to a few tenths tesla)
cost of an NMR/MRI system.1 In addition, while the strong
pre-polarization field (hereafter denoted as Bp field) that mag-
B0 field improves MRI sensitivity, it also produces artifacts
netizes or pre-polarizes the sample prior to measuring the MR
due to the increase in susceptibility change from the strong
signal. In this method, the magnetization of the sample
B0 field, making the system unsuitable for imaging cellular
depends solely on the Bp field, while MR characteristics
tissues or cancer cells.2,3
depend solely on the Bm field. Then, the Bp field can be much
stronger than the Bm field since it is turned off after providing
a)
Electronic mail: kwkim@kriss.re.kr. the sample with the magnetization needed to produce MR;

0021-8979/2011/110(5)/053906/9/$30.00 110, 053906-1 C 2011 American Institute of Physics

V

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 053906-2 Kang et al.
after it is turned off, it does not interfere with the Bm field or
with the MR signal measurement process. Therefore, such a
ULF-MRI system using pre-polarization method has a much
larger range of magnet arrangement for the Bm field genera-
tion. Also, the pre-polarization coil can be built in a much
simpler way, with significantly relaxed geometric require-
ments, since the Bp field needs not to be as homogeneous as
the B0 field of the conventional high-field MRI.
Meanwhile, the Faraday induction coil used in the conven-
tional high-field MRI as the receiver, however, cannot be used
to acquire such a low frequency resonance signal corresponding
to micro-tesla Bm field, since its sensitivity is proportional to
the MR frequency in addition to the magnetization. In order to
overcome this problem, many ULF-MRI systems utilize a
superconducting quantum interference device (SQUID), whose
sensitivity is independent of the MR frequency, to directly mea-
sure the magnetic resonance precession so that lower resonance
frequencies do not degrade the sensitivity.14
While the SQUID sensor allows magnetic field measure-
ment with high precision, its superior sensitivity makes its
operation under a high magnetic field variation highly prob-
lematic. Therefore, to incorporate SQUID sensors into ULF-
MRI systems, additional protective measures are necessary
for the SQUID sensors to operate under the highly variable
magnetic field environment required for ULF-MRI opera-
tion. One such design is to protect the SQUID sensors from
the external magnetic field. A SQUID sensor usually consists
of a SQUID and a flux transformer, which is a superconduct-
ing loop consisting of a pickup coil and an input coil, in
which the input coil is inductively coupled to the SQUID.15
A superconducting shield wraps the SQUID and the input
coil completely, with only the pickup coil being located out-
side the shield. This design can prevent a strong external
magnetic field from influencing the SQUID directly.16 But
since the pickup coil is still placed outside the shield, it will
relay the external magnetic field as a current flowing along
the superconducting flux transformer loop and feed it to the
SQUID via the input coil-SQUID inductive coupling. Since
this design cannot protect the SQUID from the excessive
current induced by the strong external magnetic field neces-
sary for operating ULF-MRI systems, techniques to limit the
current on the flux transformer loop when the SQUID sensor
does not need to operate, i.e., during the pre-polarization
phase, are also implemented.
Recently, we developed a ULF-NMR/MRI system capa-
ble of working with a Bm field of several to several hundred
microtesla and were able to perform basic nuclear magnetic
resonance (NMR) studies with the system.
In these studies, double relaxation oscillation SQUIDs
