REVIEWS

Materials discovery at high pressures

Lijun Zhang1,2, Yanchao Wang2, Jian Lv1 and Yanming Ma2,3
Abstract | Pressure is a fundamental thermodynamic variable that can be used to control the
properties of materials, because it reduces interatomic distances and profoundly modifies
electronic orbitals and bonding patterns. It is thus a versatile tool for the creation of exotic
materials not accessible at ambient conditions. Recently developed static and dynamic
high-pressure experimental techniques have led to the synthesis of many functional materials
with excellent performance: for example, superconductors, superhard materials and high-ener-
gy-density materials. Some of these advances have been aided and accelerated by first-principles
crystal-structure searching simulations. In this Review, we discuss recent progress in
high-pressure materials discovery, placing particular emphasis on the record high-temperature
superconductivity in hydrogen sulfide and on nanotwinned cubic boron nitride and diamond, the
hardest known materials. Energy materials and exotic chemical materials obtained under high
pressures are also discussed. The main drawback of high-pressure materials is their
destabilization after pressure release; this problem and its possible solutions are surveyed in the
conclusions, which also provide an outlook on the future developments in the field.

1
Key Laboratory of
Automobile Materials of MOE
and Department of Materials
Science and Engineering,
Jilin University.
2
State Key Laboratory
of Superhard Materials,
Department of Physics,
Jilin University.
3
International Center of
Future Science, Jilin
University, Changchun
130012, China.
Correspondence to Y.M.
mym@jlu.edu.cn
doi:10.1038/natrevmats.2017.5
Published online 21 Feb 2017
The discovery of new materials often lies at the base
of important innovations for industrial applications.
Moreover, it provides insight into fundamental scien-
tific issues. New materials can be obtained by tailoring
intrinsic materials parameters that can be controlled
during synthesis and processing, such as chemical com-
position, dimensionality (for example, moving from 3D
to 2D samples) and geometric size of the sample features
(controlled, for example, by nanostructuring). Another
possibility is to induce changes in the material through
external parameters, such as temperature, pressure, epi-
taxial strain, or electric and magnetic fields. In particu-
lar, pressure, which is a fundamental thermodynamic
variable determining the properties of materials, can
influence the microscopic structure, the interatomic
electrostatic interactions, the electronic orbitals and the
chemical bonding (BOX 1). For decades, pressure has been
widely used as a powerful tool in the discovery of materi-
als inaccessible at ambient conditions1–10. High pressure
enables the creation of new materials mainly through
four routes, as discussed below.
Routes for new high-pressure materials
Producing new materials through phase transitions.
By altering interatomic distances and bonding pat-
terns (BOX 1), high pressure can change the energetic
stability of the various possible structures and thus
generate new materials through structural phase transi-
tions1,11,12. A well-known example is synthetic diamond
(the hardest known material, with sp3 C–C bonding),
which is made by the compression of graphite (a lay-
ered soft material with sp2 C–C bonding) (FIG. 1a). The
high pressure reverses the energetic order of these two
carbon allotropes, so that diamond becomes energet-
ically more favourable than graphite, and at the same
time helps to overcome the high activation barrier for
the conversion between the two phases (FIG. 1b). This
facilitates the graphite-to‑diamond transformation
during the high-temperature and high-pressure syn-
thesis process. In a similar way, cubic boron nitride
(c‑BN) is synthesized from hexagonal BN (REF. 13).
Every material typically experiences several structural
transformations when compressed (FIG. 1c) up to a
pressure of a few megabars (1 megabar = 1 × 106 atmos-
pheres = 100 GPa). Exciting physical properties emerge
in structures accessible only at high pressures. Examples
include superconductivity in various insulating elements
(such as Si, B, S and O)14, record-high hardness in nano-
twinned diamond15 and c-BN16, high-energy high-
density polymeric nitrogens17–19, and insulating electride
phases20–22 of Na and Li.
Stabilizing new stoichiometries. Structural phase transi-
tions originate from qualitative changes in the potential
energy landscape. Pressure can also effectively modify
the compositional landscape, leading to stabilization of
the exotic stoichiometries that would not be expected
from the conventional wisdom based on chemical
rules at ambient conditions. Examples include alkaline-
earth/transition metal nitrides23,24, hydrogen-rich metal

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hydrides25 (such as LiHx (REF. 26), FeH2/H3 (REF. 27),
RhH2 (REF. 28), and IrH3 (REF. 29)) and unusual stoichio-
metries of sodium chloride (such as Na3Cl and NaCl3)30.
Superconductivity with a critical temperature of 203 K
was discovered31 in compressed hydrogen sulfide (H2S)
and was shown to emerge32–36 from the decomposition
of the material into the unprecedented stoichiometry
H3S. This experimental breakthrough was motivated by
theoretical predictions37.
By enabling new structures and stoichiometries, high
pressure offers a unique degree of freedom to explore the
structure–property relationships of materials.
Enabling new chemical reactions. High pressure can
affect the chemical reactivity of elements by influencing
the electronic orbitals and their occupancy (BOX 1). Several
exotic compounds inaccessible at ambient conditions
have been synthesized under pressure, such as nitrides
of elements of the group IVA (X3N4 with X = Si and
Ge)4,8,23,24, transition metal nitrides (such as PtN2, IrN2,
Zr3N4 and Hf3N4)23,24, Si‑based Zintl-phase and clathrate
compounds4,5, and H2-containing molecular complexes
(such as H2O–H2 and CH4–H2 mixtures, SiH4(H2)2 and
Xe(H2)8)3,10,25,38. Even more intriguingly, chemically inert
rare gases (He, Ar, Kr and Xe) have been theoretically pre-
dicted to react with various elements (such as Li (REF. 39),
Mg (REF. 40), Fe or Ni (REF. 41), and N2 (REF. 42)) under
pressure. The reactions available at high pressures lead to
a vast variety of materials with unprecedented bonding,
chemical stoichiometries and properties.
Changing the electronic properties of materials. Even
in the case when the structure and stoichiometry remain
unchanged under pressure, the electronic properties
can be fundamentally modified. Pressure significantly
reduces interatomic distances and strengthens inter­
atomic interactions, leading to a broadening of the energy
bands. The ensuing band overlap can cause a pressure-
induced insulator-to‑metal or semiconductor-to‑metal
transition1. High-pressure metallization enables the cre-
ation of new superconductors. Few elemental solids are
superconductive at ambient pressure, but high pressure
turns most elements (including the closed-shell rare
gases) into superconductors14. In some exotic cases, met-
als can transform into insulators and form electrides with
all the valence electrons localized in the interstitial voids
of the lattice43. Pressure can also regulate long-range spin-
or charge-ordering states1; for example, it may trigger a
transition from high to low spin state44, or destabilize
spin-45 or charge-density wave states46.
Recently developed crystal-structure searching
methods based on accurate first-principles energetic
calculations have enabled the theoretical design of
high-pressure materials, and effective collaboration

