RES EARCH | R E P O R T S

demonstrated in this study can be extended to partially supported by US Department of Energy (DOE) Basic Energy (JPMJCR15F3). K.Y. acknowledges partial support from JSPS
other bipartite honeycomb 2D materials, such Sciences (BES) grant DE-SC0018935 (early characterization Overseas Research Fellowships. Author contributions: K.Y. and
measurements and device nanofabrication); by the Center for P.J.-H. conceived the project. K.Y. and X.W. fabricated the devices
as semiconducting 2H-type TMDs like MoS2 the Advancement of Topological Semimetals, an Energy Frontier and performed the measurements. K.W. and T.T. grew the hBN
and WSe2, metallic and superconducting ones Research Center funded by the DOE Office of Science, through bulk crystals. K.Y., X.W., and P.J.-H. analyzed and interpreted the
like NbS2 and NbSe2, and group III chalcoge- the Ames Laboratory under contract DE-AC02-07CH11358 data and wrote the manuscript with contributions from all authors.
(performance measurements and data analysis); the Army Competing interests: The authors declare no competing
nides like GaS, GaSe, and InSe (25). The in- Research Office (early effort towards device nanofabrication) interests. Data and materials availability: The data shown in
version symmetry breaking of these synthetic through grant no. W911NF1810316; and the Gordon and Betty Moore the paper are available at Harvard Dataverse (43).
ferroelectrics will be coupled to the electronic Foundation’s EPiQS Initiative through grant GBMF9643 to
P.J.-H. This work made use of the Materials Research Science
band structures in a tunable manner through and Engineering Center Shared Experimental Facilities supported by
SUPPLEMENTARY MATERIALS
polarization switching. In addition to interest- the National Science Foundation (NSF) (grant no. DMR-0819762). science.sciencemag.org/content/372/6549/1458/suppl/DC1
Materials and Methods
ing physics resulting from the modification This work was performed in part at the Harvard University
Center for Nanoscale Systems (CNS), a member of the National Figs. S1 to S26
of the intrinsic properties of each material, Table S1
Nanotechnology Coordinated Infrastructure Network (NNCI),
such engineered ferroelectrics and moiré sys- References (44–54)
which is supported by the NSF under NSF ECCS award no. 1541959.
tems may substantially expand the capabil- K.W. and T.T. acknowledge support from the Elemental Strategy 19 June 2020; accepted 8 May 2021
ities of 2D materials for electronic, spintronic, Initiative conducted by the MEXT, Japan (grant no. JPMXP0112101001); Published online 27 May 2021
JSPS KAKENHI (grant no. JP20H00354); and the CREST 10.1126/science.abd3230
and optical applications (15, 39).
We note that (40) and a paper in the same
issue (41) report related findings.
FERROELECTRICS
RE FE RENCES AND N OT ES
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4. U. Schröeder, C. S. Hwang, H. Funakubo, Ferroelectricity in
M. Vizner Stern1, Y. Waschitz1, W. Cao2, I. Nevo1, K. Watanabe3, T. Taniguchi3, E. Sela1, M. Urbakh2,
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Despite their partial ionic nature, many-layered diatomic crystals avoid internal electric polarization
8. K. Chang et al., Science 353, 274–278 (2016). by forming a centrosymmetric lattice at their optimal van der Waals stacking. Here, we report a
9. F. Liu et al., Nat. Commun. 7, 12357 (2016). stable ferroelectric order emerging at the interface between two naturally grown flakes of hexagonal
10. Y. Zhou et al., Nano Lett. 17, 5508–5513 (2017).
11. C. Cui et al., Nano Lett. 18, 1253–1258 (2018). boron nitride, which are stacked together in a metastable non-centrosymmetric parallel orientation.
12. S. Yuan et al., Nat. Commun. 10, 1775 (2019). We observe alternating domains of inverted normal polarization, caused by a lateral shift of one
13. Z. Fei et al., Nature 560, 336–339 (2018). lattice site between the domains. Reversible polarization switching coupled to lateral sliding is
14. C. R. Dean et al., Nat. Nanotechnol. 5, 722–726 (2010).
15. E. Y. Tsymbal, H. Kohlstedt, Science 313, 181–183 (2006).
achieved by scanning a biased tip above the surface. Our calculations trace the origin of the
16. A. K. Geim, I. V. Grigorieva, Nature 499, 419–425 (2013). phenomenon to a subtle interplay between charge redistribution and ionic displacement and provide
17. B. Hunt et al., Science 340, 1427–1430 (2013). intuitive insights to explore the interfacial polarization and its distinctive “slidetronics” switching
18. C. R. Dean et al., Nature 497, 598–602 (2013).
mechanism.
19. L. A. Ponomarenko et al., Nature 497, 594–597 (2013).
20. R. V. Gorbachev et al., Science 346, 448–451 (2014).

