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Synthesis of Inorganic Fluorides in Molten Salt Fluxes and Ionic Liquid

Mediums

P.P. Fedorov, A.A. Alexandrov

PII: S0022-1139(19)30211-8
DOI: https://doi.org/10.1016/j.jfluchem.2019.109374
Reference: FLUOR 109374

To appear in: Journal of Fluorine Chemistry

Received Date: 28 June 2019

Revised Date: 16 September 2019
Accepted Date: 17 September 2019

Please cite this article as: Fedorov PP, Alexandrov AA, Synthesis of Inorganic Fluorides in
Molten Salt Fluxes and Ionic Liquid Mediums, Journal of Fluorine Chemistry (2019),
doi: https://doi.org/10.1016/j.jfluchem.2019.109374

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Synthesis of Inorganic Fluorides in Molten Salt Fluxes and Ionic Liquid Mediums
P.P. Fedorova*, A.A. Alexandrova,b
aProkhorovGeneral Physics Institute of the Russian Academy of Sciences, 38 Vavilov Street,
Moscow, 119991, Russia
of Fine Chemical Technologies, MIREA – Russian Technological University, 86
b Institute

Vernadsky Prospect, Moscow, 119571, Russia

*corresponding author. Tel: +7 4995038792.
E-mail: ppfedorov@yandex.ru

Graphical abstract

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The present review article covers the synthesis of inorganic fluorides using two types of
molten media – molten salt fluxes and ionic liquids (IL). Molten salt syntheses (MSS) are
applicable across widely-varying temperatures, ranging from 150 to 800°C. Lowering the
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synthetic temperature results in smaller particle sizes, from a few millimeters at 800°C to about
30 nm at 150°C, whereas increasing the reaction temperatures accelerates hydrolysis of
fluorides. IL syntheses allow the isolation of non-agglomerated nanoparticles without use of the
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sophisticated equipment. MSS syntheses at 300°C or higher allowed the synthesis of equilibrium
phases.
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Keywords: inorganic fluorides; nanoparticles; microparticles; nanofluorides; flux; molten salt

synthesis; ionic liquids
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1. Introduction
Inorganic fluorides can produce very promising materials for the modern industry. This
is especially important for photonics purposes, because of their properties such as low phonon
energy, significant band gap width, low refractive indices, high radiation resistance and great
mechanical strength. The high isomorphic capacity of some fluoride matrices allows the
introduction of rare earth element (REE) dopants, which can lead to the appearance of potentially
useful effects such as lasing, up-conversion, down-conversion, quantum cutting, etc. Such

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materials activated by REEs play crucial role in optical and optoelectronic devices, such as solid-
state lasers, optical amplifiers, up-conversion fibers, white light emitting diodes, medical
sensors, optical electronic chips, luminescence labels, 3D displays, holographic materials, etc.
[1-8]. Fluoride materials can be used as single crystals [9-12], ceramics [13-18], glasses [19-21],
glass ceramics [22], eutectics [23], films [24-26], powders [27-28], and composites [29-30]. The
special role of the recently acquired nanofluorides [31-32], especially for biomedical
applications [33-35]. In addition to photonics, inorganic fluorides are promising materials in
other areas, such as the creation of electrochemical devices [36-38], the development of catalysts
[39], etc. [40].
It should also be noted that inorganic fluorides are a classical object for theoretical
research in the field of solid state chemistry and physics.

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2. Features of the synthesis of inorganic fluorides
Inorganic fluorides can be prepared by broad variety of techniques [31-32, 41-44].

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However, in practice, however, the use of these methods on practice is always accompanied by
some experimental difficulties. The most important problem for the fluoride syntheses is reaction

MF2 +H2O → MO + 2HF↑

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of said fluorides with water, i.e., hydrolysis, i.e., reaction of fluorides with water vapor:
(1),
RF3 + H2O → ROF + 2HF↑ (2).
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Hydrolysis leads to accumulation of hydroxyl and/or oxygen impurities in the obtained
materials [11, 31]. Atmospheric water vapor, water from aqueous solutions and/or water
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adsorbed on the solid particle surfaces can participate in the hydrolysis of these fluorides. The
rate of hydrolytic chemical transformation increases significantly at higher temperatures, with
hydrolysis at elevated temperature being termed pyrohydrolysis. Some fluorides, such as ZrF4,
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and InF3 [45], are slowly and directly hydrolyzed at room temperature. Some compounds, such
as monocrystalline fluorite, are stable indefinitely at room temperature. In order for the results of
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CaF2 hydrolysis to become visible in the absorption bands in the UV range, heating up to 700C
is necessary, and for the second phase inclusions (CaO) to appear, heating up to 900C is
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necessary [46]. Authors [47-49] studied stability of various compounds toward pyrohydrolysis
and found out that it increases in the following series: UF4 - ThF4 - ZnF2 - CdF2 - PbF2 - AlF3 -
CeF3 - MgF2 - BeF2 - CaF2 - SrF2, BaF2 - NaF, and Sc, Lu – Ce – Yb – Ho – Tb – Tm – Gd – Er –
Dy – Sm - Nd, Y – Eu – Pr -La for LnF3.
The decrease in particle size accelerates the hydrolysis [50].
Fluorine ions in the lattice are changed to close in size hydroxyl ions under a small
degree of hydrolysis. In this case, the structure is preserved and the lattice parameters change
little. However, this substitution can significantly affect the functional characteristics of the

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material. In particular, the admixture of hydroxyl in powders significantly worsens the
luminescence of rare earth ions [51]. With further hydrolysis, oxygen ions appearing in the
lattice significantly affect the temperatures of phase transitions [52], lead to changes in the
structure and phase compositions of the samples [53].
In order to suppress hydrolysis, it is necessary to use an inert atmosphere and /or an
excess of fluorinating agent [11, 54].
It is also important to remember that metal fluorides usually do not react with dry
molecular oxygen. Direct oxidation are usually unfavorable from thermodynamics point of view
and, thus, as a result, they do not create additional problems for fluoride syntheses.
The second problem to keep in mind when synthesizing inorganic fluorides in the solid
state or in the molten media is the selection of crucible material. Undesirable batch reactions

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with crucible materials are important factors. At high temperatures, the use of ceramic crucibles
is not possible due to their corrosion accompanied by formation of highly volatile fluoride by-

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products, such as SiF4 and/or AlF3:
2MF2 + SiO2 → SiF4↑ + 2MO (3).
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The use of graphite crucibles results in the creation of an anhydrous reducing atmosphere
and, therefore, prevents pyrohydrolysis of the specimens. On the other hand, metal (Mo, Ni, Cu,
steel, etc.) or carbon crucibles can efficiently reduce fluorides lowering oxidation state of the
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fluoride-forming metal (europium, ytterbium) [55-56] or even completely reducing the latter to
the free element (bismuth) [57]. Gold [58] and copper [59] seem to be convenient materials for
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fluoride preparation. In all cases, hermetically sealed reactors are preferred in comparison with
opened crucibles [58, 60], for even platinum can become a reducing agent in opened systems
[61-62]. Teflon and/or other organofluorine polymers also can be used for synthesis of fluorides
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with lower melting points and higher reaction activities [63-64].

Sintering time, which is necessary for reaching the solid-phase equilibrium, increases
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exponentially with a temperature decrease, and this factor becomes an overwhelming obstacle
for the low-temperature phase synthesis [65-66].
Non-equilibrium specimens with unique functional properties (e.g., enhanced ionic
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conductivity) can be obtained by mechanochemical techniques. The use of the latter methods
leads to the product contamination with milling materials, such as zirconia (ZrO2) or tungsten
carbide (WC). However, a detailed study of potential oxygen contamination in mechanochemical
synthesis has yet to be carried out [43, 67].
Various functional fluoride materials with highly developed surfaces have been
synthesized by thermal decomposition of the corresponding trifluoroacetates [68-69]. This is a

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very attractive synthetic method, however, it leads to product contamination with elemental
carbon.
Samples prepared by sol-gel protocols frequently contain organic impurities because of
organic solvents used during the initial steps of their synthesis. The presence of OH and CH
groups in the final materials should significantly decrease their luminescence.
In contrast with the solid-phase synthesis, the use of solvents leads to a very significant
process acceleration. Water is the simplest solvent, and most of fluorides, having low solubility
in it, can be easily precipitated from aqueous solutions [31-32, 70]. The first to use co-
precipitation of fluorides from aqueous solutions was apparently Berzelius, who discovered
hydrofluoric acid [71]. Such precipitation is very inexpensive; it requires very simple
experimental arrangements and, very frequently, leads to the formation of nanofluorides.

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Precipitation at room temperature or lower minimizes hydrolysis by-products, although, the well-
developed surface of fluoride nanoparticle makes said hydrolysis easier. For example, the

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formation BiOF instead of BiF3 has been observed for bismuth fluoride precipitation [50].
Research involving co-precipitation processes in fluoride systems has shown that in this case, as
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a rule, non-equilibrium phases are formed with a wide homogeneity regions [72-75]. Formation
of low-temperature ordered phases is not observed. Low solubilities of the precipitated fluorides
hindered the attainment of chemical equilibrium.
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It is worth noting that nanofluorides, obtained by co-precipitation, are hydrated. Highly
active nanopowder surfaces causes multilayered water adsorption [76]. This hydration leads to
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the formation of quite unusual chemical compounds, such as (H3O)Ln3F10 (Ln = rare-earth
elements) [72,77], and causes luminescence quenching by OH- groups and/or water molecules in
freshly prepared nanopowders. This water, adsorbed onto nanoparticle surfaces, is not easily
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removed; however, under the thermal treatment, their pyrohydrolysis can be prevented by
forming compounds with fluorinating agents, such as BaF2•HF [78] or ammonium fluoride solid
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solutions in strontium fluoride, Sr1-x-yLnx(NH4)yF2+x-y [72, 79-80].

