Journal of Non-Crystalline Solids 521 (2019) 119493

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Journal of Non-Crystalline Solids

journal homepage: www.elsevier.com/locate/jnoncrysol

Review

Advanced applications of amorphous alumina: From nano to bulk T

a,b,⁎ a,b,⁎⁎ a a
Andraž Mavrič , Matjaz Valant , Chunhua Cui , Zhiming M. Wang
a
Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, China
b
University of Nova Gorica, Materials Research Laboratory, Vipavska 13, SI-5000 Nova Gorica, Slovenia

ARTICLE INFO ABSTRACT

Keywords: In modern technologies, the researchers are keen on top-down approaches to tailor the materials from bulk into
Amorphous alumina their nanometer forms. For the amorphous alumina, this is the other way around. The amorphous alumina was
Strain engineering receiving attention in the forms of thin films or nanoparticles many years ago, yet any attempts to increase the
Short-range structure dimensions destabilized its amorphous structure and caused crystallization at even relatively modest tempera-
Wear and scratch resistance
tures. This issue has been addressed by smart engineering of its lattice strain, which allows the formation of a
Dielectric
high-temperature stable bulk alumina. In this review, we present the recently developed synthetic methods and
Photoluminescence
Catalysis provide insights in sustaining the amorphous structure of widely used alumina. We highlight its adoptable short-
range structure and morphology, emphasize the corresponding tuning of the mechanical and electronic prop-
erties, and illuminate the advanced applications in wear and scratch resistant coatings, corrosion protection,
insulator layers, capacitor, luminescent material, and catalysis.

1. Introduction transistors [31,32], and hydrophilicity for corrosion protection

Alumina in all its forms is technologically important material. It can
exist in many crystallographic modifications with different properties.
The most frequently occurring form in nature is α-Al2O3 (corundum); it
is a thermodynamically stable phase at room temperature. Besides,
Al2O3 can be found in many metastable polymorphs. There is a wide
choice of reviews dedicated to alumina polymorphs summarizing their
structure [1], catalysis [2–4] and nanoscale properties [5]. In addition,
there are specialized reviews on anodic aluminum oxide (AAO) [6–8]
that has become its own branch of research. In this review, we focused
on amorphous alumina (am-Al2O3), emphasizing its synthesis of nano-
and micro-sized structures, thermodynamic stability, functional prop-
erties, and advanced applications.
In contrast with a variety of alumina crystalline polymorphs, an
amorphous form possesses some unique properties, originating from the
non-crystalline nature. This structural disorder leads to a decrease in
the band gap energy [9,10], a variation in photoluminescence [11–16],
a change in ferromagnetism [17], and an increase in thermal con-
ductivity [18]. A special attention has been given to the am-Al2O3 for
coating applications. For instance, the uniform amorphous matrix was
reported to exhibit excellent mechanical and optical properties
[19–30], high dielectric constant for use as a gate insulator in
[19,33–35]. Highly absorptive nanoparticles have been used for en-
hancement of thermal conductivity of nanofluids [5,18], as a catalyst
for biodiesel conversion [36] and for fluoride removal in water treat-
ment processes [37].
2. Thermodynamic stability of amorphous alumina
α-Al2O3 starts to crystallize from basic hydroxide gels at tempera-
tures as low as 420 °C [38]. If the metastable alumina polymorphs are
present, they transform to the thermodynamically stable α-phase
through different transition sequences at an elevated annealing tem-
perature around 1100 °C [1]. Many efforts have been made to lower the
transformation temperature since the high-temperature annealing leads
to strongly agglomerated α-Al2O3 particles that are hard to be pro-
cessed [39–45]. A reduction in the particle size has been identified as
the crucial factor for preventing the metastable alumina against trans-
formation to α-Al2O3 [46–49]. It was shown that the γ-phase has lower
surface energy than the α-phase, which makes it stable at a specific
surface area > 125 m2 g−1 at room temperature and > 75 m2 g−1 at
500 °C [46]. The effect of the specific surface area is so predominant
that thermodynamically prevents transitions to the α phase forming
nanocrystals with dimensions < 12 nm [50]. To produce metastable α-

Correspondence to: A. Mavrič, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, No.4, Section 2, North
⁎

Jianshe Road, Chengdu 610054, China.

⁎⁎
Correspondence to: M. Valant, University of Nova Gorica, Vipavska 13, SI-5000 Nova Gorica, Slovenia.
E-mail addresses: andraz.mavric@uestc.edu.cn (A. Mavrič), matjaz.valant@ung.si (M. Valant).