T
21. Y. Cao et al., Nature 556, 43–50 (2018).
22. Y. Cao et al., Nature 556, 80–84 (2018). he ability to locally switch a confined to find a spontaneous net electric polarization
23. A. L. Sharpe et al., Science 365, 605–608 (2019). electrical polarization is a key function- in two dimensions (2D) that is sufficiently large
24. M. Serlin et al., Science 367, 900–903 (2020). ality in modern technologies, where to read and write under ambient conditions
25. L. Li, M. Wu, ACS Nano 11, 6382–6388 (2017).
26. G. Constantinescu, A. Kuc, T. Heine, Phys. Rev. Lett. 111, 036104 storing and retrieving a large volume of (8–10). Furthermore, in naturally grown h-BN
(2013). information is vital (1). The need to re- and TMD crystals, polarization is eliminated
27. S. Zhou, J. Han, S. Dai, J. Sun, D. J. Srolovitz, Phys. Rev. B 92, duce the dimensions of individually polarized by the formation of a centrosymmetric van der
155438 (2015).
28. J. H. Warner, M. H. Rümmeli, A. Bachmatiuk, B. Büchner,
domains, from the ~100-nm2 scale (2, 3) toward Waals (vdW) structure that is lower in energy
ACS Nano 4, 1299–1304 (2010). the atomic scale, is rising (4). The main chal- than other metastable stacking configurations.
29. C.-J. Kim et al., Nano Lett. 13, 5660–5665 (2013). lenges involve long-range dipole interactions, Here, we break this symmetry by controlling
30. S. M. Gilbert et al., 2D Mater. 6, 021006 (2019).
31. H. J. Park et al., Sci. Adv. 6, eaay4958 (2020).
which tend to couple the individual domain the twist angle between two h-BN flakes and
32. K. Kim et al., Nano Lett. 16, 1989–1995 (2016). polarization orientations (5). Likewise, surface find an array of permanent and switchable
33. Y. Cao et al., Phys. Rev. Lett. 117, 116804 (2016). effects and external strains that are difficult to polarization domains at their interface. The
34. H. Yoo et al., Nat. Mater. 18, 448–453 (2019).
35. A. Weston et al., Nat. Nanotechnol. 15, 592–597 (2020).
control become dominant once the surface-to- polarization is oriented normal to the plane,
36. L. J. McGilly et al., Nat. Nanotechnol. 15, 580–584 (2020). volume ratio increases (6). To overcome these and its amplitude is in good agreement with
37. R. D. King-Smith, D. Vanderbilt, Phys. Rev. B Condens. Matter challenges, one can consider layered materials, previous first-principle predictions for a two-
47, 1651–1654 (1993). such as hexagonal boron nitride (h-BN) and layered system (11) and with our detailed
38. Q. Yang, M. Wu, J. Li, J. Phys. Chem. Lett. 9, 7160–7164 (2018).
transition-metal dichalcogenides (TMDs), where multilayer calculations.
39. J. Sung et al., Nat. Nanotechnol. 15, 750–754 (2020).
40. C. R. Woods et al., Nat. Commun. 12, 347 (2021). the bulk volume can be reduced to the ultimate To identify which stacking modes can carry
41. M. Vizner Stern et al., Science 372, 1462–1466 (2021). atomic-thickness limit, whereas the crystalline polarization, we present in Fig. 1A six different
42. See supplementary materials. surface remains intact (7). However, it is rare high-symmetry configurations of bilayer h-BN.
43. K. Yasuda, X. Wang, K. Watanabe, T. Taniguchi, P. Jarillo-Herrero,
The stacking configurations are divided into
Replication Data for: Stacking-engineered ferroelectricity in 1
School of Physics and Astronomy, Tel Aviv University, Israel.
bilayer boron nitride. Harvard Dataverse (2021); 2 two groups termed “parallel” and “antiparallel”
Department of Physical Chemistry, School of Chemistry,
https://doi.org/10.7910/DVN/JNXOIM. The Raymond and Beverly Sackler Faculty of Exact Sciences twist orientations (12); within each group, a
and The Sackler Center for Computational Molecular and relative lateral shift by one interatomic dis-
ACKN OW LEDG MEN TS Materials Science, Tel Aviv University, Tel Aviv 6997801, tance switches the stacking configuration in
We thank S. de la Barrera, D. Bandurin, Z. Zheng, Q. Ma, Y. Zhang, Israel. 3National Institute for Material Science, Tsukuba,
L. Fu, and M. Wu for fruitful discussions and J. M. Park, E. Soriano, and Japan. a cyclic manner. Typically, the crystal grows
J. Tresback for experimental support. Funding: This research was *Corresponding author. Email: moshebs@tauex.tau.ac.il in the optimal antiparallel (AA') configuration

