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Jena 2019 Jpn. J. Appl. Phys. 58 SC0801
Jena 2019 Jpn. J. Appl. Phys. 58 SC0801
Physics
The nitride semiconductor materials GaN, AlN, and InN, and their alloys and heterostructures have been investigated extensively in the last 3
decades, leading to several technologically successful photonic and electronic devices. Just over the past few years, a number of “new” nitride
materials have emerged with exciting photonic, electronic, and magnetic properties. Some examples are 2D and layered hBN and the III–V
diamond analog cBN, the transition metal nitrides ScN, YN, and their alloys (e.g. ferroelectric ScAlN), piezomagnetic GaMnN, ferrimagnetic Mn4N,
and epitaxial superconductor/semiconductor NbN/GaN heterojunctions. This article reviews the fascinating and emerging physics and science of
these new nitride materials. It also discusses their potential applications in future generations of devices that take advantage of the photonic and
electronic devices eco-system based on transistors, light-emitting diodes, and lasers that have already been created by nitride semiconductors.
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Fig. 1. (Color online) The elements contained in traditional nitride semiconductor technology are shown with those in the “New” Nitrides in the periodic
table. The color coding indicates the families of physical properties or usage of the elements in nitride crystals.
Fig. 2. (Color online) Schematic figures showing the new nitride materials such as Boron-containing hBN and cBN, Sc-containing nitrides, and transition
metal nitrides. The piezoelectric coefficients of several materials are shown against the maximum processing temperatures, adapted from.29)
2. Boron-based nitrides
Boron is the lightest group-III element. Before discussing
boron nitride, an analogy to a closely related material can
guide chemical and physical expectations. Between Boron
and Nitrogen in the periodic table is Carbon. The stable
crystal structure of carbon under atmospheric conditions at
room temperature is graphite, the layered form of sp 2 carbon,
the monolayer version of which is graphene. Diamond, the
sp3 variant, is metastable, but exhibits exceptional stability
nevertheless, because of high energy barriers to any structural
and chemical changes between the competing phases.
Diamond exhibits an exceptional thermal conductivity, and
p-type doping and hole conductivity has been demonstrated
Fig. 3. (Color online) A summary of the four broad categories of nitride in the bulk, and more readily on the crystal surface.
materials. The currently known candidates for semiconducting properties, Pure binary BN has not been investigated in as much detail
metallic and superconducting properties, magnetic properties, and high as diamond, graphene, or graphite, but potentially hosts
piezoelectric and ferroelectric properties are listed in the figure. Epitaxial remarkable undiscovered electronic, photonic, and thermal
integration offers the potential to integrate across families, such as the
semiconductor/superconductor heterostructures of GaN/NbN, or the metal/
properties. The lightest atom materials (diamond, BN) by
insulator or metal/x-piezo heterostructures of TiN/ScAlN. virtue of extremely strong chemical bonds, are refractory in
nature, demonstrating exceptional stability to chemical and
physical perturbations such as high-temperature, corrosive
chemical environments, and mechanical deformation. For the
same reasons, they are difficult to synthesize and control,
requiring extreme environments for high quality crystal substrates.26) Because hBN does not have spontaneous
growth. polarization, it has been used as a new reference to re-
The 2D layered form, hexagonal BN (hBN) has been evaluate the spontaneous and piezoelectric coefficients of the
investigated more than the cubic phase of the crystal. Around nitride semiconductors.27) A point to note is that monolayer
the turn of the century in 2001, growth of single-crystal cubic hBN has extremely high in-plane piezoelectricity. The optical
BN was achieved under high pressure/high-temperature properties of hBN can be exploited in deep-UV photonics,
(HPHT) conditions by14 using Li and Ba-solvent methods. and if electrical conductivity can be achieved in very thin
Soon thereafter, single crystals of the hexagonal form of layers, it can offer a new platform for high-voltage and high-
boron nitride (hBN) were obtained by the Ba–B–N HPHT speed electronics taking advantage of unique scaling proper-
growth conditions. Multilayer hBN obtained in this fashion ties rooted in its 2D nature.