Hydrothermal syntheses occur at elevated temperatures [81-84]. This can lead to a
solubility increase and surface energy decrease (particle faceting) for the synthesized fluorides,
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potentially affording equilibrium phases as a result. However, temperature increase is

accomplished with hydrolysis acceleration, and hydroxyl is an indispensable impurity in
hydrothermal synthesized fluoride samples, although this is rarely given proper attention. In the
hydrothermal study of KF-LnF3 systems, where Ln is a rare-earth element [82, 85-87], it was
found that the hydroxyl content increased in the K2LnF5 < KLnF4 < KLn2F7 < KLn3F10 series.
The synthesis of fluorides from high-boiling solvents using oleic acid allows the
synthesis of nanoparticles calibrated in size, not undergoing aggregation due to the fact that the

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surface is blocked by an organic layer. This technology also allows one to obtain core-shell
architecture. However, these syntheses are laborious and expensive [88-90].
3. Flux Growth of Inorganic Fluoride Crystals
Flux crystal growth (phase formation and crystallization from molten solutions) is a well-
known field of science and technology [91-92]. Flux growth is used for exploratory research
aimed at the synthesis of new bulk crystals and for the primary study of their properties and
structure. In addition, this method is used to obtain single crystals of refractory compounds that
evaporate or decompose when heated. Growing single crystals from the melt solution can also be
used for congruent-melting compounds, if the equipment does not allow heating to the required
temperature [91-92].
The flux must meet the following requirements: it requires to be in a liquid state at the

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temperature of the process, sufficient solubility of starting materials, their chemical inactivity
(i.e., solvents shall not form compounds and/or solid solutions with the target compounds or

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phases), ability to separate solvent from the products, low volatile and low toxicity of the said
solvents [92]. Of course, there is no such thing as ideal solvent, but one still can try to find the
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best fitting materials for the aforementioned Flux Growth technology.
There are three directions of Flux Growth. The first is to obtain (grow) bulk crystals by
recrystallization of the powder charge. This is somewhat beyond the scope of this review,
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although as a result of such operations, the initial powder charge is released, for example, from
adsorbed water. An example is a patent [93]. Powders of rare-earth fluorides recrystallized in the
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melt BeF2 with the addition of NH4F in a platinum crucible in a nitrogen atmosphere. The charge
was heated to 1100C, and cooled at a rate of 50/hour. The final material had an average
crystalline particle size of about 0.1 mm. No one else has used the highly toxic melt of beryllium
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fluoride as flux.
Aride et al. [94] prepared single crystals of NdF3 (m. p. 1375C) size 20 x 7 x 0.6 mm3
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from chloride KCl-NdCl3 flux in sealed Pt-10%Rh ampule while cooling of the melt from 910C
to 470C at a rate of 50C/hour. The flux-melt method for growing of single crystals of very
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refractory ScF3 (m. p. 1550C) with several mm dimensions, pure and doped with transition
metal ions, has been described previously [95-97]. LiF or NaF was used as a solvent, and the
melts with content of 20–40 (mol.) % ScF3 in platinum ampoules were cooled at a rate of up to 3
K/h.
Synthesis from its own melt solution, the so-called “solo fluxes”, is used for incongruent-
melting /crystallizing phases, i.e. in the case when the composition of the melt, which is in
equilibrium with the desired crystalline phase, differs from the composition of the crystal.

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 The method can be illustrated by the example of NaF-LnF3 systems. Phase diagrams of
NaF-LaF3, NaF-GdF3, NaF-YF3 systems are presented in Fig. 1, a-c. Low-temperature hexagonal
“NaRF4” phases (more precisely, phases of variable composition R2-xNaxF6-2x) are in equilibrium
with the melt in certain temperature and concentration intervals, namely: 800-730C, 26-36
mol% LaF3; 860-718C, 28-42 mol% GdF3; and 680-632C 26-47 mol% YF3. Thus,
crystallization of aforementioned phases must be carried out from a melt containing an excess of
NaF. Aebischer et al. [101] prepared NaLaF4 and NaGdF4 single crystals by the Bridgeman
technique from melts of composition NaF:RF3 = 0.38:0.62. Lage and Matinaga [102] have
grown single crystals of NaRF4 (R = La, Ce, Pr, Sm, Eu, and Gd) by the method of Czochralski
from the solo fluxes with excess of NaF.

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 Fig. 1. Phase diagram of the systems, (a) NaF-LaF3 [98], (b) NaF-GdF3 [99], (c) NaF-YF3
[87, 100], (d) LiF-YF3 [106]. L – melt, F – cubic Na0.5-xLn0.5+xF2+2x solid solutions with fluorite-
type structure (“α-NaLnF4”), G – hexagonal Ln2-xNa3xF6 nonstoichiometric phases (“β-
NaLnF4”), T – tysonite-type hexagonal phases, β – orthorhombic low-temperature LnF3
polymorphs with β-YF3 type structure. With permission of the “Nauka” Publishers (Moscow,
Russia).

A similar situation occurs in the preparation of single crystals of LiBaF3 [103], KYF4
[104], KLiYF5 [105], whereby the crystal growth is carried out from melt containing an excess
of lithium or potassium fluoride, respectively. LiYF4 has a transient melting character between
congruent and incongruent [106], see Fig. 1d. To ensure the stability of the process, an excess of
~3% LiF is introduced into the melt [107].
For growing incongruent-melting crystals developed a special technique top seed solution

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growth (TSSG), close to the Czochralski method. This allows one to grow single crystals of large
size and high quality, suitable not only for research, but also for practical applications [104-105].

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Own (solo) flux can be used for the synthesis of powders, as well as for the preparation of
eutectic alloys.
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The second direction of flux growing is Liquid Phase Epitaxy (IPE), which is the
preparation of a thin crystal layer on a solid substrate. Epitaxial CaF2:Yb3+ films on the {111}
plane of synthetic CaF2 single crystal were prepared from CaCl2-CaF2 flux [108]. The freesing of
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saturated solution were carried out in the range 850 - 825 C [109].
The third direction is the preparation of single crystals by synthesis of a new phases.
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Scheerer and Drechsel prepared CaF2 crystal powder from CaCl2, NaF and KCl melt as earlier as
1873 [110]. B. Wanklyn used the classic Flux Growth technique to produce single crystals of
fluorides several mm3 in size, suitable for physical measurements such as ESR, NMR, optical
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absorption spectroscopy, magnetic properties [111-120].

Table 1. — Compounds prepared in the flux.
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T, °C
Batch Product temperature Ref.
range
KHF2 + CrF3 + PbF2 K3CrF6 1055–500 [111]
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KHF2 + NaHF2 + CrF3 + PbF2 K2NaCrF6 975–600 [111]

CsF + KHF2 + CrF3 + PbF2 Cs2KCrF6 1055–500 [111]
KHF2 + NaHF2 + GdF3 + PbF2 K2NaGaF6 1060–500 [111]
RbF + KHF2 + GdF3 + PbF2 Rb2KGaF6 1060–550 [111]
FeF3 + CsCl + PbF2 + NH4HF2 CsFeF4 + Cs3Fe2F9 630–300 [111]
FeF2 + CsCl + PbF2+NH4HF2 CsFe2F7 640–300 [111]
FeF2 + CsCl + PbF2 + NH4HF2 CsFe2F7 950–350 [111]
KHF2 + NaHF2 + AlF3•xH2O + KCl + K2NaAlF6 985–700
[111]
NaCl
KHF2 + NaHF2 + CrF3 + KCl + NaCl K2NaCrF6 975–600 [111]

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KHF2 + AlF3•xH2O + KCl K3AlF6 1055–500 [111]
KHF2 + CrF3 + KCl K3CrF6 1140–880 [111]
RbF + KHF2 + GdF3 + RbCl + KCl Rb2KGaF6 1060–550 [111]
FeF3 + KCl + KHF2 + NH4HF2 KFeF4 870–300 [112]
FeF3 + PbCl2 + KHF2 + NH4HF2 KxFeF3 1020–300 [112]
FeF3 + PbCl2 + KHF2 + NH4HF2 K2FeF5 640–330 [112]
FeF3 + PbCl2 + KHF2 + NH4HF2 K2Fe5F17 850–450 [112]
FeF3 + RbCl + RbF + NH4HF2 RbFeF4 870–350 [112]
FeF3 + PbCl2 + PbF2 + NH4HF2 FeF3 1020–300 [112]
CrF3 + PbCl2 + KHF2 α-KCrF4 + K2CrF5 870–300 [112]
CrF3 + PbCl2 + KHF2 + NH4HF2 α-KCrF4 + K2Cr5F17 930–350 [112]
NiF2 + KCl + KHF2 K2NiF4 960–300 [112]
NiF2 + KCl + KHF2 + NH4HF2 KNiF3 960–300 [112]
HoCl3 + LiF + PbCl2 + PbF2 + NH4HF2 LiHoF4 870–350 [112]
DyF3 + LiF + PbCl2 + PbF2 + NH4HF2 LiDyF4 870–300 [112]
AlF3•xH2O + PbCl2 + NH4HF2 AlF3 930–710 [113]

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AlF3•xH2O + PbCl2 + NH4HF2 + PbF2 AlF3 930–650 [113]
CrF2 + PbCl2 + NH4HF2 CrF3 930–710 [113]
CrF2 + PbCl2 + NH4HF2 + PbF2 CrF3 930–650 [113]