Box 1 | Effects of pressure at the atomic scale

Changing interatomic distances and bonding patterns
The most straightforward effect of pressure on materials is the volume decrease, which leads to a reduction of the
interatomic distances. This considerably modifies the electron hybridization and the chemical bonding. High pressure can
convert weak π, van der Waals and hydrogen bonds into strong covalent or ionic bonds183,184 and increase the coordination
number (for example, from the fourfold coordination in zincblende or wurtzite structures to the sixfold coordination of
NiAs or NaCl structures11).
Electron delocalization
Pressure induces an increase in electron density that results in a faster growth of the kinetic energy of electrons as
compared with their potential energy. Therefore, there is a general tendency towards electron delocalization, which
results in pressure-induced energy-band broadening, gap closure and metallization. Sufficiently high pressures can, in
principle, convert all insulators into conductors. Under pressure, many materials that are insulating under ambient
conditions can become superconductors after metallization14.
Electron transfer among different atomic orbitals
Pressure can change the energetic ordering of the outer atomic orbitals (such as the s, p and d orbitals), which can thus
hybridize as a consequence of the distinctive changes in the slopes of the orbital energies induced by pressure43. As a
result, electrons can be transferred from occupied to unoccupied orbitals through orbital hybridization. Many intriguing
properties of high-pressure materials formed by alkali metals originate from s–p, s–d and p–d electron transfers; examples
include the formation of insulating phases of Na (REF. 20) and Li (REF. 201) and the rather complex crystal structure of the
Rb‑IV phase202, exhibiting s–p, s–d and p–d hybridizations that are rarely observed under ambient conditions20,203.
Exotic charge redistribution
On strong compression, the competition between the kinetic energy of the electrons and the various electrostatic
Coulomb interactions can lead to a charge redistribution within the lattice, with substantial energy gains for the
stabilization of new structures. Typical examples include charge localization at the interstitial sites of alkali metal
electrides20,22,191 and the formation of ionic phases in ammonia (NH4+NH2−)183,184 and NO2 (NO+NO3−)182.
Modifying the chemical identity of atoms
The chemical activity of outer-shell electrons responds to pressure differently in different atoms. Pressure can lead to
changes in the chemical identity of atoms: for example, in their electronegativity204. This substantially changes our
understanding of the chemical periodicity of the elements as listed in the periodic table: at high pressures, the alkali
metal Cs can show an oxidation state beyond +1 (REF. 178), Hg can behave as a transition metal with a +4 or +3 oxidation
state179, Au can become a 6p element exhibiting highly negative oxidation states beyond –1 (REF. 180), and the noble gas
Xe can become anionic40,41.

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a 120 b Graphite Diamond

Shock-wave
synthesis
30 Eb
Liquid
carbon
25
ΔG

Pressure (GPa)
Diamond
20

15
HPHT synthesis

10 Eb

5
Graphite
ΔG
0
0 1,000 2,000 3,000 4,000 5,000

Temperature (K)
c
14
Number of high-pressure phases

12

10

0
H

Li

Na

Al

Si

Fe

FeO

MgO

SiO2

H2O

MgSiO3

CaCO3
Figure 1 | Materials discovery through pressure-induced phase transitions. a | Phase diagram for diamond
Nature Reviewsand
| Materials
graphite, on which the area corresponding to the high-pressure and high-temperature (HPHT) synthesis of diamond is
shown. b | Schematic illustration of the potential energy profiles for the conversion between graphite and diamond in
different regions of the phase diagram. Pressure acts in two ways: it reverses the sign of the free energy difference (ΔG)
and reduces the energy barrier (Eb). c | Histogram showing the number of high-pressure phases for selected elemental,
binary and ternary solids.

between experimentalists and theorists has greatly expe-
dited materials discovery at high pressures47.
There are several review articles on high-pressure
research 1–12,14,23,24,38,48,49, mostly focusing on high-
pressure physics 1,11,12,14,48,49 or chemistry 2,3,6–8, or on
specific groups of materials23–25,38, but comprehensive
reviews addressing recent materials discovery at high
pressures4,5 are rare. In this Review, we focus on the
recent progress in materials discovery at high pressure.
We begin by summarizing the state of development of
tools for high-pressure materials discovery. We then
discuss four categories of high-pressure materials:
superconductive, superhard, energy and exotic mate-
rials. These are the predominant material systems that
have been investigated under high pressures and for
which substantial progress has been made. We select
some representative materials in each category (as sum-
marized in TABLE 1) and explore their properties and the
underlying physical mechanisms, their impact on our
fundamental understanding of materials science and
their potential for technological applications. The final
discussion highlights the key challenges in achieving
more practical discoveries of high-pressure materials
and overviews future research directions.
Tools
Experimental tools. High pressure can be applied by
using two types of equipment: systems that generate static
pressure, including diamond anvil cells and large-volume
presses (such as piston-cylinder devices, opposite-anvil
and multiple-anvil systems); and large-scale shock-wave
facilities that generate dynamic compression (BOX 2).
The diamond anvil cell is the most widely used labo-
ratory device for generating static, multi-megabar pres-
sures48. Pressures of up to 770 GPa have been attained
by using nanodiamonds as second-stage anvils in

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Table 1 | Examples of materials discovered at high pressures

Year Pressure (GPa) Material Brief description
Superconductive materials
1994 31 Hg–(Ba,Ca)–Cu–O Record Tc of 164 K in unconventional cuprate superconductors70
1997 190 S Record Tc of 17 K among non-metallic elemental
superconductors206
2002* 48 Li • Pressure-enhanced high superconductivity205 at Tc = 20 K
• Theoretical prediction207 in 2001
2006 216 Ca Record Tc of 29 K among elemental superconductors208
2008 6 Sm(O,F)FeAs Record Tc of 55 K in Fe‑based superconductors209
2008 107 Sc Record Tc of 19.6 K among transition metals210
2012 11.5 Tl/K/Rb–Fe–Se Exotic re‑emergence of a second superconducting phase71 with
Tc ≈ 48 K
2015* 155 H3S • Record Tc of 203 K among all superconductors31
• Theoretical prediction37 in 2014
Superhard materials
1998 4–5.5 B6O Synthesis of B6O that consists of Mackay packing of icosahedral B12
units119
2001 18 BC2N Synthesis of cubic BC2N with Vickers hardness of 76 GPa, higher
than that of c‑BN single crystals117
2002 20 BC4N Synthesis of well-sintered millimetre-sized bulk samples of
superhard BC4N with Vickers hardness118 of 68 GPa
2003 12–25 Nanograined Synthesis of nanograined diamond with extremely high Knoop
diamond hardness of 140 GPa, harder than single-crystal diamond124
2009 24 BC5 Synthesis of BC5 exhibiting Vickers hardness112 of 71 GPa
2012 39 BC3 Synthesis of BC3 by direct transformation from graphitic
phases113,114
2012 20 Nanograined c‑BN Synthesis of nanograined c‑BN with a twofold increase of
hardness125 (85 GPa) with respect to conventional polycrystalline
c‑BN
2013 12–25 Nanotwinned c‑BN Synthesis of new nanotwinned c‑BN with an extremely high Vickers
hardness of 108 GPa and superior thermal stability and fracture
toughness16
2014 10–25 Nanotwinned Synthesis of nanotwinned diamond with an unprecedented Vickers
diamond hardness of 200 GPa and superior thermal stability15
Energy materials
2004* 110 Polymeric N • Synthesis of a single-bonded cubic form of solidified nitrogen17
• Theoretical prediction145 in 1992
2004 120 NaN3 Transformation of molecular N3− ions into a non-molecular nitrogen
network in sodium azide at high pressures154
2014* 120–180 Polymeric N • Synthesis of a novel phase of layered polymeric N using
laser-heated diamond anvil cells18
• Theoretical prediction19 in 2009
2015 35 Polymeric N in Synthesis of the polymeric nitrogen backbone oligomer phase of
hydronitrogen hydronitrogen162–164
1996 10 H2–CH4 molecular Synthesis of a series of stable H2–CH4 molecular complexes211
complexes
2002 0.22 H2–H2O clathrates Stabilization of a third type of clathrate hydrate, H2(H2O)2, near
ambient pressure and below 150 K (REF. 170)
2011 8 RhH2 Discovery of the first dihydride in the platinum group metals with
high volumetric hydrogen density28
2013 55 IrH3 Discovery of the first trihydride in the platinum group metals29

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Table 1 cont. | Examples of materials discovered at high pressures

