376 CHIMIA 2021, 75, No.

5 Colloidal Nanocrystals
doi:10.2533/chimia.2021.376  Chimia 75 (2021) 376–386 © P. López-Domínguez, I.Van Driessche

Colloidal Oxide Perovskite Nanocrystals:

From Synthesis to Application
Pedro López-Domínguez and Isabel Van Driessche*

Abstract: Nanocrystals (NCs) are complex systems that offer a superior level of detailed engineering at the atomic
level. The large number of novel and revolutionary applications have made nanocrystals of special interest. In
particular oxide perovskites are one of the most widely investigated family of materials in solid-state chemistry,
especially for their ferroelectric and superconducting properties. In addition to these well-known properties,
perovskites show good electrical conductivity (close to metals), ion conductivity and mixed ionic-electronic
conductivity. In that sense, controlled synthesis of nanomaterials with special care over size and shape are es-
sential in many fields of science and technology. Although it is well-known that physical methods deliver excellent
quality nanomaterials, their high production cost has increased the interest to more affordable alternative chemi-
cal processes. In this review, we focus on the preparation of sub-10 nm oxide perovskite nanocrystals and the
main strategies used to control the final properties of the obtained products. In the second part, we present the
methods available for nanocrystal solutions processing together with the most remarkable applications foreseen.
Keywords: Colloids · Nanocrystals · Oxides · Perovskite · Synthesis

Isabel Van Driessche is professor at Ghent synthesis approaches for the synthesis of ceramic nanoparticles/
University (Belgium) since 2004 and Dean suspensions; iii) Synthesis of multi-metaloxide nanoparticles.
of the faculty of Sciences since 2018.
Together with Prof. De Buysser, she leads 1. Introduction
the research group SCRiPTS, (scripts. Nanomaterials have surrounded humanity longer than we
ugent.be), having activities in the broad were even aware. Advances in characterization techniques have
field of solid-state chemistry related to brought a new era of materials ‘à la carte’. From TiO2 nanopar-
the synthesis, properties and applications ticles that protect our skin from harmful UV radiation to the
of inorganic (ceramic) materials, both as new nanofiber-based FFP2 masks that are helping in the fight
bulk, nanomaterials and thin films. She is against SARS-CoV-2,[1] nanomaterials have penetrated consum-
author of approximately 500 papers (ORCID iD: 0000-0001- er products with great success. Oxide perovskites are a well-
5253-3325), co-inventor of 7 patents and has coordinated about established family among the metal oxide materials class. The
70 national and international research projects. This includes the general formula of perovskites is ABO3 (Fig. 1A), and should
coordination of 2 European projects, ‘EFECTS’ (8 partners, 2 not be confused with ilmenite and derived structures. Although
M€) and ‘SynFoNY’ (5 partners, 600 k€) and co-coordination sharing the same molecular formula, in the ilmenite case the A
of ‘EUROTAPES’ (20 partners, 12 M€) as task force leader. and B cations are similar in size and occupy an octahedral site, as
The research group of SCRiPTS is completed with 3 Post-doc can be seen in Fig. 1B. In perovskite oxides however, A cations
researchers and 8 PhD students covering the following fields of are located at 12-coordinated large sites and B cations at 6-co-
interest: i) Chemical solution deposition (CSD, ink jet printing) ordinated small sites. Different combinations of charged cations
of ceramics and metaloxides; ii) Formulation of environmentally are possible, with A2+ and B4+ as the most common disposi-
friendly based inks of metaloxides. Use of bottom-up chemical tion.

Fig. 1. Schematic illustration of

A Ba
B
Fe
perovskite oxide BaTiO3 (A) and
O O
Ti Ti ilmenite FeTiO3 (B) structures.
3D graphics obtained with
CrystalMaker®X software
(crystalmaker.com).

z z
y
y x
x

*Correspondence: Prof. Dr. I, Van Driessche, E-mail: [email protected]

Department of Chemistry, Ghent University, Krijgslaan 281 – S3, Ghent, Belgium.
Colloidal Nanocrystals CHIMIA 2021, 75, No. 5 377

Perovskites ideally have a cubic crystal structure (e.g. BaZrO3, the boundary at 10 nm due to the potential of such small nanocrys-
SrTiO3, BaMnO3, etc.). However, due to the vast number of possi- tals as attractive candidates in biomedical applications,[13] artifi-
ble combinations, many perovskite oxides have a lower symmetry cial pinning centers in superconductors[14] or in photocatalysis.­[15]
due to slight distortions in their structure, falling into the category This review tries to present the challenges faced by synthetic
of hexagonal or orthorhombic lattices.[2] The deviation from the chemists when dealing with such small materials. Therefore, the
ideal perovskite structure can be calculated with the Goldschmidt focus lies on strategies capable of both successfully preparing
tolerance factor (t),[3] an empirical index able to predict which these sub-10 nm oxide perovskite nanocrystals and stabilizing
structure is preferentially formed. The value is obtained from the them into as colloidal dispersions. Although we present different
ionic radius of the comprised atoms as expressed in Eqn. (1). compositions throughout the text, most examples will be from
BaTiO3, as it is by far the most studied material. In the second
part, we review selected examples of the application of stabilized
(1)points of colloidal design
  
𝑡𝑡 = (1) colloids, giving details about the critical
 (   )
regarding the final application.

The tolerance factor has been used with great success for 2. Nanocrystals Synthesis Methods
structure stability prediction without the use of computational Most of the perovskite oxides industrially available nowadays
electronic-structure calculations. However, its performance starts are prepared via conventional solid-state reactions. This implies
to fail when double perovskite oxides (A2BB'O6) are assessed. a high-temperature thermal process (above 1000 ºC) resulting in
New versions of the tolerance factor have been developed, suc- polycrystalline materials with poor control over shape and size.­[16]
cessfully proven for single and double perovskite oxide and ha- Some efforts have been made to reduce crystalline size in a top-
lides structures.[4] This variety of structure and chemical composi- down approach, especially by high-energy ball milling[17] or by
tions results in a broad array of properties, including: ferromag- using a surface-active etching salt.[18] Although this approach is
netism,[5] piezoelectricity[6] and ferroelectricity,[7] multiferroics,[8] simple and convenient due to the readily available technology,
superconductivity,[9] ion conductivity,[10] catalytic activity[11] and the resulting nanopowders are well above the 10 nm threshold.
electrode materials.[12] Such properties are strongly dependent There is also no procedure available for their stabilization into
on the size, shape, crystallinity and surface composition. For in- nanoparticle solutions. For advanced applications, controlled syn-
stance, the transition temperature of BaTiO3 from the ferroelectric thetic routes with special care of shape, size and size distribution
(tetragonal) to the paraelectric (cubic) phase decreases progres- become fundamental. It is here that chemical processes gain im-
sively with the nanocrystal size, due to a decrease on the distor- portance as the most flexible approach to obtaining high-quality
tion for titanium atoms in the TiO6 coordination octahedra. There nanocrystals (NCs) with controlled morphology and crystal struc-
is still not a consensus towards the critical size at which ferro- ture. In the following sections the main synthetic strategies will be
electricity is suppressed. Therefore, it is of utmost importance to discussed, illustrated with representative examples. The examples
continue developing novel material fabrication strategies to solve are also presented in Table 1 for clarity.
technological and fundamental scientific problems. Even though
an extensive number of experimental conditions are available, a 2.1 Hydrothermal and Solvothermal
general methodology for perovskite oxide nanocrystals with fine Solvothermal and hydrothermal syntheses are an important
control over size and shape is still lacking. branch of inorganic chemistry. These techniques have a history of
In this review, we discuss the leading synthetic methods to more than 100 years, which started with the synthesis of minerals
obtain sub-10 nm perovskite oxide nanocrystals. We choose to set and extraction of elements. Nowadays, it represents an effective

Table 1. Quick-access table of most representative synthesis examples.

