Lak 2021

PROGRESS REPORT
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Embracing Defects and Disorder in Magnetic Nanoparticles

Aidin Lak,* Sabrina Disch,* and Philipp Bender*
Colorful examples for nature’s design-

Iron oxide nanoparticles have tremendous scientific and technological by-disorder are butterfly wings, whose
potential in a broad range of technologies, from energy applications to vibrant colors originate from slightly
biomedicine. To improve their performance, single-crystalline and defect-free disordered arrangements of photonic
nanoparticles have thus far been aspired. However, in several recent studies, crystals,[2] and white beetle scales, whose
exceptional whiteness is caused by a very
defect-rich nanoparticles outperform their defect-free counterparts in magnetic
high degree of disorder.[3] Having learned
hyperthermia and magnetic particle imaging (MPI). Here, an overview on from nature, mimicking its powerful
the state-of-the-art of design and characterization of defects and resulting spin design-by-disorder strategy has become
disorder in magnetic nanoparticles is presented with a focus on iron oxide an emerging field of research in materials
nanoparticles. The beneficial impact of defects and disorder on intracellular science.[4] This design method has led to
novel applications, for example, within
magnetic hyperthermia performance of magnetic nanoparticles for drug
the field of disordered photonics.[5] Nowa-
delivery and cancer therapy is emphasized. Defect-engineering in iron oxide days, defect-engineering is commonly
nanoparticles emerges to become an alternative approach to tailor their mag- used in designing semiconductors,[6]
netic properties for biomedicine, as it is already common practice in established perovskite solar cells,[7] metals,[8]
[9]
systems such as semiconductors and emerging fields including perovskite multiferroics, nanocomposites,[10] and
solar cells. Finally, perspectives and thoughts are given on how to deliberately carbon materials[11,12] to tailor functional
properties. Recent years have witnessed
induce defects in iron oxide nanoparticles and their potential implications
ground-breaking work in this area,[13–16] fo-
for magnetic tracers to monitor cell therapy and immunotherapy by MPI. cusing exclusively on exploiting structural
disorder in various functional materials
such as metal–organic frameworks to
optimize specific material characteristics.
1. Introduction Notably, the electronic structure of condensed matter is signifi-
cantly affected by intrinsic defects such as vacancies, impurities,
Despite their common negative connotation, defects and disor- and dislocations,[17] which in turn modify macroscopic material
der can be highly desirable in nature and materials design.[1] characteristics, including optical[18] and magnetic properties, for
example, by domain wall pinning.[19]
Dr. A. Lak However, for magnetic materials changing our negative per-
Department of Physics and Center for NanoScience ception about defects has had a much slower pace than other
LMU Munich
Amalienstr. 54, Munich 80799, Germany fields. Recently, the generic relevance of the defect-induced
E-mail: lak.aidin@lmu.de Dzyaloshinskii–Moriya interaction for the spin microstructure of
Dr. S. Disch defect-rich ferromagnets was verified,[20] suggesting a potential
Department für Chemie for creation of local chiral spin textures, that is, skyrmions,[21] in
Universität zu Köln all kinds of disordered magnetic materials. Magnetic materials
Greinstraße 4-6 Köln 50939, Germany
E-mail: sabrina.disch@uni-koeln.de
offer wide-spread novel technological potential,[22] with magnetic
Dr. P. Bender[+]
nanoparticles,[23] especially iron oxide nanoparticles, being indis-
Department of Physics and Materials Science pensable candidates for varieties of biomedical applications,[24]
University of Luxembourg including magnetic hyperthermia[25] and magnetic particle and
162A avenue de la FaÏencerie Luxembourg L-1511, Grand Duchy of resonance imaging (MPI,[26] MRI[27] ).
Luxembourg To assess and optimize the performance of magnetic nanopar-
E-mail: philipp.bender@uni.lu
ticles, it is crucial to consider their structure and magnetism on a
The ORCID identification number(s) for the author(s) of this article variety of length scales, ranging from the atomistic to the macro-
can be found under https://doi.org/10.1002/advs.202002682 scopic regime (Figure 1). While considering magnetic nanopar-
[+] Presentaddress: Heinz Maier-Leibnitz Zentrum (MLZ), Technische ticles as mesoscale dipoles is sufficient to understand the quali-
Universität München, D-85748 Garching, Germany tative principle of magnetic hyperthermia and MPI, the internal
© 2021 The Authors. Advanced Science published by Wiley-VCH GmbH. MNP structure directly impacts magnetic properties and, hence,
This is an open access article under the terms of the Creative Commons magnetic hyperthermia and MPI performance. Due to their
Attribution License, which permits use, distribution and reproduction in large surface to volume ratio, magnetic nanoparticles are partic-
any medium, provided the original work is properly cited.
ularly prone to structural and compositional defects,[28] and thus
DOI: 10.1002/advs.202002682
Adv. Sci. 2021, 8, 2002682 2002682 (1 of 14) © 2021 The Authors. Advanced Science published by Wiley-VCH GmbH
www.advancedsciencenews.com www.advancedscience.com
Figure 1. Multiple length scales in magnetic nanoparticles. a) The macroscopic application (here: magnetic hyperthermia for the treatment of glioblas-
toma) can be understood qualitatively by considering magnetic nanoparticles b) on the mesoscale as magnetic dipoles of the respective bulk material
with nanosized dimensions. Quantitatively, magnetic nanoparticles performance is critically affected by spin disorder on both c) the nanoscale (i.e., its
distribution within the particle from surface into the particle interior) and d) the atomic scale (e.g., site-defect induced spin disorder). As shown, for
example, in ref. [63], defects in the crystalline structure cause atomistic spin disorder that can critically modify the magnetic properties of nanoparticles
and hence influence the macroscopic ensemble properties and therefore their magnetic hyperthermia performance. a) Adapted under terms of the CC-BY
licence.[45] Copyright 2014, The Authors, published by Frontiers.