(DROS) were used instead of the conventional dc-
SQUIDs.17,18 The DROS has a 10 times larger flux-to-volt-
age transfer coefficient than that of the conventional dc-
SQUID, and this large transfer coefficient permits the
detection of the output signal of the DROS with a simple
flux-locked-loop (FLL) circuit that consists of room tem-
perature pre-amplifiers.19,20 It is a great advantage to con-
struct an economical portable system or a medical
application using many sensing channels. An external feed-
back technique was used to linearize the DROS output
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J. Appl. Phys. 110, 053906 (2011)
signal.21,22 This external feedback is better suited for multi-
channel systems that consist of many SQUID sensors since
it produces less cross talk between adjacent channels than
an internal feedback technique does. In addition, a current
limiter in the form of a Josephson junction array was placed
in the flux transformer loop to prevent excessive current
from affecting the DROS and to improve its stability.23
With the abovementioned DROS ULF-NMR system, we
measured an 1H NMR signal from water under a several
microtesla Bm field and reconstructed a one-dimensional MR
image from the 1H NMR signal under a gradient (hereafter
denoted as BG) field. In addition, we measured the 1H NMR
signal from the water sample that was wrapped with alumi-
num foil of 0.55 mm thickness, and detected a scalar J-cou-
pling, indicating the presence of specific covalent bonds with
the ULF-NMR system in the microtesla Bm field.
In order to compare the performances and characteris-
tics, we conducted the same measurement with a conven-
tional dc-SQUID in exactly the same experimental
environment; the same field shielding condition, cryostat,
pick-up coil etc.
II. EXPERIMENTAL SETUP
A. DROS second-order gradiometer
A DROS second-order gradiometer was chosen as the
NMR signal detector for the ULF-NMR/MRI system. The
DROS gradiometer consists of two parts: a DROS sensor
and a pickup coil. The pickup coil detects changes in the
magnetic flux imposed inside the coil, converts the detected
flux to induced supercurrent, and transfers the energy to the
DROS through lossless inductive coupling.
A DROS sensor usually consists of two hysteretic
dc-SQUIDs: a signal SQUID and a reference SQUID. The
signal SQUID coupled to the input coil of the flux trans-
former and the reference SQUID supplied with a constant
but adjustable magnetic flux.20 In our system, however, the
reference SQUID was replaced with a simple reference junc-
tion.24,25 This measure reduces the possibility of flux trap by
the reference SQUID and can also eliminate the electrical
connections necessary for supplying and adjusting the refer-
ence flux. The DROS was fabricated on a silicon wafer via a
four-level process consisting of: Nb/AlOx/Nb trilayer deposi-
tion, junction area definition via reactive ion etching, SiO2
insulator deposition, Pd resistor deposition, and Nb wiring
deposition.
An axial second-order gradiometer configuration was
chosen for the pickup coil to prevent the first-order gradient
field from contaminating the NMR signal. The coil was
made of a NbTi wire with 125 lm diameter wound on a
fiberglass reinforced plastic (FRP) pipe with 29 mm outer
diameter. The wire was wound on three equidistant planes
across the pipe, once on each of the top and bottom planes
and twice on the middle. The single-turn windings were
wound in a direction opposite to that on the double-turn
winding in the middle. The distance between the winding
planes was 35 mm and the total self-inductance of the coil
was 604 nH. Since self-inductance of the input coil was
196 nH and the mutual inductance between the input coil
 053906-3 Kang et al. J. Appl. Phys. 110, 053906 (2011)