exhibited strong cathodoluminescence at ∼5.8 eV and lasing On its own, the electronic and photonic properties of cBN
under electron beam pumping.15) Metal-organic chemical promise significant surprises due to the light atomic masses
vapor deposition (MOCVD) has been used to grow multi- and strong electron–phonon coupling, and are expected to be
layer hBN on sapphire, exhibiting deep-UV uncovered with advances in crystal and epitaxial growth over
photoluminescence.16) More recently, ultra high-temperature the next decade. In the nearer term, cBN offers a large
molecular beam epitaxy (MBE) has been used for the growth bandgap and a high thermal conductivity comparable to
of hBN on graphite at thermocouple temperatures ∼1300– diamond, to potentially take nitride RF electronics into power
1700 C exhibiting strong luminescence at ∼5.5 eV with regimes currently limited by the highest thermal conductivity
phonon replicas and weak sub-bandgap defect emission.17,18) of the substrate on which these devices are realized. Diamond
The high-temperature MBE grown hBN exhibit properties has been investigated and found attractive for heat removal in
closer to the single-crystal hBN obtained by the HPHT high power GaN HEMTs, and cBN can offer a potential
method. High quality hBN has also been prepared by the epitaxial solution to this problem.
molten metal-flux method using Ni/Cr with isotope control of
Boron exhibiting shifts of PL peaks of bandgap energy.19) 3. Nitride extreme-piezoelectrics and ferroelectrics
Because monolayer hBN is made of sp 2 chemical bonds, it Crystalline AlN by itself is an attractive piezoelectric material
can form either planar 2D sheets, or can roll up into capable of sustaining high temperatures, with a piezoelectric
nanotubes, in close analogy to graphene and carbon nano- coefficient e33 ~ 146 mC cm-2, and boasting a spontaneous
tubes. As opposed to the zero-bandgap, linear energy polarization of Psp ~ 8.1 mC cm-2. The corresponding calcu-
dispersion bandstructure of 2D graphene, and the sensitive lated values for GaN is e33 ~ 73 mC cm-2 and
dependence of the electronic properties on the radius and Psp ~ 2.9 mC cm-2 and for InN is e33 ~ 97 mC cm-2 and
chirality of carbon nanotubes, hBN is an electrical insulator Psp ~ 3.2 mC cm-2.7) These values were calculated by the
in both the 2D planar form and in the quasi-1D nanotube application of the (then-new) Berry phase formalism of
forms. Multilayer hBN has been found to exhibit an indirect electronic polarization, by comparison to a zinc-blende
energy bandgap of ∼5.96 eV,20) though with unexpectedly crystal as the reference. In most experiments, the differences
high internal quantum efficiency compared to common in polarization across heterojunctions manifest as internal
indirect gap semiconductors.21) electric fields or mobile electron or hole gases at heterojunc-
Though synthetic methods for obtaining cubic BN were tions, and are in acceptable agreement with the calculated
known to exist in the past,22) cBN crystals of few mm sizes values. A new calculation that uses the layered (hexagonal)
were recently obtained by the catalyst-assisted HPHT growth lattice as the non-polar reference has revised these coeffi-
process.14) Cathodoluminescence spectroscopy of colorless cients significantly; in the new values, the differences in
cBN crystals show emission around 200 nm. Electrical polarization are similar to the old values, but the absolute
conductivity has been reported in these single crystals that values are significantly different.27)
are doped with Si or S (n-type), or doped with Be (p-type). In addition to the effects of the polarization fields in
Epitaxial growth of cBN is in its infancy. Very recently, electronic and photonic devices, AlN today forms the basis
radical-assisted MBE growth on (001) and (111) Diamond for bulk acoustic wave (BAW) filters for high frequency RF
single crystals has been reported.23,24) Epitaxial growth of signals, several of which go into each cellphone. The center
cBN is expected to be a next frontier for nitride materials frequency for such filters is given by f0 = vs /2L, where vs is
science and is expected to yield rich rewards. the sound velocity in the material, and L is the length of the