Year Pressure (GPa) Material Brief description
Exotic chemical materials
1996 31 Compound of K–Ni Pressure-induced reaction between alkali and transition metals212
2001 20 Ionic NO+NO3− Formation of the unusual ionic solid182 NO+NO3− by compressing
N2O at temperatures above 1,000 K
2007* 41 C2N2(NH) Prediction and synthesis of the first pure sp3-bonded carbon
nitride175
2007 ~15 Amorphous Polymerization reaction between unsaturated hydrocarbon species
hydrogenated C in benzenes under pressure172
2009* 200 Electride phase Theoretical and experimental demonstration of the
of Na pressure-induced transformation of a good metal, Na, into an
optically transparent insulating electride phase20
2009 80 Electride phase Metal‑to‑semiconductor transition in Li with the formation of an
of Li electride phase at high pressures201
2012 57 Superionic phase Discovery of superionic ammonia ice213 at high pressures and
of NH3 temperatures above 700 K
2012 56 Superionic phase Observation of superionic conduction in H2O at high pressures and
of H2O high temperatures214,215
2013* 10–80 NaxCly Theoretical and experimental demonstration of sodium chlorides
with exotic stoichiometries emerging at high pressures30
2014* ~120 Ionic NH4+NH2− • Solid molecular ammonia transforming into an ionic phase under
pressure183,184
• Theoretical prediction185 in 2008
2016* 44 C3N4 Theoretical and experimental discovery of a new C3N4 phase with
an unusual open framework structure176
c-BN, cubic boron nitride; Tc, critical temperature. *Discoveries guided by theory.

double-stage diamond anvil cells50,51; recently, a record
pressure of more than 1 TPa has been achieved52. In
addition to the extremely high generated pressures,
diamond anvil cells have the advantage of being com-
patible with a vast range of in situ measurement tech-
niques. Indeed, diamond’s excellent transmittance of
almost the entire electromagnetic spectrum allows the
use of various radiation detection approaches, includ-
ing X‑ray and neutron diffraction, as well as various
spectroscopic techniques (such as Raman and infra-
red spectroscopy, Brillouin scattering, visible light
and X‑ray emission/absorption spectroscopy; BOX 2).
By fabricating diamond anvils with embedded elec-
trodes and other measurement circuits, measurements
of electric and magnetic properties can be performed
in situ48. The disadvantage of diamond anvil cells is that
the volume of sample that can be accommodated in the
anvil (which is made of flawless diamond with a mass
of about 0.2–0.4 carat) is very small. This may result
in a signal that is too weak to be measured when using
techniques that require a large amount of sample, such
as neutron diffraction. Another drawback of the small
sample size is the inability to use diamond anvil cells
to synthesize commercial quantities of new materials.
Large-volume presses and dynamic-compression facil-
ities do not have this problem, and can be used to pro-
duce many technologically useful materials. However,
a large-volume static pressure apparatus can only reach
pressures of several tens of gigapascals, much lower than
those achievable in a diamond anvil cell. Improvements
in the design of the apparatus and the replacement of
tungsten carbide by sintered diamond allowed a max-
imum pressure of more than 90 GPa to be reached in
a multiple-anvil device that used a 14 mm sintered
diamond cube53.
Dynamic-compression facilities use shock waves
to generate pressures well into the terapascal range54.
Various techniques can be used to produce the shocks,
including gas guns, laser-driven compression and hemi­
spherically converging explosives. However, the tran-
sient nature of the shock wave means that it is generally
difficult for samples to reach thermodynamic equilib-
rium. Thus, there are usually large uncertainties in the
measured properties of the investigated materials49.
Theoretical tools. In addition to the development of
experimental techniques, first-principles density func-
tional theory (DFT) calculations have had a substan-
tial impact on materials discovery at high pressures11.
DFT calculations allow a wide range of properties (such
as electronic, elastic, vibrational, magnetic and even
superconductive properties) to be reliably obtained for
high-pressure materials. Pressure-induced structural
phase transitions can be readily investigated using total
energy minimization for different structures as a func-
tion of pressure. DFT energetic calculations can precisely

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distinguish the relative stabilities of competing phases
with a resolution of a few millielectronvolts. These cal-
culations can therefore provide new insight and help in
understanding experimental observations; for example,
they are useful to determine the actual phase stability and
to assign electronic and vibrational excitation modes.
Higher-level calculations such as quantum Monte Carlo
methods are in principle more accurate than DFT, but
are computationally more expensive; consequently, they
have been applied only to systems containing very few
atoms49, such as solid H and He. Whereas DFT calcula-
tions apply to high-pressure materials at low tempera-
tures, molecular dynamic simulations are an important
tool for the study of dynamic processes at high pressure
and high temperature.
Recently, there has been remarkable progress in the
development of first-principles crystal-structure search-
ing methods, leading to several successful high-pressure
discoveries47. Structure-searching methods combined
with reliable DFT calculations can explore compli-
cated high-dimensional free-energy surfaces to seek the
global energy minimum corresponding to the most sta-
ble ground-state structure. Knowing only the chemical
composition, these methods can identify the thermo-
dynamically stable structures of materials under pres-
sure: this gives the theory predictive power that can be
used to guide experimental studies, as highlighted (with
asterisks) in TABLE 1. Many efficient global optimization
Box 2 | Tools for high-pressure materials discovery
Several experimental and theoretical tools can be used for high-pressure (HP) materials
discovery. The characteristics of the different techniques used to generate high
pressure are summarized in the table below. Several in situ characterization techniques
can be used to investigate the properties of materials generated under high pressure,
as listed below. The various theoretical simulation methods can be divided into
standard simulation techniques and structure searching techniques, which have had a
leading role in several recent discoveries of high-pressure materials.
HP generation technique Pressure (GPa) Sample size (cm3)
Static compression
Large volume press ~90 ~10–102
Diamond anvil cell ~1,000 10–9–10–6
Dynamic compression
Shock-wave facilities 5,000 ~10
In situ characterization techniques Theoretical simulation techniques
• X‑Ray diffraction Static and dynamic calculations
• Neutron scattering • Density functional theory
• Brillouin scattering • Quantum Monte Carlo simulations
• Raman spectroscopy • Molecular dynamic simulations
• Infrared spectroscopy Structure searching techniques
• Visible light emission/absorption • Simulated annealing
spectroscopy • Minima hopping
• X‑Ray emission/absorption • Metadynamics
spectroscopy • Random sampling
• Electrical measurements • Genetic algorithms
• Magnetic measurements
• Swarm optimization algorithms
schemes for structure searching have been developed;
those frequently used in high-pressure research include
methods designed to overcome energy barriers (such
as simulated annealing 55, minima hopping 56 and meta­
dynamics algorithms57) and global minimization meth-
ods (such as random sampling 58, genetic algorithms59–62
and swarm optimization algorithms63,64).
Superconductive materials
Role of pressure in creating superconductors. High pres-
sure has long been used as an effective tool to obtain
new superconductors. Superconductors can be divided
into two categories: conventional and unconventional.
Conventional superconductors are described by the
Bardeen–Cooper–Schrieffer (BCS) theory; their super-
conductivity arises from electron pairing mediated by
the exchange of phonons, which results in a superfluid-
like behaviour. High pressure had an important role
in the discovery of conventional superconductors: of
the 53 known elemental superconductors, only 30 are
super­conductive at ambient pressure, the others become
superconductive only at high pressure65,66 (FIG. 2a).
Unconventional superconductors are not described by the
BCS theory, and their superconducting mechanism is yet
to be understood. Pressure strongly influences the prop-
erties of unconventional superconductors. Depending on
the doping levels of the investigated material, the critical
temperature (Tc) for cuprates67,68 and Fe‑based super-
conductors69 can increase, remain constant or decrease
under pressure. The underlying mechanism might be
associated with changes in the interplay among various
factors affecting superconductivity, such as charge, orbital
and spin excitations. The highest Tc for a cuprate (164 K)
was achieved at ~31 GPa in HgBa2Cam – 1CumO2m + 2 + δ (with
m = 1, 2 and 3, and the doping level controlled by δ)70.
High pressure has been reported to destroy the original
superconducting state in Fe chalcogenide superconduc-
tors, subsequently inducing an intriguing alternative
superconducting state71 with a higher Tc. Pressure can also
efficiently suppress the magnetic orders that compete with
super­conductivity, as demonstrated in heavy-fermion
systems72 and undoped Fe-based superconductors69.
Searching for new superconductors at high pressures
is promising mainly because of two effects that pressure
has on materials. In metals, pressure-induced structural
phase transitions can generate new structures that can
be superconductive — examples for elemental metals14,65
include Ca, Cs, Y, Fe, Sc, Sr and Ba. In insulators and
semiconductors, pressure induces electronic phase tran-
sitions from the insulating or semiconducting state to a
metallic state through the closure of the bandgap. Once
metallized, these materials have the potential to become
superconductive. Thus, there is a significant number
of high-pressure superconductors derived from non-
metallic elements14, including B, O2, Si, P, S, Se, Br2 and I2.
Pressure also induces the generation of free carriers for
superconductivity in an effect that to some extent resem-
bles the superconductivity induced by impurity doping
in insulating materials (such as B‑doped diamond)73.
Among insulating mat­erials that become superconduc-
tive under pressure, S shows74 a relatively high Tc of 17 K