Synthesis Sub-type Precursor Experimental Sample Phase Controllable Dispensability Ref.

method conditions obtained
140–200 ºC BTO
Hydrothermal – Ba(NO3)2, TiCl3 17–20 nm by temperature non-polar solvents [24]
24 hours STO
4–5 nm BTO O.A.-cyclohexene [32]
Ba(Sr)(OBn)x 200–220 ºC
One-phase – MEEAA-EtOH[99] [27]
Ti(Zr)(OiPr)4 48–72 hours 5–10 nm STO
Solvothermal MEEAA-PGMEA[105]
180 ºC by modifying Organic solvents, e.g.
Two-phase Ba(OAc)2, Ti(n-OBu)4 3.7 nm BTO [34]
12 hours exp. conditions DCM, PhMe
Sol-gel 160 ºC by solvent dispersed in the sol,
Ba(OH)2 + Ti(OBu)4 2.8 nm BTO [37]
precipitation 0.25–2 hours modification N,N-DMF[77]
16 ºC EtOH,[43] Phosphonic
Vapor-diffusion BaTi[OCH2CH(CH3)OCH3]6 5.9 nm BTO – [40]
15 hours acid-PhMe[44]
Sol-gel by precursor/
100 ºC
Hot-injection BaTi(O2CC7H15)[OCH(CH3)2]5 8.0 nm BTO O.A.a Hexane [47,49]
48 hours
concentration
14 ºC
by water
Self-collection Ba(OiPr)2, Sr(OiPr)2, Ti(OiPr)4 4–10 hours 7–12 nm Ba0.7Sr0.3TiO3 Polar solvents [51]
content
(aging)
Aging 24 h at
Micro-emulsion – Ba(OH)2 + Ti(OBu)4 5–10 nm BTO by micelle size [55]
R.T.
Super-critical 300 ºC by reactor
– BaTi(OiPr)6 10 nm BTO [57]
precipitation 10 MPa conditions
R.T. Tetragonal
Bio-inspired Peptide template BaTi(O2CC7H15)[OCH(CH3)2]5 12 nm by adjusting pH [62]
1–4 days BTO

O.A.: oleic acid

a
378 CHIMIA 2021, 75, No. 5 Colloidal Nanocrystals

route for the preparation of novel materials.[19] Examples of zeo-

lites,[20] metal-organic frameworks,[21] nanocrystalline titania,[22]
etc. are considered the current benchmarks for materials com-
parison. Solvothermal and hydrothermal syntheses are the most
exploited routes for preparing ternary oxides, with most of the
literature examples belonging to this strategy. These techniques
are based on the crystallization and growth of the desired product
at moderate temperatures and autogenous pressure. These con-
ditions are achieved by heating the reaction mixture in a sealed
reactor (autoclave) above the boiling point of the organic solvent
(solvothermal) or above the boiling point of water (hydrothermal).
They are typically one-step processes in which the products are
used after purification without any further crystallization step.[19]

2.1.1 Hydrothermal, Aqueous Solution-based Synthesis

The first synthetic recipes date back to the 1970s for the spe-
cific case of BaTiO3 (BTO).[23] However, it was only in 2005 that
a procedure for the synthesis of nanosized (< 20 nm) perovskite
nanocrystals was reported.[24] Although the nanocrystal size is
slightly larger than the scope of this review, the work is of spe-
cial importance due to its versatility. Barium nitrate and titanium
chloride (iii) were used as starting materials in a highly alkaline
solution of NaOH (5–10 M) at temperatures in the range 140–200
ºC. The resulting spherical NCs have an average size of 17 nm and
20 nm when 180 and 200 ºC are used respectively.[24] Alternative
synthetic conditions can also lead to the formation of nanocubes
of BTO under milder conditions and adding oleic acid, which
is retained in the resulting solution.[25] Oleic acid is an effective
surfactant that enables control over particle size, crystallographic
direction and enhances dispersibility of ternary oxides.[26]

2.1.2 Solvothermal, Non-aqueous Solution-based Synthesis

Niederberger et al.[27] presented the first example of sub-10
nm NCs using this route in 2004. The synthesis is based on a
non-hydrolytic pathway from the reaction of commercially avail-
able (Ti and Zr) isopropoxides with custom benzyl alcohol barium
and strontium alkoxides. These custom alkoxides are prepared by
reacting pure metals with different alcohols (i.e. benzyl alcohol,
BnOH), a reaction that forms hydrogen gas as by-product (Eqn.
(2)).[28] The process is performed at a temperature range from 50–
100 ºC, depending on the electropositivity of the metal. In that
sense, strontium would require higher reaction temperatures to
achieve complete dissolution of the metal compared to the barium Fig. 2. Representative TEM micrographs of as-synthesized BaTiO3
analogous process.[27a] nanoparticles. (a) An overview image proves the exclusive presence of
BaTiO3 nanoparticles without the presence of larger particles or agglom-
erates; (b) selected area electron diffraction (SAED); (c) and (d) high-
Ba + 2 BnOH → Ba(OBn)2 + H2 ­↑ (2) resolution TEM images of isolated BaTiO3 nanocrystals. Reprinted with
permission from ref. [27a]. Copyright 2004 American Chemical Society.

One equivalent mole of the corresponding (Ti or Zr) isopro-

poxide is then added, and the mixture is transferred to the auto- and titanium isopropoxides (Alfa Aesar) or even double barium
clave and heated at 200–220 ºC for 48–72 hours. The resulting titanium ethylhexano-isopropoxide (Alfa Aesar) that also lead to
products are crystalline and spherical in morphology. The mea- the formation of BTO NCs.[30b] All preparations were performed
sured size of the NCs is as follows: BTO (4–5 nm, Fig. 2),[27a] at 200 ºC for 48–96 hours depending on the metal source and
SrTiO3 (5–10 nm)[27a] and BaZrO3 (2–3 nm, agglomerated).[27b] solvent compositions.
The mechanism of this synthesis was elucidated by 1H, There is another set of reactions that use as A2+ sources differ-
13
C-NMR spectroscopy and coupled gas chromatography-mass ent aqueous solutions of hydroxides,[31] chlorides[32] or nitrates.­[33]
spectrometry (GC-MS). The reaction undergoes a C–C bond for- However, these reactions typically go through a hydrolysis and
mation from the benzyl alcohol and isopropanol species (Scheme condensation mechanism. They take advantage of the highly
1), which represents a third pathway from the well-known ester charged Lewis acidic B4+ metal centers in alkoxides (isopropox-
and alkyl halide non-aqueous eliminations.[29] ides or butoxides) to force the reactivity into the formation of the
Although this represents a pure solvothermal procedure, varia- ternary oxide. In the case where hydroxides are used, no addition-
tions from this example have employed water as an oxygen source al base is required as the reagents serve as the hydroxyl source,
for other systems that cannot proceed with the C–C mechanism and therefore the initiator of the reaction. Among them, special
described before or simply to improve crystal size tunability with- interest arose in the synthesis presented by the Caruntu group.
out compromising crystallinity.[30] Here we find custom barium Their adapted method, which is thought to go under the formation
ethoxides or isopropoxides; commercially available single barium of a microemulsion system at solvothermal conditions, is able to
Colloidal Nanocrystals CHIMIA 2021, 75, No. 5 379

range of reagent concentrations. They found that in the experi-

mental conditions where sols are formed, the system is robust in
regards to the final particle size. However, at higher concentra-
tions (high-alkaline media) the sols are no longer stable and result
in the formation of precipitates. This results in the formation of
larger aggregates and therefore an increase in the XRD measured
crystallite size.[38] STO NCs with an average size of 8.6 nm (TEM
and DLS presented in Fig. 3) could also be obtained following this
route, with the necessary addition of ammonium hydroxide.[39]

Scheme 1. Reaction mechanism for the formation of BaTiO3 nanoparti-

cles and illustrating the C–C bond formation leading to 4-phenyl-2-buta-
nol. Reprinted with permission from ref. [27a]. Copyright 2004 American
Chemical Society.

produce 10 nm BTO nanocubes that can be stabilized in polar

and non-polar media, following (if required) a ligand exchange
process.[33] Smaller BTO nanocrystals can also be obtained in a
rapid (6 hours) solvothermal method described by Yoshimura and
coworkers. The reacting solvents are slowly released, in a process
named ‘Solvothermal drying route’, that can lead to the formation
of BTO nanopowders with tunable size (smallest ca. 5 nm) and
crystal structure (cubic and tetragonal).[31b]