synthesis of defect-free magnetic nanoparticles remains highly tion: iron oxide nanoparticles are hitherto the only clinically ap-
challenging.[29] From very early aqueous synthesis of iron oxide proved heat transducers to be administered to humans;[48] 2) fo-
nanoparticle suspensions through a co-precipitation method,[30] cus on Néel relaxation: iron oxide nanoparticles have to preserve
there have been enormous efforts on controlling physicochem- their heating performance when intracellularly immobilized, as
ical properties, often with the goal to prepare single-crystalline in the cellular milieu a physical rotation of nanoparticles, that is,
iron oxide nanoparticles.[31] To date, the synthesis of defect-free Brownian relaxation, is mostly inhibited;[49–51] 3) focus on high-
iron oxide nanoparticles remains the golden standard in colloidal frequency and low-amplitude alternating fields: intracellularly
chemistry. immobilized iron oxide nanoparticles should induce hyperther-
Recently, however, it was demonstrated that in case of mic effects, that is, rising temperature to ≈42 °C, but also com-
magnetic hyperthermia (and also MPI, MRI) defect-rich iron ply with the biological safety limits.[52] Currently, most magnetic
oxide nanoparticles can actually outperform their defect-free hyperthermia devices approved for clinical trials apply magnetic
counterparts.[32–39] Motivated by these striking results, here, we fields within a frequency range of 0.05–1.2 MHz and an ampli-
will remove the common stigma of defects in iron oxide nanopar- tude range of 0–5 kA m−1 (although in some clinical trials ampli-
ticles. At first, we discuss recent studies on positive impacts of tudes of up to 18 kA m−1 are used).[53]
defects and disorder on magnetic hyperthermia performance of The macroscopic heating power of an iron oxide nanopar-
iron oxide nanoparticles. Next, we review the magnetic spin dis- ticle ensemble is usually given by the specific absorption rate
order in iron oxide nanoparticles associated with defects and dis- SAR = f ⋅ S∕c, where S = 𝜇 0 ∮M(H)dH is the area of alternat-
order. Finally, we present an overview about the state-of-the-art ing field hysteresis loops, and c is the weight concentration of
on how to incorporate and induce defects in iron oxide nanopar- the magnetic material.[54] To better compare results from differ-
ticles. ent experimental setups, the intrinsic loss parameter ILP was
introduced, which is given by ILP = SAR∕(𝜇0 H02 f ).[55,56] Within
2. Iron Oxide Nanoparticles in Biomedicine the framework of the linear response theory, that is, at first ap-
proximation valid in case of low amplitudes, the ILP is given
2.1. Designing the Ideal Iron Oxide Nanoparticles for Magnetic by ILP = 𝜋𝜇 0 𝜒′′(𝜔)/c, where 𝜒′′(𝜔) is the imaginary part of
Hyperthermia the complex ac-susceptibility.[57] It has been shown that in case
of single-crystalline maghemite, when dispersed in highly vis-
Iron oxide nanoparticles transduce magnetic energy to heat cous media, 14 nm nanoparticles exhibit the maximum heating
through magnetic losses when exposed to external alternating performance at the frequency and field amplitude of 1000 kHz
magnetic fields. They can therefore serve as remotely activated, and 24.8 kA m−1 .[58] The heating behavior of nanoparticles can
nanometric heat sources[40] to eradicate cancer cells after being be largely influenced by mesoscale ensemble effects such as
intracellularly engulfed.[25,41] Remarkably, the concept of exploit- arrangement,[59] interactions,[60] and alignment.[61,62] Addition-
ing iron oxide nanoparticles as local heat sources has been re- ally, deviation from the perfect single-crystalline structure can
cently expanded to other technologies such as catalysis,[42] water affect particles magnetization and thus their magnetic heat-
electrolysis,[43] and local polymerization.[44] ing. In case of small particles (i.e., smaller than ≈14 nm), a
Magnetic hyperthermia is especially attractive for the treat- defect-induced magnetic hardening can be useful to improve
ment of inoperable tumors such as glioblastoma (illustrated in their heating performance. Recently, Lappas et al.[63] observed
Figure 1a), the most common and a highly aggressive brain that the magnetic heating of 10 nm iron oxide nanoparticles
cancer.[45] Although magnetic hyperthermia is not yet a routine is increased by structural point defects inside the crystal lat-
treatment, clinical trials are ongoing. With the clinical applica- tice (sketch in Figure 1d). In this case, the improved heating
tion of magnetic hyperthermia in mind, the following restric- compared to defect-free particles is explained by increased ef-
tions need to be considered regarding particle design to optimize fective magnetic energy barrier KV thanks to individual point
the heating:[46] 1) focus on biocompatibility[47] and biodegrada- defects.
Figure 2. Thermally induced antiphase boundary (APB) defects and cation vacancies in iron oxide nanocubes synthesized via thermal decomposition
of iron-oleate. Low-resolution TEM images of a) as-prepared FeO-Fe3 O4 core–shell nanocubes and b) thermally annealed nanocubes at 150 °C for 2
h. c) Phase map of {220} spinel-exclusive fringe of a Fourier-filtered HRTEM image of a single particle acquired by geometric phase analysis (GPA),
indicating an APB with the dashed line that is formed where two growing magnetite sub-domains coalescent. d) Scheme of unit cells of two Fe3 O4
domains (white rectangulars) nucleated on an ideal FeO surface that are shifted by 1/4 [110]. Adapted with permission.[74] Copyright 2013, American
Chemical Society. e) High-resolution HAADF-STEM image of an FeO-Fe3 O4 core–shell nanocube: insets are Fourier analysis diffraction patterns of
regions containing FeO and magnetite/maghemite. f) High-resolution HAADF-STEM image of a nanocube after 48 h annealing at 80 °C: insets are
Fourier analysis diffraction patterns of regions containing FeO and magnetite/maghemite. g) Fe2+ and h) Fe3+ valency maps of a single thermally
treated nanocube obtained by fitting the electron energy loss spectra of each pixel to the reference spectra. i) 3D visualization of the individual nanocube
shown in (f), which was reconstructed using electron tomography technique. j) Scheme of evaluating in vitro magnetic hyperthermia performance of
thermally treated nanoparticles during interaction and uptake by IGROV-1 breast cancer cells. k) Evolution of SAR values as a function of the incubation
time were measured at field frequency and amplitude of 301 kHz and 24 kA m−1 . The SAR is virtually independent of nanoparticle cell internalization
and immobilization. Adapted with permission.[37] Copyright 2018, American Chemical Society.