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NiF2 + PbCl2 + PbF2 + NH4HF2 NiF2 950–650 [113]
NiF2 + KCl + NH4HF2 NiF2 + KNiF3 1100–650 [113]
CoF2 + KCl + NH4HF2 CoF2 + KCoF3 1050–400 [114]
FeF2 + KCl + NH4HF2 + Fe
FeF2 + KCl + NH4HF2 + Fe
VF3 + KCl + NH4HF2 + V
KFeF3
FeF2
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KxV2F6 (1≤x≤1.2)
850–510
980–500
980–500
[114]
[114]
[114]
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KF + PbCl2 + NH4HF2 + VF3 + V KVF4 960–450 [115]
RbF + FeF2 + PbCl2 + NH4HF2 RbFeF3 880–450 [115]
VF3 + V + PbCl2 VF2 830–200 [116]
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TiF4 + Ti + KCl + KF KTiF4 860–490 [116]

VF3 + V + KF + PbCl2 K5V3F14 850–490 [116]
AlF3 + KHF2 + PbCl2 + NH4HF2 KAlF4 750–350 [117]
MnF2 + KF + PbCl2 + NH4HF2 KMnF3 950–415 [117]
FeF3 + RbF + PbCl2 + NH4HF2 RbFeF4 740–300 [117]
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FeF3 + RbF+ PbCl2 + NH4HF2 Rb2FeF6 + Rb3FeF6 680–340 [117]

FeF3 + RbF + PbCl2 + NH4HF2 RbxFeF3(0.18<x<0.29) 870–520 [117]
FeF3 + CsF + PbCl2 + NH4HF2 CsxFeF3(0.18<x<0.29) 840–450 [117]
CoF2 + FeF3 + NaHF2 + PbCl2 + Na2CoFeF7 870–300
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[117]
NH4HF2
NiF2 + FeF3 + NaHF2 + PbCl2 + Na2NiFeF7 957–300
[117]
NH4HF2
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NiF2 + AlF3 + NaHF2 + PbCl2 + Na2NiAlF7 957–300

[117]
NH4HF2
ZnF2 + CrF3 + NaHF2 + PbCl2 + Na2ZnCrF7 957–300
[117]
NH4HF2
CrF3 + NaHF2 + PbCl2 + NH4HF2 NaCrF4 957–300 [117]
CrF3 + RbCl + RbF + NH4HF2 β-RbCrF4 870–300 [117]
CrF3 + RbCl + PbCl2 + NH4HF2 Rb2Cr5F17 957–300 [117]
NiF2 + BaF2 + PbF2 + PbCl2 + NH4HF2 (Ba,Pb)Ni(F,Cl)4 1000–600 [117]
CoF2 + BaF2 + PbF2 + PbCl2 + NH4HF2 (Ba,Pb)Co(F,Cl)4 860–300 [117]
CrF3 + CsCl + PbCl2 + PbF2 + NH4HF2 (Cs,Pb)CrF4 + 954–350
[117]
(Cs,Pb)2Cr4.6F17
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KCl + NiF2 + CrF3 KNiCrF6 1290–450 [118]
RbCl + CoF2 + CrF3 RbCoCrF6 1045–500 [118]
RbCl + MnF2 + CrF3 RbMnCrF6 1100–570 [118]
CsCl + CoF2 + AlF3 CsCoAlF6 1200–450 [118]
CsCl + CoF2 + CrF3 CsCoCrF6 1200–450 [118]
CsCl + CoF2 + FeF3 CsCoFeF6 1075–600 [118]
CsCl + CrF2 + AlF3 CsCrAlF6 1170–550 [118]
CsCl + MgF2 + AlF3 CsMgAlF6 1200–500 [118]
CsCl + MgF2 + CrF3 CsMgCrF6 1200–570 [118]
CsCl + MgF2 + FeF3 CsMgFeF6 1200–570 [118]
CsCl + MnF2 + AlF3 CsMnAlF6 1200–570 [118]
CsCl + MnF2 + CrF3 CsMnCrF6 1200–570 [118]
CsCl + MnF2 + FeF3 CsMnFeF6 1200–500 [118]
CsCl + NiF2 + AlF3 CsNiAlF6 1200–570 [118]
CsCl + NiF2 + CrF3 CsNiCrF6 1200–500 [118]
CsCl + NiF2 + FeF3 CsNiFeF6 1075–600 [118]

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CsCl + ZnF2 + FeF3 CsZnFeF6 1200–430 [118]
CrF2 + KF + PbCl2 KCr2F6.5 840–480 [118]
FeF2 + KCl + NH4HF2 KFe2F6 1045–600 [118]

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FeF3 + KHF2 + PbCl2 + NH4HF2 K2FeF5 760–560 [118]
BaCl2 + NiF2 + NH4HF2 BaNiF3.6Cl0.4 1100–570 [118]
NiF2 + KCl + KHF2 + KF KNiF3 1050–550 [119]
FeF3 + NiF2 + CsCl + NH4HF2
CrF3 + NiF2 + CsCl + NH4HF2
CaCl2 + NaF
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CsNiFeF6
CsNiCrF6
CaF2
1075–500
1200–500
1000-760
[119]
[119]
[121]
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CaCl2 + NaF CaF2 1000
[122]
CaF2+ MCl, M = Na, K
CaCl2 + MF, M = Na, K, Li CaF2 1050
[123]
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CaF2 + MCl, M = Na, K, Li

CaCl2 + MF, M = Na, K CaF2; CaF2:Nd3+ 750-1200 [124]
CaCl2 + NaF CaF2: Na+ 950-1050 [125]
SrCl2 + MF, M = Na, K SrF2 950-1050 [126]
NaF + KF + YF3 + LnF3 NaYF4:Yb,Er /Yb,Tm 800 [127]
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MgO +NH4HF2 (NH4)2MgF4 160-180 [128]

ZnO +NH4HF2 ZnF2 130-300 [128]
CrO3 +NH4HF2 (NH4)3CrF6 130-200 [128]
WO3 +NH4HF2 (NH4)3WO2F6 190-200 [128]
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Fe2O3+NH4HF2 (NH4)3FeF6 170 [128]

Sc2O3+NH4HF2 (NH4)3ScF6 80-180 [128]
Ln2O3+NH4HF2, Ln = La,Pr,Nd, Sm, Eu, NH4LnF4 80-180
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[128]
Gd, Dy, Y
Ln2O3+NH4HF2, Ln = Ho ,Er, Tm, Yb, (NH4)3Ln2F9 80-180
[128]
Lu
MgO +NH4HF2 MgF2 [129]
MO +NH4HF2 MF2 (M = Ca,Sr,Ba) [130]
MCO3+NH4HF2 MF2 (M = Ca,Sr,Ba) [130]
Ln(NO3)3•6H2O + NH4HF2, Ln = La, Pr, LaF3, PrF3, NdF3, 180
[131]
Nd, Eu LaF3:Eu3+
KCl + MgCl2•6H2O + NH4HF2 KMgF3 160–180 [132]
KCl + MgCl2•6H2O + Eu(NO3)3•6H2O + KMgF3:Eu3+ 160–180
[132]
NH4HF2
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LnCl3•6H2O (Ln = Y, Yb, Er/Tm) + NaF β-NaYF4:Yb3+, Er3+/Tm3+ 800
[133]
+ NaCl + KCl
YCl3•6H2O + YbCl3•6H2O + YF3:Yb3+/Ln3+ (Ln = Er, 800
[134-
LnCl3•6H2O (Ln = Er, Tm) + NaF + Tm, Ho)
135]
NaCl + KCl
Ln(NO3)3+ NaF + NaNO3 (Ln = Nd, Sm, β-NaLnF4 320
[136]
Gd, Er, Yb, Lu)
Ln(NO3)3+ KF + KNO3 (Ln = Nd, Pr, β-KLnF4 (hex), KYb3F10
[136]
Sm, Gd, Yb)
La(NO3)3 + Eu2O3 + NH4F + NaNO3 + LaF3:Eu3+ 350
[137]
KNO3
Y(NO3)3 + Ln(NO3)3 + NaF + NaNO3 + NaYF4:Yb3+, Er3+/Tm3+ 350
[138]
KNO3
NaF + LnF3 + NaNO3 (Ln = Y, Yb, Tm) NaYF4 400
NaYF4:50%Yb,1%Er [139]
NaYF4:10%Yb,1%Tm

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NaF + YF3 + LnF3 (Ln= Yb, Er, Tm) + NaYF4:Yb, (Er / Tm) 350–400
[140]
NaNO3
Y(NO3)3•6H2O + NaF + NaNO3 + KNO3 β-NaYF4 300–600 [141]

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Y(NO3)3•6H2O + Ln(NO3)3•6H2O (Ln = NaYF4: Er3+ / Tb3+ / Yb3+, 300–600
Eu, Tb, Yb, Tm, Er) + NaF + NaNO3 + Tm3+ / Yb3+, Er3+ [141]
KNO3
Y(NO3)3•6H2O + Ln(NO3)3•6H2O (Ln = LiYF4:Yb3+/ Ln3+ (Ln = Er, 400
-p
Yb, Er, Tm, Ho) + LiF + NaNO3 + Tm, Ho) [142]
KNO3
Y(NO3)3 + Ln(NO3)3 (Ln = Yb, Er) + NaYF4:Er3+,Yb3+ 160–250
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[143]
NH4F + NH4NO3
Sc(NO3)3 + NH4HF2 ScF3 310 [144]
Sc(NO3)3 + NH4HF2 + NaNO3 ScF3 310 [144]
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Sc(NO3)3 + NH4HF2 + KNO3 ScF3 350 [144]

Y(NO3)3•6H2O + Ln(NO3)3•6H2O (Ln = LiYF4:Yb3+, 350
Yb, Er, Tm, Ho) + LiF + NaNO3 + Er3+/Tm3+/Ho3+ [145]
KNO3
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Y(NO3)3•6H2O + Tb(NO3)3•6H2O + NaF β-NaY1-xTbxF4 (x = 0.05 - 400