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Fig. 1. High-symmetry interlayer stacking

configurations. (A) Top view illustration
of two layers. For clarity, atoms of the top
layer are represented by smaller circles.
Within each group of parallel or antiparallel
twist orientations, a relative lateral shift by
one lattice spacing results in a cyclic switching
between three high-symmetry stacking config-
urations. (B) Calculated local-registry index
(LRI) map of the atomic overlaps (17) in a rigid
structure made of two hBN layers stacked with
a twist angle of 0.5°. Blue regions correspond
to AA stacking, whereas AB/BA stacking appears
in orange (LRI = 0.86). (C) Calculated LRI
map after geometry relaxation of the structure
presented in (B). Large domains of uniform
untwisted AB/BA stacking appear, at the
expense of the preoptimized AA regions. The
twist is accumulated in smaller AA-like regions
and in the ~10-nm-wide incommensurate domain walls (bright lines); see fig. S3 and (17) for further discussion. (D) Cross-sectional illustration of two few-layered
flakes (blue and light blue regions mark the top and bottom flakes, respectively) of naturally grown h-BN (AA’), which are stacked with no twist. Plus (minus) signs
mark boron (nitrogen) sites. A topographical step of a single-layer switches between parallel and antiparallel stacking orientations at the interface between
the two flakes. Vertical charge displacements in eclipsed/hollow pairs (vertical/diagonal ellipses) and the resulting net polarization Pz are marked by arrows.