In case of large nanoparticles (larger than ≈14 nm), how- netic softening (i.e., decrease of coercivity) can be achieved by
ever, an increased KV would result in a complete blocking of the decreasing the grain size below the material-specific magnetic
particle moments and thus eliminating the contribution of Néel correlation length.[65–68] Further potential strategies to modify the
relaxation in the magnetic heating. In this situation, on the one magnetic heating performance of iron oxide nanoparticles in-
hand, driving field amplitudes above the coercive field are neces- clude doping and interfaces, as discussed below.
sary to heat up the particles,[64] that is, fields much larger than
18 kA m−1 . On the other hand, to achieve an effective magnetic
heating, large effective particle moments would be beneficial, 2.2. Defect-Rich Iron Oxide Nanoparticles Which Excel at
which in turn implies large particle volumes. Clearly, large parti- Magnetic Hyperthermia
cles have counteracting effects on the overall magnetic hyperther-
mia. For this reason, we propose the use of large and magnetically Structural defects, which are routinely found in iron oxide
soft iron oxide nanoparticles, so that they have an appreciable re- nanoparticles, include vacancies, twinning defects,[69] grain
sponse 𝜒′′(𝜔) at low field amplitudes. boundaries, and interfaces.[31,63,69–73] Iron oxide nanoparticles
A possible approach to reduce the effective anisotropy KV, and synthesized by thermal decomposition method tend to have de-
hence increase the initial susceptibility, is the introduction of fected structure and interfaces that can lead to anomalous mag-
structural defects. Planar defects such as grain boundaries, stack- netic properties.[74,75] Figure 2e–h shows exemplarily 23 nm
ing faults, and twinning, and linear defects like edge and screw iron oxide nanocubes synthesized by thermal decomposition
dislocations as well as point defects can cause the aforemen- of iron oleate[37,74] Combining high-angle annular dark field
tioned defect-induced magnetic softening. This approach is well scanning transmission electron microscopy (HAADF-STEM), X-
established for iron-based bulk ferromagnets, for which mag- ray diffraction (XRD), and electron energy loss spectroscopy
Figure 3. Grain boundaries and twinning defects in iron oxide nanoparticles. a) Typical TEM micrograph of an individual nanoflower-shaped iron oxide
nanoparticle synthesized via polyol process. b) HRTEM micrograph of a single flower-like nanoparticle, so-called nanoflower. The dashed lines indicate
grain boundaries between domains. c) Dark-field TEM micrograph of an individual particle showing that domains sharing the same crystallographic
orientation varies between 5 to 15 nm in size. While each domain is well coherent, domains are oriented differently with respect to each other. d)
HRTEM micrograph of an iron oxide nanoparticle synthesized via hydrothermal method. The nanoparticle shows a twinning defect along (111) plane, as
indicated by white arrows. Inset shows atom arrangement along the twinning plane that is highlighted in yellow. The flipping of the atomic arrangement
of Fe3 O4 around the (111) twinning plane is apparent. e) HRTEM micrograph of a so-called dimer iron oxide nanoparticle synthesized via hydrothermal
method, showing a grain boundary defect along (111) crystalline plane. Inset at the top shows atoms arrangement along the grain boundary that is
colored in yellow. Inset at the bottom-left presents Fourier-transform diffraction pattern and insets at the bottom-right show GPA maps of g111 ̄ and g011̄
planes. The left side GPA map indicates lattice distortion along the grain boundary plane, that is, (111), as seen by a discontinuity in the color map at the
grain boundary. No lattice distortion is observed along out-of-grain boundary planes, for example, (011), as shown in the right side GPA color map. a,c)
Adapted with permission.[35] Copyright 2018, American Chemical Society. b) Adapted with permission.[33] Copyright 2012, American Chemical Society.
d,e) Adapted with permission.[69] Copyright 2014, American Chemical Society.
(EELS), it has been observed that thermal annealing of PEGylated but which possess a nanocrystalline substructure. As a result of
nanocubes at 80 °C for 48 h induces Fe2+ vacancies in the particle the grain boundaries, however, the nanoflowers exhibit a signifi-
crystal structure. The Fe2+ vacancies together with ever remain- cant internal spin disorder,[35] something which is also observed
ing FeO-subdomains within the particles led to comparatively for nanocrystalline bulk samples of Ni.[83] This spin disorder re-
small effective KV. Remarkably, the thermally treated nanocubes sults in nearly vanishing coercivities,[84] analogous to nanocrys-
preserved their improved intracellular magnetic hyperthermia, talline bulk ferromagnets.[65–68] Consequently, such nanoflow-
as evaluated by in vitro SAR measurements during interaction ers and similar dense iron oxide nanoparticle aggregates, ex-
and uptake by IGROV-1 breast cancer cells (Figure 2k). Note that cel at magnetic hyperthermia at low field amplitudes.[32–36,84–86]
single-phase magnetite nanocubes with same size lose their heat- We attribute the increased heating to the magnetic softening,
ing performance nearly completely in viscous media.[76] Thus, which results in increased 𝜒′′(𝜔) at low-field amplitudes simi-
these mildly treated nanocubes can be regarded as a prototype lar to single-core thermally treated nanocubes discussed before
for improved magnetic heating by defect-induced magnetic soft- (Figure 2).