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H TcM (in K) SC at ambient pressure He

Li48
20.0

Li20.0 Be0.026 P* (in GPa) for TcM SC only at high pressure B11.0 C N O100
0.6
F Ne
48 250

Na Mg Al1.1 Si15
8.2
P30
13.0
S17.3
190 Cl Ar

K Ca216
29.0
Sc19.6
106
Ti3.4
56
V16.5
120
Cr Mn Fe2.1
21
Co Ni Cu Zn0.9 Ga7.0
1
Ge5.4
12
As32
2.4
Se8.0
150
Br1.4
100
Kr

Rb Sr7.0
50 Y115
19.5
Zr11.0
30 Nb10
9.9
Mo0.9 Tc7.8 Ru0.5 Rh 0.3×10-3
Pd Ag Cd0.5 In3.4 Sn11
5.3
Sb3.9
25 Te7.5
35 I1.2
25 Xe

Cs1.3
12 Ba18
5.0
La13.0
15 Hf 62
8.6
Ta4.5
43 W0.012 Re1.4 Os0.7 Ir0.1 Pt Au Hg4.2 Tl2.4 Pb7.2 Bi8.5
9 Po At Rn

Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg Cn

Ce1.7
5 Pr Nd Pm Sm Eu142
2.8
Gd Tb Dy Ho Er Tm Yb Lu12.4
174

Th1.4 Pa1.4 U2.4

1.2 Np Pu Am2.2
6 Cm Bk Cf Es Fm Md No Lr

b 250 Experimentally observed

200 Theoretically predicted
TcM (K)

150

100

50

0
Al
Al
As H 2)
B2
Ba
Be
BH
Ca
Ga
Ge
H2
KH
La
LiH
LiH
M
Nb 2
Pt
Sb
Sc
Si 2
Si
Si
Sn (H 2) 2
YH
YH
YH
H–

H–
H4
H4
gH
H6
H3
H3

H
H3
S

H3
H8

H6
H2

H4
H4

H6

S
H6
H3
H4

H4

6
6

8
(

c 1 d
150 200

125
150
100
Tc (K)

Tc (K)

75 100

50
50
Experiment H2S
25
Theory D2S

0 0
100 150 200 250 150 200 250
Pressure (GPa) Pressure (GPa)

Figure 2 | Superconductive materials obtained at high pressures. a | Superconductive periodic Nature

table Reviews | Materials
for elemental
solids. The elements that are superconductive at ambient pressure are shaded in grey, the ones that are superconductive
only at high pressure in blue. For both ambient-pressure and high-pressure elemental superconductors, the maximum
superconducting critical temperature (TcM) and the pressure needed to achieve it (P*) are indicated. The values of TcM and
P* are taken from REFS 14,65, apart from those for Li, which are from REF. 205. b | Histogram showing the TcM values for the
superconducting H‑rich hydrides that have been experimentally observed (green) or theoretically predicted (grey). H–P
represents undetermined stoichiometry of a superconductive sample and H–S represents two superconductive states in
different stoichiometries (see text). c | Pressure dependence of Tc for H2S samples prepared at low temperature (~100 K).
The experimental values for Tc below 80 K are in good agreement with the theoretical prediction (grey stars) from REF. 37.
d | Pressure dependence of Tc for H2S and for D2S samples (prepared at 220 K and then cooled to 100 K) annealed at room
temperature; the highest Tc is 203 K. SC, superconductive. Panels c and d are adapted with permission from REF. 31,
Macmillan Publishers Limited.

at 100 GPa; this high critical temperature is attributed to
the pressure-induced suppression of charge-density-wave
instabilities75. Hydrogen‑rich mat­erials that are insulating
at ambient pressure can be metallized and become good
super­conductors at high pressure, as is discussed in more
detail next.
Hydrogen-rich materials. In 1968, Ashcroft proposed
that metallic solid H obtained under pressure has the
potential to be a room-temperature superconductor 76.
According to the BCS theory, H — the lightest element,
with one unscreened electron — under pressure would
form a metallic solid with the high Debye temperature