https://doi.org/10.1016/j.jnoncrysol.2019.119493
Received 19 January 2019; Received in revised form 3 June 2019; Accepted 4 June 2019
Available online 07 August 2019
0022-3093/ © 2019 Elsevier B.V. All rights reserved.
A. Mavrič, et al.
Fig. 1. A schematic diagram of the thermodynamic stability of α-, γ- and am-
Al2O3, depending on the specific surface area. Reconstructed from data in Ref.
[46, 50, 51].
Al2O3 nanocrystals (sub-10 nm), a high energy input is necessary (e.g.
by high energy milling [50]).
Tavakoli et al. [51] compared the excess enthalpy as a function of
the specific surface area of the am-, γ- and α-Al2O3 nanoparticles with
that of the bulk corundum. The excess enthalpy is a linear function of
the specific surface area for the am-, γ and α phase. With the increase of
the specific surface area, the enthalpy increases slowly for the amor-
phous phase than for the γ and α phases, due to the smaller surface
energy of am-Al2O3 (Fig. 1). When the specific surface area exceeds
370 m2 g−1 (corresponding to a particle diameter of ~6.5 nm), am-
Al2O3 becomes the most energetically stable phase. The same trends of
lowering the transition enthalpy with the increase in the specific sur-
face area were shown for all the transitions in the system, i.e. the am- to
α, am- to γ and γ to α transitions. In comparison with the surface en-
thalpy, a contribution of interfacial energy to the excess enthalpy
arising from grain-grain interfaces was found to be negligible. Beside
the enthalpy part of the free energy, the configurational entropy, as a
result of the disorder in am-Al2O3, should also be accounted for. Be-
cause α-Al2O3 is an ordered structure, it has the configurational entropy
equal to zero [51]. On the other hand, both γ- and am-Al2O3 structures
are to some extent disordered. This results in an increase in the con-
figurational entropy. Being amorphous, am-Al2O3 is the most dis-
ordered. As a result, the positive entropy change via the α- to γ- tran-
sition is smaller relative to the α- to am-transition.
Bloch et al. [52] studied the effect of the am-Al2O3 film thickness on
structural order and crystallization induced by an electron-beam on
TEM. It was found that for a 4.16 nm thick film there is no change in the
structure after 20 min of exposure to the 300 keV electron beam.
Around twice-thicker film (7.39 nm) after exposure showed the electron
energy loss spectra resembling γ-Al2O3, without crystallization (e.g.
long-range order). Exposition of a much thicker film (63.1 nm) to the
electron beam resulted in crystalline γ-Al2O3 with some α-Al2O3-like
features. The crystallization under the exposure to TEM electron beam
was found also by other authors [53–55]. As shown in Fig. 2a, the
crystallization under the TEM electron beam at 200 keV can be in op-
erando observed, starting from local densification to nucleation and
growth of the crystalline phase. This can be confirmed by the electron
diffraction patterns (Fig. 2b), where we can notice the appearance and
intensification of the diffraction rings and dots characteristic for γ-
Al2O3 [55]. In addition, densification of the am-Al2O3 structure was
also evidenced by a synchrotron X-ray radiation during a near-edge X-
ray absorption fine structure (NEXAFS) experiment [56]. The
2
Journal of Non-Crystalline Solids 521 (2019) 119493
Fig. 2. a) TEM images of am-Al2O3, taken at 200 keV, after different e-beam
exposure time. The inset at 13 min reveals a crystal lattice embedded in the
amorphous surrounding. b) Electron diffraction patterns after different ex-
posure time. The diffraction rings correspond to 311 and 422 planes of γ- Al2O3.
Reprinted from [55], with permission from Elsevier.
densification was attributed to the loss of oxygen from the peroxy ion.
The crystallization temperature of the alumina thin films deposited
on a mesoporous silica gel was measured with Differential Scanning
Calorimetry (DSC). It was found to be strongly thickness dependent and
shifted from 1020 °C to 998 °C for the 2.7 nm and 13.9 nm films, re-
spectively. When compared to HfO2 this dependence was much weaker
[52]. Am-Al2O3, a 2–6 nm thick film within a yttrium-stabilized zir-
conia multilayer, was reported to be stable up to 1000 °C [57]. In the
case of an interface between a metal and aluminum oxide, the interface
energy of the am-Al2O3 is lower than that of the crystalline state [58].
For this reason, the am-Al2O3 thin film that forms during oxidation of
the metal aluminum remains amorphous up to 5–10 nm thickness, de-
pending on the crystallographic face of the aluminum and growth
temperature [58–61].
The main drawback of amorphous alumina film with thickness >
100 nm is its low thermodynamic stability as its unique properties fade
upon crystallization when using it for coatings or electronic devices.
Some thermal treatment of the films is necessary to achieve cohesion
with the substrate or to dehydrate the am-Al2O3 films. This often results
in the full or partial crystallization due to the low crystallization onset
temperature of ~450 °C [62]. Preparing am-Al2O3 that can be thermally
treated at higher temperatures without being crystallized requires im-
provement of its thermodynamic stability. We have seen before that
keeping the dimensions on the nanoscale and the surface area high (for
nanoparticles and thin films) the crystallization can be successfully
suppressed. In addition, it was shown that the interface formation with
metal also suppresses the crystallization onset. In some cases, the
structural disorder introduced by doping (e.g. with Y3+ [36,63,64],
P5+ [65], Er3+ [64], Eu3+ [16], La3+ [66], Si4+ [67], Fe3+ [68] or
Cr3+ [64,68], Zn2+ [69]) suppressed the crystallization. We demon-
strated yet another approach for stabilization of the amorphous alu-
mina by nanocomposite formation [23,55]. We showed that by dis-
persing polysilane molecules into the alumina matrix (Fig. 3), the bulk
am-Al2O3 can be successfully sustained at 900 °C. During the heat
treatment, the polysilane molecules are oxidized, form covalent bonds
with the matrix and induce a homogeneously distributed stress
throughout the bulk [55].
A. Mavrič, et al.
Fig. 3. Schematic presentation of forms that induce different stress: a) nanoparticles – surface stress; b) thin films – interfacial stress; and c) nanocomposites – bulk
stress. TEM images of am-Al2O3 in form of d) nanoparticles [Reprinted with permission from [51]. Copyright 2013 American Chemical Society.]; e) thin films
[Reprinted with permission from [52]. Copyright 2014 American Chemical Society.]; f) bulk nanocomposite: and g) a combination of nanocomposite and thin film.
The common strategy of all the reported approaches is to introduce
enough stress into the alumina structural matrix to thermodynamically
favor the amorphous phase over crystalline phases. The origin of the
stress seems to be not important, as the efficient suppression of the
crystallization onset has been demonstrated as a result of interfacial,
surface or bulk stress (Fig. 3).
Fig. 4 shows the correlation between the crystallization temperature
and the thin films thickness or nanoparticles diameters prepared by
different methods summarized in Table 1. A decrease in the film
thickness or particle size increases the crystallization temperature. This
is a direct consequence of the increase in the interface or surface en-
ergy, respectively. In addition, the larger sized particles, stabilized by
doping or nanocomposite formation, demonstrated high stability. Their
stability is comparable with the stability of the < 10 nm sized alumina
particles owing to the improved strain that is homogeneously in-
troduced into the amorphous structural network.
Fig. 4. Correlation between the size and crystallization temperature of thin
films and nanoparticles; the data are taken from references shown in the
brackets in the plot. The dashed lines show the crystallization temperature of
bulk particles stabilized by the Eu-doping and nanocomposite formation.
3
Journal of Non-Crystalline Solids 521 (2019) 119493
3. Structure
The absence of a distinct structural periodicity in am-Al2O3 does not
preclude the existence of characteristic atomic configurations, in which
Al3+ ions retain the type of bonding and coordination polyhedra similar
to the crystalline forms. Because the interatomic forces in the crystals
and amorphous material are essentially the same, the amorphous can be
presented as a three-dimensional network of such polyhedra, which
lack the periodicity and symmetry [70]. The XRD powder diffraction of
am-Al2O3 does not show the sharp peaks, which are observed in the
polycrystalline powders. The diffractograms of the am-Al2O3 solids
usually contain one or more broad low-intensity halos at the positions
corresponding to the strongest peaks of the related crystalline poly-
morphs (Fig. 5). The broad peaks of am-Al2O3 reflect the average dis-
tances between the atoms in the amorphous structure. Their intensity
slightly increases after annealing at higher temperatures due to the
densification of the material and the increase of the local order.
Besides 4- and 6-coordinated Al3+, [Al]4 and [Al]6, that are found in
the crystalline polymorphs (with α-Al2O3 containing only [Al]6), the
presence of 5-coordinated Al3+, [Al]5, was found in the amorphous
alumina (Fig. 6a). The presence of [Al]5 is believed to be unique for am-
Al2O3 with some minor exceptions. A small amount of [Al]5 was ex-
perimentally found in highly defective surfaces of nanosized metastable
γ- and κ- alumina [73,74] and simulated by theoretical reconstruction
of their surfaces [75]. The experimental observations of the [Al]5 in am-
Al2O3 have also been supported by theoretical calculations. Some the-
oretical calculations also reported a small amount of 3-coordinated
Al3+, [Al]3, which have not yet confirmed experimentally. The reason
might be in the fact that the calculations have been performed on
models of very low-density alumina clusters that cannot be experi-
mentally realized. The distribution of different Al coordination poly-
hedra found by different studies is presented in Fig. 7.
Different spectroscopy techniques have been used to resolve the
structure of amorphous alumina. By modeling the X-ray radial dis-
tribution function the presence of [Al]5 polyhedra in addition to [Al]4
and [Al]6 was shown for AAO films by Oka et al. [76]. They modeled
the system by mixing the structure of γ-Al2O3 and disordered phase. A
structure very similar to γ-Al2O3 was observed also for AAO by an ex-
tended electron energy-loss fine structure (EXEELFS) [77,78], EXAFS
[79], a near-edge X-ray absorption fine structure (NEXAFS) [56], and
XPS [60,80] and for the RF sputtered films by X-ray radial distribution
function [81]. Lamparter and Kneip [82] combined the X-ray and
 Table 1
Synthesis methods used for the formation of am-Al2O3. Where applicable the thermal treatment conditions resulting in crystalline form are given.
Method Source, conditions Form, size Crystallization Ref.
A. Mavrič, et al.

PLD α-Al2O3 pallet at RT thin films, ~260 nm γ at deposition temperature > 500 °C [29,105]
PLD polycrystalline Al2O3 film ≥3 μm N/A [104]
PLD Al2O3, at RT thin film 20 nm N/A [31]
PLD polycrystalline Al2O3, at RT ~40 nm N/A [127]
PLD Al2O3 sintered target, RT thin film 0.1–1 μm If deposited at substrate temperature 800 °C. [108]
ALD trimethylaluminum/water, 300 °C thin film 12 nm γ after annealing at 1000 °C, 60 s [106]
ALD trimethylaluminum/water, 300 °C thin film 20 nm > 800 °C [141]
ALD trimethylaluminum/H2O, 150 and 175 °C thin film 80-320 nm N/A [30]
ALD trimethylaluminum in Ar/O2/N2, at 200 °C thin film ~1.4 μm N/A [88]
ion beam during physical vapor Al2O3, the substrate at 200 °C 223-1209 nm N/A [107]
deposition
e-beam evaporation alumina disk, annealing at 400 and 600 °C after deposition thin films, 350 nm 600–800 °C [142]
e-beam evaporation Al2O3, annealed at 700 °C from 1 to 12 h thin film, 116-254 nm N/A [97]
CVD aluminum tri-sec-butoxide nanoparticles, ~10 nm amorphous below 1000 °C [113]
CVD from aluminum acetylacetonate, 500–700 °C a film composed of particles (15–30 nm) N/A [24]
PECVD AlCl3, H2, CO2 at T < 500 °C films, ≥3 μm N/A [109,143]
PECVD trimethylaluminum in an oxygen plasma 0.1-1 μm If deposited at substrate temperature 800 °C. [108]
Reactive magnetron sputter Al2O3 target thin films, ~200 nm Onset at 800 °C. [87]
deposition
Reactive magnetron sputter Al target, Ar-O2 gas mixture, 350 °C thin films, ~1 μm depends on the substrate bias voltage and magnetic [28]
deposition field
Reactive magnetron sputter Al target, Ar-O2 gas mixture, substrate temperature < 200 °C thin films, ~1 μm 600 °C or as deposited when substrate temperature [56,102,144]
deposition during deposition > 200 °C
Pulsed rf magnetron sputtering Al/Al2O3 substrate at RT thin films, ~1 μm annealing at 500 °C [26,145]
High power impulse magnetron Al target, Ar-O2 gas mixture thin films, 0.2-1 μm N/A [146]