ening. An additional remarkable feature of nanoflowers is that their
Flower-shaped iron oxide nanoparticles[32,33] represent a dif- already outstanding heating performance can even be further in-
ferent, prominent example for large, defect-rich iron oxide creased with magnetic interactions at the mesoscale.[34] This can
nanoparticles. As can be seen in Figure 3a,b,c, the nanoflow- be related to a parallel alignment between neighboring particle
ers are 20–100 nm aggregates consisting of small ≈5–15 nm moments within dense aggregates.[87] This behavior is in con-
maghemite crystallites.[77] The small crystallites are separated by trast to conventional interacting iron oxide nanoparticle systems
grain boundaries, as highlighted by the dashed lines in Figure 3b. (i.e., dense powder samples of single-core particles), in which
Nanoflowers belong to a special class of magnetic nanoparticles, an antiparallel alignment of neighboring particle moments has
namely multicore particles,[48,78] which are essentially stable clus- been observed,[88,89] culminating in reduced susceptibility and
ters of small iron oxide crystallites or grains.[79,80] The develop- decreased heating.[90]
ment of multicore particles was promoted by a superior perfor- As highlighted above, there are multiple iron oxide nanopar-
mance of such clusters in comparison to their individual build- ticle systems in which structural defects contribute positively to
ing blocks for a variety of biomedical applications,[81,82] includ- enhancing the performance for biomedical applications that are
ing hyperthermia.[81] The unique feature of nanoflowers is their based on the Néel relaxation mechanism such as magnetic hy-
dense structure. Due to exchange interactions between the small perthermia and MPI. In the following, we will review the in-
crystallites (Figure 3b, dashed lines), the atomic moments within terrelation of structural and spin disorder in magnetic nanopar-
the total particle volume are preferentially magnetized along the ticles that is expected to be decisive for their functionality. We
same direction, leading to large effective moments at low fields. will then expand our discussion on the current status regarding
Therefore, nanoflowers can be regarded as individual particles defect-engineering in iron oxide nanoparticles, to postulate new
Figure 4. From structural defects in nanoparticles to spin disorder and enhanced magnetic heating performance. a) Anti-phase boundary in a repre-
sentative iron oxide nanoparticle, atomically resolved using HAADF STEM. b) Magnification of the dashed area indicated in (a). c,d) Atomistic spin
calculations illustrate the spin misalignment near antiphase boundaries in model nanoparticles. e) Monte Carlo simulation of the spin ensemble in a
defected (left) and a defect-free nanocrystal (right) near field reversal after saturation. f) Specific absorption rate calculated for defected and defect-free
nanoparticles. a–d) Reproduced with permission.[71] Copyright 2017, Springer Nature. e,f) Reproduced with permission.[63] Copyright 2019, American
Physical Society.
pathways for exploiting structural defects in favor of particle per- ism (XMCD)[92] provide ensemble-averaged information on the
formance in biomedical applications. stoichiometry and crystal structure and the element-specific spin
and orbital moments, respectively.
3. Defect-Induced Spin Disorder in Iron Oxide Methodology toward spin disorder includes magnetometry,[93]
Nanoparticles Mössbauer[94] and Raman spectroscopy,[95] nuclear magnetic res-
onance (NMR),[96] Lorentz transmission electron microscopy
In the previous section, we introduced several examples of struc- (LTEM),[97] high-resolution electron loss spectroscopy (HR-
turally disordered iron oxide nanoparticles that exhibit greatly EELS),[70] and magnetic neutron diffraction[98] and small-angle
enhanced performance in biomedical applications, in particular neutron scattering (SANS).[99] Each of these techniques can pro-
magnetic hyperthermia. Structural deviations from homogene- vide unique information but only at specific length scales. There-
ity can cause atomistic disorder of the magnetic spin ensemble fore, often combinations of various techniques are needed to ac-
and thus significantly alter the particle properties. In addition, quire a self-consistent picture.
nanoscale surface effects naturally play a decisive role in nanopar-
ticles due to large surface-to-volume-ratio which can also cause
localized spin disorder. The spin disorder in magnetic nanopar- 3.1. Spin Disorder at Different Scales
ticles thus needs to be addressed to fully understand the inter-
relation between defects and disorder and the technological per- The existence of spin disorder in nanoparticles is typi-
formance of magnetic nanoparticles. Despite recent advances in cally concluded from low magnetization as compared to
both microscopy and scattering approaches, resolving the mag- the bulk materials,[93,100] accompanied by nonsaturating mag-
netization configuration at the nanoscale,[91] including the com- netic behavior[101] and exchange biasing,[102] all observed us-
plex spin configuration within magnetic nanoparticles, remains ing macroscopic magnetization measurements. Furthermore,
a key challenge in nanomagnetism. temperature- and frequency-dependent AC susceptibility mea-
Whereas long-range order is routinely characterized using surements were used in several studies to reveal the spin dynam-
diffraction techniques assuming periodic boundary conditions, ics of uncorrelated surface spins and the resulting spin-glass-like
the local, short range nature of disorder effects requires com- freezing at low temperatures.[103–105] Microscopic information
bination of a variety of techniques on different length scales as on spin disorder, that is, atomic spins deviating from the collinear
well as a model adapted to the length scale that is probed. Struc- order of the material, is accessible through the hyperfine struc-
tural defects within individual magnetic nanoparticles are typi- ture of in-field Mössbauer spectroscopy.[106] In combination with
cally investigated with high-resolution electron microscopy tech- macroscopic magnetization and X-ray diffraction, the gener-
niques (Figure 4a,b),[71] whereas advanced scattering techniques ally assumed nanoscale model of a collinear macrospin sur-
such as synchrotron X-ray total scattering coupled with pair dis- rounded by surface-near spin disorder (Figure 1c) is typically
tribution function (PDF) analysis[26,63] or X-ray circular dichro- applied.[107–110] Surface spin disorder is understood as a result of
Figure 5. Nanoscale magnetization in magnetic nanoparticles. a–f) Magnetic electron holography of vortex (a–c) and single-domain (d–f) spin config-
urations in Fe nanoparticles. a,d) Experimental hologram; b,e) magnetic induction flux line maps derived from the experimental phase image (inset:
color wheel indicating the direction of the magnetic induction). c,f) Micromagnetic simulation of the 3D magnetization of a 29.53 nm3 and a 24 × 26 ×
24 nm3 Fe nanocube in equilibrium state, indicating the vortex and single-domain configurations, respectively. g) Magnetic SANS data by cobalt ferrite
nanoparticles in applied magnetic field of 1.2 T. The non-spin-flip channels I++ and I−− give access to the structural morphology and collinear magneti-
zation distribution (i.e., the magnetization component parallel to the applied field). The spin-flip channels I+− and I−+ provide a combination of collinear
magnetization and spin misalignment. h) Field dependence of the thickness ddis of the surface-near spin disorder shell in ferrite nanoparticles. In in-
creasing applied magnetic field, the size of the collinearly magnetized nanoparticle core rmag overcomes the structurally coherent grain size rXRD , leaving
a reduced shell of spin disorder. a–f) Adapted with permission.[112] Copyright 2015, American Chemical Society. g,h) Adapted with permission.[117]
Copyright 2020, American Physical Society.