hBN has intriguing photonic and electronic properties that acoustic cavity. As the frequency of communication signals
can offer a host of potential applications. To date, hBN layers increases to provide higher bandwidth data transfer, there is
exfoliated from the bulk have been used in the field of 2D an increasing need for materials with piezoelectric coeffi-
materials with graphene, MoS2, and other layered semicon- cients higher than AlN. In 2002, it was predicted from first
ductors as an insulating barrier, or atomically smooth and principles calculations by Takeuchi that though the transition
chemically clean substrate. The strong chemical bonds of metal containing nitride, Scandium Nitride (ScN), has a
hBN also result in long-lived phonon-polariton modes for stable rocksalt structure, Scandium-containing III–V nitrides
conversion of electromagnetic waves in the optical frequen- could potentially be stabilized in the wurtzite structure upon
cies into mechanical vibrational waves in the crystal.25) alloying with Al (or In, Ga), and thereby be piezoelectric.28)
Because of the weak van der Waals bonding between layers, In 2009, Ref. 29 reported the first experimental observation
it has been used as a nucleation layer on sapphire for the of a nearly 500% increase in the piezoelectric coefficient d33
growth of nitride LEDs and HEMTs that could be “peeled- of wurtzite Sc0.4Al0.6N over AlN.
off” and transferred to other flexible, or functional
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Jpn. J. Appl. Phys. 58, SC0801 (2019) PROGRESS REVIEW
The rather remarkable experimentally observed giant potentially far-reaching consequences. Because the sponta-
enhancement in piezoelectricity may qualitatively be under- neous and piezoelectric polarization discontinuity in nitride
stood from the following arguments: Sc is a group-III semiconductor heterostructures are the basis for RF and
transition element, and can take an oxidation state of +3, power electronics, boosting the piezoelectricity by ∼500%
similar to Al (i.e. it is isovalent). Therefore, replacing some can lead to several novel device applications that combine the
Al atoms with Sc should keep the insulating nature of AlN ( high current carrying capacity with high breakdown voltages.
i.e. not dope it). The fact that the outermost electrons of Sc The first steps to integrate ScAlN in HEMTs have been taken
are in d− orbitals instead of the s and p− orbitals of Al result by MBE growth. HEMTs using such ScAlN barriers have
in a major difference when it incorporates in the crystal. been realized recently,35) and promise an exciting foray into
Because there are 5d− orbitals: dxy, d yz, dzx , d z2 and d x 2 - y 2, unknown territories for semiconductor device electronics.
the crystal-field splits the energy levels of the Sc atom d− A natural question to ask is: how high can one ramp up the
orbitals into t2g and e2g orbitals. As a result, the stable piezoelectricity? With the substitution of Al by Sc in AlN, the
structure of ScN is cubic rocksalt, not wurtzite. ScN is a piezoelectric constant increases, with a concomitant softening
semiconductor of bandgap ∼1 eV with a lattice constant of of the crystal. AlN can be either Al-polar, or N-polar, it has
4.505 Angstrom, and has been used as a better cubic substrate two stable crystal structures, something that an external
for GaN than Si. This is because its effective 111 lattice electric field cannot change due to very stiff bonds and a
constant is ( 2 /2) 4.505 ~ 3.186 Angstrom, which has a high energy barrier. Replacing Al with increasing amounts of
∼0.1% lattice mismatch to 0001 GaN of lattice constant Sc moves it closer to a cubic structure, while softening the
3.189 Angstrom, compared to the ∼17% lattice mismatch bonds. With the addition of sufficiently large amount of Sc,
with 111 Silicon (of lattice constant 3.84 Angstrom). can one obtain a crystal structure in which the ScAlN is so
Furthermore, highly conductive degenerately doped n-type close to being cubic with softened bonding, that an external
and p-type semiconducting ScN have also been realized.30,31) electric field can flip the structure from Al-polar to N-polar?