4
sputtering
Pulsed rf magnetron sputtering Al target, Ar-O2 gas mixture thin films, 1-2 μm depends on the deposition rate and substrate [146]
temperature, generally > 450 °C
RF sputtering Al target, Ar-O2 gas mixture, annealing at 300 °C thin film, ~50 nm N/A [27]
RF magnetron sputtering Al2O3 target, Ar or Ar-O2 gas mixture, the substrate at 20–500 °C thin film, < 1 μm N/A [116]
MOCVD aluminum tri isopropoxide, 420–650 °C films 0.4–1.5 μm 450–650 °C [19,20,33,110,112]
Sol-gel Al(NO3)3/glacial acetic acid/acetylacetone/polyvinyl alcohol, heat films, ~215 nm > 700 °C [25,147]
treated at 400 °C
Sol-gel boehmite (AlOOH) sol, deposited at 250 °C films, 2-3 μm N/A [34]
Sol-gel Al(NO3)3/water/glycerol/citric acid, heat treated 500–900 °C porous micro particles > 600 °C [13,25]
Sol-gel Al(NO3)3/NH3/pH = 7 heat treated at 550 °C nanoparticles, ~5 nm, agglomerated > 600 °C and when prepared in pH > 7 after first [17]
heat treatment at 550 °C
Sol-gel AlCl3/ethylene glycol monomethyl ether, annealing 600–1000 °C nanoparticles, ~50 nm > 700 °C [23]
Sol-gel AlCl3 and polysilane thin films, ~50 nm amorphous at 1500 °C [23]
Sol-gel AlCl3 and polysilane bulk < 1000 °C due to mullite crystallization [55]
Sol-gel AlCl3/Y(NO3)3/polyvinyl alcohol, calcined at 700 °C nanoparticles, BET specific surface area of N/A [36]
312 m2 g−1 (Y3+ doped)
Sol-gel aluminum isopropylate/2-ethoxyethanol/glycol ether/acetic acid, thin films, ~260 nm N/A [132]
spin-coating, thermal treatment at 450 °C
Sol-gel aluminum isopropoxide/water/HNO3 dip-coating, thermal thin films, ~250 nm N/A [134]
treatment at 550 °C
Sol-gel powder flat-Al13/pluronic-F127/water spin-coating, thermal thin films, 60–350 nm N/A [133]
treatment at 500 °C
Spray pyrolysis AlCl3/water/ethanol 250–550 °C Depending on the amount of deposited material, N/A [131]
nanoparticles or thin films are formed.
Coprecipitation AlCl3/EuCl3/ethanol, fast drying at 350 °C, annealed at 500–900 °C particles, 4-10 μm (10% Eu3+) amorphous at 900 °C [16]
(continued on next page)
Journal of Non-Crystalline Solids 521 (2019) 119493
A. Mavrič, et al. Journal of Non-Crystalline Solids 521 (2019) 119493

[140]

[148]
[37]
[15]
[11]
[12]
Ref.
Crystallization

> 600 °C

N/A
N/A
N/A
N/A
N/A

Fig. 5. XRD diffractograms of α, γ, and am-Al2O3 in nanocomposite form. The

peak positions (blue bars) for α-Al2O3 and γ-Al2O3 are taken from PDF cards
431,484 [71] and 2,015,530 [72], respectively. Each thick on the y-axis present
nanoparticles < 25 nm dispersed in toluene

200 counts, the bars from PDF card are normalized to the peak with the highest
intensity. (For interpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article.)
nanoporous membranes 40-13 nm

thin films on Al, 0.05–0.5 μm

nanostructured microspheres

nanoparticles < 4 nm
Form, size

nanotubes
Al(NO3)3/water/sodium dodecyl sulfonate/NH3 to pH~5, 120 °C,

acetic acid/aluminum isopropoxide

heat treated 500–800 °C

Fig. 6. a) Representation of distorted tetrahedral [Al]4, bipyramidal [Al]5 and

Source, conditions

octahedral [Al]6 polyhedra, Al3+ (blue) and oxygen (red). b) Two-dimensional

27
Al 3QMAS NMR spectra of the rotor background subtracted amorphous ALD
thin films distinguishing between three different Al3+ coordinations. Reprinted
Al anode
Al anode
Al anode
Al anode

with permission from [87,88]. Copyright 2010 American Chemical Society.

(For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)

neutron diffraction data of AAO with reverse Monte Carlo simulations

that showed the presence of the 3-, 4-, 5- and 6-coordinated polyhedra,
with [Al]4 being the dominant fragment. A much more direct tool for
Table 1 (continued)

analysis of the Al coordination in amorphous alumina is NMR spec-

Hydrothermal

Solvothremal

troscopy [83,84]. The solid-state NMR (SSNMR) with a Magic Angle

Anodization
Anodization
Anodization
Anodization

Spinning (MAS) of 27Al nuclei allows distinguishing 4-, 5- and 6- co-

Method

ordinated Al3+ at the chemical shifts of ~60, ~35 and ~0 ppm, re-
spectively [85,86]. Due to the local atomic environment variations in