2.1.3 Oil-(or Surfactant) Water Two-phase Solvothermal

Synthesis
This intermediate strategy is based on the crystallization and Fig. 3. (a) TEM image, (b) HR-TEM image, (c) particle size distribution of
growth of nanocrystals at the oil–water interface but the reaction is the SrTiO3 nanocubes, and (d) DLS analysis of the SrTiO3 nanocrystal
conducted under solvothermal conditions. Briefly, this approach sol prepared by the rapid sol-precipitation method at 160 °C for 2 h.
allows the use of strong alkali environments (necessary in hydro- Reproduced from ref. [39] with permission from The Royal Society of
thermal synthesis) together with the benefit of incorporating sur- Chemistry.
factants that passivate NCs surfaces, therefore avoiding secondary
growth or agglomeration. Alkali oleates from hydroxides or ace-
tates are initially produced. Acetates are typically preferred due to 2.3 Vapor-diffusion Sol-gel
the lower sensitivity to CO2 and therefore avoiding the formation Vapor-diffusion sol-gel (VDSG) methods are based on the
of barium carbonate impurities.[34] As in the solvothermal routes, hydrolysis and polycondensation of double metal alkoxide pre-
the B4+ is provided in the form of alkoxides. The thermal process cursors (commercially available, e.g. Gelest Inc.) by pumping
is conducted in the range of 180–200 ºC for a time range between water vapor (hydrolytic agent) into the reaction flask (Fig. 4).
12–78 hours. 3.7 nm BTO nanocuboids,[34] 10 nm SrTi1−xZrxO3 The Brutchey group was able to produce different oxides with
nanocuboids[35] monodisperse nanocrystal are obtained, with the the general formula of Ba1-xSrxTi1-yZryO3. Ternary oxides such as
possibility of transition-metal doping (Cr, Mn, Fe or Co).[36] BTO,[40] STO[41] and BZO[42] are prepared by a one-step procedure
in which the reagents are exposed to a humid vapor flow for 72 h.
2.2 Sol-gel Precipitation During this time, an increased viscosity is firstly observed fol-
Controlled hydrolysis and polycondensation of a metal alkox- lowed by the formation of a fully rigid, monolithic and crack-free
ide precursors (butoxides) and a metal salt (hydroxides) are the gel (after 4–8 hours depending on the flow rate). A few hours
basis for this method. The reaction takes place in alcohol-based after, cracks start to appear along with a clear supernatant. The
media (i.e. ethylene glycol (EG) and higher glycols as di-(DEG), water flow is stopped after 72 hours and the pieces of the gel
tri-(TEG) and tetra-ethylene glycol) with the presence of poly- are collected, washed with ethanol, sonicated and recovered via
vinyl pyrrolidone (PVP) as surfactant. The mixture is heated at centrifugation. An off-white powder consisting of BTO NCs was
160 ºC for 0.25–2 hours. The NCs formed are dispersed into the finally obtained (5.9 ± 0.1 nm in size, TEM),[40] which can be
sol as observed via DLS. Precipitation can be then triggered by dispersed directly in ethanol[43] or in toluene after surface modi-
adding water to the solvent mixture, which removes solvent mol- fication with n-hexylphosphonic acid.[44] This methodology also
ecules attached to the surface of the NCs and destabilizing the allows the preparation of doped NCs by addition of metal salts in
sol. The material obtained is then washed with water and etha- the reaction mixture, e.g. Ba1-xLaxTiO3[45] or Eu:BaZrO3.[46]
nol. Remarkably, this process features the formation of extremely
small BTO NCs, which are in the range of 2.8 nm using DEG 2.4 Hot-injection Sol-gel
or 5.1 nm using TEG.[37] The authors used the TEG system to Most of the examples belonging to this category depend on
investigate the effect of the experimental conditions through a the hot injection of a metallic precursor in a suitable solvent in the
380 CHIMIA 2021, 75, No. 5 Colloidal Nanocrystals

BTO NCs in a oleylamine/oleic acid reaction mixture at 320 ºC

for 48 h. In this case, the size effect was studied depending on the
caping agent (decanoic acid or oleic acid) and the effect of the
addition of oleyl alcohol during precursor synthesis. The pres-
ence of this alcohol improves morphology and leads to smaller
particles due to the improved coordination capabilities compared
to benzyl alcohol.[50]

2.5 Self-collection Growth

The self-collection growth technique refers to the controlled
hydrolysis of metallic precursors that leads to the formation of a
pure high crystalline gel monolith. It was presented by the O’Brien
Fig. 4. Employed set-up for the VDSG synthesis. Two configurations are group in 2015 for BaTiO3, BaxSr1-xTiO3 and the quaternary oxide
possible: (1) precursor injection (A open, C closed, and a septum replac- Ba0.65Sr0.35Ti0.5Hf0.5O3.[51] The reaction is initiated by mixing me-
es B), and (2) vapor diffusion (A closed, and B and C open). Reproduced tallic isopropoxides in ethanol/water mixtures and applying mild
from ref. [43] with permission from The Royal Society of Chemistry. heat (55 ºC). The formation of the gel is started after 2 hours, with
gelation completed after 5 hours (Fig. 5A). The main feature of
this approach is the absence of post-processing, as no by-products
presence of a ligand that impacts colloidal stability. In a typical are observed. The collected monolith is only rinsed with etha-
BTO run, barium titanium ethyl hexane-isopropoxide precursor nol and the NCs are directly dispersed into the selected solvent.
is injected in a mixture of diphenyl ether and oleic acid at 140 ºC Contrary to most of examples reviewed before, the nanoparticles
under an inert atmosphere. Argon or nitrogen are required to avoid obtained via this method can be dispersed in polar solvents (e.g.
the premature hydrolysis of precursors due to their high sensitivity ethanol or furfural alcohol) leading to transparent solutions with
to moisture. Hydrogen peroxide is subsequently injected once the a total concentration of 10–50 mg·mL–1. The NCs have a tunable
mixture is at 100 ºC to promote further hydrolysis and crystal- size in the range of 7–12 nm, mainly affected by the water content
lization of the product. After 48 h the product obtained consists and not by the experiment temperature (Fig. 5C).[51] Following the
of spherical monodisperse BTO NCs with an average diameter same procedure, iron substituted Ba(Ti1-xFex)O3 and pure BaFeO3
of 8 nm. The authors could establish a relation between the re- may be also produced.[52]
agent concentration (precursor to oleic acid ratio) and final size
of particles. By increasing this parameter (and adding extra H2O2) 2.6 Microemulsion
bigger particles in the range of 9–12 nm were obtained with a The use of microemulsion for the preparation of oxides or
cubic morphology, whereas decreasing this parameter would lead mixed oxide particles is known since the late 1980s. In this
to 4–6 nm NCs.[47] Using a similar procedure, but in this case with wet-chemistry method, the control is based on the nanoreactors
metallic glycolate precursors (preparation described in ref. [48]), formed by the inverse micelles. This system was presented in
spherical STO and BTO nanoparticles were successfully produced 1995 for a wide variety of compositions, including double titania
in the range of 3–5 nm[49] with a similar reagent concentration- (TiO2) and zirconia (ZrO2) and ternary BaZrO3, BaTiO3, SrTiO3,
size dependence as observed before.[47] Alternatively, a custom and SrZrO3.[53] Metal alkoxides were mixed with the microemul-
barium-benzyl alcohol (described elsewhere)[27] together with sion formed by cyclohexane and polyoxyethylene-(4)-laurylether.
Ti-isopropoxide as metal precursors were used to obtain 3–5 nm BTO and STO were analyzed after synthesis, whereas BZO and

A B Fig. 5. (A) Photo images. (B) TEM

image of BST nanocrystals (inset:
high-resolution image of a parti-
cle oriented along the [111] direc-
tion). (C) Diameter of BST nano-
crystals as a function of water
content in ethanol solvent. The
crystal size range is the error bar
nanocrystals synthesized at the
temperature of 15–190 °C (red tri-
angle: 15 °C, black circle: 45 °C,
and blue cube: 190 °C). (D) Size
distribution of BST nanocrystals
200 nm
by number (measured by dynam-
ic light scattering). Adapted from
ref. [51] with permission from The

C D Royal Society of Chemistry.