broken exchange bonds and low symmetry near the particle sur- both spatially and element-sensitive and has elucidated the site-
face. Moreover, the correlation of structural and spin disorder is dependent surface spin canting in cobalt ferrite nanoparticles,
widely accepted. Within the macrospin model, spin disorder is revealing surface spin canting for the cobalt sites, but not for the
hence mostly attributed to surface effects based on a particle size iron sites.[70]
dependence of macroscopic magnetization properties, or based Magnetic SANS is sensitive to nanoscale magnetic fluctua-
on a structurally coherent magnetic grain size smaller than the tions with sub-nanometer spatial resolution, giving access to
particle itself, as accessible through neutron diffraction.[98] To un- the spatially resolved magnetization distribution as well as
ambiguously confirm the location of spin disorder near the parti- directionally resolved magnetization correlations in magnetic
cle surface, spatially sensitive techniques are required with sub- nanoparticles.[99] Through the spatial sensitivity with length
nanometer resolution. scales of 0.1–500 nm, surface spin disorder[113] and correlated
LTEM provides information on the stray field magnetization surface spin canting[114,115] become accessible. Using magnetic
with spatial resolution of a few nanometers and can hence SANS, a significant reduction of surface spin disorder was found
be applied to individual particles with sizes as small as a few upon cooling to low temperatures of 10 K.[116] More recently, a
nanometers.[97] Electron holography provides higher spatial res- strong field-dependence of surface spin disorder was revealed,
olution and is sensitive to the entire nanoparticle spin configu- expressed by a gradual polarization of initially disordered sur-
ration and has been applied to the magnetic interparticle cou- face spins even beyond the structurally coherent grain size (Fig-
pling in arrangements of nanoparticles.[111] On the individual ure 5h).[117] The field dependence of the spatial distribution of
nanoparticle level, high-resolution magnetic maps of individual surface spin disorder ultimately gives access to the spatially re-
Fe nanocubes have been generated to reveal the size-induced solved disorder energy toward the particle surface.[117]
transition between vortex (Figure 5a–c) and single-domain states Nanoscale surface effects have recently been exploited toward
(Figure 5d–f) within the nanoparticles.[112] Whereas defect-free hollow nanoparticles. The high magnetic disorder in these par-
nanoparticles have been targeted for such proof-of-principle ticle shells was attributed to two antiferromagnetically coupled
studies, application of electron holography techniques to the noncollinear structures close to speromagnets based on a broad
defect-induced spin structure in magnetic nanoparticles will distribution of hyperfine fields as determined from Mössbauer
be a challenging and highly interesting endeavor. HR-EELS is spectroscopy.[118]
3.2. Spin Disorder—Correlated or Not? Indeed, structural distortions changing the local coordination
geometry in the vicinity of defects have a direct influence on
Spin disorder may in a first approach be understood as the devi- interatomic exchange and hence spin disorder.[123] For ferrite
ation of individual atomic spins from a long-range ordered, of- nanoparticles, strong variations of the degree of spinel inversion
ten times collinear order. An important distinction is whether are commonly observed.[124–128] The synthesis technique has
spin disorder is entirely random, that is, without any correla- been reported to substantially influence the ferrite nanopar-
tion between adjacent spins, or correlated, that is, exhibiting ticle magnetization and, hence the spin disorder,[71] through
short-range correlations, a scenario we will refer to as spin cant- structural defects such as antiphase boundaries resulting from
ing as opposed to random spin disorder in nanoparticles. De- topotactic oxidation from FeO to maghemite (see Figures 2a–d
pending on surface and magnetocrystalline anisotropies, differ- and 4a–d).[74] Antiphase boundaries have further been found
ent types of spin canting toward the particle surface have been to induce local ferromagnetic coupling and enhance the mag-
suggested by theory, including so-called artichoke, throttled, and netic properties of magnetic nanoparticles.[129] Local disorder,
hedgehog spin structures.[119] However, experimental evidence resulted by atomic-scale defects, that triggers a correlated
for such structures is scarce. The size-dependent spin struc- structural distortion has recently been discovered in core–shell
tures in manganese–zinc ferrite nanoparticles were studied us- Fex O-Fe3−𝛿 O4 nanocrystals by analysis of the atomic pair dis-
ing unpolarized SANS in combination with micromagnetic sim- tribution function and correlated with atomistic spin disorder
ulations, revealing increased magnetic inhomogeneity with par- and enhanced magnetic heating efficiencies (Figure 4e,f).[63]
ticle size and correlated, non-collinear spin states occurring for Despite only few studies published to date, we expect more
particle sizes beyond 20 nm.[120] studies to appear on technological benefits of defect-induced
Correlated spin canting has been reported for assemblies of magnetic lattice distortions in magnetic nanoparticles in the
smaller, ≈10 nm nanoparticles,[114,115] without directly discrimi- near future. All these findings illustrate that for a comprehensive
nating one of the suggested spin structures. In contrast, noninter- understanding of the macroscopic performance of magnetic
acting ferrite nanoparticles of similar size reveal random surface nanoparticles, it is indispensable to consider both structural and
spin disorder without a traceable coherent transversal magneti- spin disorder on a variety of length scales (Figure 1), including
zation component.[117] In consequence, a strong impact of inter- the nanoscale magnetization distribution, but also the atomistic
particle interactions on spin disorder and spin canting is evident scale defect-induced disorder in magnetic nanoparticles.
and needs to be considered for applications of spin disorder to- Having established the potential of structural and magnetic
ward magnetic heating. disorder for improved magnetic hyperthermia performance, we
next highlight current synthetic approaches on how to deliber-
ately engineer defects and disorder in iron oxide nanoparticles.