5
A. Mavrič, et al.
the amorphous phase, the NMR peak broadening is high [84]. The three
different Al coordination environments can be better distinguished
from 2D NMR spectra (Fig. 6b) [87,88]. NMR was used to show the
presence of [Al]5 in amorphous aluminum oxide films prepared by
anodization [89], RF sputtering [87], ALD and PVD [88], sol-gel [90].
Gutiérrez and Johansson [91] performed a molecular dynamic (MD)
study of amorphous alumina structure. They revealed the presence of a
short-range order dominated by two- to five-fold rings of alternating Al-
O bonds, resulting in the structure dominated by [Al]4 tetrahedra. They
show that the structures of amorphous and liquid alumina are very si-
milar and resemble the surface structure of γ-Al2O3 at room tempera-
ture. Similar structural characteristics were later obtained by others by
MD [92–98] and Density Functional Theory (DFT) [84] calculations.
Oxygen is preferred on the surface of am-Al2O3 and Al is enriched just
below the surface [99].
It was found both theoretically [92,97,100] and experimentally
[55,87,97] that with thermal annealing of am-Al2O3 the distribution of
the different coordination polyhedra changes. The coordination number
of the aluminum ion increases. The transformation from the corner-
sharing [Al]4 and [Al]5 polyhedra to more stable edge-sharing [Al]6
octahedra occurs with temperature [87,97]. This transformation results
in the densification of the alumina structural matrix. Pores and nano-
voids are formed during this process [92,97,100]. During further an-
nealing, the nucleation in the amorphous alumina matrix occurs by
short-range reordering of the structure that resembles the γ phase. In-
itially, the crystallization of the amorphous alumina results in γ-Al2O3
[10,52,68,101]. Further transformation to more stable α-Al2O3 can be
direct or indirect (over θ- or κ-phases) [102]. If an initial film already
contains some γ-phase nanocrystals, am-Al2O3 transforms to the α
phase via γ phase only, otherwise the transformation proceeds over a
mixture of polymorphs [102].
Fig. 7 shows the distribution of the Al polyhedron coordination in
the amorphous alumina obtained with various theoretical methods and
experimental techniques. The theoretical calculations performed on low
density am-Al2O3 structural models gave a high share of [Al]4 poly-
hedra (> 50%) followed by the [Al]5 polyhedra and the [Al]6 poly-
hedra with < 5%. As expected, by increasing the structural density the
share of the polyhedral with higher coordination increases. The similar
trend can be observed from the experimentally reported polyhedron
distributions. As deposited films that tend to have lower density have a
high amount of the [Al]4 polyhedra, exceeding 50%. The samples ex-
posed to higher temperatures have a higher amount of [Al]6 polyhedra,
6
Journal of Non-Crystalline Solids 521 (2019) 119493
Fig. 7. Distribution of the Al polyhedron coordina-
tion in the am-Al2O3 obtained with various theore-
tical methods and experimental techniques.
Theoretical results are ordered by increasing the
density of modeled unit cell: low density (here
chosen as < 3.1 g cm−3), middle dense distribution
(3.1 g cm−3 ≤ ρ ≥ 3.25 g cm−3) and high density
(> 3.25 g cm−3). Experimental results are ordered
by the temperature of heat treatment. The references
to the original data are labeled on the X-axis. (For
interpretation of the references to colour in this
figure legend, the reader is referred to the web ver-
sion of this article.)
showing on the higher density of the structure and large degree of the
corner- to edge-sharing structural transition. This is especially true for
the samples that have been exposed to very high temperatures [55,83].
The experimental results on the low-density am-Al2O3 state are in
fairly good agreement with the theoretical studies while for the high-
density state certain deviations exist. The reported concentration of
[Al]4 polyhedra is not much lower than predicted by calculations on the
high-density models while the concentration of [Al]5 is significantly
lower. It seems that [Al]5 is energetically the most unfavorable and at
elevated temperatures tends to change to [Al]4 which can further un-
dergo corner-to-edge-sharing transition [55]. With the increase in the
share of [Al]6, the structure is becoming more and more similar to the γ-
Al2O3 until it finally crystallizes.
4. Synthesis
Dehydration of different aluminum hydroxide species above 300 °C
gives the polycrystalline polymorphs. Depending on the hydroxide
structure the material changes through a series of phase transitions and
converts to α-Al2O3 on heating between 900 and 1100 °C. These tran-
sitions are of high technological importance and are well studied.
During the transitions, aluminum hydroxide precursor undergoes loss of
water and densification. At the ambient conditions, am-Al2O3 cannot be
prepared just by dehydrating aluminum hydroxides. Moreover, most of
the aluminum hydroxide precursors are by themselves crystalline. The
phase transformation to the alumina proceeds without degradation of
crystalline structure and the polytype of the resulting transition alu-
mina is in fact determined by the crystalline structure of the precursor
[1]. Nevertheless, am-Al2O3 has been prepared from finely powdered
aluminum trihydroxide by vacuum drying at 425 °C. It has crystallized
at heating to 450 °C [103]. Due to problems with transforming alu-
minum hydroxide precursors to amorphous alumina the research has
moved towards the synthesis from vapor phase such as physical vapor
deposition (PVD) and chemical vapor deposition (CVD). Up-scalable
techniques, such as sol-gel synthesis, have also been adopted. However,
the production was mostly oriented to nanoparticles and thin films due
to the low-temperature stability of amorphous bulk alumina. The syn-
thetic methods used for the synthesis of am-Al2O3 are collected in
Table 1. Am-Al2O3 is prepared under thermodynamically non-equili-
brium conditions; therefore, its structure largely depends on the
synthesis conditions.
A. Mavrič, et al.
4.1. Vapor phase methods
For the preparation of the thin films and powders, PVD and CVD
have been frequently used. PVD is carried out in an ultrahigh vacuum
where pure alumina is vaporized by a laser or a radiofrequency source.
The as-deposited alumina thin films or nanoparticles are amorphous
[24,26,29,101,104–108]. The PVD films deposited on a heated sub-
strate or by heating just above 500 °C have been reported to crystallize
to polycrystalline γ-Al2O3 or a mixture of the polymorphs.
[26,29,101,105,106,108].
The alumina thin films by CVD at 350 °C include aluminum oxide
hydroxide (AlOOH) [109–112]. Thermal treatment is necessary to re-
move the hydroxide groups. Since CVD results in hydroxylated alumina,
precise temperature control is needed to dehydrate alumina and to
prevent the crystallization. For example, CVD films (300 nm thick)
prepared from aluminum tri-isopropoxide [111] deposited at tem-
perature lower than 415 °C resulted in the hydroxylated film, while
crystallization was induced at deposition temperatures over 700 °C.
Amorphous nanoparticles ranging from 5 to 100 nm were produced by
introducing aluminum alkoxide vapors into a high-temperature furnace
at 1000 °C [113]. The exact temperature of crystallization depends on
the thickness of the deposit.
Based on the reported studies, we can conclude that CVD technique
that requires the dehydration at temperatures above 600 °C, cannot
produce thicker am-Al2O3 films as the PVD technique that does not
need the heat treatment. However, after heat treatment above 1000 °C
the PVD and CVD films and powders of a high surface area result in a
mixture of different polymorphs. Even more, pure α-Al2O3 crystallizes
only at 1500 °C [102,114,115]. This demonstrates that the high surface
area stabilizes not only amorphous but also metastable aluminas.
The difference between different vapor phase deposition techniques
is remarkable. For example, the as deposited films prepared by the
atomic layer deposition (ALD) contain much higher fraction of [Al]5
with polyhedra more disordered than in the PVD film [88]. The films
produced by the radio frequency magnetron sputtering showed the
variation in density from 3.1 to 3.6 g cm−3 with an O/Al ratio of 1.5 or
higher, depending on the process conditions. Another group showed a
local oxygen deficiency in the films prepared by the direct current
magnetron sputtering [93]. Di Fonzo et al. [104] showed three growth
regimes for the pulsed laser deposition of alumina films. At low oxygen
pressure, the films were homogeneous and dense. An increase in the
deposition pressure led to columnar film growth. At even higher pres-
sure it led to a film assembled from clusters with dendritic and porous
morphology with significantly lower density (under 3 g cm−3).
4.2. Oxidation of metal aluminum
The thin films can also be prepared on metal Al by thermal or anodic
oxidation. Immediately after exposure of metal Al to oxygen, an oxide
phase starts to form on its surface [117,118]. Brune et al. [117] studied
oxygen interaction with the Al(111) surface by STM at 27 °C. They
showed that oxygen starts to stick to the surface already at a 0.005
monolayer (ML) surface coverage. The coverage is random, but oxygen
species are mobile and start to form islands. Oxidation starts by nu-
cleation of the first oxide nuclei already at low oxygen surface coverage
(0.2 ML). With further oxygen intake, the oxidation continues by the
formation of new nucleation spots rather than the grain growth. Before
a continuous oxide layer is formed the surface consists of the small
oxide granules. The oxide formation already occurs at low pressures
(10−7–10−6 Torr) and temperatures around liquid nitrogen [118–121].
During the initial stages of the thermal oxidation of Al surfaces the
oxide layer is amorphous [59–61,122,123]. The growth of the oxide
layer depends on the heat treatment parameters. The limiting factor is
the diffusion of the Al ions from the metal to the surface. At higher
temperatures, the diffusion kinetics increase and the oxide layer starts
to become thicker. At some point, depending on the Al surface
7
Journal of Non-Crystalline Solids 521 (2019) 119493
orientation, temperature, heating rate and time of the thermal treat-
ment, the amorphous film starts to crystallize to γ- and α-Al2O3
[59,60,80,123,124]. The crystallization temperature was found to lar-
gely depend on an oxide layer thickness [59–61,125].
Similarly, the electrochemical oxidation gives the amorphous phase
[78,79,82] during the first stages of the growth and later a mixture of
am-, γ- and α-Al2O3. The crystallization can be induced by increasing
the oxide layer thickness or by a thermal treatment [8,126]. However,
the crystallization temperature does not only depend on the layer
thickness but also on the electrolyte that was used during anodic oxi-
dation. The AAO is during the growth in contact with the electrolyte,
causing the electrolyte anions, water, and hydroxyl groups to be in-
corporated in the structure. The crystallization can occur only when
these inclusions are thermally removed from the structure [126].
4.3. Solution methods
Based on the described mechanism for the stabilization of am-Al2O3
with the introduction of stress, it is clear why am-Al2O3 was success-
fully synthesized only in a thin film or nanoparticle form, mainly by
PVD [127] and CVD [108], or by electrochemical aluminum oxidation
[11,12,15]. More convenient up-scalable techniques, as for example
sol-gel methods, have been considered but have also remained limited
to the nanoparticles and thin film production [14,25,128–134]. An-
nealing of the films and nanoparticles, prepared with such methods, is
required for dehydration and conversion of the initial product to the
alumina [13,135,136]. The conversion is associated with full or in the
most cases partial crystallization of the oxide [108,137–139]. Recently,
we demonstrated a method for high-temperature stabilization of bulk
amorphous alumina, prepared from sol-gel [23,55]. The stabilization
was achieved by dispersing polysilane dendritic molecules in the alu-
minum hydroxide gel. During heat treatment of the gel above 600 °C the
polysilane molecules oxidized, form covalent bonds with the matrix and
induce a homogeneously distributed stress throughout the bulk of the
am-Al2O3 matrix (Fig. 3f). The stability towards crystallization depends
on the amount of the dispersed polysilane molecules and is limited at
1000 °C. At this temperature, mullite crystallizes on the interface be-
tween the dispersed oxidized polysilane and alumina matrix. This high-
temperature stability allows for complete dehydration of the sol-gel
derived am-Al2O3 and its use in high-temperature applications.
In addition to the sol-gel synthesis, solvothermal reactions have
been used to prepare nanostructured am-Al2O3. Nanotubes with a
diameter from 6 to 8 nm and a length up to 200 nm have been prepared
hydrothermally from aluminum nitrate and sodium dodecyl sulfonate
as a structure-directing template. The amorphous nanotubes have
formed after a heat treatment at 500 °C and crystallized to γ-Al2O3 at
800 °C [140]. Microspheres consisting of branched nanorods have been
prepared solvothermally from aluminum isopropoxide in acetic acid.
No template was used to prepare these structures. At first 1D nanorods
were formed. By increasing the reaction time the nanorods self-orga-
nized into the microspheres [37].
5. Advanced applications of amorphous alumina
5.1. Mechanical properties and related applications
α-Al2O3 was successfully produced in the form of a thin film on a
stainless steel substrate with a laser-induced deposition and retained
the hardness of the bulk form [149]. Presence of the γ-phase in the α-
Al2O3 decreases the mechanical properties of the coatings [150]. On the
other side, it is reported that the pure γ thin films produced by a pulsed
reactive magnetron sputtering can exhibit even better mechanical
properties than the α phase [151]. Molecular dynamics calculations of
am-Al2O3 structural and elastic properties showed that the bulk and
shear moduli are consistently lower in amorphous than the crystalline
Al2O3 phases [96].
A. Mavrič, et al. Journal of Non-Crystalline Solids 521 (2019) 119493

