Discovery of the new superconductor
MgB2 and its recent development
by Yuji Zenitani and Jun Akimitsu

We recently discovered that the intermetallic compound magnesium diboride (MgB2)
exhibits the highest superconducting transition temperature (Tc = 39 K) of all metallic
superconductors. In this paper we report on
the basic superconducting characteristics of
MgB2 and the current status of the search
for applications for this material. In particular, we summarize the research into its critical current (Jc) and critical magnetic field (Hc),
which are important parameters for practicalapplications of this material.

1. Introduction
The search for practical applications ofsuperconductors was spurred on by the discovery of high-temperature copper oxide
superconductors in 1986, and after that every university research center and private
corporation joined in the search for new superconductor materials and applications forthem. But in practice, the difficulty of processing oxide-based superconductors prevented them from finding many practicalapplications. Although the superconducting transition temperature of oxide materials
is substantially greater than that of metallic
compound superconductors, finding practicalapplications for them still involved overcoming the hurdle of having to cool them to lowtemperatures. However, in the 15 or so years
that have passed since then, remarkableprogress has been made in the developmentof highly efficient cooling equipment that isable to cool superconductors without the useof liquid helium, and it now seems that practical applications for this equipment will soon
begin to appear.
Although superconductors are thus facedwith various obstacles on the path to practical applications, the reason why many people are looking for practical applications forthese materials is that superconductors havethe potential to radically alter the basis onwhich technology is built in the future. Specifically, it could lead to major developments
such as: (i) a revolution in transport and distribution methods, such as linear motor cars,(ii) highly efficient electric power generationand lossless power distribution using superconductors, (iii) faster and higher-capacity
information devices using superconducting integrated circuits, (iv) high-performance
medical sensors such as MRI scanners, andapplications to standard measurement devices, and (v) applications to small high-performance superconducting magnets, which
would be useful for a wide range of industrial and commercial applications. Even in thesebroad categories, superconductors shouldfind a wide range of applications by creatinga technological paradigm shift.
But in order for superconductors to be
widely applied until they achieve social andeconomic recognition, it is necessary to carefully ascertain the benefits and drawbacks ofcopper oxide high-temperature superconductors and intermetallic compound superconductors. We have investigated the possibilityof superconductivity appearing in various different types of material from various different viewpoints, and recently discovered thatmagnesium diboride (MgB2) has the highest
superconducting transition temperature of all
metal superconductors.
This paper describes how we made this
discovery, and describes the superconductivity and other physical properties of MgB2. We
also report on our current expectations for
future applications of this material.

2. MgB2 : A New Superconductor
In intermetallic compound superconductors, which are referred to as BCS-based superconductors, or in superconductors that
do not contain copper-oxide, the limit of thesuperconducting transition temperature has

Department of Physics, College of Science and Engineering, Aoyama Gakuin University (6-16-1 Chitosedai, Setagaya-ku, Tokyo 157-8572)
E-mail: zeni@soliton.phys.aoyama.ac.jp

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JSAP International No.6 (July 2002)

so far been in the region of 30 K, and no superconductors had been found to have higher superconducting transition temperatures.
Until now, the highest superconducting transition temperature of an intermetallic compound superconductor was that of Nb3Ge(23 K). However, we have discovered that theintermetallic compound MgB2 exhibits superconductivity with a transition temperature of
Tc=39 K, which is the highest yet recorded
for an intermetallic compound.1)

3. Synthesis Method
Powdered magnesium (99.9% pure) andboron (amorphous, 99% pure) are mixed
together in a molar ratio Mg:B = 1:2 inside
a dry box filled with highly pure argon gas,
and the mixture is press-formed into pellets.
Pelletized samples are then wrapped in tantalum foil and placed in a graphite crucible,
and using an O2-Dr. HIP made by Kobe Steel
Co. Ltd., they are fired at 973-1173 K for
1-10 hours in an atmosphere of argon gas
at 196 MPa to obtain single-phase samplesof MgB2.
Other possible synthesis methods include
sealed vacuum tube synthesis, ultra-highpressure pyrogenic synthesis, and synthesis
by a solid-phase reaction in a stream of argon gas. However, the HIP method is got themost efficient results in MgB2 samples withthe greatest purity.
A possible reason for this is that magnesium has low melting and boiling points andreacts with elements such as oxygen to form
highly stable compounds. When using an arc
welding synthesis method, only the magnesium melts, and as a result the raw materials
separate out into magnesium and boron. Ultra-high pressure pyrogenic synthesis entails
very high costs for each time synthesis is performed. In the sealed vacuum tube synthesis
method and the method involving low-temperature synthesis in a stream of argon gas,(101)