with full overlap between nitrogen (boron) are obtained with no interlayer twist. In the constant potential is observed with a clear dif-
atoms of one layer and boron (nitrogen) atoms experiments, we also introduce a topographic ference DVKP between the AB and BA domains,
of the adjacent layer (13). In the parallel twist step at the interface between the flakes. A step as shown in Fig. 2C. Whereas KPFM measure-
orientation, however, the fully eclipsed confi- thickness of an odd number of layers guaran- ment nullifying the tip response at the electric
guration (AA) is unstable because it forces tees antiparallel stacking (AA', AB1', or AB2') bias frequency gives an underestimated po-
pairs of bulky nitrogen atoms atop each other, on one side and parallel stacking (AA, AB, or tential difference of DVKP e100 mV because of
resulting in increased steric repulsion (14). BA) on its other side (Fig. 1D). Thus, one can averaging contributions from the tip’s canti-
Instead, a lateral interlayer shift occurs to a compare all possible configurations at adja- lever (17), more quantitative measurements
metastable AB stacking with only half of the cent locations in space. obtained through sideband tip excitations yield
atoms overlapping, whereas the other half are To measure variations in the electrical po- DVKP values ranging between 210 and 230 mV
aligned with the empty centers of the hex- tential, VKP, at surface regions of different for both closed-loop scans and local open-loop
agons in the adjacent layer (15, 16). The AB and stacking configurations, we place the h-BN measurements (fig. S1). Similar values are mea-
BA stacking form equivalent lattice structures sandwich on a conducting substrate (Si/SiO2, sured for several samples with different sub-
(only flipped), and all depicted antiparallel graphite, or gold) and scan an atomic force strate identities and various thicknesses of the
configurations (AA', AB1', AB2') are symmetric microscope (AFM) operated in a Kelvin probe top h-BN flake (for flakes thicker than 1 nm),
under spatial inversion. mode (KPFM) (Fig. 2A) (17). The potential map and when using different AFM tips. These
To explore these different configurations, above the various stacking configurations is findings confirm that DVKP is an independent
we artificially stamped two exfoliated h-BN shown in Fig. 2B. We find clear domains (black measure of the intrinsic polarization of the
flakes on top of each other, each consisting of and white) of constant VKP, extending over system that, in turn, is confined within a few
a few AA' stacked layers, with a minute twist areas of several square micrometers, which are interfacial layers.
angle between the otherwise parallel interfacial separated by narrow domain walls. Dark gray Although our force field calculations for
layers (17). The small twist imposes interlayer areas of average potential are observed above slightly twisted bilayer h-BN show a uniform
translations that evolve continuously and form (i) positions where only one h-BN flake exists triangular lattice of alternating AB and BA
a moiré pattern owing to the underlying crystal (outside the dashed yellow line); (ii) above two stacked domains (Fig. 1C), in the experiment
periodicity (Fig. 1B). In this rigid lattice picture, flakes but beyond the topographic step marked we observe large variations in their lateral
the three nearly commensurate stacking con- by dashed red lines in Fig. 2B (and topography dimensions and shape. This indicates minute
figurations (AB, BA, AA) appear at adjacent map fig. S2), as expected; and (iii) beyond deviations in the local twist, which are un-
positions in space. Notably, this picture breaks topographic folds that can further modify the avoidable in the case of small twist angles
for a sufficiently small twist angle as a result interlayer twist angle (dashed green lines). (19–22). Specifically, the ~1-mm2 domains in
of structural relaxation processes, as shown These findings confirm that white and black the left part of Fig. 2B correspond to a global
by our molecular dynamics calculation based domains correspond to AB and BA interfacial twist of less than 0:01° (23). In addition, any
on dedicated interlayer potentials (Fig. 1C) stacking that host a permanent out-of-plane external perturbation to the structure, caused
(17, 18). Instead, the system divides into large electric polarization. Such polarization is not either by transferring it to a polymer, heating,
domains of reconstructed commensurate AB observed at the other side of the step, where or directly pressing it with the AFM tip, usually
and BA stackings separated by sharp incom- centrosymmetric AA', AB1', AB2' configura- resulted in a further increase in domain size.
mensurate domain walls that accommodate tions are obtained, or at the AA configuration In a few cases, high-temperature annealing
the global twist (fig. S3, A and B) (19–22). Not- expected at domain-wall crossings (blue dots resulted in a global reorientation to a single
ably, near the center of the extended commen- in Fig. 1C). Sufficiently far from the domain domain flake, many micrometers in dimen-
surate domains, perfectly aligned configurations walls (toward the center of each domain), a sions. This behavior confirms the metastable