Table 2
Mechanical properties of the am-Al2O3 thin films.
Method Deposition temperature Film thickness (substrate) Hardness [GPa] (method) Young modulus [GPa] Ref
[°C]

PLD RT ~1 μm (Si(100)) 20.8 (nanoindentation) N/A [29]

PLD N/A ≥3 μm (Si(100)) ~11 (nanoindentation) ~190 [104]
PLD RT 1 μm (Si(100)) 11.7 ± 0.3 (Berkovich diamond tip) 182 ± 5 [108]
PECVD RT 1 μm (Si(100) and SiO2/SiO) 6.4 ± 0.2 (Berkovich diamond tip) 116 ± 4 [108]
PECVD 300 ≥3 μm (Corning 7059 glass) 5.3 N/A [143]
350 9.6
500 11.3
(ultra-microhardness)
Reactive magnetron sputter 350 ~1 μm (Si(100)) 10–12 (Berkovich diamond tip) N/A [28]
deposition
e-beam evaporation 400 350 nm (SiO2) 5–8 (nanoindentation) 110–125 [142]
e-beam evaporation 700 116-254 nm (Si(100)) N/A 190–240 (increases with [97]
annealing time)
MOCVD 480 0.4–1.5 μm (Ti alloy) ~11 (nanoindentation) ~155 [19]
MOCVD 480 ~1 μm (Ti alloy and Si) 10.8 ± 0.8 (nanoindentation) 155 ± 6 [20]
Sol-gel 750 ~50 nm (glass) 7.4 ± 0.4 (Berkovich tip nano- 81 ± 5 [23]
indenter)

Table 2 summarizes the mechanical properties of the thin films
prepared by different deposition techniques. Based on the reported
results it can be concluded that the hardness of the thin films containing
the crystalline forms of Al2O3 is higher than that of the amorphous films
[19–22,28,29,108,142,143]. The hardness of the am-Al2O3 is largely
affected by a density of the thin films. The hardness increases with the
substrate temperature due to the increase in Al3+ average coordination
number and bond density [21,97,108,142,143]. This is in accordance
with the molecular dynamic simulations that showed that the annealing
results in the formation of the 6-coordinated Al and denser amorphous
structure [91]. The calculations confirmed that these structural changes
increase Young's modulus and yield stress [98]. In accordance with the
density, a decrease in the amount of impurities (chlorine, carbon, hy-
drogen…) also increases the hardness [19,108,143]. Because the alu-
mina films prepared by PLD are very pure, they have superior char-
acteristics compared to other methods. In addition, the PLD films can be
thicker because they are deposited at room temperature without further
need for thermal treatment. From the point of morphology, it is im-
portant that the film stays homogeneous and dense to achieve good
mechanical properties. Growth regimes that lead to columnar film
growth, a film assembled from clusters or a dendritic and porous
morphology have a significantly lower density and deteriorated me-
chanical properties [104].
Despite the lower hardness compared to the crystalline polymorphs,
the am-Al2O3 thin films are favorable as wear and starch resistant
coatings [20,21,28]. The continuous amorphous thin films without
grain boundaries experience adhesive failure; after a critical load,
buckling of the material occurs on a deformation edge. In contrast, the
nanocrystalline coating experience a cohesive failure resulting in a
plastic deformation already at a minimum load (Fig. 8a). The material
of the amorphous coating is buckling rather than cracking after the load
is applied. As in the case of hardness, the annealing and the consequent
increase in density also cause an increase in the elasticity [21,142]. In
addition, the coatings containing polycrystalline alumina polymorph
embedded in the amorphous matrix were found to benefit from both,
the increased hardness due to the partial crystallinity and the increased
wear resistance due to more compact morphology, good adhesion,
surface smoothness and change in the coating deformation behavior
[21,22,152]. The impurities are mostly affecting the CVD and sol-gel
films. Higher temperatures are required to produce the OH-free high-
density films with sufficient adhesion to the substrate. In the range of
400–600 °C, most of the am-Al2O3 films crystallize. This prevents fur-
ther densification and elimination of the impurities from the film.
We applied the am-Al2O3 coating onto a glass substrate [23]. The
coating was prepared in the nanocomposite form (Fig. 3g), by disper-
sing the polycarbosilane molecules into the alumina matrix. The com-
pletely transparent coating behaved in a plastic manner. The wear re-
sistance exceeded that of the boro-aluminosilicate glass by a factor of
35 and the scratch resistance by more than an order of magnitude
(Fig. 8b,c). The plastic deformation of the am-Al2O3 coatings in contrast
to fracture deformation of the polycrystalline coatings has also been
observed by others [20–22,28]. The plasticity is attributed to the su-
perior wear resistance of the amorphous coatings when compared to the
polycrystalline alumina due to the buckling rather than the cracking.
5.2. Optical properties and related applications
The am-Al2O3 band gap is in the range of 3.2–4.3 eV [9,55,153]
depending on the structural short-range order [9,141]. This value is
much lower in contrast to the bulk crystalline phases, ~8.8 eV [154].
Interestingly, ultrathin crystalline films with abundant defects have
been reported to have the bandgap in the range from 2.5-5 eV similar to