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and strong electron–phonon coupling required for
high-temperature phonon-mediated superconductivity.
Unfortunately, studies77 at up to 388 GPa failed to real-
ize the metallization of solid H. A recent report on the
metallization of solid H at 495 GPa (REF. 78) has received
great attention. More experimental results are needed
to confirm this extroadinary claim. In 2004, Ashcroft
shifted his attention to H‑rich materials, which mimic
the solid phases of H, but can be metallized at much
lower pressures79. This proposal motivated many theo-
retical studies predicting that compressed H‑rich mate-
rials would show high-temperature superconductivity
with Tc up to 264 K (for example, Tc = 166 K was pre-
dicted for SiH4 (REFS 80,81), 20 K for Si2H6 (REF. 82), 64 K
for GeH4 (REF. 83), 100 K for SiH4(H2)2 (REF. 84), 235 K
for CaH6 (REF. 85), and 264 K for YH6 (REF. 86); FIG. 2b).
However, the experimental results were not encouraging:
only SiH4 exhibited superconductivity with a relatively
high Tc of 17 K (the origin of the superconductivity in
this system is still under debate87,88). The experimental
challenge hindering the production of these predicted
high‑Tc superconductors lies in the difficulty of synthe-
sizing the material structures identified by theory.
Solid hydrogen sulfide (H 2S) had not initially
been considered as a high-pressure superconductor,
because it was believed to dissociate into its constit-
uent elements before metallizing under pressure89,90.
Theoretical calculations that used a first-principles
structure-searching method64 demonstrated that such
elemental dissociation would not occur and that H2S
pressurized at 160 GPa would show superconductivity 37
with Tc = 80 K. Experimental investigations motivated
by this result demonstrated that H2S exhibits two super-
conductive states at pressures31 above 100 GPa. The first,
low-­temperature superconductive state (Tc = 30–75 K;
FIG. 2c,d) might be related to stoichiometric H2S, as the
measured values of Tc are consistent with the values cal-
culated37 for pressures below 160 GPa. In this pressure
region, the solidified H2S phase might be kinetically sta-
bilized against decomposition35. The abrupt Tc increase
(75–150 K) observed above 160 GPa might be ascribed to
the formation of a Magnéli phase derived from the mix-
ture91,92 of H2S and H3S. A second superconductive state
with Tc as high as 203 K is obtained in samples annealed
at room temperature (FIG. 2d) and can be ascribed to a
stoichiometric change from H2S to H3S. H3S is a known
stoichiometry of hydrogen sulfide that can be synthe-
sized under high pressure32; its further compression is
predicted to lead to high-temperature superconductiv-
ity 33 with Tc = 191–204 K. The superconducting samples
show a strong isotopic effect, as Tc significantly changes
if hydrogen is substituted by deuterium (FIG. 2d), pointing
toward a phonon-mediated pairing mechanism. The Tc
value of 203 K is the highest known for superconductors,
surpassing the earlier record of 164 K set by cuprates70.
The superconducting phase of H3S was experimen-
tally demonstrated34 to have an Im‑3m structure, as pre-
dicted by theory 33; superconductivity in this system is
accompanied by a strong anharmonic effect 35,93 and by
quantum H‑bond symmetrization94. Strong H–S covalent
bonding was suggested36 to be responsible for the large
electron–phonon coupling in H3S. More recently, it was
observed95 that in PH3, which is also a high-temperature
superconductor, Tc increases continuously from ~30 to
100 K as pressure increases up to 200 GPa. The super-
conductive structure of PH3 and the underlying physical
mechanism are yet to be determined, but all theoretical
models96–99 predict that PH3 decomposes under pressure,
and PH2 is a likely product96,99.
Room-temperature superconductivity is the focus
of intensive research. The experimental work on H2S
has disproved the conventional wisdom that 40 K is the
maximum Tc that can be obtained in phonon-mediated
superconductivity and, more significantly, demonstrated
the potential of H‑rich materials for high-temperature
superconductivity 31. A broad range of H‑rich systems is
available, offering the tantalizing prospect of imminently
achievable room-temperature superconductors.
Two properties of hydrides are beneficial for strong
electron–phonon coupling and thus high‑Tc super­
conductivity: the high H‑derived electronic density of
states at the Fermi level, and the strong dependence of
the electronic structure modifications on the motion of
the H atoms. Hydrides with very high H content sta-
bilized under high pressures are most likely to satisfy
the first criterion. The theoretical design of a series of
hydrides with high H content (such as H4I (REF. 100),
H4Te/H5Te2 (REF. 101), SnH8/SnH12/SnH14 (REF. 102), SbH4
(REF. 96) and AsH8 (REF. 96)) was attempted, but the high-
est predicted Tc was less than 150 K (REFS 96,100–102),
lower than that of H3S (REFS 33,36,93). This is attributed
to a particular feature of the structures of these materi-
als, because they all contain quasi-molecular H‑units,
unlike H3S, which is composed of 3D covalent-bonding
networks. As a result, their electronic structures are only
weakly affected by the motion of H atoms, and the sec-
ond criterion is not satisfied. Experimental efforts are
called for to focus on the synthesis of the 3D sodalite-like
cage structures of atomic H predicted for CaH6 (REF. 85)
and YH6 (REF. 86), in which the quasi-molecular H units
are absent and the maximum predicted Tc is 260 K.
Superhard materials
Superhard materials (with Vickers hardness HV > 40 GPa)
are of great industrial importance and find application
as, for example, cutting and polishing tools, coatings and
abrasives. Diamond and c‑BN are two traditional super-
hard materials. Diamond is the hardest known material
(HV = 60–100 GPa), but it has well-known limitations:
it is brittle, oxidizes to carbon dioxide at 800–900 °C
in air and reacts with Fe‑containing materials during
cutting. Although c‑BN is chemically and thermally
more stable than diamond, its hardness is much lower
(HV = 40–60 GPa), and the synthesis of large crystals
is difficult, which hinders its industrial application.
Therefore, finding alternative superhard materials that
are chemically and thermally stable is an important goal
for materials scientists.
Light-element-based materials. For a material to be
superhard, its structure must consist of densely packed,
3D, strongly covalent bonding networks. Pressure has

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become an important technique for synthesizing such
materials, because it induces volume decreases that
stabilize densely packed structures. Materials formed
from light elements (such as B, C and N) with high
electro­negativity have attracted considerable attention,
as they can form the necessary strong and short cova-
lent bonds. Examples include the traditional superhard
materials diamond and c‑BN, and many new super-
hard materials that have been synthesized under high
pressure103. Carbon has various allotropes (such as dia-
mond, graphite, nanotubes and fullerenes) because of
its ability to form sp-, sp 2- and sp 3-hybridized bonds.
Without a catalyst, graphite converts to diamond at
pressures above 15 GPa and temperatures above 1,600 K.
Conversely, if compressed at room temperature, above
14 GPa graphite transforms into a new superhard phase
that can indent diamond104. This room-temperature
post-graphite superhard phase adopts a monoclinic
C2/m structure (named M‑carbon), as demonstrated
by theoretical calculations105 and subsequently exper-
imentally confirmed106. This C2/m structure had been
already proposed61 as a metastable phase of carbon.
The compression of solvated C60 fullerenes has led to
another unprecedented superhard carbon phase able to
indent diamond, which is stabilized above ~32 GPa. The
structure is peculiar, composed of collapsed amorphous
carbon clusters occupying the lattice points of a peri-
odic hexagonal close-packed structure107. In this pres-
sure-induced phase transition, the solvent in the solvated
C60 has an important role as a bridge and spacer that
preserves the stability of the deformed or amorphized
C60 molecules108. Yet another carbon allotrope, a fully
sp3-bonded amorphous state possessing diamond-like
strength, has been produced by compressing glassy
carbon above 40 GPa (REF. 109). However, subsequent
Raman spectroscopy measurements have challenged
this finding 110.
The compounds formed by mixing B and C are prom-
ising materials, as they simultaneously display superhard-
ness and superconductivity 111: for example, B‑doped
diamond is a known superconductor 73. Diamond-like
BC5 (REF. 112) and BC3 (REFS 113,114) (synthesized at
high pressure and high temperature) exhibited a super-
hardness exceeding that of c‑BN (HV = 71 GPa for BC5),
and BC5 has been theoretically predicted115 to become
superconductive at 45 K. The crystal structure of the
diamond-like BC3 was solved using a first-principles
structure search that revealed a highly symmetric cubic
diamond structure containing a distinctive B–B bond-
ing network along the body diagonals of a large 64‑atom
unit cell116. Given that B incorporation into the diamond
lattice is notoriously hard, the synthesis of other B–C spe-
cies remains challenging. Similar experimental difficul-
ties apply to the synthesis of ternary B–C–N compounds
— only BC2N (REF. 117) and BC4N (REF. 118) have been
obtained after several decades of research. The superhard
materials based on B, C and N that have been theoreti-
cally predicted or experimentally realized and the corre-
sponding HV values are summarized in FIG. 3a. In addition
to B, C and N, other light elements (such as O and Si)
can participate in the formation of superhard materi-
als when compressed, such as B6O (REF. 119) and Si3N4
(REF. 120). The understanding of the interplay between
chemical bonding and mechanical performance of these
light-element-based superhard materials is a topic that is
attracting considerable interest121,122.
Hardening by nanostructuring. The search for materials
harder than natural diamond has been long and elusive.
Extensive hardness-driven design simulations on carbon
excluded the existence of any energetically competitive
crystalline carbon structure harder than diamond123. An
alternative route for the production of superhard mate-
rials involves applying Hall–Petch hardening, a method

a Diamond b 240
(60–120) Nanotwinned
diamond
200 HP-annealed
C CVD diamond
BC7 (78)
160
BC5 (71) BC4N C3N2 (86) Nanograined
H (GPa)

(68) diamond
BC3 (62) Aggregated
BC2N 120 Synthetic diamond Nanotwinned
(62–76) C3N4 (92) diamond nanorods c-BN
B4C (45)
80 Nanograined
CN2 (70) Aggregated c-BN
B13C2
BN nanocomposites
(56–58)
40
Threshold of superhardness
α-B (42) Synthetic c-BN
B N
β-B (45) B6N B13N2 c-BN 0
γ-B (50–58) (41) (40.8) (46–66)
55 57 03 04 06 07 12 13 14
19 19 20 20 20 20 20 20 20

Figure 3 | Light-element-based superhard materials. a | Composition triangle for B–C–N; the synthesizedNature Reviews | Materials
and predicted
superhard materials are shaded in grey and blue, respectively. Experimental Vickers hardness values (GPa; in brackets) are
given if available (grey shading), otherwise theoretical values are listed (blue shading). b | Historical timeline showing the
hardness (H) enhancement of diamond (in green) and cubic boron nitride, c-BN (in grey). The dashed line shows the
threshold of superhardness (40 GPa), and the grey-shaded area depicts the hardness range of natural diamond (60–120 GPa).
HP, high pressure; CVD, chemical vapour deposition. Panel b is adapted with permission from REF. 103, Annual Reviews.