4. The Structure and Superconducting Characteristics of
MgB2
Figure 1 shows the X-ray diffraction
spectrum of powdered MgB2.
These results indicate that the material has a hexagonal crystal structure in spacegroup P6/mmm (no. 191), where a = 0.3086
nm and c = 0.3524 nm. All the peaks havecorresponding indices, so the sample mustbe single-phase. Figure 2 shows a model of
MgB2 crystal structure based on parameters
derived from this structural analysis.
As you can see from this model, thestructure is made from an alternating sequence of Mg and B2 layers. The Mg layers
consist of triangular lattice planes, and theB 2 layers consist of hexagonal honeycomb
lattice planes similar to those of graphite.
Since these planes have a two-dimensional
structure, the material is expected to exhibit
two-dimensional superconductivity as a result of its crystalline structure. The distance
between adjacent B sites in the B 2 layers isabout 0.178 nm, and the distance between
Mg sites in the Mg layers is about 0.3086
nm, which is the same as the a-axis length.
The Mg atoms are located on the central ax-

30

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(201)

(200)

20

(110)
(102)
(111)

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(002)

(001)

(100)

Intensity (arbitrary units)

the magnesium can easily become oxidized.
When the inert gas argon is used in a hothydrostatic compression method, the melting and boiling points of the magnesium areincreased, and it becomes possible to synthesize MgB2 at higher temperatures than in theabove mentioned sealed vacuum tube synthesis method or the method involving lowtemperature synthesis in a stream of argon
gas. This method also suppresses the generation of impurities such as oxides and can synthesize single-phased MgB2. It is also capableof synthesizing large volumes of samples atthe same time. For these reasons, we used
the O2-Dr. HIP made by Kobe Steel Co. Ltd.

CuK�a=0.3086nm
c=0.3524nm

80

Diffraction angle �/180 (degrees)Fig. 1: X-ray diffraction spectrum of synthesized MgB2. This spectrum corresponds to a hexagonal crystal structure inspace group P6/mmm (no. 191), where a = 0.3086 nm and c = 0.3524 nm. All the peaks have corresponding indices, so
the sample must be single-phase.

c

a

a

Fig. 2: The crystalline structure of MgB2 based on the parameters derived from structural analysis. As the upper figure
shows, the crystal consists of Mg planes containing only magnesium and B2 planes containing only boron, which arelayered alternately along the c axis. The lower figure shows the appearance from the [001] direction. The Mg layers
consist of triangular lattice planes, and the B2 layers consist of hexagonal honeycomb lattice planes similar to those ofgraphite.

JSAP International No.6 (July 2002)

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Fig. 3: The temperature variation of DC susceptibility in MgB2. After the MgB2 has been cooled to 5 K in a zero field, it
is measured while increasing the temperature of the sample in an external field of 1 mT (zero field cooling: ZFC), andthen its temperature is reduced again and measured in the same field (field cooling: FC). In both cooling processes it
exhibits the Meissner paramagnetism characteristics of superconductors from 39 K, and the volumetric proportion ofsuperconductor at 5 K as determined from the susceptibility when cooling in a magnetic field (FC) is found to be 49%.

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Fig. 4: Variation of DC magnetization with magnetic field in MgB2. This graph shows the typical behavior seen in type
2 superconductors. Based on this graph, the estimated lower critical field Hc1 and magnetic field penetration length at
0 K are approximately 75 mT and 97 nm, respectively.