and the signal SQUID of the DROS was 4.78 nH, the mag- TABLE I. Important parameters of DROS second-order gradiometer.
netic field-to-flux transfer coefficient of the flux transformer
Signal SQUID
consisting of the pickup coil and input coil was 0.524 nT/u0.
Critical current 2I0 10  20 lA
Figures 1(a) and 1(b) show an equivalent circuit diagram,
SQUID inductance Lsq 144 pH
and a photograph of a fabricated DROS second-order gradi- bL ( ¼ 2I0  L/U0) 1
ometer. As shown in Fig. 1(b), the DROS part is wrapped bC (¼ 2p  2I0  Rsh  Csq/U0) <1
with the superconductor, Pb of 99.9% purity, to shield the Damping resistor RW 5X
DROS from strong external magnetic fields; only the pickup Reference junction
coil is placed outside the superconductor shield. Table I Critical current Ic2 8  15 lA
summarizes the parameters of this DROS second-order Junction area 5 lm  5 lm
gradiometer. Relaxation circuit
To linearize the signal from the DROS sensor in our Shunt resistor Rsh 1.5 X
study, an external feedback method was used. This external Shunt inductance Lsh 2 nH
Damping resistor Rd 50 X
feedback consists of a secondary coil installed to the flux
Input coil
transformer and a feedback coil inductively coupled to the
Number of turns 20 turns
secondary coil and driven with the sensor output from the Line-width 5 lm
FLL circuit, which contains the linearization part and keeps Inductance Li 196 nH
track of the detected magnetic flux level from the DROS sen- Mutual inductance with SQUID Mi 4.78 nH
sor. In such a configuration, the sensor output signal fed to Damping resistor RX 30 X
the feedback coil tends to nullify the current flowing in the Damping capacitance CX 400 pF
flux transformer via inductive coupling to the secondary coil, Feedback coil
which now forms a part of the flux transformer loop. Such an Mutual inductance with flux transformer Mf 5.44 nH
external feedback based linearization method is especially Flux transformer
advantageous with a multichannel system in which multiple Field gradient-to-flux transformer 0.524 nT/u0
pickup coils attached to their respective sensor channels are
located close to each other. If the currents in the pickup coils
were allowed to flow freely, the inductive couplings between ductive cross-talk, which makes the external feedback based
the closely packed pickup coils could give rise to inductive linearization method even more effective.
cross-talk between the individual channels. Without the cur-
rent nulling that the external feedback linearization is capa-
B. Current limiter
ble of, the current induced by the external magnetic flux on
one pickup coil can produce a stray magnetic field that Due to its extreme sensitivity, SQUID cannot operate in
affects the other pickup coils, effectively creating inductive a stable manner under strong magnetic fields and should be
cross-talk between the sensor channels. Furthermore, in protected against such fields. One way to achieve such a
cases in which a superconducting shield is placed around the high-field protection is to limit the current flowing in the flux
DROS sensors, the shielding effect tends to increase the in- transformer so that strong magnetic fields detected by the
pickup coil are not transferred to the SQUID. A Josephson
junction, due to its small and well-defined critical current,
below which the junction is superconducting but which
otherwise behaves as an ordinary resistor, can be used to
implement such a current limiter.23 The actual current limiter
implemented and used in the experiments is composed of a
Nb/AlOx/Nb junction and consists of 20 Josephson junctions
in series array to improve current cut-off efficiency. The area
of a single Josephson junction is 5 lm  5 lm; its critical
current is approximately 10 lA, and its normal state resist-
ance RN is 100 X.
The current limiter cuts into the flux transformer in se-
ries; it is located between the pickup coil and the input coil,
and the connection between the elements and the flux trans-
former is made via superconducting Nb wires of diameter
25 lm with ultrasonic bonding. The current limiter, along
with the DROS, is shielded with a superconducting shield
made of 99.9% pure Pb. The pickup coil was placed about
20 cm away from the superconducting shield to reduce its
influence on the pickup coil. Figure 2(a) shows the detail
FIG. 1. (Color online) Equivalent circuit diagram DROS second-order gra-
diometer (a), and photograph of a fabricated DROS second-order gradiome-
view of the fabricated Josephson junction array and Fig.
ter (b). All parts of DROS second-order gradiometer except the pick-up coil 2(b) shows the current limiter and the DROS inside the Pb
are wrapped with a superconducting shield. shielding shield.