Fig. 8. a) The schematic of cross-section after adhesive and cohesive failure mode. b) Am-Al2O3 coated and d) uncoated glass surface after 1000 cycles with an
applied force 5 N. Reprinted with permission from [23]. Copyright 2016 by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

8
A. Mavrič, et al.
am-Al2O3 [9,155]. The low band gap of the am-Al2O3 is caused by the
stress-induced defects that give mid-bandgap states [9,153,156] and a
change in the bottom of the conductive band due to the different Al
coordination symmetries [56,96,141]. Although the early studies hy-
pothesized that the defect states originate from the oxygen vacancies
[96,141,153], the NEXAFS measurements showed trapped O-O pairs
inducing mid-band states [56]. Nevertheless, the oxygen vacancies, and
the O-O pairs vanish upon the densification and so do the mid-band
states.
Although the crystalline alumina does not absorb visible light, it is
not easy to prepare transparent polycrystalline Al2O3 films. The pre-
sence of boundaries between crystallites and interfaces with pores and
voids causes light scattering that lowers the transparency. To produce
the transparent polycrystalline films, it is necessary to avoid light
scattering, which can be avoided by decreasing the number of scat-
tering centers or by decreasing the size of the scattering centers much
below the wavelength of visible light. This is done either by keeping the
low thickness of the films and coatings, or by preparing extremely well
sintered dense films with the particles in a range of 10 nm, low surface
and interface roughness, and small pore size [29,127,142,145,157]. On
the other hand, the am-Al2O3 films have a big advantage to be free from
the crystallite boundaries that cause light scattering. The continuous
am-Al2O3 films were successfully prepared and showed transparency in
the visible range [23–27,134].
Am-Al2O3 has a lower refractive index than the crystalline phases
[28–30,108,146]. Since the refractive index is related to a density of the
material it is not surprising that less dense am-Al2O3 has the refractive
index closer to the amorphous glass substrates. According to Snell's law,
this leads to smaller refraction on the coating-substrate interface,
making am-Al2O3 more suitable for the glass coatings than the crys-
talline films. Although the refraction index is lower than that of the α
phase; dense amorphous films can have the refraction index similar to
the γ structure [146].
Another approach for manipulating optical properties of am-Al2O3
is by doping. Such doped alumina can absorb light in visible range due
to electron transitions in atomic levels of the dopant ion. Co3+ ions can
be completely dispersed in the alumina matrix up to 7 vol% [158]. The
tetrahedral coordinated Co3+ gives broad overlapping peaks in the
range from 500 to 700 nm. Cu2+ doping gives penta-coordinated Cu2+
that absorbs visible light above 500 nm [159]. The broad absorption
peaks are a consequence of a different local environment of dopant
metal ions, causing different energy level distortions of their energy
levels.
5.3. Other advanced applications
5.3.1. Protective coatings
In contrast with the hydrophilic polycrystalline structures (contact
angle ~50°) [19] the amorphous form is hydrophobic (contact
angle > 100°) making it great catalyst support for anti-fouling and self-
cleaning applications where low wettability is desirable. The amor-
phous alumina coatings were tested for corrosion protection in a saline
environment. The am-Al2O3 MOCVD films on a titanium alloy, with a
thickness ranging from 300 to 1500 nm, [19,33] increase the corrosion
resistance for more than two orders of magnitude compared to the
uncoated alloy. Other forms of alumina provide much more limited
protection. The reason is in the microstructure. A laminar structure of
aluminum hydroxide and grain boundaries of crystalline coatings allow
for electrolyte penetration towards the metal surface while the con-
tinuous amorphous layer tightly closes down the substrate surface and
prevents the contact with the oxidizing environment. Similar observa-
tions have been reported for the 2000–3000 nm thick sol-gel coatings
on magnesium [34] and the mixed amorphous/nanocrystalline coatings
on aluminum alloy [152]. Ultrathin (< 5 nm) ALD thin films have been
used to protect silicon photocathodes for hydrogen evolution reaction
[160–162], stability exceeded 100 h [161].
9
Journal of Non-Crystalline Solids 521 (2019) 119493
5.3.2. Electronic applications
The dense am-Al2O3 thin films have been successfully used as ca-
pacitors [116,132], gate dielectrics or insulators [31,147,148,163] with
high dielectric constant (up to 11), low leakage current, low factor loss
and high breakdown field (300–700 MVm−1). The am-Al2O3 films were
successfully used as an insulator in thin film electroluminescence de-
vices [134]. The sol-gel and ALD deposited am-Al2O3 films were com-
pletely transparent in the visible range and showed no charge transport
at the am-Al2O3/ZnS interfaces.
Momida et al. [94] calculated that am-Al2O3 has a lower average
Al3+ coordination number than the crystalline Al2O3. This causes a
wide Al-O-Al bond angle distribution due to several types of the Al sites
([Al]4, [Al]5 and [Al]6) that are strongly geometrically distorted due to
the lack of symmetry. As a consequence, a contribution of lattice po-
larization to the dielectric constant is higher in the amorphous than
crystalline material. The am-Al2O3 dielectric constant depends on its
structure. It can be tuned by increasing the average coordination
around Al ion and the material density. The tunability has never been
possible for the crystalline polymorphs [94]. In addition, the similar
trend was experimentally observed and theoretically evaluated by
Evangelisti et al. [148]. Combining an electron impedance spectroscopy
and an Auger analysis they showed that the main contribution to the
dielectric constant comes from the lattice polarization that pre-
dominantly depends on the atomic arrangement rather than on the
electronic configuration and corresponding electronic polarization.
By controlling the characteristics of the prepared films such as in-
creasing density and maintaining the stoichiometric ratio, the am-Al2O3
dielectric constant can reach that of the crystalline alumina. Cibert
et al. [108] prepared the amorphous thin films with a dielectric con-
stant of 9–10. After annealing and crystallization to γ-Al2O3, the di-
electric constant slightly increased to 11–13. The insulating properties
get worse with oxygen deficiency [116] and porosity [134]; in contrast,
they improve with the increasing am-Al2O3 density [148]. Thus, the
insulating properties largely depend on the preparation conditions.
Vanbeisen et al. [134] compared the leaking current of the sol-gel and
ALD prepared am-Al2O3 thin films. The sol-gel films have more leakage
and lower break-down fields due to the higher film porosity. The
sputtering parameters affected the stoichiometry of the r.f. magnetron
sputtered films [116]. An Al/O ratio below the stoichiometric value of
1.5 gave the films with poorer insulator properties than that of the
oxygen-rich films, demonstrating the effect of the oxygen vacancies on
the conductivity. Interestingly, the cation doping can control the
amount of oxygen vacancies. The presence of the cation vacancies
prevents formation of the oxygen vacancies and increases a breakdown
strength [163–165]. The am-Al2O3 co-doped by 2% of Si4+ and 1% of
Mg2+ gives the breakdown strength of 544 MV m−1, which is twice as
high as 276 MV m−1 of the un-doped film [164]. Doping with 10% of
Ti4+ gives breakdown strength of 530 MV m−1 [165]. Doping with
10% of Zr4+ increased dielectric constant from 6.2 to 11.8 for sol-gel
deposited thin films [163]. Zou et al. investigated the effect of La3+
doping in the range from 5 to 10% [166] that was shown to increase the
breakdown strength. Due to the same oxidation state as Al3+, La3+ does
not introduce the cation vacancies. Because of a significantly bigger
radius, the La3+ ions make the structure of am-Al2O3 thin films more
compact, which suppresses the ionic mobility. In addition, it was pro-
posed that La3+ might help to trap and scatter the charge, thus en-
hancing the breakdown strength. The described studies showed that the
cation doping is an efficient technique for tuning the am-Al2O3 elec-
tronic properties, which is essential for the applications in the field of
protective coating and dielectrics.
5.3.3. Energy storage
Sol-gel derived am-Al2O3 was used in a multilayer Al/am-Al2O3/Pt
capacitor [132]. The leakage current density was suppressed to
~5.4 × 10−5 A cm−2, the operating voltage was enhanced to 591 MV
m−1 and the energy density was ~14 J cm−3. The increased
A. Mavrič, et al. Journal of Non-Crystalline Solids 521 (2019) 119493