Because of the cubic crystal structure of ScN, one would If this happens, ScAlN can become a ferroelectric!
expect that the effect of incorporating Sc into AlN should be Ferroelectrics, one of the newest material families (discov-
to (a) distort the lattice structure from wurtzite towards cubic, ered in 1920), have typically been limited to oxide crystals,
and (b) shrink its bandgap. Furthermore, the chemical several of which are of the perovskite lattice structure. There
bonding becomes increasingly soft: this implies a more were no known nitride ferroelectrics to date; the only one
compliant crystal that undergoes far more atomic or lattice predicted from a high-throughput first principles
displacements for the same strain, boosting its piezoelec- calculations38) of a vast number of possible nitride com-
tricity. pounds is the perovskite nitride LaWN3 - a material that is
Since the initial report in Ref. 29, there has been awaiting synthesis and characterization. As amazing as it may
substantial interest in increasing the piezoelectric polarization sound, it seems we have the glimmers of a major break-
of AlN by alloying transition metals. The group III transition through in ScAlN, with extremely high piezoelectricity and
metal below Sc in the periodic table, Yttrium (Y) has been potentially also ferroelectricity.
suggested from first principles to lead to a high electro- Every ferroelectric is a piezoelectric, but not all piezo-
mechanical coupling coefficient when substituting Al to form electric are ferroelectrics. For example, AlN is a piezo-
YAlN. Alloying in small amounts of B, which shares the +3 electric, but not a ferroelectric. That Sc-containing nitride
oxidation state, but forms much stronger chemical bonds with semiconductors can potentially exhibit ferroelectricity was
N, is predicted to counteract the decrease in stiffness caused anticipated in first principle calculations.36) An experimental
in the crystal by Sc or Y substitution alone. This is expected observation of ferroelectricity has very recently been reported
to maintain a high electromechanical coupling coefficient, in ScAlN.37) Not only is the ferroelectricity observed in
which is attractive for BAW filters.32) Instead of relying on ScAlN, it seems to be very strong, at ∼100 mC cm-2 (much
the +3 oxidation state Sc or Y isovalent with Al, it has been higher than PbZrTiO3, or PZT), and boasts coercive fields of
predicted that co-doping AlN with Mg of oxidation state +2 ∼1 MV cm−1, and breakdown fields in excess of a few MV
and Hf or Zr of oxidation state +4 in 1:1 ratio can lead to a cm−1, something that is currently unachievable in established
giant enhancement in the piezoelectricity of AlN.33) Rather ferroelectrics.
remarkably, it has been experimentally found that co doping If stable, and repeatable ferroelectricity can be tamed and
AlN with Mg and Nb leads to a 400% giant piezoelectricity brought to the nitride platform, it opens up vast areas of
enhancement.34) This is counterintuitive, because Nb is a applications. Ferroelectric memory can significantly add to
group 5 transition metal, and a Mg:Nb atomic ratio of 2:1 the value chain created by nitride electronics. Like magnets,
would be naively needed to maintain a net +3 oxidation state ferroelectrics can potentially provide significant opportunities
when substituting for Al sites. However, it is observed that a for energy storage in power electronics. Layers of ferro-
Mg:Nb ratio of ∼Mg0.40Nb0.25Al0.35N is able to remain electrics can reduce short channel effects in ultrascaled
electrically insulating, and lead to the giant piezoelectric transistors by an effective negative capacitance at the drain
enhancement. By probing the oxidation states of Nb by XPS side. Energy-efficient sub-Boltzmann transistors that require
it was concluded that Nb atoms exist in the crystal in various less than 60 mV/decade can potentially be realized using
oxidation states: +3, +4, and +5, pointing towards a much negative capacitance in the gate of FETs. Since ferroelectric
richer chemical bonding status than was previously believed. layers can be poled by an electric field, reconfigurable
These alloys of transition metals with Al(Ga,In)N should periodically poled arrays can be used for second harmonic
be considered as extreme-piezoelectrics (x-piezos), a valuable generation and new sorts of devices in non-linear optics.