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 053906-4 Kang et al. J. Appl. Phys. 110, 053906 (2011)

the center. This field gradient corresponds to the relaxation

frequency change per space of 0.1741 Hz/mm.
The pre-polarization, measurement, and gradient field
coils had their current supplied by a 12 V lead-acid battery
placed outside the magnetically shielded room (MSR) and
controlled by MOSFET-type solid state relays (SSRs), which
prevent surge voltage while switching the currents to the
coils on and off. The SSRs were controlled remotely via
optical fibers to prevent outside electronic noises from con-
taminating the generated magnetic fields. The switching time
of the SSR was less than 5 ms.
Figure 3(a) shows the pickup coil in the DROS axial
second-order gradiometer and the directions of the Bp, Bm,
FIG. 2. (Color online) Fabricated Josephson junction array (a), overall and BG fields relative to the coil. Figure 3(b) shows the pulse
image of the Josephson junction array and the DROS (b). Two parts are
superconductively connected with Nb wire and covered with a Pb of 99.9%
sequence for operating each magnetic field. In the figure, the
purity. tp can be changed to the experimental situation, but the tp
was between 5 and 7 seconds in almost all of our studies.
The excessive current cut-off characteristics of the cur- The tG and tFLL were 10 ms, respectively. The BG field, how-
rent limiter were confirmed by investigating the flux-to-volt- ever, is applied only in a MR imaging process.
age modulation curve of the DROS sensor with the current
limiter for which the SQUID sensor output was monitored in III. RESULTS
an open-loop state, i.e., without feedback, while a time-vary- A. Performance of DROS second-order gradiometer
ing magnetic field composed of a dc magnetic field and an ac and current limiter
magnetic field was applied to the pickup coil. The amplitude
of the ac magnetic field was kept small compared to that of The flux-to-voltage transfer coefficient of the DROS
the dc magnetic field. When the current induced in the flux axial second-order gradiometer with the current limiter was
transformer by the dc magnetic field is smaller than the criti- measured at more than 1 mV/u0, which is roughly 10 times
cal current of the Josephson junction, the SQUID output will larger than that of conventional dc-SQUID sensors. A small
correspond to the smaller ac magnetic field input. If, on the
other hand, the dc magnetic field is so high that the induced
current becomes larger than the junction critical current, the
whole flux transformer stops superconducting with the junc-
tion array, dissipating the current via ohmic heating, result-
ing in the SQUID output no longer corresponding to the ac
magnetic field input.
For the pickup coil, however, to allow a simpler investi-
gative process and analysis, a simple magnetometer was
used instead of the axial second-order gradiometer used in
other parts of the study. In addition, the same investigation
was done without a current limiter in the flux transformer to
compare the effectiveness of the current limiter.

C. Coil configuration and pulse sequence

The pre-polarization coil that magnetizes the sample
was constructed as a thick solenoid with an inner diameter of
26 mm, outer diameter of 30 mm, and length of 60 mm. The
solenoid was made of wound enamel-coated copper wire of
1 mm diameter with 240 turns. The coil resistance was
0.75 X at room temperature and produced a magnetic field of
53 mT at the center of its cavity with a current of 16 A.
The Bm field was generated with a square Helmholtz
coil with side length of 1340 mm; the coil produced 2.82 lT
at the center. The magnetic resonance frequency correspond-
ing to the Bm field was 120.2 Hz. FIG. 3. (Color online) The orientation of the pickup coil, pre-polarization
coil, measurement coil, gradient coil, and sample for the ULF-MRI system
The BG field was generated with two square coils with (a). The pulse sequence for a pre-polarization MRI system (b). The DROS
side length of 1420 mm in a Maxwell-pair configuration. second-order gradiometer is switched to the FLL state after turning-off the
The field gradient produced by the coil was 4.09 nT/mm at Bp; its delay time (tFLL) is 5 ms.

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 053906-5 Kang et al. J. Appl. Phys. 110, 053906 (2011)