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A 0.3
B in excellent agreement with the side-band
[V]
Bottom hBN measurements (red star in Fig. 2D). Similar
results were reported in recent computational
studies (11). However, to obtain quantitative
0.1 agreement with the experimental measure-
250 ments, the results should be carefully con-
VKP (mV)

200 verged with respect to the various calculation

parameters (figs. S5 and S7). By further ap-
150 C plying an electric field of 0:1 V=nm normal
0.0 0.5 1.0 1.5 to the plane, we find, from our calculations, a
x ( m)
0.6 minute piezo-electric deformation of 0.1 pm
0.4
and a 5% variation in the polarization magni-
tude (fig. S10).
0.2 It is instructive to further translate the mea-
D
0.0 sured potential difference into intralayer dis-
placements in a simplistic point-like charges
0.4 model (Dd in Fig. 1D), where each atom is
AB AB
allowed to displace from its layer’s basal plane
0.0 in the vertical direction. With the lattice site
AA
density of n = 37 nm−2 and the on-site charge
E BA value, q e e=2, for single-layered h-BN (28, 29),
-0.4
Position
our measured DVKP gives out-of-plane atomic
displacement of the order of Dd ¼ DVKP e0 =
Fig. 2. Direct measurement of interfacial polarization. (A) Illustration of the experimental setup. An
4nq e 1  10 3 Å (e0 is vacuum permittivity),
atomic force microscope is operated in Kelvin-probe mode to measure the local potential modulation, VKP, at
which is much smaller than the intralayer
the surface of two 3-nm-thick h-BN flakes, which are stacked with a very small twist angle. (B) VKP map
(1.44 Å) and interlayer (3.30 Å) spacings. This
showing oppositely polarized domains of AB/BA stacking (black and white), ranging in area between ~0.01
implies that the polarization is determined
and 1 mm2 and separated by sharp domain walls. (C) Surface potential measured along the purple line
by a delicate competition between the var-
marked in (B) by first-harmonic KPFM. (D) DFT calculations of the polarization, Pz, per unit area obtained for
ious interlayer interaction components and
finite h-BN bilayer flakes of different lateral dimensions (1:1 and 2:9 nm2 , black triangles) and for laterally
charge redistribution. Intuitively, we expect
periodic stacks made of 2 to 10 layers (marked as PBC, green square). The red star marks the polarization
the vdW attraction to vertically compress the
value evaluated from the measured DVKP data. (E) Calculated polarization for different interlayer shifts.
nonoverlapping interfacial sites (diagonal
dashed ellipse in Fig. 1D) closer together than
the overlapping sites (vertical dashed ellipse
nature of the AB/BA stacking mode, as well plementary laterally periodic system calcu- in Fig. 1D), which are more prone to Pauli
as the possible superlubric nature of the in- lations at various thicknesses. The detailed repulsion. This direction of motion, for exam-
terface (24, 25). At the other extreme, much methods used for these calculations are dis- ple, reduces the average interlayer separation
smaller domains are observed in the top right- cussed in (17). For the AB stacked periodic and favors Bernal (AB like) stacking in graph-
hand section of Fig. 2B. The smallest triangle bilayer, we find a polarization of Pz =A ¼ ite over the AA configuration (30). In h-BN,
edge that we could identify over many sim- 0:33 Debye=nm2, changing by only 10% when however, the partial ionic nature of the two
ilar flakes was 60 nm in length, which corre- including additional two and eight AA' stacked lattice sites (12, 31, 32) makes the fully eclipsed
sponds to a twist angle of 0:24°. We therefore layers above and below the AB stacked inter- AA' stacking more stable (13). Hence, impos-
conclude that, below this angle, atomic re- face (see Fig. 2D and fig. S7). Adding more ing a polar AB interface, as in our case, may
construction to create untwisted domains is AB-stacked layers, however, reveals a linear favor overlapping sites of opposite charges
energetically favored. Naturally, this consti- increase of the calculated polarization with to come closer together than the nonoverlap-
tutes a lower bound on the maximal angle for the number of added interfaces (fig. S9). The ping pairs and the polarization to point in the
domain formation as smaller domains below latter is a highly appealing control mechanism opposite direction.
our experimental resolution may form at larger to engineer the magnitude of the polarization To quantify these arguments, we present a
twist angles. in future 2D systems, independent of external reduced classical bilayer model that captures the
To trace the microscopic origin of the mea- effects such as surface chemistry and local intricate balance between Pauli, vdW, and Cou-
sured polarization, we performed a set of den- strains. Lateral shifts of the periodic bilayer lomb interatomic interactions at different stacking
sity functional theory (DFT) calculations on system show a gradual evolution of the pola- modes. In our model (17), the interfacial ener-
finite bilayer and quad-layer h-BN flakes. For rization when shifting between the AA, AB, X   12  6  
s s qi qj
gy E ¼ 21 i;j
4e rij rij þ rij
the finite bilayer calculations, we constructed and BA stacking modes, from zero to +0.33
two model systems, where hydrogen passi- and −0.33 Debye=nm2, respectively (Fig. 2E). includes a Lennard-Jones (LJ) potential char-
vated h-BN flakes of either 1 or 3nm2 surface This is crucial when considering the com- acterized by the cohesive energy, e , and the
area are stacked in the AB stacking mode plex response at domain walls, where lattice interlayer spacing scale, s, and Coulomb inter-
(fig. S4). The calculated polarizations per unit deformations induce additional flexo (26) actions between the dimensionless partial
area, Pz =A, of these systems were 0.55 and and piezo (27) responses. In fig. S8, we pre- atomic charges on the boron and nitrogen sites
0.45 Debye=nm2 , respectively (black triangles sent also the charge density redistribution in q ¼ Tqi =e . Although neglecting any charge
in Fig. 2D), pointing perpendicular to the in- the periodic bilayer system owing to interlayer transfer processes between the layers that are
terface only (table S1). Because edge effects coupling. The corresponding interlayer poten- explicitly taken into account in our DFT cal-
may influence the results of such finite system tial difference at the experimental configuration culations, this model captures both the mag-
calculations (17) (fig. S4), we performed com- is calculated to be 21 DVKP ¼ 120mV (fig. S7), nitude and orientation of the polarization by