addition to the nitride family of semiconductors, with When combined with the electronic and optical nitride
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Jpn. J. Appl. Phys. 58, SC0801 (2019) PROGRESS REVIEW
devices, the possibilities enabled by epitaxial ferroelectric temperature for such carrier-mediated ferromagnetism is
layers seamlessly integrated with transistors, LEDs, and given by Tc » CNMn b 2m v☆ p1 / 3 , where C is a constant, NMn
Lasers are limited only by our imagination. is the concentration of Mn spins, β is an exchange interaction
constant (called the p - d coupling between mobile holes in
4. Magnetic nitrides p− states and localized spin d− states at Mn sites), m v☆ is the
Nitride RF and power electronics platforms can benefit effective mass of holes, and p is the hole concentration. To
tremendously if magnetic materials could be integrated date, a maximum Tc ~ 200 K has been achieved in GaMnAs,
seamlessly with the GaN material system. For example, in which falls short of room temperature for practical applica-
power electronics, the storage of electrical energy occurs in tions.
magnets and inductors, and RF systems require circulators The hopes of achieving a room temperature dilute mag-
and non-reciprocal elements that are magnetic (e.g. magnetic netic semiconductor in GaN by magnetic doping with Mn
insulators, or ferrites). Magnetism is a phenomena origi- was high. This expectation was based on theoretical predic-
nating in the spin of fermionic particles such as electrons. tions based on a carrier-mediated (Ruderman–Kittel–
Spin is the intrinsic angular momentum of all fermions that Kasuya–Yosida) RKKY-type interactions, which is similar
has no classical analog. The nucleus hosts neutrons and to a Zener model in which the Friedel-like oscillations of a
protons that are fermions, each of spin 1 /2, or spin angular typical RKKY interaction are washed out because of the large
momentum /2. Each electron in the core energy levels as distances between the spin centers at the Mn ions, when
well as those participating in the formation of bonds and mediated by free carriers.41) Carrier mediated ferromagnetism
bands of a crystal possess the same spin angular momentum in dilute magnetic semiconductors such as in GaMnAs occurs
of /2. Adding up the total nuclear and electronic spin in conductive material with free carriers that get spin-
angular momentum vectors in crystals of typical group IV polarized due to their interaction with the magnetic sublattice
semiconductors, III–V semiconductors GaAs, GaN (or AlN of the Mn sites. However, it is believed that Mn in the +2
and InN), or II–VI semiconductors such as CdTe, results in a oxidation state introduces an energy level that is rather deep
net zero spin: meaning they are non-magnetic materials in the gap of GaN, and as a result is unable to provide mobile
(actually they are very weakly diamagnetic, meaning they holes: GaMnN is found to be semi-insulating. The Curie
oppose an external magnetic field). In 1996, it was discov- temperature for ferromagnetism is experimentally observed
ered in Ref. 39 that adding dilute concentrations of the to be rather low, about Tc ~ 1 K at a Mn concentration of
transition metal Mn to GaAs made the alloy GaMnAs ∼3%. The mechanism is thought to be by short-range
ferromagnetic at low temperatures. The existence of Mn- ferromagnetic superexchange interactions. Compared to
doped dilute magnetic semiconductors was developed in II– GaMnAs, the GaN crystal possesses a far higher piezoelectric
VI semiconductors such as CdMnTe well before the dis- effect. It is then possible to use the piezoelectricity to control
covery of GaMnAs,40) but they are typically not ferromag- the magnetic interactions, as was shown recently.42) This is
netic: they exhibit paramagnetic, antiferromagnetic, or spin- an indirect electrical control of magnetism, mediated by the
glass behavior. A crucial difference between Mn-based II–VI strain and piezomagnetism. Even though the interaction is
and III–V dilute magnetic semiconductors is in their elec- weak and occurs at low temperatures, this is a magneto-
tronic conductivity: for example, CdMnTe is electrically electric property, because the magnetization can be con-
insulating, whereas GaMnAs has p-type conductivity. The trolled, via the strain by electric fields. It would be of high
holes in GaMnAs are responsible for carrier-mediated interest if stronger magnetoelectric properties closer to room
ferromagnetism, which is absent in CdMnTe due to its lack temperature could be found in nitride materials in the future.
of mobile carriers. Instead of alloying Mn with GaN, it is possible to create
The transition metal Mn has the electronic orbital structure binary phases of its nitride: for example, MnN, and Mn4N.