[146]
+ NaNO3 + KNO3 0.4)
Bi(NO3)•5H2O + Yb(NO3)3•5H2O + NaBiF4:Er3+/Yb3+ 160–250
[147]
Er(NO3)3•5H2O + NaF + NH4NO3
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Ba(NO3)2 + Gd(NO3)3 + Ln(NO3)3 (Ln = BaGdF5:Ce3+/Er3+/Yb3+ 150–210

[148]
Ce, Er, Yb) + NH4F + NH4NO3
Ln(NO3)3 + NaF + NaNO3 – KNO3 / β-NaYF4: 20%Yb3+, 400
NaNO3 – LiNO3 / KNO3 – LiNO3 /
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0.5%Tm3+ [149]
NaNO3 – KNO3 – LiNO3
M(NO3)2•6H2O + NaNO3+ NaF CaF2, SrF2 [150]
Ln(NO3)3•6H2O + NaF + NaNO3 β-NaLnF4, LaF [151]
Bi(NO3)•5H2O + NaF + NaNO3 BiO0.65F1.70 350 [53]
Сa(CF3COO)2 + KNO3 + NaNO3 CaF2 250
[152]
+NaNO2

In addition to the processes of fluoride recrystallization, in particular, the preparation of

AlF3 single crystals from commercial hydrated reagents, Wanklin also synthesized many

10
complex fluoride compounds presented in Table 1. The reverse order of the operating
temperature range in the Table means that the initial charge was initially heated to the maximum
temperature, and then, at strictly defined cooling rates, brought to the lower temperature limit.
Examples of chemical reactions:
MnF2 +KF = KMnF3 (3),
AlF3• xH2O + 2KHF2+ NaHF2 = K2NaAlF6 + 3HF + xH2O (4),
CoF2 + KCl + NH4HF2 = KCoF3 + NH3+ HCl + HF (5).
Wanklin has tried many different fluxes, such as PbF2, PbCl2, KCl, KCl+NaCl,
RbCl+KCl, KF, etc, including a widely used combination of fluxes. The compositions of some
initial compositions of the charge and the obtained crystals are shown in Fig. 2.

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Fig. 2. Triangular composition diagram for the system, showing starting compositions
that produced the compound indicated: KF-KCl-FeF3 (a), KF-PbCl2-FeF3 (b), KF-PbCl2-CrF3

11
(c), KF-KCl-NiF2 (d), KF-PbCl2-NiF2 (e), - according to Ref. [112]; RbF-PbCl2-FeF3 (f) and
CsF-PbCl2-FeF3 (g) - according to Ref. [117]. With permission of the Springer Nature.
Special attention was paid to the problem of contamination of the target product. “With
chloride fluxes, the presence of cations common to flux and crystal and the large difference
between the ionic radii of Cl- and F- reduce the chance of contamination of the crystal” [111].
However, for example, crystals of BaNiF4, which have been grown from BaCl2 as flux,
contained 6% Cl [118].
While alkali metal fluoride and chloride fluxes can be easily removed by washing with
water, the use of lead fluxes presented a number of disadvantages. The attempt to use PbF2 flux
for preparation of AlF3 crystal leads to the formation of Pb3Al2F12 [113]. The addition of lead
chloride prevented the formation of this by-product, and allowed the growth of AlF3 crystals up
to 2 mm3. However, due to the high density of lead fluxes, fluoride crystals formed float on the

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surface, and fluxes in this case can’t play the same role as in metallurgy – namely, to protect the
product from interaction with the atmosphere. In addition, the separation of the grown crystals

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presented considerable difficulties. “The crystals were separated from the flux by soaking of the
broken-up melt in water for several days, and finally cleaned by heating in dilute HNO 3 for a few
-p
minutes.” [113]. Halides of lead are characterized by a high volatility of the melt and toxicity
[62].
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Conducting syntheses under air (in Pt crucibles) required the use of fluorinating agents to
prevent pyrohydrolysis. This was carried out by introducing alkali metals into the initial reaction
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mixture in the form of hydrofluorides (KHF2, NaHF2), or addition of ammonium fluoride NH4F
or ammonium bifluoride NH4HF2. This compound is an effective scavenger of charge from
oxygen contamination:
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NH4HF2 + MO = MF2 + NH3+ H2O . (6)

It is necessary to note the high temperatures of the synthesis, which is accompanied by
the release of toxic and corrosive gases.
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In addition to synthesis under the air Wanklin et al. developed special equipment
allowing to carry out the flux growth process under inert gas flow (nitrogen) or reducing
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conditions, see Fig. 3. This made it possible to replace platinum crucibles with crucibles made of
nickel, iron, molybdenum and graphite.

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 (a)

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(b)

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Fig. 3. Controlled atmosphere furnaces for flux growth of fluorides: (a) [114], (b) [115].

Leckebush and Recker [121], Desai and John [122], and Glikin [123] have completed a
large cycle of works on research of crystallization of fluorite from a variety of fluxes, paying
particular attention to the morphology of the resulting crystals.

13
 4. Molten Salt Synthesis of Inorganic Fluorides
Molten salt synthesis (MSS) represents an additional group of synthetic techniques [153].
MSS is focused on obtaining powders, usually as a result of a chemical reaction. This process
uses a molten salt as a solvent for the constituent compounds (e.g., reactants). MSS
has been used extensively to prepare oxides powders [ 153]. Molten salt synthesis of
fluorides includes the interaction of metal ions with fluoride ions in the liquid phase, namely in
the melt of inorganic salts. Thus, a fluorinating agent must be entered into the initial load.
The flux in these syntheses is subject to the above requirements, and the requirements for
flux washing are more stringent than in Flux Growth. Accordingly, low-soluble fluoride and lead
chloride are of little use for these purposes.
Sodium fluoride can be considered as one of the most promising MSS materials due to its

of
sufficient water solubility and relatively low melting point (994°С). The advantage of this flux is
that NaF (as well as KF) practically does not hydrolyze in moist air up to 1000°C [154], but is

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highly soluble in water. These fluorides are also successfully used as fluorinating agents in MSS
[53, 110, 121-126, 133-136, 138-141, 146-147, 149-151].
-p
K. Teshima et al. [127] used an excess of NaF as a solo flux for synthesizing up-
conversion NaYF4:Yb, Er powders. As starting materials, a mixture of fluorides NaF, YF3, YbF3,
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ErF3 was taken, heated to 1100C and after cooling the excess flux was washed with water. The
use of the NaF-KF mixture as a solvent reduced the synthesis temperature to 800C.
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However, sodium and potassium fluorides, as well as fluorides of other alkali metals
easily forms numerous phases with the other fluorides, like in the NaF-BaF2-GdF3 system [87,
155], which increases the risk of obtaining side-product phases. Sodium fluoride can also
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partially dissolve in the fluorite matrix structure, contaminating them [125].

As for other fluoride solvents, Hoppe [156] used the exotic but very toxic thallium
fluoride (Tmelt ~ 320°С) as a flux for the synthesis of fluorides such as Ba3In2F12, Sr2InF7, TlZrF5,
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Ba5Mn3F9.
As mentioned above, highly reactive NH4HF2 is often used as a fluorinating agent to
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prevent pyrohydrolysis. However, in some cases, this compound can also play the role of the
flux itself. Ammonium bifluoride melts at 126.5°C and decomposes at normal pressure at ~
238°C, i.e. has a narrow region of liquid state. However, with the decomposition product –
ammonium fluoride –forms a eutectic with a melting temperature of 109С. Table 1 shows
numerous examples of syntheses involving ammonium fluoride. With metal oxides in most
cases, the interaction begins below 100С, accompanied by the release of heat and rapid gas
evolution (see Figs. 4, 5). Reactions are carried out in a platinum dish. At the temperature where
the liquid phase exists , as a rule, complex fluorometallates are formed (Table.1), which at higher
14
temperatures decompose to form the corresponding fluorides. The following reaction equations
are proposed for the processes of interaction with alkali-earth metal oxides [130]:
Ca(Sr)O +2NH4HF2 = Ca(Sr)F2 + 2NH4F+ H2O (25-140 C), (7)
2NH4F = NH4HF2 + NH3 (170-180 C), (8)
Ca(Sr)O +NH4HF2 = Ca(Sr)F2 + NH3+ H2O (180-250 C), (9)
BaO +NH4HF2 = BaF2 + NH3+ H2O (25 -140 C). (10)

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Fig. 4. Thermogram of MgF2 formation from mixture of MgO + NH4HF2 [157].
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Fig. 5. Thermograms of MF2 formation from 1:1 mixture of MO + NH4HF2 (a) M = Ca,
(b) M = Sr, (c) M = Ba [158].

Interaction with carbonates of alkaline earth metals occurs more quietly than with oxides
[130]. Nitrates [131] and chlorides [132] were also used as precursors for the synthesis of
fluorides in interaction with NH4HF2.