magnetic flux sinusoidal modulation applied to the gradiom-

eter showed an almost step-like response in the gradiometer
output with a voltage amplitude of around 80 lV. Figure 4
shows the magnetic field noise spectrum as measured by the
DROS axial second-order gradiometer in the MSR. The
measured noise level was 9.2 lu0/HHz at 100 Hz. As men-
tioned in Sec. II A, since the magnetic field-to-flux transfer
coefficient is 0.524 nT/u0, the flux noise, referred to the bot-
tom loop of the gradiometer, is 4.8 fT/HHz. Most of this
noise is thought to have been caused by the dewar using the
metallic thermal shield and the superinsulation and it can be
expected to be much improved by doing modifications in the
cryostat design.
Figure 5 shows current cut-off characteristics of the cur-
rent limiter fabricated as in Fig. 2 with and without 6 mT dc
magnetic field. As mentioned in Sec. II B, a magnetometer,
instead of the axial second-order gradiometer, was used in
investigating the current cut-off characteristics of the cur-
rent limiter. Without a high strength dc magnetic field, both
sensors, with the current limiter and without, exhibited the
same response to the small ac modulation corresponding to
the flux-to-voltage modulation curve. With the dc magnetic FIG. 5. (Color online) Current limiting characteristics of a current limiter.
field, however, the difference was prominent: With the cur- Slowly-varying wave of (a) and (b) are DROS flux-to-voltage modulation
rent limiter on line, the SQUID output practically disap- curves in the response to an AC magnetic field of 0.5 Hz without and with
the Josephson junction array, respectively. (c) shows the change in the dc
peared when the dc magnetic field was turned on. On the magnetic field. The DROS modulation is suppressed by the Josephson junc-
other hand, SQUID output showed high-amplitude white tion array in the high magnetic field (6 mT) region.
noise without the current limiter when the dc field was
turned on. These results confirm that the current limiter was
able to dissipate the excessive current induced from the
B. Measurement of 1H NMR in water with DROS
strong external dc magnetic field when the current exceeded
second-order gradiometer
the critical current of the Josephson junction but passed the
weaker ac magnetic field through to the SQUID after the The performance of the DROS axial second-order gradi-
strong dc field was removed and the Josephson junction ometer with a current limiter in the flux transformer was
recovered. The current limiter started cutting off the induced validated by measuring the NMR signal of 1H from 30 cc of
supercurrent with a dc field of 1 mT or more. The dc mag- water. The pulse sequences of Bp and Bm fields were as
netic field was produced by a thick solenoid coil wound shown in Fig. 3(b), i.e., Bp of 53 mT was delivered for 5 sec-
with 1180 turns of 1 mm diameter copper wire. The dc mag- onds, while Bm of 2.82 lT was present all the time.
netic field was measured with a gauss meter (Lake Shore Figure 6(a) shows the measured 1H free induction decay
410-SCAT). (FID) signal after Bp was turned off and Fig. 6(b) shows the
spectral components of the 1H FID signal measured with fast
Fourier transform (FFT). The spectrum shows the main fre-
quency component at 120.4 Hz, which clearly corresponds to
the expected MR frequency of water with the applied Bm
field (120.2 Hz). The spectral resolution Dx/2p, which deter-
mines the spatial resolution of the MR image with the BG
field, as measured with the full-width half-maximum
(FWHM) of the main frequency peak, was 0.6 Hz.
A one-dimensional MR image with BG field was
obtained from a sample consisting of water in a cylindrical
quartz bottle with an inner diameter of 25 mm and a volume
of 30 cc; there was a vertically placed 5 mm-thick rubber
partition inside the bottle along its axis. Figure 7(a) shows
the 1H FID signal measured from the sample with Bm of
2.82 lT and BG of 4.09 nT/mm; Fig. 7(b) shows a one-
dimensional MR image obtained with a FFT of the FID sig-
nal. As shown in Fig. 7(b), the water and the rubber partition
in the sample are clearly visible in the spectrum; there is a
FIG. 4. Noise spectrum of a DROS second-order gradiometer in a magneti- pair of broad peaks representing the divided bodies of water
cally shielded room. and a sharp notch between them representing the rubber

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 053906-6 Kang et al. J. Appl. Phys. 110, 053906 (2011)

FIG. 7. (Color online) The single-scanned FID signal under a magnetic field
FIG. 6. (Color online) The single-scanned 1H NMR FID signal measured gradient (a), one-dimensional MR image of the water sample, which is sepa-
with a DROS second-order gradiometer (a). The FFT spectrum derived from rated by a rubber partition (b).
1
H NMR FID signal (b). The FFT was performed after the zero-filling to
enhance spectral resolution.
In addition, we measured a scalar J-coupling indicat-
ing the presence of specific covalent bonds with the ULF-
partition, which shows that there is enough spatial resolution NMR system in the microtesla Bm field. The J-coupling is
to distinguish object sites of 5 mm or less.26 an indirect interaction between each nuclear spins; the
In addition, we measured the 1H NMR signal in water interaction is mediated by the electrons participating in
that was wrapped with aluminum foil with our DROS based the chemical bond(s) connecting the nuclei. Because the
ULF-NMR system. In contrast to the conventional high field
NMR system, the ULF-NMR system, due to its low reso-
nance frequency, can detect without spatial distortion the
NMR signal of a sample that is wrapped with a metal con-
ductor.27 For example, we measured the NMR signal of the
water sample under a 1.8 lT Bm field and a 53 mT Bp field
after wrapping the sample with aluminum foil of 550 lm
thickness. The resonance frequency of the 1H, corresponding
to 1.8 lT, is 77 Hz. The skin depth of the aluminum, of
which the electric conductivity is 3.77  107 S/m corre-
sponding to the 77 Hz, is calculated at 9.7 mm. Accordingly,
the NMR signal of 77 Hz can be detected by the SQUID sen-
sor without a significant distortion due to the aluminum foil,
of which the thickness is much thinner than that of the skin
depth. These characteristics are shown well in Fig. 8. As
shown in Fig. 8, the NMR signal of the sample wrapped with
aluminum foil shows a nearly identical NMR signal com-
pared to the NMR signal of the sample that was wrapped
with paper of the same thickness as that of the aluminum FIG. 8. (Color online) The NMR spectrum derived from the single-scanned
1
foil. H NMR signal, which was wrapped with aluminum foil and paper.