Colloidal Nanocrystals CHIMIA 2021, 75, No. 5 381

SZO required a sintering process at 800 ºC and 900 ºC, respec- precursor concentrations, the minimum concentration condition
tively. All phases contained crystallites below 20 nm, mostly in for nucleation is quickly not present and therefore growth will
the form of aggregated nanopowders. In more recent examples, start to occur, consuming the rest of precursor present and in-
the direct synthesis (without crystallization step) of ternary ox- creasing crystallite size via various growth mechanism. For high
ides via emulsion systems was realized. Yang and coworkers,[54] precursor concentrations, nucleation will play a more significant
published in 2007 the preparation of BaTiO3, SrTiO3 and mixed role, occurring at a faster time scale in a ‘burst-nucleation’-like
BaxSr1-xTiO3 NCs in a cyclohexene, Triton X-100 (surfactant), behavior. The fast depletion of precursor concentration results
n-butanol water mixtures (80 ºC) while Zhou and coworkers,[55] in very limited growth and therefore crystallites being formed
used an hexanol-water based microemulsion (70 ºC) with OP-10 by precursor condensation and not by ripening. This explana-
and cyclohexane as surfactant and assisted surfactant for their tion was used by the authors to rationalize the effect of the Zr
BTO route. Both systems present similarities in the experimen- concentration. The minimum concentration for burst-nucleation
tal observations of size dependence. The size of the micelles can decreases with increased Zr content, being nucleation the simply
be adjusted by varying the water-surfactant ratio, and therefore dominant at high Zr concentrations.
different sets of sizes can be obtained, with the smallest set in
the range of 5–10 nm. 2.8 Biological and Biomimetic Systems
Production methods that take place at room temperature are
2.7 Supercritical Fluid Technology probably the ultimate goal of any synthetic chemist. Biological
Supercritical fluids represent a consolidated green platform and biomimetic methods provide economically viable, environ-
for the synthesis and processing of materials, including the di- mentally benign and energy-conserving processes.[61] As in nature,
rect crystallization of nanomaterials under supercritical condi- these systems can produce crystals controlled by the properties of
tions.[56] This process may be considered a solvothermal process the biological templates. This is especially important in BaTiO3,
that takes place at supercritical conditions. The main advantage where the tetragonal phase is of interest whereas the cubic phase is
is easy implementation in a continuous production due to the generally obtained for being the most thermodynamically stable.
readily available technology. Based on the hydrolysis and poly- To force a cubic to tetragonal phase conversion, extra high-tem-
condensation of the BaTi(OiPr)6 in a water/ethanol mixture at perature steps are required, which may result in particle aggrega-
supercritical conditions, BTO nanoparticles of average size 10 tion or coarsening. Nuraje et al.[62] provided the first example of
nm were recovered.[57] This process was then used for the syn- a ternary oxide (BTO) using a peptide nanoring as template. The
thesis of different BaTi1-yZryO3 (0 ≤ y ≤ 1) nanocrystals. Philippot controlled hydrolysis of a Ba-Ti alkoxide occurs inside the nano-
et al.[58] studied the whole range of compositions at higher tem- reactor formed by the self-assembled peptide. After time periods
peratures obtaining the entire solid solution, confirmed with the ranging from 1–4 days, ring-shaped self-assemblies appear. The
linear variation of the lattice parameter (Vegard’s law). Pure templates are removed by irradiating the solution with UV light
BTO was the largest composition obtained (20 ± 6 nm). The (λ = 355 nm) for 10 h. The nanocrystals obtained are monodis-
size decreased by increasing the zirconium content, until pure perse in the range of 6–12 nm. The sizes can be tuned by modifying
BZO with an average size of 10 ± 2 nm was obtained (Fig. 6A). the solution’s pH since this parameter has a direct influence over
A more in-depth study was presented one year after[59] by ap- the template diameter. Surprisingly, the NCs present a tetragonal
plying in situ synchrotron wide-angle XRD scattering (WAXS). structure, possibly induced by the surface structure of the pep-
The authors were able to study the effect of the Zr content and tide template and the high surface tension inside the cavity. The
found to have a direct impact over the growth of nanocrystals. resulting NCs show ferroelectric behavior. Biological methods
The crystallite size was the studied parameter across the differ- are then able to crystallize metastable crystal structures. Another
ent zirconium compositions of the BaTi1-yZryO3 (BTZ) ceramic. alternative approach relies on the use of microorganisms for the
Increasing the zirconium content resulted in a decrease of the formation of BTO. Conventionally synthetized BTO powder was
crystallite size (Fig. 6A), together with a significant decrease in digested by yeast cells resulting in spherical BTO nanoparticles
the amount of relative crystal growth. For example, the case of in the range of 8–21 nm.[63] Improved results were obtained when
y = 0.3 the crystallite size at 8 minutes is almost the same as after barium and titanium compounds were used together with fungus
only 10 seconds (Fig. 6B). This phenomenon is similar to the F. oxysporum.[61] This technique was also used by the same group
one observed in this same work by screening the precursor con- for other binary phases such as silica,[64] titania,[64a] zirconia,[65] or
centration and may be explained on the basis of the nucleation magnetite.[66] The reaction undergone under ambient conditions
and growth theory developed by LaMer and Dinegar.[60] During for 24 h resulted in the formation of nanocrystalline BTO of 4–5
nucleation the amount of available precursor decreases. At low nm in average size. The authors claimed that the nanoparticles can

Fig. 6. (A) Variation of the BTZ

A B mean nanocrystals size, to-

gether with size distributions from
HR-TEM images (> 150 NCs).
(B) in situ synchrotron WAXS
study of the BTZ system with
variation of the crystallite size
as a function of time for BaTiO3,
BaTi0.85Zr0.15O3, and BaTi0.7Zr0.3O3 .
Adapted with permission from ref.
[59]. Copyright 2016 American
Chemical Society.
382 CHIMIA 2021, 75, No. 5 Colloidal Nanocrystals

be dispersed in PMMA/chlorobenzene or water, but no solution

characterization is provided.

3. From Stable Colloids to Applications

Above, we presented the main strategies developed for the
preparation of oxide perovskite NCs. There are still some chal-
lenges that need to be overcome to arrive at a general strategy.
While the research in this area continues, an important number
of applications are starting to emerge. In this second part, the
main benefits of stable colloids will be highlighted in low-tem-
perature solution-based processes. Therefore, the direct utiliza-
tion of nanocrystalline powders will not be discussed.
Fig. 7. Tapping mode AFM images of BTO NCs on Pt-coated SiO2/
3.1 Ferroelectric Thin Films Si substrates, with (A) showing a large degree of aggregation and (B)
Ferroelectric materials exhibit spontaneous electric polariza- presenting well dispersed NCs by addition of P123 surfactant. Adapted
tion that can be reversed by applying an external electrical field. from ref. [69], with the permission from AIP publications.
The switchable polarization has been exploited in several ap-
plications, such as memory devices in the form of ferroelectric
capacitators or integrated microelectronics.[67] Lead zirconate 3.2 Nanocomposites for Flexible Ferroelectric
(PZT) is the most well-known representative of this class. Capacitors
Nevertheless, researchers have sought to develop lead-free alter- The combination of nanocrystals and organic polymeric struc-
natives, especially BaTiO3 (BTO) and derived compositions.­[68] tures has gained interest in recent years due to the synergetic rela-
The use of BTO nanocrystals as nanoscale building blocks al- tionship between the individual components, resulting in superior
lows for (i) a more detailed control over the grain size of the final performances. All-solid dielectric capacitors are ideal candi-
film, (ii) an increasing polarization or dielectric constant, or (iii) dates for some niche applications as in portable electronic devic-
a better control over a range of electrical characteristics by selec- es, electrical power systems, and hybrid electric vehicles in the
tive annealing to different grain sizes.[69] A more fundamental form of multi-layer ceramic capacitators (MLCCs). Although
research interest arises also from the study of the size-effect BaTiO3 has been traditionally the dominant material, its poor
on the ferroelectric properties.[70] A typical fabrication process mechanical properties have limited its applicability in flexible
will include two steps: a first deposition of the material on the capacitors. On the other hand, polymers are widely investigated
desired surface (i.e. Si, Ni, Pt-TiO2, etc.) and a second anneal- in flexible electronics due to their excellent mechanical proper-
ing step for film densification. The straightforward strategy is ties and easy solution processability. However, their dielectric
the dispersion of BTO NCs in a proper solvent like 2-methoxy- constant values are several orders of magnitude lower compared
ethanal or 2-methoxyethanol and deposition via spin-coating to conventional ceramics and low energy densities are thus ob-
or electrophoretic deposition.[71] On the other hand, alternative tained (in linear dielectric behaviour, energy density is directly
methods rely on stabilized BTO NCs as initial building blocks. proportional to the dielectric constant).[73] To overcome this, in-
Alcohol[69] and water-based[72] solutions also lead to the forma- corporation of BTO NCs in the form of 0–3 composites (connec-
tion of BTO films. Robinson and coworkers,[69] reported that tivity classification for piezoelectric composites, 0 for the active
NCs dispersions can be used in different methodologies, from phase (NCs) and 3 for the passive phase (3D polymer)) has been
deposition of individual NCs on a substrate to soft-lithography proposed as an efficient solution to obtain high dielectric con-
in forms of micromolding in capillaries (MIMIC). Nevertheless, stants from the ceramic filler with high DC-breakdown strength
each strategy requires a different approach regarding the colloi- from the polymer matrix. The process is illustrated in Fig. 8. The
dal engineering. This becomes crucial when BTO NCs are in- BTO NCs are used as building blocks. They are stabilized by
dividually deposited on different substrates. For instance, BTO oleic acid ligands, and dispersed in toluene.[74] If DMF would be
NCs deposited on Si and Si3N4/Si show different size distribu- preferred, the original ligands should be exchanged for inorgan-
tions due to the interaction with the surface of the substrate. ic ligand BF4–[75] (methodology adapted from ref. [76]) or other
And this situations worsens when the solutions are deposited on ligands like TEG should be used.[77] Then the desired polymer
Pt-coated silicon substrates, where the NCs tend to aggregate is added (typically PVDF-HFP, PMMA-ABS or SBS) followed
(AFM tapping mode image, Fig. 7A). The addition of triblock by sonication/stirring. The precursor is then cast or spin-coated
copolymer P123 improved the dispensability of the NCs (Fig. in the desired substrate. Toluene-based precursor solutions have
7B) due to a possible different surface binding and compatibility the advantage that they can be processed at ambient, mild condi-
enhanced by the incorporation of additional surfactants. tions whereas DMF requires a thermal process above the boil-

BaTiO3

Fig. 8. Schematic illustration for the formation of BTO/PVDF-HFP nanocomposite film.