15
 Water-soluble chlorides are of interest as a medium for the synthesis of fluorides [121-
124]. M. Ding et al. [133, 135] used a melt of potassium and sodium chlorides as a solvent to
produce β-NaYF4:Yb3+,Er3+/Tm3+ particles. Sodium fluoride was used as a fluorinating agent.
LnCl3•6H2O, NaF, NaCl, KCl, which were used in molar Ratios of 1:6:25:25 (Y:Yb:Er = 78:20:2
or Y:Yb:Tm = 79.5:20:0.5), were mixed with ethanol in an agate mortar and ground for 15
minutes. The mixture was transferred to a crucible, which was installed in an electric furnace,
heated to 800°C at a rate of 10°C/min and left for 2 hours under the air. The samples were cooled
at a rate of 100°C/hour to 100°C. After cooling to room temperature inside the furnace, the
samples were washed with hot deionized water three times and dried at 60°C for 24 hours. A
similar technique was used by the same authors to obtain YF3:Yb3+/Ln3+ (Ln = Er3+, Tm3+) [134].
Note that the high temperature to which the melt was heated under air can lead to partial

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hydrolysis due to the presence of water from the crystallohydrate salt precursors.
Fedorov et al. [125-126] prepared CaF2 and SrF2 utilizing as fluxes water soluble calcium

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and strontium chlorides, respectively. The contamination of the calcium fluoride by sodium
impurity by the reaction:
(1-x)CaCl2 + (2-x)NaF = Ca1-xNaxF2-x↓ + (2-2x)NaCl ,
-p (11)
was discovered. In the case of strontium fluoride, no contamination was observed with
both sodium fluoride and potassium fluoride as fluorinating agents.
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Note also that Courbion et al. synthesized KGaF4 from exotic 3KCl:ZnCl2 molten
solution [159].
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Although nitrate melts is known as a medium for the MSS synthesis [160], apparently,
Batsanova et al. [136,161] was the first to discover the possibility of using them for the synthesis
of inorganic fluorides. Bengtson, Frostemark et al considered the thermodynamics of fluorides
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formation in molten nitrate media [162,163]. Later nitrate melts were implemented again for
preparing luminophore powders.
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Mixtures of KNO3, NaNO3, LiNO3 are actively used by researchers in their work, and the
ratio of components varies significantly [149]. A typical synthetic procedure is described in
[138]. Powders of Y(NO3)3, NaF, NaNO3, KNO3 mol. the ratio of 1:4:50:25 was ground for 30
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minutes with ethanol in an agate mortar. Then, this mixture was transferred to the crucible and
heated to 350°C, while different experiments utilized different heating times. The samples were
washed with deionized water and then dried at 100°C. A similar procedure was used for the
synthesis of both up-conversion and down-conversion luminophores: NaYF4: 5% Eu3+, NaYF4:
5% Tb3+ [141], NaYF4: 20% Yb3+, 2% Er3+, NaYF4: 20% Yb3+, 0.5% Tm3+ [142], β-NaYF4:Tb3+
[146]. LiF was used as a fluorinating agent for synthesis of LiYF4:Yb3+/Ln3+ (Ln = Er, Tm, Ho)
[142] and LiYF4:Yb3+,Er3+/Tm3+/Ho3+ [145].

16
 An interesting option is to obtain down-conversion particles LaF3:Eu3+, which was used
by Tian et al. [137]. In it, the nitrate melt was prepared separately, and the fluorinating agent
NH4F, lanthanum nitrate and Eu2O3 were introduced directly into the melt, after which the
mixture was kept for 1 hour at a temperature of 350°C.
The mixture of 53 wt% of KNO3, 7 wt% NaNO3 and 40 wt% NaNO2, which is known as
HITEC, has the melting temperature as low as 142С. Ha et al. prepared CaF2 microspheres by
thermal decomposition of trifluoroacetate precursor in molten HITEC salt medium [152]. It was
found that the temperature of trifluoroacetate decomposition decreased to 250°C due to reactions
in the ionic melt.
Another solvent used by researchers is NH4NO3 [143,147]. However, when trying to
synthesize the phase BaGdF5:Ce3+/Er3+/Yb3+ [148] at low temperatures, the second phase

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NH4Gd2F7, appears, precisely because of the use of NH4NO3 as a flux. Note that the connection
“BaGdF5” does not exist. In the corresponding area of the phase diagram, a phase of variable

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composition is formed on the basis of the Ba4Gd3F17 [42] compound. Huang et al. [143] obtained
up-conversion particles NaYF4:Er3+:Yb3+ by MSS method from the melt of NaNO3-NH4NO3
mixture. -p
Sodium nitrate has a beneficial advantage over KNO3-NaNO3 mixtures, as it reduces the
possibility of adding additional impurities to the product. The synthesis temperature differs
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slightly [139]. Hu et al has received scandium fluoride at 310°C and a 30-minute exposure of the
furnace in [144]. The fluorinating agent was NH4HF2, and NaNO3 was taken as the solvent. The
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researchers compared the samples obtained using NaNO3 and without it; the data suggest that in
the synthesis without the use of NaNO3 there is a second phase with a conditional composition of
ScF2.76.
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Fedorov et al. [150-151] repeated the syntheses of Batsanova et al. [136,161]. A series of
phases NaLnF4 (Ln = Pr-Lu, Y) were synthesized from the sodium nitrate melt (Fig. 6). For
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lanthanum LaF3 was synthesized, in the case of cerium a mixture of phases was formed. The
samples of the corresponding reagents were mixed in an agate mortar and then transferred to
glazed crucibles and covered with a lid. The temperature in the furnace varied from 300-435°C.
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The holding time and the heating rate were 1 hour and 10°C/min, respectively. After natural
cooling in the furnace, the samples were removed from the crucible into a polypropylene reactor
and washed with doubly-distilled water to remove the solvent and the non-reacted fluorinating
agent. After washing, the powders were air-dried at 40°C. To obtain the phases of NaLnF4, it is
necessary to introduce an excess of sodium fluoride, which corresponds to the data [135, 141], as
well as the results of the synthesis of these phases by co-precipitation from aqueous solutions
[70].

17
 In addition, Fedorov et al. synthesized CaF2 and SrF2 [150]. Note that the SrF2
microparticles had good faceting in the form of a rhombic dodecahedron and a cube, while under
the same conditions, amorphous CaF2 particles of smaller size were obtained (Fig. 6c, 6d).

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Fig. 6. SEM images of fluoride particles, prepared in NaNO3 flux. (a) LaF3 [151], (b)
NaGdF4, (c) CaF2 [151], (d) SrF2 [151].
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It should be noted that nitrates of rare earth elements form crystallohydrates with water.
Table 1 shows some nitrates of rare earth elements without crystallohydrate water, in these
works the authors dissolved the initial compounds in alcohol, which was then removed by
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vacuum distillation.
The МSS technique used for the synthesis of not only powders, but also crystal layers
[140]. First, mixed paste of solute (NaF, YF3 and dopants) were coated onto the glass substrate,
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and then flux pastes (NaNO3 or NaNO3+ NaF) were coated onto the solute layer. Then raw
material-coated substrates were heated at 350-400°C. To remove the remaining flux, the crystal
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layers were washed with warm water.

Oxide glasses can also be considered as a kind of flux, as well, for fluorides nanoparticles
[22,164-166]. Thus, for example, such phases as PbxCd1-xF2 [22], Ba4Ln3F17 [164], KLaF4 [165],
KGd3F10 [166] etc., can be synthesized. Nanofluorides particles can be obtained from
oxyfluoride glass ceramics by dissolution of the silicate matrix in hydrofluoric acid [22].
Another example of the use of exotic type fluxes: orthorhombic single CaF2 crystal
polymorph has been grown under high pressure from molten Ca(OH)2 flux [167].
The properties of some fluxes used for fluoride synthesis are summarized in the Table 2.
18
Table 2. — Fluxes.

Substances Тmelting, °C The possibility of Toxicity

water flushing
NaF 992 + –
KF 856 + –
NaF – KF (eutectics) 721 + –
PbF2 824 – +
NH4HF2 126 (238*) + +
NaCl 800 + –
KCl 774 + –
RbCl 726 + –

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CsCl 646 + +
NaCl – KCl 665 + –
–

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PbCl2 496 +
NaNO3 308 (500*) + –
KNO3 337 -p + –
NaNO3 – KNO3 223 + –

LiNO3 – NaNO3 (eutectics) 195 + –

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LiNO3 – KNO3 (eutectics) 125 + –
LiNO3 – NaNO3 – KNO3 120 + –
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(eutectics)
KNO3– NaNO3 – NaNO2 142 + -
NH4NO3 169 (210*) + +
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* – Temperature of decomposition

5. Ionic Liquid Synthesis of Inorganic Fluorides

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Ionic Liquid (IL) is a common name for organic compounds of ionic nature that are in a
liquid state at temperatures below 100°C. These compounds consist of a large asymmetric
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organic cation and an organic or inorganic anion. Due to their structure, they can be used as
solvents for organic and inorganic substances [1, 168].
For the synthetic chemistry, ILs can play several roles: solvent, template, reactant, and
surfactant. First of all, ILs are used as a medium in which fluoride ions interact with metal ions.
To increase the solubility of the reagents, binary mixtures IL with alcohols (ethanol and
methanol) are used. However, the ILs themselves can also serve as a source of fluorine. Note

19
that the role of the fluorinating agent IL can perform only in the presence of water in the reaction
mixture, ensuring the flow of the hydrolysis reaction of IL:
BF4- + 3H2O → H3BO3 + 3HF + F-. (12)
This leads to the use in the ILs synthesis of inorganic fluorides initial crystallohydrates
(e.g. Ln(NO3)3·6H2O ), or syntheses in aqueous solutions.
Ionic liquids are used in the two-phase synthesis technique, in which chemical reactions
of the formation of an insoluble fluoride phase occur at the interface. The ethylene glycol
(EG)/1-octyl-3-metylimidazolium hexafluorophosphate ([C8mim]PF6) is the example of such
system [169]. Aggregation of some ILs in aqueous solutions leads to formation of
microemulsions, which were also used for the synthesis of nanofluorides [168]. Microwave
heating of Teflon vessels is the most efficient and simple synthetic procedure.

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Table 3 shows the most commonly used IL and their role in synthesis.
Table 3. — Ionic liquids and their application purposes.