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 053906-7 Kang et al.
J-coupling arose due to the local influence between nuclei,
its coupling strength usually has a value of around several
tens of hertz and has characteristics of being independent
of the external magnetic field while the chemical shift is
proportional to the external field strength.3,28 Therefore,
the ULF-NMR system under a micro-tesla Bm field, having
spectral resolution of less than 1 Hz, is a more proper tool
to measure scalar coupling than is a conventional high
field NMR system.
Therefore, we measured the J-coupling between 31P and
1 based ULF-NMR system and compared the characteristics of
H with the fabricated DROS based ULF-NMR system in
this study. The sample is a trimethylphosphate of 99.5%
purity (Tokyo chemistry) that is contained in a cylindrical
quartz bottle with inner diameter of 25 mm and volume of
30 cc. Figure 9(a) shows the measured FID signal under a
5.4 lT Bm field and a 53 mT Bp field, and Fig. 9(b) shows
the FFT spectrum derived from the FID signal. In Fig. 9(b),
it is clearly shown that the proton resonance is split into a
doublet with the coupling strength J3[P,H] ¼ 10.4 6 0.8 Hz
due to the J-coupling between 31P and nine equivalent pro-
tons. It was possible to obtain this J-coupling signal by just a
single-scan without an averaging process because the spec-
tral resolution of the DROS based ULF-NMR system is
much higher than that of the coupling strength.
FIG. 9. (Color online) The single-scan FID signal of trimethylphosphate
measured in a field of 5.4 mT (a), the NMR spectrum derived from the FID
signal of trimethylphosphate (b). A heteronuclear J-coupling between 1H
and 31P of trimethylphosphate, which splits the NMR line as a doublet.
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J. Appl. Phys. 110, 053906 (2011)
C. Comparison of signal characteristics between
DROS and dc-SQUID based ULF- NMR system
Until now, we have reported research results on the pro-
gress of a DROS based ULF-NMR system. As mentioned in
the Introduction, however, because the existing ULF-NMR
studies have mostly been performed with dc-SQUID based
systems, it is necessary to compare the characteristics of the
systems that consist of two different SQUID types.
Therefore, for this study, we developed a dc-SQUID
two different systems by operating the dc-SQUID system
under experimental conditions identical to those for the
DROS based ULF-NMR system.
The dc-SQUID used in this experiment is a CE2Blue
model of the Supracon AG company (www.supracon.com).
The most important factors, that is, the pickup coil, the
insert, the dewar, and the MSR, were the same as those in
the case of the DROS based system. However, in the case of
power supply, the DROS based system used a mains ac
power, while the dc-SQUID based system used a 15 V lith-
ium ion battery as its power supply.
Figure 10 shows the magnetic flux noise spectrum. As
shown in the figure, the dc-SQUID axial second-order gradi-
ometer has a magnetic flux noise level of 10 lu0/HHz at 100
Hz; this is a very similar noise level to that of the DROS
axial second-order gradiometer.
In case of dc-SQUID, because the self-inductance of
input coil and mutual inductance between input coil and
SQUID are 604 nH and 8.1 nH, respectively, the magnetic
field-to-flux transfer coefficient is 0.396 nT/u0. Therefore,
the magnetic field noise of the dc-SQUID second-order
gradiometer is 3.96 fT/HHz referred to the bottom loop of
the gradiometer.
Meanwhile, we measured the 1H ULF-NMR signal in
water with the dc-SQUID based system and compared the
characteristics of the ULF-NMR signal that was measured
with the two different systems. The coil configuration and
pulse sequence for the Bm field and the Bp field described in
Sec. II C were also used in the NMR experiment using the
FIG. 10. Noise spectrum of dc-SQUID second-order gradiometer in mag-
netically shielded room.
 053906-8 Kang et al. J. Appl. Phys. 110, 053906 (2011)