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Fig. 3. Dynamic flipping of

polarization orientation by
domain-wall sliding. Kelvin-
probe maps measured consec-
utively from left to right above a
particular flake location showing
domains of up (white) and
down (black) polarizations. The
middle image was taken after
biasing the tip by a fixed DC voltage of −20 V and scanning it above the blue square region shown on the left-hand image. Then the tip was biased by 10 V and
scanned again over the same region before taking the right-hand image. Consecutive domain-wall positions are marked by dashed red, green, and yellow lines.
Larger white (black) domains appear after positive (negative) bias scans as a result of domain-wall motion beyond the scan area. Note that the number of domain
walls is apparently not altered.

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(green) line before (after) the scan. A succes- charge redistribution implies that external 33. L. Jiang et al., Nat. Nanotechnol. 13, 204–208 (2018).
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sive scan by a positively biased tip resulted in stimuli such as pressure, temperature, and/ 35. J. Sung et al., Nat. Nanotechnol. 15, 750–754 (2020).
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ping. Hence, by applying negative or positive polarization, thus offering many opportuni- [cond-mat.mes-hall] (2019).
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main. Similar switching behavior was attained reports similar findings. During the review P. Jarillo-Herrero, Science 372, 1458–1462 (2021).
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41. M. Vizner Stern et al., Replication Data for: Interfacial
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RES EARCH | R E P O R T S