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Name of IL Abbreviation Role in the synthesis References
1-butyl-3- [Bmim][BF4], Medium and [170-197]
methylimidazolium [C4mim][BF4] fluorinating agent
tetrafluoroborate
1-butyl-3-
methylimidazolium
[Bmim][PF6],
[C4mim][PF6]
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Medium (template)
and fluorinating
[172, 181, 198-205]
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hexafluorophosphate agent
1-octyl-3- [Omim][BF4], Fluorinating agent [184, 199, 206-207]
methylimidazolium [C8mim][BF4]
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tetrafluoroborate
1-octyl-3- [Omim][PF6], Medium and [169, 199, 206, 208-209]
methylimidazolium [C8mim][PF6] fluorinating agent
hexafluorophosphate
1-ethyl-3- [Emim][BF4] Fluorinating agent [184]
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methylimidazolium
tetrafluoroborate
However, the choice of IL is not limited to the use of the above compounds only. Thus,
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Wang et al. [210] prepared YF3:Eu3+ using diallyldimethylammonium tetrafluoroborate

([DADMA]BF4), which was obtained from the chloride precursor of this organic salt by
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fluorination with sodium tetrafluoroborate. Based on their presented excitation and absorption
spectra for YF3:Eu3+ samples, produced using NaF, NaBF4, or [DADMA]BF4 as fluorinating
agents for comparison, it can be concluded that there is no significant difference between these
fluorinating agents. This calls into question the expediency of using a difficult-to-obtain organic
analogue of inorganic fluorinating agents.
In his work, Lorbeer C. et al. [211] studied the influence of organic IL cations on the
luminescent properties of europium fluoride. Tetrafluoroborate [BF4]- was selected as the
inorganic anion of the IL. Wide halos are visible on the X-ray diffraction patterns. Particle sizes,

20
calculated from the Scherrer equation, ranged from 3.8 to 8.2 nm for various cations, including
C4mim, C4mpyr, C4py, C6py, P44414, P66614 and choline.
In another work, the same group of researchers [212] used [choline][BF4] in the first
stage of preparation of GdF3:Eu particles coated with GdPO4. Synthesis was carried out by the
following method: 100 mg of GdOAc3•4H2O and 4.5 mg of EuOAc3•H2O were dissolved in 2 ml
of ethylene glycol. The solution was then added to 0.3 g [choline][BF4] and kept in the
microwave furnace for 10 minutes at 120°C. In the second stage, a phosphate coating was
created. 100 mg of GdOAc3•4H2O in ethylene glycol and 0.1 g [choline][H2PO4] were added to
the reaction mixture. Re-maintained in a microwave oven, but at a different temperature –
140°C. The resulting colloidal solution was centrifuged. The precipitate was washed several
times with dichloromethane-ethanol mixture and dried at 70°C. It is obvious that in this case IL

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is used as a source of fluoride ions.
Kuzmanoski et al. [207] used for preparation of CaF2:Pr3+, Mn2+ two IL, different in

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composition and purpose. A mixture of a fluorine source [Omim][BF4] and a medium for the
behavior of the tributylmethylammonium bis(trifluoromethanesulfonyl)imid
-p
[Bu3MeN][N(SO2CF3)2] was obtained in a microwave at 100°C and then added to a solution of
calcium, praseodymium and manganese chlorides in ethanol. After holding at 200°C for 20
minutes in the microwave, a suspension was obtained, in which ethanol was again added to
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reduce the viscosity of IL. Precipitates were centrifuged and air dried at 60°C.
Hydrothermal synthesis is one of the most common synthesis techniques using IL. So it
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was used by Zhang et al. [175]. First, there was obtained an aqueous solution of the nitrates of
the REE, then to it was added [Bmim][BF4] and stirred for 2 hours. The resulting mixture was
loaded into a Teflon autoclave for 12 hours at 180°C. Products of the reaction were filtered,
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washed with ethanol and deionized water. The precipitate was dried for 6 hours at 80°C. In some
works, a variation of this synthesis is used, in which the mixture subjected to microwave
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irradiation [170, 174, 182, 213]. Classical heating in an autoclave is found in [210, 214].
An analog of hydrothermal synthesis, using organic solvents instead of water, is called
solvothermal synthesis. In this case, IL is most often used as a fluorinating agent. Nuñez et al.
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[173] used this method. A fixed amount of Ln3+ acetates was dissolved in EG or DEG by heating
to 100°C and stirring. Then, IL was added and the mixture was transferred to closed tubes for 15
hours at different temperatures then centrifugation was performed. The precipitate was washed
twice with ethanol and once with doubly-distilled water, dried at 50°C. The additional thermal
treatment of the samples was used also.
Bartunek et al. proposed their own method of obtaining cerium fluoride [202]. The
experiment was performed in sealed Teflon tubes, in which holes were made, and the tubes were

21
placed in silica gel. First, 0.1 g CeO2 and 10 ml BmimPF6 were placed in a tube in an oven for
90 minutes at 200°C. After cooling, the samples were washed with methanol and distilled water,
and then dried in air. According to the same procedure, KErF4 [203], LaF3 [198], and other REE
fluorides [201] were obtained.
The synthesis of nanoparticles at the two-phase interface of a ethylene glycol-IL system
is also described. Chao Zhang et al. [199] prepared the EG/[C8mim][PF6] system to perform the
precipitation reaction of NaYF4 nanoparticles at the interface of these two phases. REE nitrates
and sodium nitrate were first dissolved in EG, which is the upper phase, while the lower phase is
the IL. The system was maintained for 24 hours at 80°C. The same idea is used in other works
[177, 204, 209, 215].
The original technique using ultrasound is presented in [192]. In it, Tb4O7 was dissolved

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in 10% nitric acid and then mixed with an aqueous solution of Ce(NO3)3 (18 ml, 3.60 mmol) in a
polytetrafluoroethylene dishes. Stirred for 5 minutes, and then added drop by drop 2 ml

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[Bmim][BF4]. The homogenized solution was exposed to ultrasound for 2 hours. After that, the
precipitate was centrifuged at 9000 rpm, washed with deionized water and ethanol twice, and
then dried at 70°C for 12 hours. -p
It is described the preparation of set of fluoride compounds using IL (Table 4).
LaF3 was synthesized by several groups of researchers. [Bmim][BF4] and EDTA
re
disodium salt were added to the solution of REE nitrates, which made it possible to obtain
particles of LaF3:Ce15%,Tb5% size of 17-20 nm [176], because the EDTA protects the nuclei by
lP

shell and slows their growth. Disodium EDTA was added to the [Bmim][BF4] solution of the of
the REE nitrates.
Preparation of YF3:Eu3+, YF3:Tb3+ [171] was carried out in ethylene glycol with the
na

addition of [Bmim][BF4] at 120°C and 15 hours of holding time. Zhong et al. [172] to obtain
YF3:Eu3+ used distilled water as a solvent. Orthorhombic YF3 was obtained in studies [173, 203].
ur

The choice of matrix for doping is not limited to rare-earth fluorides. Xu et al. [185]
prepared fluorides of some alkaline earth elements. As the precursors, of alkaline earth element
hydrates nitrates of were selected. In this work, the effect of NaH2PO4•2H2O on particle
Jo

morphology was investigated. In a typical synthesis, tis as follows: 0.236 g Ca(NO3)2•4H2O and
0.156 g NaH2PO4•2H2O, which were dissolved in 35 ml of deionized water, and then added to
this mixture 2 ml of ionic liquid – [Bmim][BF4]. After that, the solution was transferred to a
Teflon autoclave, heated to 120°C and held for 10 minutes. Magnesium fluoride was obtained by
a similar procedure. The weight of the sample Mg(NO3)2•6H2O is 0.256 g, the synthetic
conditions are as follows: 150°C, 30 minutes. To obtain strontium fluoride, 0.211 g

22
Sr(NO3)2•4H2O was taken, in this case the synthesis conditions are the same as in the preparation
of calcium fluoride.
Song et al. [206] managed to introduce into the crystal lattice of calcium fluoride 0.01 M
Ce3+ and 0.002 M Mn2+. The precursor for CaF2 was four aqueous calcium nitrate, which was
dissolved in absolute ethyl alcohol and added [Omim][PF6] or [Omim][BF4]. After 30 minutes of
intensive mixing, the solution was transferred to a Teflon dish and placed in an autoclave for 24
hours at a temperature of 140°C. After natural cooling to room temperature, the precipitate was
centrifuged and washed with ethanol, followed by drying at 60°C for 12 hours.
Table 4 — Materials prepared by methods using IL
Substance Precursors Synthesis method Ref.
MgF2, CaF2, SrF2 M(NO3)2•xH2O Initial reagents were dissolved in [185]
(M=Mg, Ca, Sr), deionized water, and IL was added.
NaH2PO4•2H2O

of
Solution was transferred into Teflon
autoclave and microwave-heated to
120°C (150°C).
CaF2:Ce3+/Mn2+ Ca(NO3)2•4H2O,

ro
Initial reagents were dissolved in [206]
Mn(CH3COO)2•H2O, absolute ethanol, and IL was added.
Ce(NO3)3•6H2O Solution mixture was transferred into
Teflon bottle held in a stainless steel

3+
CaF2:Ln (Ln =
Er, Yb, Eu, Tb)
Ca(NO3)2 (aq.) and
-p
autoclave and maintained at 140°C.
Inital reagents were mixed with IL, and
Ln(NO3)3 (aq.), (Ln = EDTA-Na2 were added. Solution was put
[188]
re
Er, Yb, Eu, Tb) into Teflon-lined stainless steel autoclave
and heated at 180°C.
3+
CaF2:Yb /Er 3+ Er(NO3)3 (aq.), Inital reagents were dissolved in [194]
lP