dc-SQUID based system. However, in this experiment, we IV. CONCLUSIONS

applied a Bm field that was about 3.4 lT stronger than the
An ultra-low field (ULF) MRI system using a DROS-
Bm field that was applied in the DROS-based system.
based axial second-order gradiometer developed by the
Similar to the prior noise measurement of the dc-SQUID
authors has been shown to operate reliably with a several tens
based system, the ULF-NMR experiment using the dc-
of millitesla-scale pre-polarization field and a microtesla-
SQUID based system was also performed under the same
scale measurement field. The main advantage of the DROS is
conditions (pickup coil, insert, dewar, and MSR) as those of
its high flux-to-voltage transfer coefficient, which is roughly
the DROS based system. Figure 11(a) shows the signal that
10 times higher than that of a conventional dc-SQUID; this
enlarged only the FID region of Fig. 6 (a); Fig. 11(b) shows
better coefficient allows the detection of the output signal of
the 1H FID signal that was measured with the dc-SQUID
the DROS with a simpler and cheaper FLL circuit that con-
based system. Because we focused on the comparison of
sists of room temperature pre-amplifiers.
ULF-NMR signals that were measured with two different
This advantage of DROS is important to develop a
systems, we only represented the FID region with emphasis
sophisticated multichannel sensing MR system or an eco-
in the figure. The insets of Fig. 11 show the FFT spectra
nomical MR system; however, DROS has been suspected to
derived from each of the FID signals. As shown in the figure,
have a shortcoming in that the performance of DROS can
two FID signals have nearly identical amplitude and enve-
abruptly deteriorate due to external high-frequency noise
lope. In addition, spectral resolution, which determines the
because the DROS is a sensor type using a 2 GHz internal
spatial resolution of the MR image, showed a similar value
relaxation oscillation between SQUID and the relaxation cir-
of 0.6 Hz, although the peak of the resonance frequency was
cuit. This characteristic of the DROS becomes a hostile fac-
different because a different Bm field was applied to each
tor when applying the DROS to the ULF-NMR/MRI system
system. Through these results, we were able to verify that
using a strong pulse type transient Bp field.
the physical differences are not so significant in the ULF-
In this study, we adopted a current limiter formed with a
NMR signal measured with two different systems.
Josephson junction array and a superconductor shield to pro-
tect the DROS sensor from the strongly and rapidly changing
Bp field; the DROS based ULF-NMR system fabricated with
this method reliably measures ULF-NMR signals with supe-
rior signal-to-noise ratio.
So far, we have demonstrated that the DROS based
ULF-NMR system has performance comparable to that of
the dc-SQUID based system and verified that the DROS
could be used to develop a ULF-NMR/MRI system by repro-
ducing most results of the ULF-NMR experiments that had
been done with the dc-SQUID.
The present ULF-NMR/MRI systems consist of one or a
few SQUID sensors; actually, the advantages that can be
obtained by applying the DROS method are not that great in
such systems, because the complexity of the system is not
high. However, studies of the ULF-NMR/MRI system will
progress in the future, and a multichannel system that has
many SQUID sensors, enough to cover the entire area of a
subject, will be constructed to image the whole or parts of a
human body using the ULF-MRI system, just as present MRI
systems do. The complexity and manufacturing cost of cir-
cuits for operating the multichannel system increase in pro-
portion to the number of sensors. Therefore, we expect that
the DROS can be a more economical sensor type for multi-
channel systems with many sensors.

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