Colloidal Nanocrystals CHIMIA 2021, 75, No. 5 383

ing point of this solvent. The resulting films contain BTO NCs tor (CMOS) circuits, thus promoting further miniaturization of
homogeneously distributed in the polymer matrix, allowing a electronic components.[84] Resistive switching can be defined
high dielectric homogeneity throughout the layer. The dielectric as the reversible change in resistance between a high resistance
properties are improved thanks to the incorporation of the NCs state (HRS) and a low resistance state (LRS) that depends on the
compared to pristine polymeric layer, with high permittivity and historic applied external bias.[85] In contrast to expensive ultra-
increased energy densities as the most remarkable features. high vacuum nanodot fabrication approaches, solution-processed
nanocrystal (NCs) research gained interest due to the physical
3.3 Superconducting Nanocomposites, Performance flexibility and low fabrication cost. The Nonemann group used
with Zero Energy Loss the flow-coating technique to deposit NCs dispersions in toluene
Superconducting materials, exhibiting zero current loss, are in the form of nanoribbons. SrTiO3[86] and BaZrO3/SrZrO3[87] have
essential materials especially in the field of magnets, where ex- successfully shown memristive behavior (Fig. 10). Special care of
tremely high magnetic fields cannot be achieved with traditional the selected ligands is required since they affect the performance
electromagnets. REBa2Cu3O7 (REBCO, RE = rare earth or Y) of the assemblies.[88]
coated conductors (CC) represent the second generation of su-
perconducting materials, and combine high performance with
competitive production cost. Nanocomposite architectures (with
NCs incorporated in the superconductor), are required to maintain
performance at high magnetic fields.[78] Economically feasible
Chemical Solution Deposition (CSD) combined with preformed
ternary oxide nanocrystals is the most promising approach[79] for
the expansion of coated conductors in the power market. The
main challenge is the introduction of the stabilized nanoparticles
(alcohol-based solutions) in the highly ionic TFA-REBCO (pH
= 2) or low-fluorine (pH = 6) precursor solutions.[80] The choice
of the ligand has been proven to be crucial for the properties of
the final superconducting nanocomposite.[81] The Obradors[78,82]
and the Van Driessche[83] groups have successfully incorporated a
variety of sub-10 nm ternary oxides (i.e. BaZrO3, BaHfO3, BaTiO3, Fig. 10. Illustration of the stop-and-go flow coating process. Inset shows
SrZrO3) by using triethylene glycol (TEG) and 2-(2-methoxye- the assembly of the NCs driven by solvent evaporation. Adapted with
thoxy)acetic acid (MEEAA) as surfactants, which resulted in sev- permission from ref. [88b]. Copyright 2018 American Chemical Society.
eral weak, stable solutions that deliver epitaxial nanocomposite
superconducting films. According to the work of Díez-Sierra et
al.[83] BZO, BHO and SZO NCs can be homogeneously distrib-
uted in the superconducting nanocomposite, with coarsening of 3.5 Aerogels as a Photocatalysis Platform
nanoparticles not affecting the growth of the YBCO layer. In Fig. Aerogels are highly porous, low-density inorganic materials
9 a graphical illustration of the superconducting composites is traditionally based on oxides such as silica, alumina, zirconia,
shown. The nanocrystals are depicted together with secondary stannic, or tungsten oxide or a mixture of these oxides.[89] More
phases and intergrowth. The best performance was obtained for recently, organic aerogels have emerged with graphene oxide[90]
the BHO-YBCO composites. The small size (ca. 7 nm) of the as the most prominent representative. Their outstanding properties
BHO NCs in the film, maintained through the YBCO thermal pro- are leveraged in several applications which include catalysis[91] and
cess at high temperature, translates into a high concentration of adsorbents[90a,92] to name a few. Their porous structure together with
pinning centers, resulting in enhanced superconducting behavior the possibility of tailoring their chemical properties,[93] material-
under magnetic environments. izes into a powerful platform that bridges nano with macroscale.
The traditional route (supercritical drying) developed by Kistler
3.4 Memristors, beyond Moore’s Law et al.[94] in 1931 is the most used strategy for aerogel preparation.
Resistive switches exhibit faster switching speeds, lower The procedure starts with gel formation, based on the polymeriza-
power consumption, higher scalability, and greater 3D stack- tion and formation of M-OH-M or M-O-M bridges between the
ability than standard complementary metal oxide semiconduc- metallic atoms (M) of the precursor molecules.[95] This results in

Fig. 9. Schematic illustration of the four nanocomposites showing the main defects present: homogeneously distributed nanocrystals [for BZO
(green), SZO (blue), and BHO (cyan)], intergrowths (for BHO), small secondary phases such as Y2O3 [for SZO (gray)], and highly coherent twin bound-
aries [for BTO (pink)]. Reprinted with permission from ref. [83]. Copyright 2020 American Chemical Society.
384 CHIMIA 2021, 75, No. 5 Colloidal Nanocrystals

a 3D network that contains trapped solvent molecules (i.e. water). derstanding and design of NCs synthetic routes. We foresee the
Water is a solvent that is not removed via supercritical drying as it use of kinetically controlled synthesis and precursor design as a
requires high temperatures and high pressure and becomes highly robust strategy for size and shape detailed control, already proven
oxidizing.[96] Therefore, water is usually exchanged by alcohols for single oxides or semiconductor nanocrystals. In the second
or acetone and then brought into supercritical conditions. The sol- section of this review, the main applications that can take advan-
vent is then removed through gas expansion while preserving the tage of the stabilized nanocrystal solutions have been reviewed.
macro/microporous structure of the material. Nanoparticles can Flexible electronics keep pushing for innovative energy storage
be used in aerogels by direct incorporation to traditional metal solutions, which translate into new flexible ceramic-polymer
oxide gel-forming composites,[97] or by being employed as nano composites that can store high energy densities. Superconductors
building blocks (Fig. 11), in which the NCs self-assemble form- and non-volatile memory devices also benefit from NCs as indi-
ing the 3D aerogel structures. The latter strategy is based on the vidual building blocks, improving current performances or pro-
controlled destabilization of functionalized nanoparticles, leading moting new forms of information storage.
to higher dimensional structures.[98] Specific examples for ca. 4
nm MEEAA functionalized BaTiO3[99] and Cr-doped SrTiO3[100] Acknowledgements
have led to the formation of aerogels with a surface area over The authors acknowledge the funding received from the European
300 m2/g. In both examples highly concentrated solutions (200 Union’s Horizon 2020 Research and Innovation Programme under the
mg/mL) are destabilized by incorporating water to the ethanolic Marie Skłodowska-Curie Grant agreement No. 722071 (SynFoNY,
www.synfony.eu).
NCs solutions and inducing gelation either by heat or ultrasonic
treatment. The aerogel monolith is then formed by using a super-
critical drying approach, which successfully avoids pore collapse. ORCID iD
This can be verified by BET measurements, giving information Pedro López-Domínguez: 0000-0002-8222-6200
about surface area and pore structure. BaTiO3-based aerogels have Isabel Van Driessche: 0000-0001-5253-3325
been successfully tested regarding their photocatalytic activity in
methyl orange degradation.[101] A more thorough review on inor- Conflicting Interests
ganic aerogels[102] and the applications in photocatalysis[103] may The authors declare no competing financial interest.
be found elsewhere.
Received: December 17, 2020