performance of the capacitor was attributed to the am-Al2O3 layer that

was grown by the anodic oxidation of Al electrode on the sol-gel de-
posited Al/am-Al2O3 interface (Fig. 10a-NAO) and provided the ultra-
high resistivity (9.4 × 1012 Ω cm−1). With this, they demonstrated the
application of the interface formed by two am-Al2O3 films that are
structurally different. Although the disorder and O-vacancies are fa-
vorable for electron trapping, they also lower the dielectric constant,
resulting in a high leaking current. Dense anodic film (Fig. 10a - NAO)
provided high resistivity, whereas more disordered sol/gel film pro-
vided a volume for energy storage (Fig. 10a-AmAO).
The supercapacitor in which the am-Al2O3 is not structurally
homogenous was also prepared by Fukuhara et al. [167]. They prepared
the am-Al2O3 supercapacitor by anodic oxidation of the metallic AlY3
amorphous alloy. The growth of am-Al2O3 films by anodic oxidations
results in different density and structure near the metal/oxide interface
and the oxide/electrolyte interface that results from the diffusion and
inclusion of the ions through the oxide layer. The [Al]6 clusters were
accumulated on the surface, the surface resistance was high and the
leaking of charge was prevented. The structure in the core of the film
was more disordered. This resulted in enhanced electron trapping on
the positive charged O-vacancy and improved energy storage. Inter-
estingly, with an increase of the film thickness, the film partially
crystalized into the mixture of γ-Al2O3 and α-Al2O3. Regardless of the
higher amount of the material, the amount of the stored charge was
decreased due to lower population of O-vacancies in crystalline do-
mains.
Another approach for decreasing the leaking of the am-Al2O3 su-
percapacitor was introduced by Feng et al. [164]. With co-doping by
Si4+ and Mg2+, the cation vacancies were generated. This prevented
the formation of oxygen vacancies and increased the breakdown
strength. Compared to the un-doped am-Al2O3 thin film, the energy
density of (Al.97Si.02Mg.01) was enhanced from 6.2 J cm−3 to
9.2 J cm−3. However, with a further increase in dopant concentration,
the stored energy density decreased significantly, revealing the im-
portance of the oxygen vacancies for the charge storage.

5.3.4. Photoluminescent applications

The oxygen vacancies have been found to be responsible for in- Fig. 9. a) Fluorescence image of the dendritic cells after the uptake of am-Al2O3
tensive blue photoluminescence in the am-Al2O3 particles [12–14] and nanoparticles excited at 370 nm and examined with a fluorescence microscope.
porous membranes [15]. The oxygen vacancies cause F+ center defects The inset shows the microscopic image of a contrast cell without am-Al2O3
nanoparticles uptake. Reprinted with permission from [12]. Copyright 2012
(singly ionized oxygen vacancies) in the band gap. These defects act as
American Chemical Society. b) Room temperature photoluminescence emission
charge traps and cause the luminescence [12,15]. For the 3-nm am-
from am-Al2O3 doped with 10% Eu3+. The light emission shows the char-
Al2O3 nanoparticles, higher photoluminescence intensity was observed acteristic peaks associated with radiative transitions between the electron en-
in contrast to the same sized γ- and α- phase nanoparticles [12]. These ergy levels of Eu3+ ions. Reprinted with permission from [16]. Copyright 2002
am-Al2O3 nanoparticles are small enough (smaller than the spread of by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
wave function) for the quantum confinement effect to occur [11,12].
Although crystalline nanoparticles show weak blue photoluminescence
Eu3+ doped am-Al2O3 after excitation in the UV range, due to the most
[12], its intensity is low due to the low concentration of oxygen va-
intensive 5D0-7F2 transition at approximately 615 nm [16,171,172].
cancies. It was shown, by combining EELS and photoluminescence
The luminescence intensity depends on the concentration of Eu3+
measurements with quantum simulations, that the oxygen vacancies
[16,171]. It increases with increasing the Eu3+ concentration and
have similar energy positions in the crystalline and am-Al2O3, however,
reaches a peak at 10% of Eu3+ [16]. Similar luminescence, due to the
the oxygen deficiency in am-Al2O3 is higher [153]. In addition to the F
transitions between the energy levels of the dopant ion, has also been
+ centers, weak photoluminescence is also produced by the F center
observed for other rear-earth metal ions (Gd3+, Ho3+, Pr3+, Sm3+,
defects (doubly ionized oxygen vacancies) [15,153] and carbonyl im-
Dy3+ and Tm3+) [173].
purities [13,168]. Ultrathin am-Al2O3 nanoparticles (< 4 nm), pro-
Interestingly, in addition to the luminescence, an upconversion
duced by ultrasonication of anodic am-Al2O3 membranes, were used as
emission has been observed for Er3+ and Nd3+ doped am-Al2O3 and
fluorescent biological labels [12]. After the exposure of the dendritic
excited with 800 nm laser light [174]. The upconversion from Er3+
cells to the am-Al2O3 nanoparticles for 24 h, the labeled cells excited at
emits at 548 nm (4S3/2–4I15/2) and 640 nm (4F9/2–4I11/2), and Nd3+
370 nm showed a clear blue fluorescence (Fig. 9a). Most likely, the am-
emits at 640 nm (4G7/2–4I11/2). The emission is weak and the origin of
Al2O3 nanoparticles penetrate the cell membrane by endocytosis. Nei-
the upconversion is unknown. It is speculated that it may be related to a
ther detectable toxicity nor inhibitory effect on cell proliferation was
multi-phonon relaxation resulting from inhomogeneity of the alumina
observed after continuous exposure for two days.
matrix [174,175].
In contrast to wide photoluminescence peaks of pure am-Al2O3, the
doping with lanthanide ions (e.g. Eu3+ [16,169–172]) gives sharp
emission lines, due to transitions between atomic levels of the dopant 5.3.5. Ferromagnetism
ion (Fig. 9b). In general, a red light luminescence has been reported for The oxygen vacancies, in particular F+ centers, are also responsible