6

JSAP International No.6 (July 2002)

is of the hexagonal columns formed by theB atoms. This structure is referred to as an
AlB2-type structure,2,3) and is expressed by thegeneral formula MB2 (where M represents a
metallic element).
Figure 3 shows how the DC susceptibility varies with temperature. After the sample
has been cooled in the absence of a magnetic field, it is measured while increasing thetemperature of the sample in an externallyapplied field of 1 mT (zero field cooling: ZFC),
and then its temperature is reduced again
and measured in the same field (field cooling: FC). As you can see from the results, it
exhibits a large Meissner diamagnetism (acharacteristic of superconductors) from 39 K
in all the cooling processes, and the superconducting volume fraction at 5 K as determined from the susceptibility when cooling ina magnetic field (FC) is found to be 49%.
It can thus be seen that the superconducting transition temperature of MgB2 is 39
K. Since the volumetric proportion of superconductor at 5 K as determined from the susceptibility in a magnetic field (FC) is 49%, weknow that it is a bulk superconductor. Next,
Fig. 4 shows how the DC magnetization depends on the magnetic field (M-H curve).
In the measurements made below thesuperconducting transition temperature, it
exhibits typical behavior seen in type 2 superconductors, and based on this graph, theestimated lower critical field Hc1 and magnetic field penetration length at 0 K are approximately 75 mT and 97 nm, respectively. The results of measurements made byother groups are reported as 28-48 mT and
85-180 nm. In general, when estimating Hc1
from the magnetization curves of type 2 superconductors, any irregularities such as crystalline defects and impurities in the crystal
act so as to pin the magnetic flux, so that theobserved magnetization increases even when
Hc1 is exceeded, and it is thus important totake care when entering such discussions.
This is probably the reason for the wide distribution in the values measured by eachgroup.
Also, the magnetization of mixed statesin a type 2 superconductor reflects the magnetic characteristics due to flux pinning, and
it is possible to estimate the superconducting critical current Jc from the magnetization
curves of flux in a trapped state using models
such as those proposed by Bean4) and Kim.5)
Numerous reports have already been
made regarding the variation of Jc with magnetic field and temperature in bulk samples,
powder samples, wires, tapes and thin films.
The values obtained in bulk samples are ≈105 A/m2 at H=0 T, ≈108 A/m2 at H=6 T, and
62
6)≈10 A/m at H=10 T. These values are all
1-2 orders of magnitude smaller than thoseobtained with metallic superconductors thatare already in practical use (Nb3Sn and Nb-Ti).
In powder samples, a value of 3 1010 A/m2
is obtained at H≤1 T, which is larger than thevalue obtained with Nb3Sn or Nb-Ti. However, it decreases rapidly in the presence of an
external magnetic field, and it has been reported to drop down to 106 A/m2 in a strong
magnetic field of H=7 T.7,8) Also, the valueof Jc in wire9-13) and tape14-19) samples is lower than the values obtained from bulk andpowder samples, especially at low magnetic
fields. However, the attenuation resulting
from external magnetic fields is suppressed
due to the shielding effects of the processedshape, so these samples has a high Jc of 109
A/m2 at H=5 T.
In other papers, Suo et al. reported thatin tape processing the value of Jc could be increased approximately tenfold by an annealing process,20) Wang et al. reported that in Fe
coated wire processing it is possible to obtain
performance similar to that of prolonged sintering by performing repeated sintering,10) Jin
et al. reported that in the processing of wires

DC electrical resistivity ( � �m)

1.4
1.2
1.0

Tc=39(K)

0.8
0.6
0.4
0.2
0

0

50

100

200

150

250

300

Temperature (K)Fig. 5: The temperature dependence of electrical resistivity in MgB2. The electrical resistivity decreases linearly fromroom temperature down to about 150 K, below which it decreases in proportion to the second or third power of temperature. Since a sintered sample was used for these measurements, it has a large electrical resistivity of approximately
0.7 µV/A·m above the superconductivity transition temperature (Tc). Like the results for the temperature dependenceof DC susceptibility, the electrical resistivity drops sharply at 39 K, and at 38 K it exhibits zero resistance.