ACKN OW LEDG MEN TS 1586/17, the Naomi Foundation for generous financial support via some of the technology and materials discussed here, on which
We thank Y. Lahini for useful discussions, A. Cerreta (Park the 2017 Kadar Award, and the Ministry of Science and Technology M.V.S., Y.W., and M.B.S. are listed as co-inventors. Data and
Systems) for AFM support, and N. Ravid for laboratory support. We of Israel under project number 3-16244. M.B.S. acknowledges materials availability: All data needed to evaluate the conclusions
further thank J. E. Peralta for helpful discussions regarding the funding by the European Research Council (ERC) under the in the study are present in the main text or the supplementary
DFT calculations. Funding: W.C. acknowledges the financial European Union’s Horizon 2020 research and innovation materials. The data have also been uploaded to Zenodo (41).
support of the IASH and the Sackler Center for Computational programme (grant agreement no.852925), the Israel Science
Molecular and Materials Science at Tel Aviv University. Growth of Foundation (grant 1652/18), and the Israel Ministry of Science and SUPPLEMENTARY MATERIALS
hBN was supported by the Elemental Strategy Initiative conducted Technology project no. 3-15619 (Meta-Materials). O.H. and M.B.S. science.sciencemag.org/content/372/6549/1462/suppl/DC1
by the MEXT, Japan (grant JPMXP 0112101001), JSPS KAKENHI acknowledge the Center for Nanoscience and Nanotechnology of Materials and Methods
(grant JP20H00354), and the CREST (JPMJCR15F3), JST. E.S. TelAviv University. Author contributions: M.V.S. and Y.W. Figs. S1 to S12
acknowledges support from ARO (W911NF-20-1-0013), the Israel performed the experiments, supported by I.N. and supervised by Table S1
Science Foundation (grant 154/19, and US-Israel Binational M.B.S.; W.C. performed the DFT calculations supervised by M.U. References (42–59)
Science Foundation (grant 2016255). M.U. acknowledges financial and O.H.; K.W. and T.T. grew the hBN crystals; E.S. devised the
support of the Israel Science Foundation (grant 1141/18) and the adhesion model. All authors contributed to the writing of the 16 September 2020; accepted 10 May 2021
ISFNSFC (joint grant 3191/19). O.H. is grateful for the generous manuscript. Competing interests: Ramot at Tel Aviv University Published online 10 June 2021
financial support of the Israel Science Foundation under grant Ltd. has applied for a patent (US application no. 63/083,947) on 10.1126/science.abe8177

MATERIALS SCIENCE complete fusion of ACC particles to result in

a transparent calcium carbonate monolith.
Pressure-driven fusion of amorphous particles into The monolith exhibits optimal mechanical
strength with a hardness (H) of 2.739 GPa and
integrated monoliths a Young’s modulus (E) of 49.672 GPa; these
values are superior to those of common cement
Zhao Mu1†, Kangren Kong1†, Kai Jiang2, Hongliang Dong3,4, Xurong Xu5, Zhaoming Liu1*, Ruikang Tang1,6* materials and almost reach those of single-
crystal calcite (24).
Biological organisms can use amorphous precursors to produce inorganic skeletons with continuous structures The chemical formula of ACC is CaCO3·nH2O,
through complete particle fusion. Synthesizing monoliths is much more difficult because sintering techniques with n frequently being ≥1 (20, 25, 26). In our
can destroy continuity and limit mechanical strength. We manufactured inorganic monoliths of amorphous experiments, we synthesized ACC particles
calcium carbonate by the fusion of particles while regulating structurally bound water and external pressure. with an average size of 450 ± 100 nm (fig. S1)
Our monoliths are transparent, owing to their structural continuity, with a mechanical strength approaching while controlling n between 0 and 1.6 (fig.
that of single-crystal calcite. Dynamic water channels within the amorphous bulk are synergistically controlled S2A). We confirmed that ACC particles with
by water content and applied pressure and promote mass transportation for particle fusion. Our strategy n ≥ 1 cannot coalesce under external P, be-
provides an alternative to traditional sintering methods that should be attractive for constructing monoliths of cause phase transformation–based crystalli-
temperature-sensitive biominerals and biomaterials. zation happens instead (fig. S3), but keeping
n < 1 enables us to avoid this issue. We used