[Ar]3d 54s 2 , with 5 electrons in the d-shell: it is half-filled. In MnN (called the θ-phase), has a cubic crystal structure, in
a II–VI semiconductor such as Cd1-xMnxTe, when Mn which Mn is in a +3 oxidation state and N in the −3 state,
substitutes a group II metal site, the two 4s-orbital electrons similar to a III–V crystal. MnN crystals are antiferromag-
of Mn participate in chemical bonding, leaving the 5 d-orbital netic. Mn4N on the other hand (the -phase) has an fcc anti-
electrons highly localized on the Mn site. These five electrons perovskite crystal structure, and is found to be electrically
are unpaired with spin configuration , leading to a conducting (metallic), and ferrimagnetic. N occupies the
net spin angular momentum of S = 5/2 per Mn atom. Mn body-center sites, and Mn the corner sites, and the face-center
thus incorporates in the +2 oxidation state, and is isovalent sites. The Mn atoms at the corner sites have magnetic
with the group II metal it replaces (e.g. Cd) in II–VI moments of 3.85mB per formula unit, and the face-center
semiconductors, and does not introduce extra mobile carriers, Mn atoms have a magnetic moment of -0.9mB per formula
it is not a dopant. Since the spins on Mn sites are localized unit aligned along the 100 (c-) axis. The ferrimagnetic
and do not have strong interactions with neighboring Mn transition temperature of Mn4N is Tc ~ 740 K, well above
sites, the Cd1-xMnxTe crystal is not able to become ferro- room temperature.43) When deposited on nearly lattice-
magnetic. On the other hand, in GaMnAs, Mn also exists in matched SrTiO3 substrates, Mn4N exhibits remarkably large
the +2 oxidation state, and thus acts as an acceptor dopant. magnetic domains, approaching millimeters in size.44) The
Since Mn introduces an unoccupied energy level close to the magnetization points perpendicular to the plane of the thin
valence band edge of GaAs, it introduces holes in the valence film, which makes it attractive for high-density magnetic
band, making it p-type. The mobile holes mediate the storage, with spin-torque switching for non-volatile energy-
interactions between Mn spin centers, making the entire efficient memory applications. It may be considered for
GaMnAs crystal ferromagnetic. The critical (Curie) power electronic circuits in the future. Finally, the rare-earth
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Jpn. J. Appl. Phys. 58, SC0801 (2019) PROGRESS REVIEW
nitride crystal GdN is ferromagnetic with a Curie temperature GaN/AlGaN/InGaN heterostructures for various electronic,
Tc = 70 K, and EuN has Tc = 120 K. Unlike Mn containing photonic, and plasmonic device applications. For example,
Nitrides in which the magnetism originates from d-shell recently it was shown that AlGaN/GaN layers epitaxially
electrons, in GdN and EuN the magnetism is due to unpaired grown on thin NbN layers exhibited high mobility 2DEGs
spins of electrons in the f-shell.45–47) exhibiting quantum oscillations in magnetotransport, and
could be processed into high performance HEMTs interfaced
5. Metallic and superconducting nitrides with the superconducting properties of NbN.52) This leads to
The transition metals in the groups headed by Ti, V, and Cr the feasibility of epitaxial metal/semiconductor Schottky
in the periodic table all form highly refractory and chemically diodes and epitaxial gate junctions for transistors. Buried
stable nitride compound metals. Several of them are heavily epitaxial metal (epimetal) layers of low resistivity can be
used in electronics (e.g. WN for contacts in Silicon tech- inserted if needed for electric field management in high-
nology). The room temperature electrical resistivities of voltage or high-speed electronic devices. Low resistivity
typical transition metal nitrides range from r ~ 7 mW cm epimetals could potentially be used for mirrors and reflective
for TiN and ZrN to r ~ 200 mW cm for TaN and CrN.48,49) contacts, and for plasmonic applications in conjunction with
For comparison, the room temperature electrical resistivity of GaN photonic devices.