NATURE REVIEWS | MATERIALS VOLUME 2 | ARTICLE NUMBER 17005 | 9

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that hardens materials by reducing the average grain
size (FIG. 3b). The underlying mechanism is based on
the fact that grain boundaries in polycrystalline mate-
rials impede dislocation movements between grains.
Experimentally synthesized nanograined diamonds124
with grain sizes of 10–30 nm have shown extremely high
Knoop hardnesses of 110–140 GPa. Nanograined c‑BN
samples125,126 with grains as small as 14 nm were syn-
thesized at pressures of ~20 GPa, and showed a record
Vickers hardness of 85 GPa. Nanograined diamonds in
polycrystalline form are produced in industrial-scale
quantities and are widely used in static pressure genera-
tion devices50–52 and in various superhard tools. Progress
has been made using onion-like nanoparticles as pre-
cursors to synthesize hitherto unexpected nanotwinned
(nt) c‑BN and diamond15,16. The resulting nt‑c‑BN (with
an average twin thickness of ~3.8 nm) possessed a strik-
ing combination of physical properties: an extremely
high Vickers hardness (>100 GPa), a high oxidation
temperature (1,294 °C) and a large fracture toughness
(>12 MPa m1/2). Synthetic nt‑diamond (with an aver-
age twin thickness of 5 nm) shows an unprecedented
Vickers hardness of up to 200 GPa and a superior oxi-
dation temperature, more than 200 °C higher than that
of natural diamond. It is worth noting that the hardness
of materials harder than diamond can be reliably meas-
ured, provided that a permanent plastic indentation can
be formed on the surface of the sample. To realize the
permanent plastic indentation, the shear strength of the
sample has to be lower than the compressive strength of
the indenter diamond, a condition that does not depend
on the relative hardness of the indenter and sample4,103.
Notably, nt‑c‑BN hardens continuously as the twin
thickness decreases down to the smallest size investi-
gated (3.8 nm), in contrast with the reverse Hall–Petch
effect observed in metals and alloys, which is caused
by grain boundary accommodation (such as sliding
and migration) and leads to materials softening when
the grain size decreases below a critical value. A possi-
ble explanation for this surprising behaviour is that the
quantum-confinement hardening effect (materials hard-
ening resulting from the quantum-confinement-induced
increase of the electronic bandgap) observed in covalent
nanocrystals103,127 might counteract the grain boundary
accommodation. Thus, the creation of nt‑microstruc-
tures in covalent systems offers a general pathway for
manufacturing new advanced superhard materials with
exceptional thermal stability and mechanical properties.
Transition metal/light-element compounds. Materials
formed by heavy 4d and 5d transition metals and light
elements (such as B, C, N and O) have also received con-
siderable attention. This class of materials can resist both
elastic and plastic deformation owing to the high density
of electrons in transition metals and the strong direc-
tional bonds formed between the metals and light ele-
ments128. Some transition metal carbides and borides can
be synthesized at ambient pressure by arc melting; W–B
compounds are the most widely investigated129–132, and
WB4, the material with the highest B content, was sug-
gested to be the hardest known heavy-transition-metal/
light-element compound 132. Most transition metal
nitrides can only be synthesized under high pressures
(this is the case, for example, for PtN (REF. 133), PtN2
(REF. 134), OsN2 (REF. 135), IrN2 (REFS 134,135), and NbN
(REF. 136)). These heavy-transition-metal/light-element
compounds typically possess large bulk moduli com-
parable to those of B–C–N compounds, but have much
lower hardness, in the range of 20–30 GPa. For example,
NbN has a bulk modulus of 348 GPa, comparable to that
of c‑BN, but its hardness is only 20 GPa, close to that of
sapphire136. Despite having low hardness, the excellent
ductility and superior chemical and thermal stability of
these materials can be of interest for industry. Challenges
remain for the synthesis of a true superhard material —
with HV above 40 GPa — in this class of compounds.
Theoretical design of superhard materials. Hardness,
in general, is understood as the extent to which a solid
resists permanent plastic deformation when a compres-
sive force is applied. However, hardness is not a well-­
defined physical quantity, and thus in principle it cannot
be calculated, posing a considerable challenge to the
theoretical design of superhard materials. In 2003, a pio-
neering work137 proposed a semi-empirical model for the
evaluation of hardness in covalent materials. The model
established a direct link between macroscopic hardness
and microscopic atomic and electronic structure through
the explicit consideration of bond density, bond length
and bond ionicity, making the calculation of hardness
feasible and portable. Inspired by this work, several other
empirical hardness models were proposed, and they all
work well for covalent systems138–140. The theoretical
design of superhard materials has thus become possible,
especially when the empirical models are combined with
crystal-structure searching techniques63,64. Thus, even the
hardness-driven design of superhard materials is now
feasible123,141. Notably, the ideal strength, which sets an
upper limit for the stress that can be applied to a perfect
crystal without leading to structural failure, is widely con-
sidered as a good approximation of hardness121.
Energy materials
High-energy-density materials. High-energy-density
materials (HEDMs) for propellants and explosives
synthesized at high pressures also attract considerable
research interest. Polymeric solids consisting of molecu-
lar units made of low-atomic-number elements forming
extended 3D structures are promising HEDMs, because
a large amount of energy can be released during the
transformation from the high-energy polymeric phase
to the energetically favoured molecular phase142.
Owing to the remarkable difference in the average
bond energy between the single N–N bond (160 kJ mol−1),
the double N=N bond (418 kJ mol−1) and the triple N≡N
bond (954 kJ mol−1), polymeric nitrogen solids have been
regarded as the best HEDMs. High pressure can efficiently
break the strong intramolecular N≡N bonds for the syn-
thesis of the polymeric nitrogen phases. The first efforts to
create polymeric nitrogen can be traced back to the 1980s,
when the phase boundary between the low-pressure dia-
tomic N2 phase and the high-pressure polymeric phases