[1] J. M. L. Cabello, M. De Las Mercedes Pardo Figuerez, A. C. Flor, Spanish

Patent Appl. No. ES2765374A1, 2020.
[2] T. Ishihara, in ‘Springer Handbook of Electronic and Photonic Materials’,
Eds. S. Kasap, P. Capper, Springer International Publishing, Cham, 2017, p.
1, https://doi.org/10.1007/978-3-319-48933-9_59.
[3] V. M. Goldschmidt, Naturwissenschaften 1926, 14, 477,
https://doi.org/10.1007/BF01507527.
[4] C. J. Bartel, C. Sutton, B. R. Goldsmith, R. Ouyang, C. B. Musgrave,
L. M. Ghiringhelli, M. Scheffler, Sci. Adv. 2019, 5, eaav0693,
https://doi.org/10.1126/sciadv.aav0693.
[5] S. Ray, Y. V. Kolen’ko, K. A. Kovnir, O. I. Lebedev, S. Turner,
T. Chakraborty, R. Erni, T. Watanabe, G. V. Tendeloo, M.
Yoshimura, M. Itoh, Nanotechnology 2011, 23, 025702,
https://doi.org/10.1088/0957-4484/23/2/025702.
Fig. 11. Schematic illustration of colloidal nanocrystal 3D assembly into [6] K. Mimura, K. Kato, H. Imai, S. Wada, H. Haneda, M. Kuwabara, Appl.
aerogels. Reproduced from ref. [104] with permission from The Royal Phys. Lett. 2012, 101, 012901, https://doi.org/10.1063/1.4731198.
Society of Chemistry. [7] R. E. Cohen, Nature 1992, 358, 136, https://doi.org/10.1038/358136a0.
[8] F. A. Pearsall, J. Lombardi, N. Farahmand, B. v. Tassel, E. S. Leland,
L. Huang, S. Liu, S. Yang, C. Le, I. Kymissis, P. Kinget, S. R. Sanders,
D. Steingart, S. O. Brien, IEEE Trans. Nanotechnol. 2020, 19, 255,
https://doi.org/10.1109/TNANO.2019.2939093.
4. Summary and Outlook [9] a) P. Cayado, H. Rijckaert, T. Thersleff, M. Erbe, J. Hänisch, I. V.
The demand for smaller electronic components has driven Driessche, B. Holzapfel, IEEE Trans. Appl. Supercond. 2020, 30, 1,
much of the research in the field of perovskite oxide nanocrys- https://doi.org/10.1109/TASC.2020.2966429; b) M. K. Wu, J. R.
tals. The bottom-up approach appears to be the route with the Ashburn, C. J. Torng, P. H. Hor, R. L. Meng, L. Gao, Z. J. Huang, Y. Q.
Wang, C. W. Chu, Phys. Rev. Lett. 1987, 58, 908, https://doi.org/10.1103/
most significant potential due to reduced cost. However, reduc- PhysRevLett.58.908.
ing the dimensions to a few nanometers brings new challenges [10] M. Li, M. J. Pietrowski, R. A. De Souza, H. Zhang, I. M. Reaney,
regarding a controlled synthesis, specifically in terms of size and S. N. Cook, J. A. Kilner, D. C. Sinclair, Nat. Mater. 2014, 13, 31,
shape. In this review, we have presented the primary synthetic https://doi.org/10.1038/nmat3782.
strategies. Most attention has been dedicated to those which were [11] J. Zhu, H. Li, L. Zhong, P. Xiao, X. Xu, X. Yang, Z. Zhao, J. Li, ACS Catal.
2014, 4, 2917, https://doi.org/10.1021/cs500606g.
able to prepare sub-10 nm crystals as well as stabilize NCs in [12] S. Sengodan, S. Choi, A. Jun, T. H. Shin, Y.-W. Ju, H. Y. Jeong,
solution. All this information has been summarized in Table 1 J. Shin, J. T. S. Irvine, G. Kim, Nat. Mater. 2015, 14, 205,
as a quick-access guide with the most prominent examples. A https://doi.org/10.1038/nmat4166.
general synthesis route should be pursued, in which nanocrystal [13] J. Li, Y. Chen, Y. Yang, N. Kawazoe, G. Chen, J. Mater. Chem. B 2017, 5,
1353, https://doi.org/10.1039/C6TB03276A.
growth is controlled and understood at the nanometer level. The [14] N. Moutalbi, A. Ouerghi, A. M’chirgui, J. Supercond. Novel Magn. 2011,
Niederberger group has made significant advances in elucidat- 24, 165, https://doi.org/10.1007/s10948-010-0912-8.
ing the mechanism of solvothermal reactions. At the same time, [15] L. Li, J. Yan, T. Wang, Z.-J. Zhao, J. Zhang, J. Gong, N. Guan, Nat.
there are still many unknowns about nanocrystal growth in a vast Commun. 2015, 6, 5881, https://doi.org/10.1038/ncomms6881.
number of synthetic routes. When NC size becomes key for the [16] C. Ando, R. Yanagawa, H. Chazono, H. Kishi, M. Senna, J. Mater. Res.
2004, 19, 3592, https://doi.org/10.1557/JMR.2004.0461.
applications pursued, controlled precision synthesis is crucial. [17] a) K. Tsunekawa, Y. Hotta, K. Sato, K. Watari, J. Ceram. Soc. Jpn. 2006,
Techniques able to monitor the progress of the reaction are at 114, 651, https://doi.org/10.2109/jcersj.114.651; b) J. Peng, T. Peng, L.
an early stage, but they provide essential information for the un- Zhang, Y. Tang, Chinese Patent Appl. No. CN104828858B, 2015.
Colloidal Nanocrystals CHIMIA 2021, 75, No. 5 385