I
norganic materials, especially minerals skeletons that have continuous structures with ACC with n = 0.7 (fig. S2B) for our typical
and ceramics, play important roles in flexible morphology (16). Accordingly, these samples in a subsequent compaction treat-
modern society (1–4), but the manufacture inorganic skeletons are superior to artificial ment under P. In all of our experiments, the
of their monoliths is a great challenge (5). skeletons because of their structural integra- treatment time was 5 min at room temperature.
In practice, many inorganic materials are tion. Increasing evidence has demonstrated At P ≤ 0.5 GPa, we did not observe fusion be-
produced in powder forms and then conso- that these biological organisms use amorphous cause we could observe the particles and their
lidated by pressing and sintering (6–10). How- particles as precursors to produce skeletons via boundaries under scanning electron microscopy
ever, mass transportation among particles is particle-particle fusion (17–19). Inspired by this (SEM) (Fig. 1A). When P increased to 0.8 GPa,
often insufficient through sinter treatment, biological phenomenon, we suggest that the some ACC particles began to coalesce, but we
complete particle-particle fusion cannot be manufacture of monolithic inorganic materials could still identify their original spherical mor-
achieved within bulk materials, and particle can be achieved by fusion of their amorphous phology. The particles further coalesced at a
boundaries remain. Owing to internal dis- precursors under pressure (P). However, many large scale, and the spherical shape disappeared
continuities, the properties of sintered inor- previous attempts using amorphous mineral as P increased to 1.5 GPa. At P = 2.0 GPa, all ACC
ganic bulks are not ideal (11, 12), especially phases such as amorphous calcium carbonate particles coalesced completely to form a con-
with respect to mechanical strength (13). In (ACC) and amorphous calcium phosphate have tinuous and uniform bulk. To clearly express
nature, biological organisms [e.g., sea urchins revealed that external P frequently induces the coalescence behavior of ACC particles, we
(14) and coccoliths (15)] can produce inorganic crystallization of amorphous particles rather additionally processed their SEM images with
than particle-particle fusion (20–23). These binarization (Fig. 1A; blue areas represent non-
amorphous mineral phases contain abundant coalesced particles). The structural discontinu-
1
Department of Chemistry, Zhejiang University, Hangzhou water, which induces dissolution and recrys- ities decreased as P increased from 0.2 to 2.0 GPa,
310027, China. 2Engineering Research Center of Nanophotonics tallization of the intermediate amorphous and finally, all individual particles were fused
& Advanced Instrument (Ministry of Education), Department of
Materials, East China Normal University, Shanghai 200241,
phases under P. into an integral whole. We used Au nanopar-
China. 3Center for High Pressure Science and Technology By controlling the water content (n) within ticles to confirm complete coalescence at the
Advanced Research, Shanghai 201203, China. 4State Key amorphous precursors and the external P, we nanoscale (Fig. 1B and fig. S4). In this exami-
Laboratory of High Performance Ceramics and Superfine nation, the ACC particle surfaces were labeled
can achieve biomineralization-like particle fu-
Microstructure, Shanghai Institute of Ceramics, Chinese
Academy of Sciences, Shanghai 200050, China. 5Qiushi sion, which follows the discovery of pressure- with Au nanoparticles (Fig. 1C). After fusion
Academy for Advanced Studies, Zhejiang University, Hangzhou driven mass transportation through dynamic treatment, these Au particles “moved” from
310027, China. 6State Key Laboratory of Silicon Materials, water channels in amorphous phases. By using the surface into the interior and were com-
Zhejiang University, Hangzhou 310027, China.
*Corresponding author. Email: oldliu@zju.edu.cn (Z.L.); rtang@ ACC as a typical amorphous precursor, we ex- pletely surrounded by the uniform ACC phase
zju.edu.cn (R.T.) †These authors contributed equally to this work. perimentally demonstrated this control of (Fig. 1D and fig. S5). We verified the surrounding

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