alloyed with metals such as Ti, Ag, Cu andMo the value of Jc increases almost independently of Tc,9) and Soltanian et al. reported
on the shielding effect of the Fe sheath withrespect to external magnetic fields in the processing of Fe-coated tape.5)
Kim et al.,2) Eom et al.,22) and Paranthaman et al.23) have reported on thin film samples, and suggest that it has a performance
better than the value of 1010 A/m2 obtainedwith Nb3Sn and Nb-Ti, albeit at low magnetic
fields. However, at high magnetic fields it
has a Jc smaller than that of Nb3Sn and NbTi in the same way as a powder sample. Asa method for addressing these drawbacks,
Eom et al. also reported that it is possible toobtain a large Jc of 108 A/m2 even under highfields of H=14 T by incorporating oxygen or
MgO into the sample.
Figure 5 shows the temperature dependence of electrical resistivity. The electricalresistivity decreases linearly from room tem-

perature down to about 150 K, below which
it decreases in proportion to the second or
third power of temperature.
For these measurements we used a sintered sample with a large grain size and arather rough structure. As a result, the electrical resistivity above Tc is quite large at 0.7µΩm. However, a much smaller value ofapproximately 0.0038 µΩm was obtained
above Tc in measurements made with adense sample obtained by ultra-high-pressure
synthesis, and this is substantially lower thanthe value of 0.11 µΩm obtained with theconventional intermetallic compound superconductor Nb3Sn. This low resistivity should
allow it to transfer large electrical currents
even in the normal conduction state.
The DC resistivity drops sharply at thesame temperature of 39 K where a reductionin DC susceptibility is seen, becoming zero at
38 K. Even though the measured sample was
not finely structured, a very narrow transition

JSAP International No.6 (July 2002)

7

Thermoelectromotive force ( � V/K)

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Temperature (K)Fig. 6: The temperature dependence of thermoelectromotive force in MgB2. After jumping discontinuously at the superconductivity transition temperature of 39 K, the sign of the thermoelectromotive force becomes positive (hole carriers) and increases in proportion to the temperature up to about 150 K (a behavior often exhibited by ordinary metals). As the temperature increases further, it approaches a fixed value.

0.6
0T
0.5T
1T
1.5T
2T
3T
4T
5T
7T
9T

DC resistivity ( � �m)

0.5
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Temperature (K)Fig. 7: Variation of electrical resistivity with temperature in MgB2 in a magnetic field. As the applied magnetic field increases, the temperature at which the superconductivity transition starts and the temperature at which the resistancebecomes zero both tend to decrease. This behavior is very similar to that observed in conventional metallic superconductors (e.g. A15 type superconductors).

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JSAP International No.6 (July 2002)

range of about 1 K is still obtained, thus indicating the favorable nature of the superconducting characteristics.
Figure 6 shows the variation of thermoelectromotive force with temperature. After making a discontinuous jump at Tc, thesign of the thermoelectromotive force becomes positive (indicating that the carriers
are holes), and increases in proportion to thetemperature up to about 150 K (a behavior
often exhibited by ordinary metals). As thetemperature increases further, it approaches
a fixed value.
This sort of temperature dependence
variation is observed not only in the electricalresistivity as described above, but also in theHall effect. Below 150 K, the proportional coefficient of the thermoelectromotive force isabout 3-4 times the value for ordinary metals such as Cu and Au. However, it does notagree with the high carrier density value of1023 cm-3 estimated from the Hall coefficientby other groups. Such a large carrier density
is about 2 orders of magnitude greater thanthat of the intermetallic compound superconductor Nb3Sn,24) and one possible explanation
for such a large figure is the existence of two
types of carrier as mentioned above.
Next, Fig. 7 shows the temperature dependence of electrical resistivity in a magnetic field. As the applied magnetic field
increases, the temperature at which the superconductivity transition starts and the temperature at which the resistance becomeszero both tend to decrease. This behavior isvery similar to that observed in conventional
metallic superconductors (e.g. A15 type superconductors), and contrasts with the behavior of copper oxide high-temperature superconductors (such as YBa2Cu3O7).
Figure 8 shows the temperature variation of the upper critical magnetic field Hc2 (T)as derived from the temperature dependenceof electrical resistivity in a magnetic field.