3.3. Spin Disorder in the Particle Interior 4. Defect-Engineering in Iron Oxide Nanoparticles
Whereas the commonly accepted macrospin model including 4.1. Colloidal Synthesis: A Journey toward Disordered Iron Oxide
surface spin disorder is sufficient to explain a large fraction of Nanoparticles
macroscopic phenomena, the potential existence of atomistic
spin disorder in the particle interior (Figure 1d) is often disre- The quest to synthesize defect-free and single-crystalline
garded. The spin disorder distribution within magnetic nanopar- magnetic nanoparticles dates back to almost 20 years ago
ticles is only accessible using techniques that are both quan- when the first colloidal thermal decomposition syntheses
titative and spatially sensitive. Indeed, polarized SANS has re- emerged. Varieties of iron precursors including organometallic
vealed significant contributions of spin disorder even in the par- Fe(C6 H5 N(O)NO)3 ,[130] metal organic Fe(CO)5 ,[131] Fe(acac)3 ,[132]
ticle interior,[121] expressed as a reduced local magnetization in metal hydroxide FeO(OH),[133] and iron salts such as Fe(II)
the particle core.[113,116,117] In several reports, the spin disorder acetate,[134] have been used for synthesis of iron oxide nanopar-
in the particle interior has even been found to dominate surface ticles. Large-scale size and shape-control synthesis of iron oxide
spin disorder.[113,122] Such a reduced magnetization has been at- nanoparticles have been realized after developing Fe(oleate)3 by
tributed to canting of Fe moments in both tetrahedral and octa- Hyeon et al.[135] Despite differing in solvent, capping ligands, and
hedral sites, revealed by a combination of NMR and Mössbauer growth temperature, in these non-hydrolytic syntheses, nanopar-
spectroscopies, and related to reversed moments and frustrated ticles are mostly a product of kinetically driven processes, for ex-
topology.[96] ample, through adsorption/desorption of capping ligands on cer-
A clear particle size dependence of spin disorder in iron ox- tain crystalline facets.[136] Thanks to the kinetic pathways, the for-
ide nanoparticles has been established using Mössbauer spec- mation of uniformly sized and shaped iron oxide nanoparticles
troscopy, revealing enhanced spin canting in an intermediate par- often takes no longer than an hour in these methods.[137] The
ticle size of 8–12 nm.[31] Combination of magnetic SANS with nu- chemical nature of the iron precursor used for the synthesis has
clear resonant X-ray scattering has further revealed a clear atomic a substantial influence on the type, distribution, and abundance
site dependence of the spin misalignment.[122] The significant of defects in nanoparticles. Whereas Fe(acac)3 often results in
amount of spin disorder found in the nanoparticle interior under- particles with nearly absent surface spin canting,[138,139] detailed
lines that disorder and defects on the atomic scale are highly rel- characterization studies have revealed that Fe(CO)5 , Fe(oleate)3 ,
evant to understand and control the nanoscale and macroscopic and Fe(II) acetate lead to FeO-Fe3 O4 /Fe2 O3 and Fe-Fe3 O4 [140]
magnetic properties in nanoparticles. core–shell iron oxide nanoparticles with degraded magnetization
and structural disorders.[134,141–144] Several groups have developed was treated by co-precipitation synthesis method. It was there-
twists in the decomposition chemistry[145] and modified the syn- fore discussed that an intensive activity and mobility of the cap-
thesis involving protective gas[146,147] to eliminate the FeO phase, ping ligands on crystallites, given to the synthesis reaction by
showing a weak paramagnetic behavior at hyperthermia relevant high temperature hydrothermal reaction conditions, is required
temperatures, and obtain single-phase Fe3 O4 nanoparticles. Fur- to form defect-rich iron oxide nanoparticles. Remarkably, it was
ther approaches reduce surface spin disorder in superparamag- demonstrated that iron oxide nanoparticles with stacking fault
netic ferrite magnetic nanoparticles by changing the nature of internal defects have a higher Ms and SAR than defect-free iron
alkaline capping agents.[148] oxide nanoparticles.[69]
Despite the progress, we know from solid state chemistry
and materials science that defect-free crystals are the product of
thermodynamically driven processes, forming at much higher 4.3. Defects and Vacancies Induced by Oxidation
temperatures and longer reaction times than that of colloidal
syntheses (i.e., 220–340 °C, <1h). Moreover, recent magnetic hy- Most iron oxide nanoparticles synthesized via thermal decom-
perthermia studies have strikingly shown that defect-free and position syntheses have to some extent defects, disorders, and
highly crystalline single-core iron oxide nanoparticles lose nearly sub-domains. Iron oxide nanoparticles synthesized via the ther-
entirely their hyperthermia efficacy in highly viscous media,[76] mal decomposition of Fe(oleate)3 and Fe(CO)5 are among the
in vitro,[49] and intracellularly.[37,51] Di Corato et al. have system- most heavily characterized nanoparticle systems due to the syn-
atically shown this phenomenon in vitro for multicore and cubic- thesis robustness and particle size uniformity.[26,144,153] How-
shape single-core iron oxide nanoparticles.[49] ever, these two precursors predominantly lead to FeO-Fe3 O4
The tendency to compare physicochemical properties of syn- core–shell morphologies instead of phase-pure Fe3 O4 com-
thetic iron oxide nanoparticles such as saturation magnetiza- position. Such a core-shell formation, having the often non-
tion and magnetic anisotropy with the bulk-like properties has stoichiometric Fex O (x ≈0.95) phase,[37,154] leads to a large disper-
thus far distracted us from exploring defects and disorders in fa- sion of magnetic properties that requires a very detailed system-
vor of biomedical applications. In the following, we will briefly atic characterization.[154] Studies on post synthesis thermal treat-
discuss current synthetic approaches for defect- and disorder- ment of these iron oxide nanoparticles toward single-phase iron
engineering in single-phase and interfaces in core-shell iron ox- oxide have led to new insights into oxidation-induced defects. It
ide nanoparticles with particular focus on their impact on mag- has been shown that the nucleation and growth of Fe3 O4 on the
netic hyperthermia. FeO phase (i.e., the topotaxial oxidation from FeO to magnetite
and maghemite) lead to formation of antiphase boundary (APB)
defects at the interface between growing magnetite domains.