Yb(NO3)3 (aq.), deionized water and then ethylene glycol

CaCl2•2H2O and IL were added into solution. The
resulting solution was transferred into
autoclave and microwave heated at
150°C.
na

CaF2:Pr, CaF2:Mn, CaCl2, MnCl2•H2O, Microwave-assisted synthesis was [207]

CaF2:Pr, Mn PrCl3•H2O performed in ionic liquids under argon
atmosphere. Two solutions were
prepared, first consisted of initial
ur

reagents dissolved in ethanol, second

consisted of IL and fluoride precursor.
Solutions were mixed and heated to
Jo

100°C.
SrF2 Sr(NO3)2 IL solvent and metal precursor nitrate [174]
salts were heated in microwave oven
(2.45 GHz, 900 W).
3+
BaF2:Eu , Gd 3+ A(CH3COO) (A = Li, Precursor salts of alkali-earth and rare- [182],
CaF2:Eu3+, Gd3+ Na, K), M(CH3COO)2 earth elements were dissolved in [186]
SrF2:Eu3+, Gd3+ (M = Ba, Sr), ethylene glycol and mixed with IL.
+
BaF2:M , Gd , 3+ Ln(CH3COO)3•xH2O Resulting solution was microwave
Eu3+ (A=Li, Na, (Ln = Eu, Gd) heated to 120 – 160°C.
K)
Ba0.3Lu0.7F2.7: Ba(NO3)2, Initial reagent were dissolved in ethylene [189]

23
Nd3+ Lu(CH3COO)3•xH2O/ glycol and IL was dropwise added to
Lu(NO3)3/ solution. Mixture were heated to 120°C.
([CH3COCHC(O)
CH3]3Lu·xH2O,
Nd(NO3)3•H2O
BaLuF5:Ce, Tb, Ba(NO3)2, Lu(NO3)3, Two-phase interfacial reaction method [209]
Eu (Sm) Ln(NO3)3•xH2O (R = was applied. Initial reagents were
Ce, Tb, Eu, Sm) dissolved in ethylene glycol. IL was used
as bottom phase. System was maintained
at 160°C.
CaF2:Eu2+ CaBr2, BaBr2, EuBr2 Alkali-earth and europium(II) bromides [190]
BaF2:Eu2+ were dissolved in ethanol under argon
atmosphere. IL was added and mixture
was microwave heated to 190°C.
BaCaLu2F10:Ln3+ Ba(NO3)2, Precursors were dissolved in deionized [214]
(Ln = Eu, Dy, Tb, Ca(NO3)2•4H2O, water and mixed with IL. Resulting

of
Sm,Yb/Er, Yb/Ho) Ln(NO3)3 (aq.) solution was transferred into Teflon-
lined stainless autoclave and maintained
at 180 °C.
Y(NO3)3•xH2O

ro
YF3 IL solvent and metal precursor nitrate [174]
salts were heated in microwave oven
(2.45 GHz, 900 W).
YF3, YF3:Eu3+, (Ln(CH3COCHCOC Precursors were dissolved in ethylene
-p [171,
YF3:Tb3+, H3)3•xH2O/ glycol or ethanol. Resulting solution was 173]
YF3:Yb,Er (Ln(CH3COO)3•xH2O mixed with IL and maintained at 100–
/(Ln(NO3)3•6H2O, 140°C.
re
(Ln = Y, Eu, Er, Tb,
Yb), LnCl3•xH2O (Ln
= Y, Er, Yb)
lP

YF3:Ln3+ (Ln=Eu, Ln(NO3)3 (aq.), (Ln = Precursors were dissolved in ethylene [208]
Tb, Ce, Dy) Y, Eu, Tb, Ce, Dy) glycol. Resulting solution was mixed
with IL and maintained at 140°C.
YF3, YF3:Eu3+ Y(NO3)3•6H2O, Precursors and IL were dissolved in [172],
na

Eu(NO3)3 (aq.) distilled water. Resulting solution was [175],

poured into autoclave and maintained at [210]
120–180°C.
YF3:Yb, Er LnCl3•xH2O (Ln = Y, Precursors were mixed with NaBF4. [216]
Yb, Er) Prepared powder was introduced to
ur

melted IL. Resulting mixture was

maintained at 240°C.
LnF3 (Ln = La, Ln(NO3)3•xH2O (Ln Initial reagents were dissolved in ethanol [199]
Jo

Ce, Pr, Nd, Sm, = La, Ce, Pr, Nd, Sm, and were added to IL. Resulting solution
Eu, Er) Eu, Er) was maintained at 70°C.
LnF3, (Ln = La, Ln(oleate)3 (Ln = Y, Precursors were dissolved in oleic acid. [177],
Gd, Yb, Y) La, Gd, Yb) Solution was transferred into Teflon- [200]
lined autoclave containing IL. Two-
phase system was maintained at 240°C.
LnF3 (Ln = Y, La- Ln(NO3)3•xH2O (M = IL was added to nitrate precursor [178]
Nd, Sm-Lu) Y, La-Nd, Sm-Lu) solution. Mixture solution was
microwave heated to 150°C.
LnF3, (Ln = La, Ln(NO3)3 Initial reagents and IL were mixed and [198],
Ce, Pr, Nd, Sm, placed into PFA tubes and maintained at [201]

24
Eu, Gd, Tb, Dy, 200°C.
Ho, Er, Yb)
CeF3 CeO2 Initial reagents and IL were mixed and [202]
placed into PFA tubes and maintained at
200°C.
LaF3:Eu3+, Ln(NO3)3 (aq.) (Ln = IL was added to Gd(NO3)3 solution. [175],
LaF3:Ce3+,Tb3+ La, Ce, Tb, Eu) Mixture was placed in Teflon-lined [210]
stainless autoclave and heated at 160 –
180°C.
LaF3:Eu3+ Ln(NO3)3•xH2O (Ln Initial reagents were dissolved in ethanol [199]
= La, Eu) and were added to IL. Resulting solution
was maintained at 70°C.
LaF3:Dy3+ La(NO3)3•6H2O, Initial reagents were dissolved in ethanol [217]
Dy(NO3)3•5H2O and IL, NH4F were added afterwards.
Mixture was placed into Teflon-lined
autoclave and maintained at 200°C.

of
LaF3:Ce3+, Tb3+ Ln(NO3)3 (aq.) (Ln = IL was added to aqueous nitrate solution [176]
La, Ce, Tb) of rare-earth metals. EDTA-Na2 was
added to mixture. Resulting solution was

ro
placed in Teflon-lined stainless autoclave
and heated at 180°C.
LaF3:Dy3+, Tm3+, Ln(acetate)3•xH2O Precursors were dissolved in ethylene [170],
LaF3:Tm3+, Tb3+, (Ln = La, Tm, Dy, glycol. Solution was transferred into
-p [179]
Eu3+ Tb, Eu) glass vessel equipped with a Teflon
septum containing IL. Resulting mixture
was microwave heated to 120°C.
re
CeF3 Ce(NO3)3•xH2O Initial reagents were dissolved in ethanol [199]
and were added to IL. Resulting solution
was maintained at 70°C.
lP

CeF3:Tb3+ Ce(NO3)3•6H2O, Initial reagents were dissolved in ethanol [217]

Tb(NO3)3•5H2O and IL, NH4F were added afterwards.
Mixture was placed into Teflon-lined
autoclave and maintained at 200°C.
na

CeF3, CeF3:Tb3+ Ln(NO3)3 (aq.) (Ln = IL was added dropwise to aqueous [192]
Ce, Tb) nitrate solution of rare-earth metals.
Resulting solution was exposed to
ultrasound irradiation in ambient air.
Nd(NO3)3•5H2O
ur

NdF3 Initial reagents were dissolved in ethanol [217]

and IL, NH4F were added afterwards.
Mixture was placed into Teflon-lined
autoclave and maintained at 200°C.
Jo

EuF3 Eu(CH3COO)3•xH2O IL was added to ethylene glycol [211]

precursor solution. Mixture was
microwave heated to 120°C.
EuF3 Eu(NO3)3•6H2O IL was mixed with ethanol. Europium [183]
nitrate was added to IL-solution and
mixture was maintained in autoclave at
40 – 120°C.
GdF3, GdF3:Eu3+ Gd(NO3)3 (aq.), IL was added to Gd(NO3)3 solution. [175],
Eu(NO3)3 (aq.) Mixture was placed in Teflon-lined [210]
stainless autoclave and heated at 160 –
180°C.

25
GdF3:Eu3+ Gd(acetate)3•4H2O, Precursors were dissolved in ethylene [170],
Eu(acetate)3•3H2O glycol. IL was added and mixture was [212]
stirred until a homogenous solution was
obtained. This solution was heated in a
microwave to 120°C.
GdF3:Ce3+, Ln(NO3)3 (aq.) (Ln = IL was added to nitrate precursor [178]
(Tb3+/Eu3+/Dy3+) Ce, Eu, Gd, Tb, Dy) solution. Mixture was microwaved
at150°C.
LuF3, LuF3:Yb3+, Ln(NO3)3 (aq.) (Ln = IL was added to rare-earth nitrate [175],
Tm3+, Ho3+ Lu, Ho, Tm, Yb) solution. Mixture was placed in Teflon- [193]
lined stainless autoclave and heated at
180 °C.
PrF3, EuF3 praseodymium All experiments were carried out under [195]
amidinate, tris (2, 2, nitrogen or argon atmosphere. Precursors
6, 6-tetramethy l-3, 5- were dissolved in IL with thermally
heptanedionato) reduced graphene oxide (TRGO) and

of
europium (III) microwaved heated at 220°C with 50 W
power.
PrF3, EuF3, GdF3, PrCl3, Tris (2, 2, 6, 6- All experiments were carried out under [197]

ro
ErF3 tetramethy l-3, 5- nitrogen or argon atmosphere. Rare-earth
heptanedionato) precursors were dissolved in IL at room
europium (III), temperature and decomposed under
microwave irradiation at 230°C and a
-p
power of 50 W.
NaLnF4 (Ln = Yb, Ln (oleate)3 (Ln = Y, Precursors were dissolved in oleic acid. [177],
Y) La, Yb), sodium Solution was transferred into Teflon- [200]
re
oleate lined autoclave containing IL. Two-
phase system was maintained at 240°C.
NaYF4:Yb3+, Ln(NO3)3•6H2O (Ln Initial reagents and NaCl were added [180]
lP

Er3+/Tm3+ = Y, Yb, Er, Tm) into a beaker containing IL. Mixture was
transferred into Teflon-lined autoclave
and kept at 160°C.
NaYF4:Yb3+, Ln(NO3)3•xH2O (Ln Precursors and NaCl were dissolved in [169]
Er3+/Tm3+/Ho3+
na

= Y, Yb, Er, Tm, Ho) EG under ultrasonic conditions.