αMg of the isotopic effects of Mg atoms isabout 0.02.28) From these reports, it can easily be inferred that superconductivity in MgB2
is strongly related to the mechanism whereby
superconductivity is expressed in the B2 layers.
Also, since there are numerous materials that have an AlB2-type structure, it is easy
to perform atomic substitution, and thus numerous attempts are being made to increase
Tc particularly by carrier doping whereby theMg sites (metal sites) are substituted withvarious other elements. 29) Substitution of
the B sites with other elements is also being
tried, and the effects of substituting themwith carbon has already been reported. 30)
However, nobody has yet reported any significant increases in Tc as a result of substi-

Upper critical magnetic field Hc2 (T ) (T)At temperatures close to Tc, the temperature dependence of Hc2 (T) is not proportional
to temperature, and this behavior is also observed in intermetallic compound superconductors such as YNi2B2C. At other temperatures, its behavior is proportional to thetemperature, and the gradient of this line is-0.69 T/K. Therefore, by considering this value together with the dirty limit in type 2 superconductors,25,26) the value of Hc2 (T) at 0 K
is estimated to be approximately 18.6 T. Furthermore, the coherence length can be estimated to be about 4.18 nm from this valueof Hc2, which basically agrees with the resultsof measurements made by other groups.
So far we have discussed the research
into the basic superconducting characteristicsof this material, but in addition many groups
have reported on experimental and theoretical research into the mechanism whereby thissuperconductivity is expressed.
After our group reported the discovery ofthis superconductor, it was quickly followed
by a report from Bud'ko et al. regarding experiments on isotopic effects.27) Isotopic effects make it possible to ascertain whether or
not the superconducting state is mediated byelectron-phonon interactions as described by
BCS (Bardeen-Cooper- Schrieffer) theory.
According to their report, the onset of superconductivity occurs at 40.2 K in Mg10B2 andat 39.2 K in Mg11B2, and the coefficient αB of
the isotopic effect for B atoms is αB = 0.26,
which is lower than the value of αB = 0.5 predicted by BCS theory. This result shows that
this superconductivity is basically mediated byelectron-phonon interactions, but this is notentirely so and it is expected that the superconducting state includes a complex mixtureof other factors.
On the other hand, in experiments todetermine the isotopic effects of 24Mg and26
Mg, Hinks et al. reported that there is almost no change in Tc and that the coefficienttution with other elements. Although theseexperimental results suggest that it is difficult
to increase Tc by substituting with other elements, the comparative ease with which elements can be substituted is worth investigating for application in other areas. However,it may be necessary to devise different approaches.
The superconducting gap formed in the
superconducting state has been studied by avariety of spectral measurements, and is now
broadly understood in terms of BCS theory. However, there are also many examples
where different measurement techniques
produce different results, so further clarification is still required. To address this situation,
there is a need for detailed measurements
using high purity single crystals.

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Temperature (K)Fig. 8: The upper critical magnetic field Hc2 of MgB2 at various temperatures. This graph was obtained from the resultsof the electrical resistivity temperature dependence in a magnetic field by plotting the upper critical magnetic field
Hc2 at each temperature against the change in temperature. At temperatures close to the superconductivity transition
temperature, the temperature dependence of Hc2 is not proportional to temperature, and this behavior is also observed in intermetallic compound superconductors. At other temperatures, its behavior is proportional to the temperature.

JSAP International No.6 (July 2002)

9

The successful production of single crystals-albeit very small ones-was recently reported, 31) and the anisotropic parameters
obtained by making measurements such as
those described above with single crystals
have also been reported.
With regard to the Hc2 anisotropy, a value of 2-3 has been reported for Hc2ab/Hc2c,
and it has been suggested that this material has two-dimensional superconducting
properties as expected from the crystalline
structure, although this anisotropy is not aslarge as in oxide superconductors. However,in measurements made with single crystals,
smaller values are estimated for Hc2 and Jc
than with other types of sample such as bulk
samples, and it is thought that the higher values obtained for Hc2 and Jc are due to extrinsic factors such as phase boundaries rather
than intrinsic factors within the material.