the highest conductivity metals Cu and Ag is r ~ 1.5 mW cm. At low temperatures, the metal → superconductor transi-
When the compound metallic nitrides TiN, ZrN, HfN, VN, tion of nitride layers offer several unique possibilities and
NbN, TaN, MoN, and WN are cooled to cryogenic tempera- device applications. Current transport in the superconducting
tures, they undergo an electronic phase transition from the regime in, for example, NbN is a genuine dissipation-less
metallic to the superconducting phase. Among them, NbN mechanism, when a finite current flows through the super-
shows the highest superconducting transition temperature at conducting layer for zero voltage drop. The physical me-
Tc ~ 17 K. These properties of metallic and superconducting chanism responsible for standard superconductors (such as
transition metal nitrides have been investigated heavily in the the transition metal nitride superconductors) is the pairing of
past few decades. The chemical bonding is between the d- electrons to form Cooper pairs, and their condensation to a
orbitals of the transition metal elements, and the outermost p- correlated macroscopic quantum state below the critical
orbitals of N. Most of these crystals have a stable rocksalt temperature. The critical magnetic fields that NbN can sustain
crystal structure, though hexagonal forms can also exist. The before losing superconductivity can be in excess of 15–20 T -
normal metallic state resistivities, and the superconducting which makes them very robust against phase transition due to
transition temperatures are sensitive to the stoichiometry, the Meissner–Ochsenfeld effect. A finite energy is required to
impurity densities, and the lattice constants of these nitride break the Cooper-pairing, characterized by an energy
crystals. D ~ kb Tc, where Tc is the critical temperature; this may be
Most of these metallic and superconducting nitrides have thought of similar to the bandgap of a semiconductor, and is
been grown in the thin film form in the past by RF magnetron indeed referred to as the superconducting gap. For example,
sputtering based techniques, or more recently by atomic layer when a photon of energy larger than the superconducting gap
deposition. The III-Nitride semiconductor material hetero- is incident on the superconductor, it causes a localized
structures are grown by epitaxial techniques with electronic superconductor → metal transition (similar to an electron-
grade purity and control. The development and high level of hole pair generation by a photon in semiconductor).
maturity of MOCVD and MBE of nitride materials today In 2001, it was discovered that narrow NbN supercon-
offers a tantalizing possibility of re-examining the growth of ducting strips could use the above mechanism for ultrafast
transition metal nitride crystals at a level of purity, thickness, detection of single photons.53) Because a finite voltage must
and compositional control commensurate with electronic drop across a metal to carry a current, the event of the
grade semiconductors. In addition, an exciting possibility is detection of a single photon appears as a voltage pulse that
their potential epitaxial integration with the III-nitride semi- dies out within picoseconds as the superconductor recovers.
conductors to form metal/semiconductor and superconductor/ This mechanism is now used for NbN based single photon
semiconductor heterostructures. detection, counting, and imaging at high data rates and high
The closeness of the lattice constant of metallic cubic TiN efficiencies, as long as the detector is cooled sufficiently
and semiconducting cubic AlScN has recently enabled the below Tc. Such nitride superconducting detectors are expected
epitaxial growth of low defect-density metal/semiconductor to play an increasingly important role in the future for single
nitride multilayers.49) In a similar vein, the (111) lattice photon secure quantum communications, and also for
constant of the cubic crystal structure of NbN, HfN, and other astronomy. Epitaxial integration of such superconducting
transition metal nitrides is close to the c-plane a-lattice NbN layers with active nitride electronic and photonic
constants of wurtzite SiC, AlN, and GaN, and offers the emitter structures (e.g. single photon emitters) can lead to
required hexagonal symmetry. This has led to recent demon- new forms of single photon detection paradigms, and to a
strations of epitaxial growth of heterostructures of NbN, SiC, unique platform for secure quantum communications.