[18] T. Charoonsuk, N. Vittayakorn, Mater. Des. 2016, 110, 233, [46] F. A. Rabuffetti, J. S. Lee, R. L. Brutchey, Adv. Mater. 2012, 24, 1434,
https://doi.org/10.1016/j.matdes.2016.07.137. https://doi.org/10.1002/adma.201104645.
[19] S. H. Feng, G. H. Li, in ‘Modern Inorganic Synthetic Chemistry [47] S. O’Brien, L. Brus, C. B. Murray, J. Am. Chem. Soc. 2001, 123, 12085,
(Second Edition)’, Eds. R. Xu, Y. Xu, Elsevier, Amsterdam, 2017, p. 73, https://doi.org/10.1021/ja011414a.
https://doi.org/10.1016/B978-0-444-63591-4.00004-5. [48] V. W. Day, T. A. Eberspacher, M. H. Frey, W. G. Klemperer, S. Liang, D. A.
[20] A. K. Cheetham, G. Férey, T. Loiseau, Angew. Chem. Int. Ed. 1999, 38, 3268, Payne, Chem. Mater. 1996, 8, 330, https://doi.org/10.1021/cm950547q.
https://doi.org/10.1002/(sici)1521-3773(19991115)38:22<3268::aid- [49] Q. J. Cai, Y. Gan, M. B. Chan-Park, H. B. Yang, Z. S. Lu,
anie3268>3.0.co;2-u. C. M. Li, J. Guo, Z. L. Dong, Chem. Mater. 2009, 21, 3153,
[21] O. M. Yaghi, H. Li, C. Davis, D. Richardson, T. L. Groy, Acc. Chem. Res. https://doi.org/10.1021/cm900532q.
1998, 31, 474, https://doi.org/10.1021/ar970151f. [50] Z. Chen, L. Huang, J. He, Y. Zhu, S. O’Brien, J. Mater. Res. 2006, 21, 3187,
[22] a) Y. V. Kolen’ko, A. A. Burukhin, B. R. Churagulov, N. N. Oleynikov, https://doi.org/10.1557/jmr.2006.0389.
Mater. Lett. 2003, 57, 1124, https://doi.org/10.1016/S0167- [51] S. Liu, L. Huang, W. Li, X. Liu, S. Jing, J. Li, S. O’Brien, Nanoscale 2015,
577X(02)00943-6; b) C.-S. Kim, B. K. Moon, J.-H. Park, B.-C. Choi, H.- 7, 11766, https://doi.org/10.1039/C5NR02351C.
J. Seo, J. Cryst. Growth 2003, 257, 309, https://doi.org/10.1016/S0022- [52] J. Lombardi, L. Yang, F. A. Pearsall, N. Farahmand, Z. Gai,
0248(03)01468-4. S. J. L. Billinge, S. O’Brien, Chem. Mater. 2019, 31, 1318,
[23] a) Christen.An, Acta Chem. Scand. 1970, 24, 2447, https://doi.org/10.3891/ https://doi.org/10.1021/acs.chemmater.8b04447.
acta.chem.scand.24-2447; b) [53] H. Herrig, R. Hempelmann, Mater. Lett. 1996, 27, 287,
1975, 1975, 985, https://doi.org/10.1246/nikkashi.1975.985. https://doi.org/10.1016/0167-577X(96)00011-0.
[24] X. Wang, J. Zhuang, Q. Peng, Y. Li, Nature 2005, 437, 121, [54] K. Su, N. Nuraje, N.-L. Yang, Langmuir 2007, 23, 11369,
https://doi.org/10.1038/nature03968. https://doi.org/10.1021/la701877d.
[25] S. Adireddy, C. Lin, B. Cao, W. Zhou, G. Caruntu, Chem. Mater. 2010, 22, [55] Z. Deng, Y. Dai, H. Xiao, M. J. Zhou, Adv. Mat. Res. 2014, 1004-1005, 63,
1946, https://doi.org/10.1021/cm9038768. https://doi.org/10.4028/www.scientific.net/AMR.1004-1005.63.
[26] a) F. Dang, K.-i. Mimura, K. Kato, H. Imai, S. Wada, H. [56] P. López-Domínguez, A. M. López-Periago, F. J. Fernández-Porras,
Haneda, M. Kuwabara, CrystEngComm 2011, 13, 3878, J. Fraile, G. Tobias, C. Domingo, J. CO2 Util. 2017, 18, 147,
https://doi.org/10.1039/C1CE05296A; b) Q. Ma, K.- https://doi.org/10.1016/j.jcou.2017.01.019.
i. Mimura, K. Kato, J. Alloys Compd. 2016, 655, 71, [57] F. Bocquet, K. Chhor, C. Pommier, Mater. Chem. Phys. 1999, 57, 273,
https://doi.org/10.1016/j.jallcom.2015.09.156; c) Q. https://doi.org/10.1016/S0254-0584(98)00233-8.
Ma, K. Kato, Cryst. Growth Des. 2017, 17, 2507, [58] G. Philippot, M. Albino, U. C. Chung, M. Josse, C. Elissalde,
https://doi.org/10.1021/acs.cgd.7b00025; d) M. Maglione, C. Aymonier, Mater. Des. 2015, 86, 354,
Q. Ma, K. Kato, Mater. Des. 2016, 107, 378, https://doi.org/10.1016/j.matdes.2015.07.111.
https://doi.org/10.1016/j.matdes.2016.06.065; e) R. I. Walton, F. [59] G. Philippot, E. D. Boejesen, C. Elissalde, M. Maglione,
Millange, R. I. Smith, T. C. Hansen, D. O’Hare, J. Am. Chem. Soc. 2001, C. Aymonier, B. B. Iversen, Chem. Mater. 2016, 28, 3391,
123, 12547, https://doi.org/10.1021/ja011805p. https://doi.org/10.1021/acs.chemmater.6b00635.
[27] a) M. Niederberger, G. Garnweitner, N. Pinna, M. Antonietti, J. Am. [60] a) V. LaMer, R. Dinegar, J. Am. Chem. Soc. 1950, 72, 4847, https://doi.
Chem. Soc. 2004, 126, 9120, https://doi.org/10.1021/ja0494959; b) M. org/10.1021/ja01167a001; b) T.-D. Nguyen, T.-D. Do, in ‘Nanocrystal’,
Niederberger, N. Pinna, J. Polleux, M. Antonietti, Angew. Chem., Int. Ed. Eds. Y. Masuda, Intech, 2011, p. 55-84, https://doi.org/10.5772/17054.
2004, 43, 2270, https://doi.org/10.1002/anie.200353300. [61] V. Bansal, P. Poddar, A. Ahmad, M. Sastry, J. Am. Chem. Soc. 2006, 128,
[28] R. C. Mehrotra, A. Singh, S. Sogani, Chem. Soc. Rev. 1994, 23, 215, 11958, https://doi.org/10.1021/ja063011m.
https://doi.org/10.1039/CS9942300215. [62] N. Nuraje, K. Su, A. Haboosheh, J. Samson, E. P.
[29] A. Vioux, Chem. Mater. 1997, 9, 2292, https://doi.org/10.1021/ Manning, N.-l. Yang, H. Matsui, Adv. Mater. 2006, 18, 807,
cm970322a. https://doi.org/10.1002/adma.200501340.
[30] a) K. Nakashima, M. Kera, I. Fujii, S. Wada, Ceram. Int. 2013, 39, [63] A. K. Jha, K. Prasad, Integr. Ferroelectr. 2010, 117, 49,
3231, https://doi.org/10.1016/j.ceramint.2012.10.009; b) L. Huang, https://doi.org/10.1080/10584587.2010.489422.
Z. Jia, I. Kymissis, S. O’Brien, Adv. Funct. Mater. 2010, 20, 554, [64] a) V. Bansal, D. Rautaray, A. Bharde, K. Ahire, A. Sanyal, A. Ahmad, M.
https://doi.org/10.1002/adfm.200901258. Sastry J. Mater. Chem. 2005, 15, 2583, https://doi.org/10.1039/B503008K;
[31] a) H. T. Pham, J. H. Yang, D.-S. Lee, B. H. Lee, H.-D. Jeong, ACS Appl. b) V. Bansal, A. Sanyal, D. Rautaray, A. Ahmad, M. Sastry, Adv. Mater.
Mater. Interfaces 2016, 8, 7248, https://doi.org/10.1021/acsami.6b00109; 2005, 17, 889, https://doi.org/10.1002/adma.200401176.
b) Y. V. Kolen’ko, K. A. Kovnir, I. S. Neira, T. Taniguchi, T. Ishigaki, [65] V. Bansal, D. Rautaray, A. Ahmad, M. Sastry, J. Mater. Chem. 2004, 14,
T. Watanabe, N. Sakamoto, M. Yoshimura, J. Phys. Chem. C 2007, 111, 3303, https://doi.org/10.1039/B407904C.
7306, https://doi.org/10.1021/jp0678103. [66] A. Bharde, D. Rautaray, V. Bansal, A. Ahmad, I. Sarkar,
[32] J. Zhou, Z. Yang, CrystEngComm 2013, 15, 8912, S. M. Yusuf, M. Sanyal, M. Sastry, Small 2006, 2, 135,
https://doi.org/10.1039/C3CE41549J. https://doi.org/10.1002/smll.200500180.
[33] D. Caruntu, T. Rostamzadeh, T. Costanzo, S. Salemizadeh Parizi, [67] C. H. Ahn, K. M. Rabe, J. M. Triscone, Science 2004, 303, 488,
G. Caruntu, Nanoscale 2015, 7, 12955, https://doi.org/10.1039/ https://doi.org/10.1126/science.1092508.
C5NR00737B. [68] M. E. Villafuerte-Castrejón, E. Morán, A. Reyes-Montero, R. Vivar-
[34] H. Du, S. Wohlrab, M. Weiß, S. Kaskel, J. Mater. Chem. 2007, 17, 4605, Ocampo, J.-A. Peña-Jiménez, S.-O. Rea-López, L. Pardo, Materials 2016,
https://doi.org/10.1039/B708914G. 9, 21, https://doi.org/10.3390/ma9010021.
[35] a) H. Du, C.-L. Jia, J. Mayer, Chem. Mater. 2016, 28, 650, [69] L. Huang, Z. Chen, J. D. Wilson, S. Banerjee, R. D. Robinson, I. P.
https://doi.org/10.1021/acs.chemmater.5b04486; b) C. Friderichs, Herman, R. Laibowitz, S. O’Brien, J. Appl. Phys. 2006, 100, 034316,
N. Zotov, W. Mader, Eur. J. Inorg. Chem. 2015, 2015, 288, https://doi.org/10.1063/1.2218765.
https://doi.org/10.1002/ejic.201402724. [70] C. Liu, B. Zou, A. J. Rondinone, Z. J. Zhang, J. Am. Chem. Soc. 2001, 123,
[36] T. Costanzo, J. McCracken, A. Rotaru, G. Caruntu, ACS Appl. Nano 4344, https://doi.org/10.1021/ja001893y.
Mater. 2018, 1, 4863, https://doi.org/10.1021/acsanm.8b01036. [71] a) J. G. Barbosa, M. R. Pereira, C. Moura, J. A. Mendes,
[37] Y. Hao, X. Wang, J. Kim, L. Li, J. Am. Ceram. Soc. 2014, 97, 3434, B. G. Almeida, J. Nanosci. Nanotechnol. 2011, 11, 8700,
https://doi.org/10.1111/jace.13153. https://doi.org/10.1166/jnn.2011.3494; b) F. Nakasone, K. Kobayashi,
[38] Z. He, Y. Hao, M. Bi, L. Guo, K. Bi, Micro Nano Lett. 2019, 14, 289, T. Suzuki, Y. Mizuno, H. Chazono, H. Imai, Jpn. J. Appl. Phys.
https://doi.org/10.1049/mnl.2018.5559. 2008, 47, 8518, https://doi.org/10.1143/jjap.47.8518; c) Y. J. Wu, J.
[39] Y. Hao, X. Wang, L. Li, Nanoscale 2014, 6, 7940, Li, H. Tanaka, M. Kuwabara, J. Eur. Ceram. Soc. 2005, 25, 2041,
https://doi.org/10.1039/C4NR00171K. https://doi.org/10.1016/j.jeurceramsoc.2005.03.008.
[40] R. L. Brutchey, D. E. Morse, Angew. Chem., Int. Ed. 2006, 45, 6564, [72] H. Yaseen, S. Baltianski, Y. Tsur, J. Mater. Sci. 2007, 42, 9679,
https://doi.org/10.1002/anie.200602571. https://doi.org/10.1007/s10853-007-1944-8.
[41] C. W. Beier, M. A. Cuevas, R. L. Brutchey, J. Mater. Chem. 2010, 20, [73] Q. Wang, L. Zhu, J. Polym. Sci., Part B: Polym. Phys. 2011, 49, 1421,
5074, https://doi.org/10.1039/C0JM00845A. https://doi.org/0.1002/polb.22337.
[42] F. A. Rabuffetti, R. L. Brutchey, Chem. Commun. 2012, 48, 1437, [74] a) S. S. Parizi, G. Conley, T. Costanzo, B. Howell, A. Mellinger, G. Caruntu,
https://doi.org/10.1039/C1CC14166J. RSC Advances 2015, 5, 76356, https://doi.org/10.1039/C5RA11347D;
[43] F. A. Rabuffetti, R. L. Brutchey, Dalton Trans. 2014, 43, 14499, b) D. Caruntu, B. Kavey, S. Paul, A. C. Bas, A. Rotaru, G. Caruntu,
https://doi.org/10.1039/C4DT01376J. CrystEngComm 2020, 22, 1261, https://doi.org/10.1039/C9CE01912J.
[44] C. W. Beier, M. A. Cuevas, R. L. Brutchey, Langmuir 2010, 26, 5067, [75] S. S. Parizi, A. Mellinger, G. Caruntu, ACS Appl. Mater. Interfaces 2014, 6,
https://doi.org/10.1021/la9035419. 17506, https://doi.org/10.1021/am502547h.
[45] R. L. Brutchey, G. Cheng, Q. Gu, D. E. Morse, Adv. Mater. 2008, 20, [76] A. Dong, X. Ye, J. Chen, Y. Kang, T. Gordon, J. M. Kikkawa, C. B. Murray,
1029, https://doi.org/10.1002/adma.200701804. J. Am. Chem. Soc. 2011, 133, 998, https://doi.org/10.1021/ja108948z.
386 CHIMIA 2021, 75, No. 5 Colloidal Nanocrystals