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became the subject of considerable interest 143,144. The
cubic gauche structure (cg-N) of solid nitrogen (FIG. 4a)
was the first predicted nitrogen polymeric phase, with a
calculated energy storage capacity more than three times
as high as the most powerful energetic materials in use at
the time145. Following this pioneering work, many other
polymeric phases were theoretically proposed, including
metastable phases that required high pressures for their
production19,146–149. On compression to 500 GPa, the ener-
getically stable phase-transition sequence for polymeric
N is cg‑N → orthorhombic Pba2 → body-centred cubic
I-43m (FIG. 4b,c). Of particular interest is the I-43m dia-
mondoid N10 phase148 that is predicted to be stable above
263 GPa and that is unique to solidified N. This crystalline
phase has a highly symmetric body-centred cubic struc-
ture with lattice sites occupied by diamondoids, each
of which consists of 10 nitrogen atoms that form a N10
tetracyclic cage.
The synthesis of polymeric nitrogen under pressure
is challenging, and initially only amorphous products,
probably composed of small clusters of non-molecular
phases, were obtained during compression at room tem-
perature150–152. The purely singly bonded crystalline form
remained elusive until 2004, when the cg-N phase17,153
(FIG. 4a) was synthesized at high pressure (110 GPa) and
high temperature (2,000 K). More recently, in another
remarkable high-pressure experiment 18 that used laser
heating at pressures of 120–180 GPa, the theoretically
predicted layered Pba2 polymeric phase (FIG. 4b) was
successfully synthesized19. The synthesis of the dia-
mondoid N10-cage phase148 is a highly desirable goal for
future research.
Although the crystalline cg‑N and Pba2 phases of pol-
ymeric nitrogen have been experimentally realized, the
ultrahigh pressures required to stabilize them (>110 GPa)
a b
preclude their preservation at ambient pressure for prac-
tical use. In an effort to reduce the required synthetic
pressure, an alternative route involving the pressur­
ization of N‑rich compounds through the introduction
of other elements has been explored. Alkali-metal azides
(AN3, with A = Li, Na, K or Cs) have been extensively
investigated for this purpose154–157. A sequence of phase
transitions is indeed observed, but the high-pressure
structures are yet to be solved. Theoretical predictions of
the stabilization of peculiar benzene-like planar rings of
polymeric nitrogen158,159 (FIG. 4d) received particular atten-
tion because of the unusual structure and high energy
density of these structures. Besides the study of known
N‑containing compounds under pressure, the compres-
sion of mixtures of N2 and other molecular species, such
as LiN3 (REF. 160), NaN3 (REF. 161), CO (REF. 161) and H2
(REFS 162–164), has also been explored. This is a prom-
ising route to the fabrication of polymeric nitrogen near
ambient pressure, because the polymerization pressure is
substantially reduced. For example, a pressure of 9.9 GPa
was predicted160 to be sufficient for the stabilization of
polymeric nitrogen networks in LiN3/N2, and a pressure
of 18 GPa for CO/N2 mixtures165. For the N2 + H2 systems,
the polymeric nitrogen backbone oligomer phase was
synthesized at 35–50 GPa, but its crystalline structure
has still to be determined162–164. Theoretical structure
searches have predicted more polymeric phases of N–H
materials166,167 that are awaiting experimental verification.
Experiments that used a mixture of NaN3 and N2 as pre-
cursor showed that cg‑N can form at a lower pressure
(50 GPa) than that needed with a pure N2 precursor 161. Of
particular interest is the stabilization of N5− rings of poly-
meric nitrogen that are predicted for LiN5 (REFS 160,168)
(FIG. 4e). Besides the relatively low synthetic pressure
(~9.9 GPa) and the unusual structure of the N5− rings,
the decomposition of LiN5 is expected to be highly exo-
thermic, releasing an energy of approximately 2.72 kJ g−1.
These findings on compressed N2 mixed solids offer an
alternative route for the practical synthesis of polymeric
nitrogen as a HEDM under relatively mild conditions.

Materials for hydrogen storage. In addition to HEDMs,

materials for hydrogen storage are another class of
energy materials that has been extensively studied
N under high pressures. One category of such materials is
Li the family of H2-containing molecular complexes that
are formed by compressing together high-density H2
c d e molecules and other simple molecules. The synthesis
of these H2-containing molecular complexes through
high-­pressure routes has been attempted by placing H2
molecules into matrices of rare gases, silane, germane,
hydrogen sulfide, methane and water ice3,10,25,38. Of these,
H2O–H2 systems are particularly promising. Two types
of H2-filled clathrate hydrates can be synthesized with
H2O:H2 ratios of 6:1 (above 0.7 GPa) and 1:1 (above
2.3 GPa)169. A third type of clathrate hydrate, H2(H2O)2
(REF. 170), was synthesized38,171 at ambient pressure below
Figure 4 | Crystal structures of different phases of polymeric nitrogen. Cubic
gauche145 (panel a), Pba2 (REF. 19) (panel b) and I-43m (REF. 148)Nature Reviews | Materials
(panel c) nitrogen phases ~150 K and at ~0.36 GPa below ~274 K. The other cat-
are shown. The structures of LiN3 (REFS 158,159) (panel d) and LiN5 (REF. 160) (panel e), egory of materials for hydrogen storage comprises
which exhibit intriguing sixfold and fivefold rings of polymeric nitrogen, respectively, are metal hydrides with high hydrogen content. At ambient
also shown. The dashed rectangles and rhombus indicate the unit cells. pressure, most known late-transition-metal hydrides
C Carbon Cl Chlorine (or Fluorine, F)
O Oxygen Br Bromine
NATURE REVIEWS | MATERIALS
H Hydrogen VOLUME 2 | ARTICLE NUMBER 17005 | 11
He Noble gases: He, Ne, Ar, Xe, Kr
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N Nitrogen Na Alkali metals: Li, Na, K, Cs, Fr