4.2. Defects and Discontinuities Induced by Growth Pathways Interestingly, APBs remained after four hours of thermal treat-
ment at 150 °C (Figure 2a–d).[74] The oxidation of core–shell iron
Capping ligands are an indispensable part of thermal decomposi- oxide nanoparticles, synthesized by decomposition of Fe(CO)5 ,
tion syntheses, as they control size and morphology of nanocrys- via mild cyclic magnetic stimulations has also resulted in the
tals by influencing the reaction kinetics. Playing with the binding APBs.[155]
nature and strength between capping agents and nanocrystals A step toward exploiting structural defects for biomedical ap-
has always been an effective strategy to control particle shape and plications was taken by mild thermal treatment of FeO-Fe3 O4
size.[149,150] Recently, capping ligands were exploited to change nanoparticles after being capped with catechol-terminated func-
the internal structure of iron oxide nanoparticles. A prime exam- tional poly(ethylene glycol) polymers. A 48 h thermal treatment
ple is iron oxide nanoflowers (Figure 3a–c), wherein short length at 80 °C induced Fe2+ vacancies in the Fe3 O4 phase of core–
polyols such as diethylene glycol allows packing small crystal- shell iron oxide nanoparticles, which result in the magnetic
lites into dense disordered structures, being separated by grain softening and thus the domination of the Néel relaxation. As
boundary defect (dashed lines in Figure 3b).[77,151] The effect of discussed in the previous section, such a magnetic softening
competition between short and long ligands on the particle struc- can lead to improved magnetic hyperthermia performance of
ture has recently been shown in zinc ferrite nanoparticles. In- 23 nm cubic-shape particles compared to single-phase counter-
creasing the ratio of acetylacetone to oleic acid ligands results in parts (Figure 2e–k).[37] It is worth mentioning that in case of small
assembly of small magnetic zinc ferrite subdomains into 100 nm nanoparticles a defect-induced magnetic hardening may be nec-
cubic-shape particles, due to less bulkiness and higher mobility essary to tailor the magnetic heating performance.[63]
of acetylacetone ligands as compared to oleic acid.[152]
Hydrothermally synthesized iron oxide nanoparticles showed
to possess twinning and stacking fault defects (Figure 3d,e).[69] 4.4. Structural Defects Associated with Interfaces and Doping
Formation of twinning defects and stacking faults along (111)
crystalline planes was attributed to the oriented-attachment crys- Interfaces are additional promising sources of breaking compo-
tal growth mechanism. A growth mechanism similar to the sition continuity and inducing atomic scale exchange interac-
nanoflowers was proposed for these defected iron oxide nanopar- tions in magnetic nanoparticles. The magnetic anisotropy can
ticles. The fusion of initial Fe3 O4 crystallites, that is promoted be tuned by magnetic coupling in bi-magnetic hard-soft and
by desorption of capping ligands, into a single particle accounts soft-hard core-shell magnetic nanoparticles such as CoFe2 O4 -
for twinning and stacking fault defects. Interestingly, none of MnFe2 O4 [156] and Fe3 O4 -CoFe2 O4 .[157] More in depth insight into
these defects were observed when a similar synthesis mixture these nanosystems can be found in the review by López-Ortega
et al.[158] The effect of thickness and composition of the shell on for improving magnetic particle properties. Inspired by other re-
the magnetization of bi-magnetic exchanged bias nanosystems search fields such as semiconductors and perovskite solar cells,
has already been discussed more than a decade ago.[159] How- we here attempt to redirect the attention of the magnetic nanopar-
ever, the implication of bi-magnetic nanoparticles in in vivo mag- ticle community toward exploiting defect-engineering in iron ox-
netic hyperthermia was realized some years later. A systematic ide nanoparticles to enhance and adapt particle magnetic proper-
study on the effect of core size, particle shape, and shell thick- ties for in vivo magnetic hyperthermia. Approaches to the design
ness has revealed an enhanced magnetic-to-heat energy trans- of defected structures have very recently been summarized for
formation in core–shell nanoparticles.[160] It was recently shown bulk crystalline materials.[171]
that forming an ultrathin shell of soft magnets (e.g., Fe3 O4 and Recent experimental and computational studies emphasize
MnFe2 O4 ) on CoFe2 O4 nanoparticles leads to increased mag- a clear benefit of structural defects and associated magnetic
netic anisotropy.[161,162] The shell thickness turned to be critical spin disorder in various biomedical applications. Defect-rich iron
to observe a so-called enhanced spin canting phenomenon. In- oxide nanoparticles appear particularly promising candidates
serting a paramagnetic FeO interlayer spacer between Fe core for intracellular magnetic hyperthermia and magnetic-heating-
and iron oxide shell in layered iron oxide nanoparticles led to triggered drug delivery, wherein transducing heat based on the
magnetostatic interactions between the core and the shell and Néel magnetic relaxation mechanism is crucial. Sharing sim-
enhanced magnetic hyperthermia performance.[73] Recently, tri- ilar nanomagnetism principles to magnetic hyperthermia,[172]
magnetic Fe3 O4 -CoO-Fe3 O4 core–shell–shell nanoparticles have MPI, an emerging molecular imaging modality, will largely ben-
been developed via seed-mediated thermal decomposition syn- efit from defect-engineering in iron oxide nanoparticles. The re-
thesis. Hard–soft exchange couplings at Fe3 O4 -Co doped ferrite search on developing iron oxide based tracers for MPI is grow-
and Co-doped ferrite-Fe3 O4 interfaces largely influenced the su- ing rapidly owing to outstanding features of MPI compared to
perparamagnetic blocking temperature and magnetization hys- MRI such as high sensitivity, deep tissue imaging, and capabil-
teresis loops.[163] Despite being a promising approach, one has ity of live imaging.[173] It is well known that the MPI imaging
to bear in mind that synthesis of multi layered nanoparticles technique works based on the Néel relaxation mechanism. There-
is much more challenging than those iron oxide nanoparticles fore, iron oxide nanoparticles with the characteristics highlighted
formed via one-pot reactions. here for large and defect-rich iron oxide nanoparticles, that is,
Theoretical studies have contributed substantially to our un- large magnetic susceptibility and low magnetic anisotropy, are
derstanding of magnetization mechanisms in such multilayered well suited for MPI. This correlation was verified by several stud-
particle systems. The Monte Carlo approach has been exploited ies which conclude that nanoflowers are excellent candidates for
to reconstruct the magnetic spin configuration in Fe-Fe3 O4 core– MPI.[38,39]
shell nanoparticles with different shapes[164] and has proven an- We have here summarized studies on synthesis of defect-rich
tiferromagnetic coupling in soft-hard Fe3 O4 -Mn3 O4 core–shell iron oxide nanoparticles, yet our focus is on those studies in
nanoparticles, in accordance with the experimental results.[165] which defects and disorder have been mainly included deliber-
Breaking the cation ordering by doping magnetic[166] and non- ately. We have highlighted few one-pot synthesis reactions and
magnetic ions into the iron oxide crystal structure has emerged as post synthesis thermal treatments in organic solvents and aque-
a strong tool to tune magnetic properties in the past years.[138,167] ous media that promote structural defects and compositional dis-
For spinel ferrite nanoparticles, the cation distribution between continuities in iron oxide nanoparticles. Anti-phase boundaries,
A and B sites is decisive for the macroscopic magnetization, stacking faults, grain boundaries, and twinning defects have been
and strong variations of the inversion degree have been ob- induced in iron oxide nanoparticles.