[77] Y. Hao, X. Wang, K. Bi, J. Zhang, Y. Huang, L. Wu, P. Shi, Y. Nan, Y. Sun, Z. Jiang, ACS Appl. Mater. Interfaces 2015, 7, 25693,
Zhao, K. Xu, M. Lei, L. Li, Nano Energy 2017, 31, 49, https://doi.org/10.1021/acsami.5b09503.
https://doi.org/10.1016/j.nanoen.2016.11.008. [91] a) R. W. Pekala, J. Mater. Sci. 1989, 24, 3221,
[78] a) H. Rijckaert, P. Cayado, R. Nast, J. Diez Sierra, M. Erbe, P. López https://doi.org/10.1007/BF01139044; b) Z.-S. Wu, S. Yang, Y. Sun,
Domínguez, J. Hänisch, K. De Buysser, B. Holzapfel, I. Van Driessche, K. Parvez, X. Feng, K. Müllen, J. Am. Chem. Soc. 2012, 134, 9082,
Coatings 2020, 10, 17, https://doi.org/10.3390/coatings10010017; b) https://doi.org/10.1021/ja3030565.
K. Iida, P. Cayado, H. Rijckaert, M. Erbe, J. Hänisch, T. Okada, I. Van [92] A. K. Meena, G. K. Mishra, P. K. Rai, C. Rajagopal, P. N. Nagar, J. Hazard.
Driessche, S. Awaji, B. Holzapfel, Supercond. Sci. Technol. 2020, 34, Mater. 2005, 122, 161, https://doi.org/10.1016/j.jhazmat.2005.03.024.
015009, https://doi.org/10.1088/1361-6668/abb205. [93] a) I. Smirnova, P. Gurikov, Annu. Rev. Chem. Biomol. Eng. 2017, 8, 307,
[79] X. Obradors, T. Puig, Z. Li, C. Pop, B. Mundet, N. Chamorro, F. Vallés, M. https://doi.org/10.1146/annurev-chembioeng-060816-101458; b) Z. Li,
Coll, S. Ricart, B. Vallejo, F. Pino, A. Palau, J. Gázquez, J. Ros, A. Usoskin, S. Zhao, M. M. Koebel, W. J. Malfait, Mater. Des. 2020, 193, 108833,
Supercond. Sci. Technol. 2018, 31, 044001, https://doi.org/10.1088/1361- https://doi.org/10.1016/j.matdes.2020.108833.
6668/aaaad7. [94] S. S. Kistler, Nature 1931, 127, 741, https://doi.org/10.1038/127741a0.
[80] F. Martínez-Julián, S. Ricart, A. Pomar, M. Coll, P. Abellán, F. [95] A. C. Pierre, G. M. Pajonk, Chem. Rev. 2002, 102, 4243,
Sandiumenge, M. J. Casanove, X. Obradors, T. Puig, I. Pastoriza- https://doi.org/10.1021/cr0101306.
Santos, L. M. Liz-Marzán, J. Nanosci. Nanotechnol. 2011, 11, 3245, [96] M. D. Bermejo, M. J. Cocero, AIChE J. 2006, 52, 3933,
https://doi.org/10.1166/jnn.2011.3762. https://doi.org/10.1002/aic.10993.
[81] a) H. Rijckaert, G. Pollefeyt, M. Sieger, J. Hänisch, J. Bennewitz, K. De [97] W. Chen, S. Li, C. Chen, L. Yan, Adv. Mater. 2011, 23, 5679,
Keukeleere, J. De Roo, R. Hühne, M. Bäcker, P. Paturi, H. Huhtinen, https://doi.org/10.1002/adma.201102838.
M. Hemgesberg, I. Van Driessche, Chem. Mater. 2017, 29, 6104, [98] a) J. Polleux, N. Pinna, M. Antonietti, M. Niederberger, Adv. Mater. 2004,
https://doi.org/10.1021/acs.chemmater.7b02116; b) H. Rijckaert, J. De 16, 436, https://doi.org/10.1002/adma.200306251; b) J. Polleux, N. Pinna,
Roo, M. Van Zele, S. Banerjee, H. Huhtinen, P. Paturi, J. Bennewitz, S. J. L. M. Antonietti, C. Hess, U. Wild, R. Schlögl, M. Niederberger, Chem. - Eur.
Billinge, M. Bäcker, K. De Buysser, I. Van Driessche, Materials 2018, 11, J. 2005, 11, 3541, https://doi.org/10.1002/chem.200401050.
1066, https://doi.org/10.3390/ma11071066. [99] F. Rechberger, F. J. Heiligtag, M. J. Süess, M. Niederberger, Angew. Chem.,
[82] Z. Li, M. Coll, B. Mundet, N. Chamorro, F. Vallès, A. Palau, J. Int. Ed. 2014, 53, 6823, https://doi.org/10.1002/anie.201402164.
Gazquez, S. Ricart, T. Puig, X. Obradors, Sci. Rep. 2019, 9, 5828, [100] F. Rechberger, G. Ilari, C. Willa, E. Tervoort, M. Niederberger, Mater.
https://doi.org/10.1038/s41598-019-42291-x. Chem. Front. 2017, 1, 1662, https://doi.org/10.1039/C7QM00155J.
[83] J. Díez-Sierra, P. López-Domínguez, H. Rijckaert, M. Rikel, J. Hänisch, M. [101] Y. Li, J. Wu, X. Wu, H. Suo, X. Shen, S. Cui, J. Sol-Gel Sci. Technol. 2019,
Z. Khan, M. Falter, J. Bennewitz, H. Huhtinen, S. Schäfer, R. Müller, S. A. 90, 313, https://doi.org/10.1007/s10971-019-04948-x.
Schunk, P. Paturi, M. Bäcker, K. De Buysser, I. Van Driessche, ACS Appl. [102] C. Ziegler, A. Wolf, W. Liu, A.-K. Herrmann, N. Gaponik,
Nano Mater. 2020, 3, 5542, https://doi.org/10.1021/acsanm.0c00814. A. Eychmüller, Angew. Chem., Int. Ed. 2017, 56, 13200,
[84] a) R. Waser, M. Aono, Nat. Mater. 2007, 6, 833, https://doi.org/10.1002/anie.201611552.
https://doi.org/10.1038/nmat2023; b) A. Sawa, Mater. Today 2008, 11, 28, [103] W. Wan, R. Zhang, M. Ma, Y. Zhou, J. Mater. Chem. A 2018, 6, 754,
https://doi.org/10.1016/S1369-7021(08)70119-6. https://doi.org/10.1039/C7TA09227J.
[85] J. J. Yang, M. D. Pickett, X. Li, D. A. A. Ohlberg, D. R. [104] D. Wen, A. Eychmüller, Chem. Commun. 2017, 53, 12608,
Stewart, R. S. Williams, Nat. Nanotechnol. 2008, 3, 429, https://doi.org/10.1039/C7CC03862C.
https://doi.org/10.1038/nnano.2008.160. [105] D. Taroata, W. Fischer, T. A. Cheema, G. Garnweitner, G. Schmid, IEEE
[86] J. Wang, S. Choudhary, W. L. Harrigan, A. J. Crosby, K. R. Kittilstved, Trans. Dielectr. Electr. Insul. 2012, 19, 298, Spanish Patent Appl. No.
S. S. Nonnenmann, ACS Appl. Mater. Interfaces 2017, 9, 10847, ES2765374A1, 202010.1109/TDEI.2012.6148531.
https://doi.org/10.1021/acsami.7b00220.
[87] Z. Zhou, P. López-Domínguez, M. Abdullah, D. Barber, X. Meng, I.
Van Driessche, J. Schiffman, K. Kittilstved, A. Crosby, J. De Roo, S. S.
Nonnenmann, 2021, submitted.
[88] a) J. De Roo, Z. Zhou, J. Wang, L. Deblock, A. J. Crosby, J. License and Terms
S. Owen, S. S. Nonnenmann, Chem. Mater. 2018, 30, 8034, This is an Open Access article under the
https://doi.org/10.1021/acs.chemmater.8b03768; b) J. Wang, S. terms of the Creative Commons Attribution
Choudhary, J. De Roo, K. De Keukeleere, I. Van Driessche, A. J. License CC BY 4.0. The material may not be
Crosby, S. S. Nonnenmann, ACS Appl. Mater. Interfaces 2018, 10, 4824,
used for commercial purposes.
https://doi.org/10.1021/acsami.7b17376.
[89] H. D. Gesser, P. C. Goswami, Chem. Rev. 1989, 89, 765, The license is subject to the CHIMIA terms and conditions: (http://
https://doi.org/10.1021/cr00094a003. chimia.ch/component/sppagebuilder/?view=page&id=12).
[90] a) X. Mi, G. Huang, W. Xie, W. Wang, Y. Liu, J. Gao, Carbon 2012, 50, The definitive version of this article is the electronic one that can be
4856, https://doi.org/10.1016/j.carbon.2012.06.013; b) Z. Tong, D. Yang, J. found at https://doi.org/10.2533/chimia.2021.376