REVIEWS

exhibit a close-packed host lattice with H atoms occu-
pying the octahedral or tetrahedral interstitial sites.
The H:metal ratio in these hydrides is typically less
than 1. Hydrogen‑rich metal hydrides with H:metal ratios
larger than 1 (such as RhH2 (REF. 28), FeH2/FeH3 (REF. 27),
and IrH3 (REF. 29)) can be synthesized at high pressure.
Among them, RhH2 was found to be recoverable at ambi-
ent pressure and liquid-nitrogen temperature, making it
promising for practical hydrogen storage28.
Exotic chemical materials
Materials with unprecedented stoichiometries. Pressure
can fundamentally modify the chemical identity of
elements (BOX 1), and thus it can lead to materials with
unprecedented stoichiometries and chemical properties.
The main role of pressure is to enable chemical reactions
by altering the reaction kinetic barriers. For example, the
application of pressure is an efficient approach for the
manipulation of the polymerization reaction between
unsaturated hydrocarbon species, such as in benzenes172.
At ambient pressure, LiH, CaH2, NaCl, and H2S are
the only known chemical species in the Li–H, Ca–H,
Na–Cl and H–S systems, respectively. However, on strong
compression, the unusual stoichiometries LiH2 and LiH6,
CaH6 and CaH12, Na3Cl and NaCl3, and H3S can be
obtained through the pressure-initiated chemical reaction
of Li + H2 (REFS 26,173), Ca + H2 (REF. 85), Na + Cl2 (REF. 30)
and H2S + H2 (REF. 32), respectively. For the C–N systems,
a series of compounds with intriguing structural features
has been discovered by joint experimental and theoreti-
cal studies. These compounds include a pillared-layered
carbon nitride with mixed sp2/sp3 hybridization among
the C and N atoms in adjacent layers174, pure sp3-bonded
carbon nitride (C2N3H) with a defect wurtzite structure175,
and a new C3N4 phase with an unusual open frame-
work structure (belonging to the space group P43212)176.
Compression can also make normally unreactive ele-
ments bond with each other to form stable compounds.
Theoretical works predicted the stabilization of various
compounds through the pressurization of typically unre-
active mixtures of elements (such as Fe–Ni and Fe–Xe
(REF. 41), Mg–Xe (REF. 40), and Xe–N2 (REF. 42)), which are
awaiting experimental verification. Recently, a thermo-
dynamically stable Na–He compound, Na2He, has been
synthesized at high pressure above 113 GPa (REF. 177).
Chemical rules established at ambient pressure
are frequently violated when high pressure is applied.
For example, the well-established inertness of inner-
shell electrons is not always observed at high pressure.
Structure searches based on swarm intelligence64 pre-
dict that if Cs reacts with F2 under high pressure178, the
F‑rich compounds CsF3 and CsF5 can be stabilized. In
these compounds, the Cs atom shares its inner-shell 5p
electrons, which become oxidized beyond the +1 state
and take part in covalent or ionic bonding with F atoms;
thus, Cs effectively behaves like a 5p element. In a similar
way, calculations on the reaction between Hg and F2 to
form HgF4 under pressure179 indicate that electrons are
transferred from the Hg 5d inner shell to F, and thus Hg
behaves as a transition metal by adopting a 5d electronic
configuration. More intriguingly, through alloying with
Li under pressure, Cs and Au are predicted to reach
highly negative valence states well beyond −1 in Li‑rich
Li–Cs and Li–Au compounds180,181; in these systems, Au
behaves like a 6p element180.
Materials with unusual chemical bonding. High pressure
can induce significant charge redistribution and thus give
rise to unusual chemical bonding. A good example is the
emergence of ionic phases in certain molecular solids
under compression, such as the ionic NO+NO3− solid182
observed when solid N2O is compressed to 20 GPa. Other
instances include NH3 and NH3·H2O solids, which can
transform into the ionic phases NH4+NH2− and NH4+OH−,
respectively, at high pressures183–185. A partially ionic
phase of H3O+OH− is predicted to emerge from water
ice at zero temperature and extremely high pressures186
(>1,400 GPa). Even more intriguingly, according to the-
oretical calculations, H2O and NH3 at high temperature
and high pressure can dissociate into superionic solids,
in which O and N remain at the lattice sites, whereas
H diffuses completely 187. At the transition to the ionic
phases, either oxygen or proton transfer occurs between
molecules, and pressure has a dominant role in helping to
overcome the energy barrier. For the superionic phases,
proton diffusion is mainly driven by high temperature.
Electrides. Electrides are a special family of exotic chem-
ical materials that can be synthesized at high pressure.
They are ionic solids that consist of a cationic framework
with excess electrons trapped in the lattice voids that act
as anions. The modification of the electron distribution
by high pressure can lead to electron trapping in the
interstitial voids and thus to the formation of electrides.
Although the formation of electron-density maxima at
interstitial sites in dense metals (Ca (REF. 188), Li (REF. 189)
and Cs (REF. 190)) was predicted decades ago, it was not
until 2009 that the concept of electrides was first used
to describe the transparent insulating phase of Na at
megabar pressures20. The strong localization of valence
electrons in the interstices was identified in a six-coordi-
nated, highly distorted double hexagonal-close-packed
structure. The semiconducting electride phase of Li in
the Aba2‑40 structure at high pressures was predicted
theoretically 191 and later observed in experiments21,22.
High-pressure electrides have been predicted for other
elements, including Mg (REF. 192), Ca (REF. 188), Cs
(REF. 190) and Al (REF. 193), and for compounds of alkali or
alkaline earth metals, such as Mg3O2 (REF. 194), Li(NH3)4
(REF. 195) and Na3/Na4Fe (REF. 196). The mechanism
underlying electron localization is the displacement of
valence electrons away from the atomic cores caused by
strong core–valence electron overlap43. Electride phases
are expected to arise also in other elements and com-
pounds under the application of a pressure sufficient to
cause a strong overlap between atomic cores.
Conclusions and outlook
Sustained progress in high-pressure experimental
techniques has led to the discovery of numerous new
high-pressure materials, and developments in supercom-
puting and first-principles structure searching methods

12 | ARTICLE NUMBER 17005 | VOLUME 2 www.nature.com/natrevmats

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 REVIEWS

have given theoretical simulations the predictive power
needed to aid discoveries in this field. Guided by the-
ory, design-oriented experiments have greatly expedited
materials discovery, leading to the synthesis of materials
that challenge the conventional principles of materials
science and hold great promise for several technologies.
One of the greatest challenges for the use of high-­
pressure materials for practical applications is that they
are usually unstable under ambient conditions. Different
strategies have been explored for stabilizing high-­pressure
materials at ambient pressure. As demonstrated in the
context of the industrial-scale synthesis of diamond,
two approaches can be used. One is high-temperature,
high-pressure synthesis (sometimes catalysis-assisted)
followed by immediate quenching. The other is non-equi-
librium growth of metastable materials on solid substrates
by methods such as molecular beam epitaxy or chemical
vapour deposition. The first approach has been used to
synthesize many high-pressure materials, but the resulting
products are usually small-sized, polycrystalline powders,
which precludes their practical application in devices.
The second technique in principle can be used to grow
large-scale thin films, but so far only a few high-pressure
materials have been synthesized in this way (examples are
diamond24 and c-BN (REF. 197)). Alternatively, high-pres-
sure metastable phases can be obtained by introducing
stress through nanostructuring 198. Either way, knowledge
of the high-temperature and high-pressure phase dia-
gram of the desired material is essential for the elabora-
tion of feasible synthetic routes; for most materials, this
information is not yet available. This poses a challenge
for high-pressure theoretical studies, which to a great
extent are limited to zero temperature. Methods for the
accurate evaluation of high-temperature energetics and
for finite-temperature crystal-structure searches would
complement the phase diagram knowledge, allowing
the identification of useful pathways for the recovery of
high-pressure materials at ambient conditions.
Although several functional materials exhibit inter-
esting and potentially useful properties at high pres-
sures, it is still believed that pressure will be most useful
for the fabrication of superior superconductive and
superhard materials. The experimental observation31 of
superconductivity with a Tc of 203 K in H3S is a prom-
ising step towards room-temperature superconductiv-
ity in highly compressed H‑rich materials. To obtain
high‑Tc superconductive hydrides, it will first be neces-
sary to eliminate H2 molecular units from the hydrides,
because they attract too many electrons in low-lying
energy levels, which leads to a much-­reduced electronic
density of states at the Fermi level. One possible strat-
egy is to introduce additional electrons to occupy the
unfilled antibonding σ* orbitals of the H2 units, which
would weaken the intramolecular H–H bonds, result-
ing in H2 dissociation. This method can be applied, for
example, to ternary hydrides containing electropositive
metals (such as alkali and alkali earth elements) acting
as electron donors.
For superhard materials, the growth of high-quality
nanotwinned microstructures in strongly covalent sys-
tems other than diamond15 and c-BN (REF. 16) at high
pressure offers a route for the creation of materials
with superior mechanical properties. The exploitation
of the unconventional structure–property relations129
observed in a broad range of transition metal/light-­
element compounds may lead to the discovery of new
superhard materials with excellent ductility and thermal
and chemical properties.
This Review has focused on a selection of high-­
pressure materials, which by no means represents an
exhaustive list of all possible examples. The field of
high-pressure materials is a rich one. The first oxynitride
perovskite with strong spontaneous polarization, YSiO2N
— which holds promise for ferroelectric, piezoelectric
and nonlinear optical applications — has recently been
synthesized at high temperature and high pressure199.
A new type of superconductor 200 was created through a
pressure-induced phase transition obtained by compress-
ing a Dirac semimetal, ZrTe5. We anticipate that the appli-
cation of high pressure to various material systems will
create vast opportunities for future materials discoveries
that would not be possible at ambient pressure.

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Acknowledgements
The authors acknowledge funding support from the National
Key Research and Development Program of China (under
Grant No. 2016YFB0201200), National Natural Science
Foundation of China (under Grants No. 11404131,
11674121 and 11534003), 2012 Changjiang Scholar of
Ministry of Education, Recruitment Program of Global Youth
Experts in China, and Science Challenge Project (under Grant
No. JCKY2016212A501).
Competing interests statement
The authors declare no competing interests.
How to cite this article
Zhang, L., Wang, Y., Lv, J. & Ma, Y. Materials discovery at
high pressures. Nat. Rev. Mater. 2, 17005 (2017).

16 | ARTICLE NUMBER 17005 | VOLUME 2 www.nature.com/natrevmats

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