5. The Development of Applications
As discussed above, although some of
the most basic quantities of this material
such as the superconducting transition temperature have been clarified, there is still alack of reliable figures for the basic physicalproperties and characteristics of this material concerning other physical quantities ofimportance to practical applications, such as
anisotropy. But even though the necessary
characteristics are still unclear, MgB2 is still regarded as a promising candidate for practicalapplications because it has several advantages such as the following:(1)It has the highest superconducting transition temperature (39 K) of all intermetallic
compounds.
(2)MgB2 consists of the two elements magnesium and boron. It has fewer constituent

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JSAP International No.6 (July 2002)

elements than oxide superconductors, andsince there is no uncertainty in its composition, it is a material that is easy to synthesize and stable.
(3)Compared with the intermetallic compound superconductors that have so far
been used in practical applications, it consists of lighter atoms and thus weighs less.
First, (1) its superconducting transition
temperature is about 20 K higher than thatof conventional intermetallic superconductors. This has the advantage of providing agreater temperature margin for maintaining
a superconducting state.
Next, (2) since it consists of just the twoelements magnesium and boron, it can bemade with fewer raw materials than copperoxide high-temperature superconductors andis comparatively easy to synthesize. And since
MgB2 has a stable composition and structure,
its superconducting transition temperaturedoes not vary greatly. In other words, it has
the advantages of being a stable material
that is easy to make. It also seems to lend itself to the production of forms such as thinfilms and wires.
Finally, (3) since it is a lightweight material that can even be used for power transmission lines, it can alleviate the load on power
installations and the like because it functions
as a superconductor.
Although this only a simple general view,
MgB2 has a number of advantages for practical applications.
Superconductivity, which is the most important attribute in terms of practical applications, is characterized by a critical current
density (J c) and an upper critical magnetic
field (Hc2). In MgB2, the upper critical magnetic field (Hc2) has been measured by a number of organizations, and its reported value

for bulk materials is reported to lie in therange from Hc2 (0) = 12 T to 18 T. The values
obtained in measurements made with highdensity bulk samples synthesized by ultrahigh pressure synthesis range from Hc2 (0) =18 T to 26.5 T. The variation of these values
arises because the quality of the samples is
not constant. Compared with Nb3Sn and NbTi, which have already found practical applications, it has an intermediate value for Hc2(0), and the increase in dHc2/dT is small. This
indicates that it has a small mean free path.
Accordingly, it is predicted that it will bepossible to improve Hc2 by doping with otherelements to reduce the mean free path. In
practice, it has been reported that the valueof Hc2 in a thin film can be substantially increased by doping with oxygen. As for thecritical current density (Jc), according to calculations using the Bean model from the historyof magnetization curves, the value of Jc at 10
K and 10 kA/m is 5 109 A/m2 inside grains
and 0.4 109 between grains. The value of
Jc at 5 K is lower than that of conventional
superconductor materials such as Nb3Sn, but
it is thought that the Jc characteristics will improve as purer samples become available andthe pinning mechanism becomes more clearly understood.
Today, research establishments all over
the world are continuing to research the fundamental physical properties of MgB2 anddevelop techniques for processing it into
forms such as wires, tapes and thin films witha view to developing practical applications
for this material. So far, although a large volume of data has been obtained by these establishments, it has not yet coalesced into an
integrated model. But this is only to be expected from a material discovered so recently. For future study, comprehensive studies

are required in areas such as the following:(1)Why does MgB 2 have a high superconducting transition temperature of Tc = 39
K? To answer this question, the conformityof this material with conventional BCS theory needs to be studied, and a comparison
with real experimental results is also required.
(2)The production of samples with higher purity and single-crystal samples. These samples could be used for more reliable andaccurate measurements of the transportphenomena and magnetic/optical/thermal
characteristics of MgB2, thereby clarifying
the mechanism for the expression of superconductivity.
(3)The establishment of processing techniques for the formation of wires, thinfilms and the like for practical applications,
optimization of the processing parameters
required for these techniques, and measurement of the superconducting characteristics of each form.
Finally, the reader should bear in mind
that the authors of this paper are physicistswe are not the ideal people for finding practical applications for this material. As wewrite, a lot of research into MgB 2 is being
conducted overseas, especially into its practical applications, and although this material
was born in Japan it is in the process of being
developed overseas. We would be much happier if this superconductor could be brought
up in the country of its birth. We would liketo finish by acknowledging the assistance received in this study by our research students
J. Nagamatsu, N. Nakagawa, and T. Muranaka.

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