10
A. Mavrič, et al.
Fig. 10. Advanced properties of am-Al2O3. a) TEM image of a cross-section of
the Al/am-Al2O3 capacitor layer for energy storage with newly formed alu-
minum oxide (NAO) providing high resistivity. Republished with permission of
Royal Society of Chemistry (Great Britain), from [132]; permission conveyed
through Copyright Clearance Center, Inc. b) Room temperature M-H curves of
9–12 nm nanoparticles heat treated at different temperatures (S600 – am-Al2O3;
S700 – am−/γ-Al2O3; S800 and S900 – γ-Al2O3; S1000 – α-Al2O3. The M-H
curves of bulk Al2O3 shown in the inset. Reprinted with permission from [17].
Copyright 2011 American Chemical Society. c) Temperature dependence of
thermal conductivity (TC) enhancement of am-Al2O3/ethylene glycol nano-
fluids for am-Al2O3 loadings of 0.25, 0.50, and 1.0 vol%. Reprinted from [18],
with the permission of AIP Publishing. d) Schematic representation of an in-
teraction of the amorphous and crystalline nanoparticles in ethylene glycol (EG)
fluid, showing stronger solvation of amorphous nanoparticles. Reprinted from
[18], with the permission of AIP Publishing.
for intrinsic ferromagnetism that has been reported for the am-Al2O3
nanoparticles at room temperature [17]. As the magnetization is related
to the concentration of vacancies and is the highest for am-Al2O3, it
decreases with improved crystallinity (formation of γ) and higher
average coordination number of the Al ions (α) (Fig. 10b). In bulk
alumina, no ferromagnetism was detected.
5.3.6. Thermal conductivity enhancement
Due to the high thermal conductivity of Al2O3, its nanoparticles
were used for thermal conductivity enhancement of heat transfer fluids.
The thermal conductivity of ethylene glycol increased for up to 75%
after the addition of 1% Al2O3 [18] (Fig. 10c). The enhancement is
higher by the addition of am-Al2O3 particles relative to the γ-Al2O3 and
α-Al2O3. The amorphous nanoparticles contain a larger amount of
randomly distributed tetra-, penta- and octahedra that serve as active
sites for glycol adsorption [5,18]. These results in stronger solvation
and better dispersion of the amorphous nanoparticles compared to
crystalline nanoparticles (Fig. 10d). As a result, a higher volume frac-
tion of the dispersed nanoparticles can be achieved, which improves the
thermal conductivity.
5.3.7. Catalysis and adsorption
The metastable alumina polymorphs are generally poorly crystal-
lized [1]. This results in highly defected structures with many active
sites for catalysis and adsorption [4,176]. In the fully dehydrated alu-
mina polymorphs, the active site is [Al]4, that acts as a strong Lewis
acid [2,3]. Because the completely dehydrated alumina is hard to
produce at mild temperatures, required to avoid structural changes, the
catalytic reactions mainly take place in a water medium. The alumina
catalysts normally contain OH groups or water molecules bonded on
their surface. Depending on the chemical surrounding of the OH groups
11
Journal of Non-Crystalline Solids 521 (2019) 119493
and pH, these OH sites can act as acid or base active sites [2,4].
However, am-Al2O3 has rarely been considered for the purpose of the
catalysis or adsorption. The nanoparticles doped with La have been
used as the catalyst for the biodiesel conversion [36] and the nanofibrils
for the fluoride removal from water [37].
The molecular dynamics studies have shown that the am-Al2O3
surface is oxygen terminated, causing Al3+ enrichment just below the
surface [99]. The surface relaxes by decreasing the average coordina-
tion of Al ions, i.e. higher amount of three coordinated Al3+ and edge-
sharing tetrahedra near the surface in contrast to the bulk. Although the
surfaces of the crystalline alumina are also terminated with oxygen
atoms, the surface is reconstructed by cation vacancies rather than
lower Al coordination, due to significant inward relaxation of Al atoms.
Due to the higher distribution of low coordinated Al3+ on the surface,
the amorphous surface is superior catalyst to the crystalline surfaces.
The importance of exposed Al3+ sites was shown on the (100) facets of
nanosized γ-Al2O3, where the thermal annealing and dehydration at
300 °C result in some amount of under-coordinated [Al]5 sites [74,177].
When preparing a Pt/γ-Al2O3 catalyst, firstly Pt is bound to those [Al]5
sites resulting in uniform atomic dispersion. It is suggested that the
presence of the [Al]5 sites could potentially lead to favorable dispersion
of deposited guest metals [74]. The presence of the [Al]5 sites has been
experimentally confirmed in amorphous silica-alumina (ASA) and on
the surface of some zeolites [178,179]. It was shown that [Al]5 and
[Al]4 coexist on such surfaces, serving as Brønsted acid sites (proton
donating sites). By increasing the Al concentration in the ASA, the
number of [Al]5 increases. Consequently, the amount of acid sites in-
creases. As an example, at the alumina concentration of 70%, phe-
nylglyoxal conversion to ethyl mandelate in ethanol proceeds with a
highest yield of 99.8% [179]. Thus, we conclude that am-Al2O3 with its
high and adaptable amount of [Al]5 sites offers a good perspective for
alumina supported catalysis.
6. Conclusions
Aluminum is an earth-abundant, inexpensive element; therefore its
crystalline oxide polymorphs have anchored in many fields of tech-
nology. Yet, a little attention has been given to applications of the
amorphous alumina, both in the fields where crystalline polymorphs
dominate (catalysis, catalysis support, coatings, adsorption, etc.) and
for more advanced applications. Certainly, the reason lies in its ther-
modynamic stability issue that makes amorphous alumina hard to be
processed in a bulk form. Recently, our group and other authors de-
veloped new preparation methods to sustain the amorphous structure
under hostile conditions, characterized their unique structures and
successfully applied in many fields. This has triggered new interests in
the amorphous alumina and new attempts to stabilize it to resist the
high-temperatures, for instance by the smart engineering of the lattice
strain. This high temperature crystallization issue has been addressed so
nicely that the potential applications of this unique material will have
received great attention.
The main advantages of am-Al2O3 originate from its amorphous
structure consisting of randomly distributed polyhedra that results in
lower coordination number and density in contrast to the crystalline
polymorphs. Due to the absence of crystallite boundaries, thin films are
usually uniform and transparent. By controlling the density, thin films
with various hardness, elasticity, resistivity, and dielectric constant can
be obtained. This further extends into better wear and scratch re-
sistance, hydrophobicity, corrosion protection properties, light ab-
sorption, photoluminescence, ferromagnetism, and catalysis. Moreover,
tailoring the coordination of Al ions and lattice density of am-Al2O3 can
easily control all these properties.
Up-to-date different structures of am-Al2O3 have exploited in many
advanced applications. For instance, a combination of two am-Al2O3
layers with different densities has been used as a supercapacitor for
energy storage. Controlling over nanoparticle size was demonstrated to
A. Mavrič, et al.
allow tuning of the photoluminescence wavelength. Nanoparticles were
employed as photoluminescent labels and heat exchange fluids. The
am-Al2O3 thin film dielectrics were used in electronic devices and
super-capacitors. The surface of am-Al2O3 has higher amount of ex-
posed Al3+ sites in contrast to the crystalline alumina, making it a
promising candidate for catalysis and adsorption. Evidently, there is a
lot of room for further investigations of am-Al2O3. By now, little at-
tention has been given to applications in catalysis, extremely aggressive
oxidizing environment, corrosion coatings, superhydrophobicity, oleo-
phobicity, icephobicity and optomagnetics. It is almost certain that in
the next decades the scientists' and engineers' ingenuity will come up
with a number of very exciting new applications that will take ad-
vantage of the uniqueness of amorphous alumina.
Declaration of interest statement
That there are no known conflicts of interest associated with this
publication and there has been no significant financial support for this
work that could have influenced its outcome.
Acknowledgment
AM and MV acknowledge the financial support from the Slovenian
Research Agency (research core funding No. P2-0412). MV acknowl-
edges the distinguished international expert program appointed by the
Chinese Ministry of Education. ZW acknowledge National Program on
Key Basic Research Project (973 Program) 2013CB933301 and National
Natural Science Foundation of China 51272038.
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Andraž Mavrič received his PhD at the University of Nova
Gorica, Slovenia where he developed a method for high-
temperature stabilization of bulk amorphous alumina. He is
currently a postdoctoral researcher at Molecular
Electrochemistry Laboratory, Institute of Fundamental and
Frontier Sciences, University of Electronic Science and
Technology of China. He works in the area of electro-
catalysis and is actively involved in the development of
catalysts and materials for corrosion protection.
15
Journal of Non-Crystalline Solids 521 (2019) 119493
Matjaz Valant is Head of Materials Research Laboratory
and Dean of School for Environmental Sciences at the
University of Nova Gorica in Slovenia. He is Adjunct
Professor at Institute of Fundamental and Frontier Sciences,
University of Electronic Science and Technology of China
and a visiting professor at London South Bank University.
His main research interest is oxide semiconductors, di-
electrics, magnetoelectric, topological insulators, and elec-
trocaloric materials as well as the synthesis of new nanos-
tructured functional materials.
Chunhua Cui has been engaged as Professor of Molecular
Electrochemistry since 2017 in the Institute of Fundamental
and Frontier Sciences at the University of Electronic Science
and Technology of China. Prior to his appointment, he was
an independent researcher within URPP LightChEC of the
University of Zurich. His group concentrates on molecular
electrochemistry, semiconductor electrochemistry, in-situ
spectroelectrochemistry, and electrochemical micro-reac-
tions.
Zhiming M. Wang received his PhD degree in Condensed
Matter Physics from the Institute of Semiconductors at the
Chinese Academy of Sciences in Beijing, China in 1998. He
is now a Professor of the National 1000-Talent Program,
working in the University of Electronic Science and
Technology of China. His research on the optoelectronic
properties of low-dimensional semiconductor nanos-
tructures and corresponding applications in photovoltaic
devices.