served as nanoparticles often represent a non-equilibrium cation Looking into the correlation between structural and magnetic
distribution.[124–126] Zinc and manganese are the most commonly lattice, we have realized that one important aspect that is of-
substituted cations into iron oxide nanoparticles.[168] Despite be- ten overlooked is the different characteristics of spin disorder
ing nonmagnetic, Zn2+ replaces Fe3+ in tetrahedral crystalline on nanoscale and atomistic length scales. The magnetic struc-
sites and thus reduces antiferromagnetic couplings between Fe3+ ture of iron oxide nanoparticles is directly determined by their
in tetrahedral and octahedral sites. Depending on the ionic size structural features, implying that structural defects lead to disor-
and concentration of the substituting cation, lattice strain was dered magnetic lattice and eventual modification of the magnetic
induced in cobalt ferrite nanoparticles.[169,170] Such approach ap- properties. Despite the progress in atomistic analyses, the pre-
pears promising to tailor the lattice strain and in result control cise characterization of spin disorder within the particles remains
the magnetization of iron oxide nanoparticles. one of the key challenges in nanomagnetism. However, it is cru-
cial to distinguish between surface-induced nanoscale spin dis-
5. Conclusions and Perspectives order and atomistic, structurally induced intraparticle spin disor-
der when assessing macroscopic magnetic properties and hence
The strong research interest on iron oxide nanoparticles is partic- technological performance of magnetic nanoparticles.
ularly driven by their unique potential for a wide range of biomed- Admittedly, the programmed defect inclusion in iron oxide
ical applications. To optimize their magnetic properties, histor- nanoparticles is yet in its infant stage, when compared to other
ically, the usual strategy has been to strive for the synthesis of fields such as semiconductor technology. However, the number
defect-free single crystalline nanoparticles. The particle charac- of research articles on revealing and harnessing positive contri-
teristics have been then primarily varied by their morphologi- bution of defects is rapidly growing. In the following, we add our
cal features such as size and shape. In this progress report we perspectives and ideas on how to systematically engineer defects
have compiled recent findings indicating an alternative approach into the crystal structure of iron oxide nanoparticles.
One of the potential approaches to synthesize iron oxide Conflict of Interest

nanoparticles with grain boundaries like nanoflowers discussed
here is to use a combination of short and long capping ligands The authors declare no conflict of interest.
with different binding affinities to iron. A combination of short
phosphonate-based and oleic acid ligands in thermal decomposi-
tion synthesis could lead to the formation of iron oxide nanopar- Keywords
ticles with grain boundaries via a competitive ligand binding to
defect-engineering, design-by-disorder, iron oxide nanoparticles, mag-
different positions on particles. The nature of binding between netic hyperthermia, magnetic spin disorder
capping ligands and particles is yet largely unknown and thus
more elucidations in this regard will facilitate designing disorder Received: July 16, 2020
in iron oxide nanoparticles. Revised: October 30, 2020
We envision a great opportunity in combining crystalline dis- Published online: February 15, 2021
order and in vivo clearance of magnetic nanoparticles in devel-
oping defect-rich nanoheaters and MPI tracers. We believe a
novel synthetic approach could be to fabricate nanoparticle or-
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Aidin Lak received his Ph.D. in physics in 2013 from the Technical University of Braunschweig, Ger-
many. He then moved to Genoa, Italy, to carry out a postdoctoral research in the group of Nanoma-
terials for Biomedical Applications at the Italian Institute of Technology. From 2018 to 2020, he was
an Alexander von Humboldt Postdoctoral Fellow at Ludwig-Maximilians-University in Munich and
since then he is a senior postdoctoral researcher at LMU, Munich. His research interests include syn-
thesis, bio-functionalization, and characterization of hybrid magnetic nanostructures for biomedical
diagnostics and therapeutics as well as understanding the underlying physics.
Sabrina Disch is an Emmy-Noether research group leader in the Department of Chemistry at Uni-
versität zu Köln, Germany. After obtaining her Ph.D. degree from Forschungszentrum Jülich/RWTH
Aachen (Germany) in 2010, she was a postdoctoral fellow at the University of Oregon (USA) and In-
stitut Laue-Langevin in Grenoble (France) before joining Universität zu Köln in 2014. Her research
interests include the structure and magnetism of magnetic nanoparticles and self-organized nanos-
tructures as studied using x-ray and polarized neutron scattering techniques.
Philipp Bender received his Ph.D. in physics in 2013 from the Saarland University (Germany). After
working as a postdoctoral researcher at the Saarland University and the University of Cantabria (San-
tander, Spain), he has been at the University of Luxembourg since 2018. His research focuses on the
application of magnetic nanoparticles for biomedicine and their characterization by magnetometry
and magnetic small-angle neutron scattering.

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