AlN, and GaN by MBE.50) The transition metal nitride layers Epitaxial nitride metals can potentially serve as buried
offer several features that can be exploited in future genera- interconnect layers in structures that have several transistor
tions of devices. Similar to layered hBN nucleation layers, layers vertically stacked for 3D integration. These intercon-
they offer a way to be selectively etched chemically, allowing nects can become lossless at temperatures below which the
complete liftoff of epilayers or processed devices on top.51) nitride metals become superconducting. The possibility of
Epitaxial transition metal nitride epitaxial layers of desired epitaxial growth of superconductor/insulator/superconductor
thicknesses down to a few nanometers can be inserted in tunnel junctions (e.g. NbN/AlN/NbN) offers a possibility to
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Jpn. J. Appl. Phys. 58, SC0801 (2019) PROGRESS REVIEW
realize Josephson junctions with low variation of properties of semiconductors, ferroelectrics, magnets, and superconduc-
that depend sensitively on the tunnel barrier thickness, and its tors. Because of the richness of these material properties, the
chemical, electronic, and structural properties. Such new nitrides have the potential to significantly expand the
Josephson junctions have been grown epitaxially in the past electronic and photonic applications space of nitride materials
by sputtering, proving their feasibility.54) Epitaxial growth in the classical information systems for computation,
offers the possibility of scalability to large wafer sizes, and memory, and communications. Furthermore, because of the
the potential integration with GaN electronic devices such as confluence of these material properties in a single epitaxial
RF amplifiers, transistor switches, AlN based micro-electro- nitride material platform, it offers unique opportunities for
mechanical systems and acoustic wave structures. These quantum information systems of the future.
building blocks offer opportunities for superconducting
Acknowledgments
digital (von-Neumann) electronics using established para-
digms such as the Rapid single-flux quantum (RFSQ)55), The authors acknowledge financial support from the
while significantly enhancing the toolset than in the past. Semiconductor Research Corporation (SRC/DARPA) Joint
More interestingly, the combination of nitride Josephson University Microelectronics Program (JUMP), an Office of
junctions with NbN based transmission lines for super- Naval Research grant (#N00014-17-1-2414) monitored by
conducting qubits, NbN single photon detectors, GaN Dr. Paul Maki, a US Air Force Office of Scientific Research
HEMT based RF amplifiers, and AlN based acoustic wave grant (AFOSR FA9550-17-1-0048) monitored by Dr. Ken
structures provide the ingredients necessary for a all-nitride Goretta, a NSF EFRI-2DARE (#1433490), a NSF DMREF
platform for quantum computation and communications.56,57) (#1534303), a NSF E2CDA (#1740286), and a NSF RAISE
The combination of the high RF powers generated by GaN TAQs (#1839196) monitored by Dr. D. Dagenais. The
HEMTs today, with the potential for superconducting NbN authors are grateful for a research collaboration with Dr.
based lossless microwave cavities offer the potential for David Meyer and his research group at the Naval Research
superconducting RF cavities that generate high powers in Laboratory. Discussions with Profs. Darrell Schlom, Dan
very narrow frequency ranges with quality factors in the Ralph, Bruce Van Dover, Bob Buhrman, Farhan Rana, David
billions. Such devices are of interest in on-chip precision Muller, Katja Nowack, and Greg Fuchs of Cornell
clocks, particle accelerators, and also for various medical University, Prof. Guillaume Cassabois of the University of
applications. Of course, for all such applications the nitride Montpellier, Prof. Sergei Novikov of the University of
superconducting materials must be cooled below the critical Nottingham, Prof. Hong Tang of Yale University, Prof. Dr.
temperature, the highest of which is Tc ~ 17 K for NbN. We Detlef Hommel and Dr. Edyta Piskorska of the Polish
are still far from higher temperature nitride superconductors. Academy of Sciences, Dr. Takashi Taniguchi of NIMS
In 1987, a new class of “high-Tc ” superconductors were (Japan), Dr. Tom Kazior of Raytheon, Dr. Han Wui Then
discovered in layered oxides, called the cuprates (such as of Intel, Dr. Young-Kai Chen of DARPA, and Dr. Yu Cao of
Yttrium Barium Copper Oxides).58) The highest critical Qorvo are gratefully acknowledged.
temperatures such “high-Tc ” superconductors today stands
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