Resulting solution was added to IL to
form biphasic system and kept at 80°C.
NaYF4:Yb3+, Er3+ Ln(NO3)3•6H2O (Ln Initial reagents and NaCl were added [184]
= Y, Yb, Er) into a beaker containing ILs. Mixture
ur

was transferred into Teflon-lined

autoclave and heated at 180°C.
NaGdF4, Ln(oleate)3 (Ln = Gd, Precursors were dissolved in oleic acid. [177],
Jo

NaGdF4:Yb3+, Er3+ Yb, Er, Ho, Tm) Solution was transferred into Teflon- [200],
(Ho3+, Tm3+) lined autoclave containing IL. Two- [215]
phase system was maintained at 240°C.
NaGdF4: Er3+, Ln(CH3COO)3•xH2O Precursors and NaCl were added to IL. [191]
Tb3+ (Ln = Gd, Er, Tb) Resulting mixture was microwave heated
for 5 min at 60°C and then heated at
200°C.
NaGdF4:Eu3+ Ln(NO3)3•6H2O (Ln Initial reagents and NaCl were added [218]
= Gd, Eu) with aqueous solution of IL. To the well
stirred solution aqueous NH4F solution
was added. Mixture was stirred at room

26
 temperature or 80°C.
NaYxGdyYbzEr(1-x- Rare-earth chlorides Mixture of rare-earth chlorides and [213]
y-z)F4 NaOH was dissolved in water and IL was
added to solution. Mixture was stirred for
5 min and NH4F was added to it.
Resulting solution was placed into
microwave oven and kept at 1000 W
power for 1 min.
NaYF4, Ln(CF3COO)3 (Ln = Initial reagents were added into IL. [181]
3+ 3+
NaYF4:Yb , Er , Y, Yb, Er, Tm), Resulting solution was microwave
NaYF4:Yb3+, Tm3+ Y(CH3COO)3, heated to 200°C by two steps.
Na(CH3COO),
Na(CF3COO)
NaYF4:Eu 3+ NaCl, Initial reagents were dissolved in ethanol [217]
NaSmF4 Ln(NO3)3•xH2O (Ln and IL, NH4F were added afterwards.
NaGdF4:Eu 3+ = Y, Eu, Sm, Gd, Dy, Mixture was placed into Teflon-lined

of
NaTbF4:Ce3+ Tb, Yb, Er) autoclave and maintained at 200°C.
NaDyF4
NaErF4:Yb3+
NaYbF4:Er3+

ro
NaLuF4:Yb3+, Er3+ Ln (oleate)3 (Ln = Lu,Precursors and sodium oleate were [204]
Yb, Er) dissolved in oleic acid. Resulting
solution was transferred into Teflon-
-p
lined autoclave containing IL to form
two-phase reaction system. Ethanol
solutions of surfactants were added and
re
system was maintained at 250°C.
FeF2, CoF2, ZnF2 M(NO3)2•xH2O (M = IL solvent and metal precursor nitrate [174]
Co, Zn), salts were heated in microwave oven
lP

Fe(NO3)3•9H2O (2.45 GHz, 900 W).

FeF2, CoF2 FeCl2, CoCl2 All experiments were carried out under [195]
nitrogen or argon atmosphere. Precursors
were dissolved in IL with thermally
na

reduced graphene oxide (TRGO) and

microwave heated to 220°C with 50 W
power.
KErF4 Er(NO3)3•6H2O, KCl Initial reagents and IL were mixed and [203]
placed into PFA tubes and maintained at
ur

200°C.
A2SiF6 (A = Li, ABr (A = Li, Na, K, Alkali metal bromide and tetraethyl [205]
Na, K, Rb, Cs) Rb, Cs) orthosilicate were dissolved in ethanol-
Jo

IL mixture. Resulting solution was

microwave heated at temperature 150°C,
pressure 6 bar, 55 W power.
BaFCl, BaCl2, EuSO4 or Barium chloride was dispersed in IL [196]
BaFCl:Eu2+ EuBr2 or EuCl3 + Eu containing Eu-source under ultrasonic
conditions, power 3 W.
LaF3, LaF3:Eu3+, Ln(NO3)3•xH2O (Ln Precursors and IL were dissolved in [219]
LaF3:Tb3+ = La, Eu, Tb) distilled water. Solution was transferred
into Teflon-lined stainless steel autoclave
and maintained at 180°C.
NaGdF4:Eu3+ Ln(NO3)3 (aq.) (Ln = Water solution of NaCl and water [220]

27
 Gd, Eu) solution of precursors were added to
ethanol containing IL. Aqueous NH4F
was added to resulting solution. The
mixture was poured into Teflon-lined
autoclave and heated at 200°C.
NaGdF4:Ce3+, LnCl3•6H2O (Ln = Ethylene glycol solution of NaCl and [221]
Sm3+, Gd, Ce, Sm, Eu, Tb, precursors was placed with
NaGdF4:Ce3+, Dy) polyethyleneimine aqueous solution in
Eu3+, Teflon-lined autoclave. After addition of
NaGdF4:Ce3+, IL the autoclave was heated at 200°C.
Tb3+,
NaGdF4:Ce3+,
Dy3+
NaGdF4:Ce3+, Ln-trihalide hydrates Sodium oleate and precursors were [222]
Tb3+, (Ln = Gd, Yb, Er, added to oleic acid and octadecene. The
NaGdF4:Yb3+, Tm, Ce, Tb) mixture was heated to 150°C under

of
Er3+, argon flow to form clear solution. After
NaGdF4:Yb3+, addition of IL the solution was heated to
Tm3+ 300-310°C under argon flow.

ro
CaF2 CaCl2 (aq.) Aqueous precursor solution mixed with [223]
C8mimPF6. After 48 hours CaF2 crystals
isolated by filtration
-p
It should be noted that the washing of samples from solvent residues or ionic liquid in
different studies are carried out using different substances. Among them, acetone [174], ethanol
re
[207], their mixture [190], water of varying degrees of purification [175,189], methanol [202],
and a mixture of ethanol and dichloromethane [179]. After several washings, the mother liquor is
lP

removed by filtration or centrifugation of the precipitate. Some researchers dry samples under
vacuum [200], some under air [179], while the drying temperature ranged from 50 to 100°C.
This variety of solvents may serve as an additional factor for future experiments.
na

6. Discussion
It is worth noting that even if the temperature ranges of syntheses in ionic liquids and
ur

nitrate melts are practically overlapping, MSS and IL syntheses are essentially different synthetic
methods: MSS lacks water as a solvent (with the exception of crystallization water introduced
Jo

with precursors), so the syntheses take place in the salt media, but IL techniques systematically
utilize water and/or organic solvents as synthetic media. Nevertheless, each venue has its own
advantages and drawbacks. Thus, MSS preparations generally produce powders of micron size,
whereas IL methods generate nanopowders.
It is useful to compare ILs-syntheses with the methods of syntheses from high-boiling
organics. As well as the syntheses in the high-boiling organics, ILs-syntheses allow obtaining
isolated non-agglomerated nanoparticles. However, ILs-syntheses usually require less
sophisticated equipment. The latter also includes use of IL for preparing core-shell
28
nanostructures [212], cellulose/alkali earth metal fluoride nanocomposites [187], extremely
simple syntheses of FeF2, CoF2, ZnF2 [160], and CeF3 [199, 201-202].
MSS techniques are applicable in the wide temperature range from 150 to 800°C (see
Tables 1 and 2). Lowering the synthesis temperature results in the smaller particle size:
preparations at about 800°C produced crystals of several cubic millimeters in volume, MSS at
300-450°С gave micropowders (i.e., powders made up by particles of several micrometers in
their sizes), and manufacturing of “BaGdF5” at 150°C resulted in a sample with 30 nm
nanoparticles [148].
Increasing the synthetic temperatures also accelerates hydrolysis of fluorides. For
example, elevation of preparation temperature from 400 to 500°C in NaNO 3 flux caused the
product contamination with Y7O6F9 impurity as a result of NaYF4 partial pyrohydrolysis [139].

of
Similar effect has been observed for the preparation of NaYF4 film in NaNO3 flux as a result of
the temperature elevation from 350 to 400°C [140]. The attempted synthesis of NaBiF4 from

ro
hydrated precursor in nitrate melt at 350°C produced oxofluoride phase [53], whereas the desired
NaBiF4 product was easily obtained at 160°C [147].
-p
IL syntheses may be accompanied by hydrolyses of both the target product and the
corresponding IL itself (eq. 12), e.g., Er4O3F6 oxyfluoride formation has been observed at the
attempt to synthesize “KErF4” [189]. Apparently, pyrohydrolysis should be the cause of fantastic
re
formation of the so-called “cubic YF3” [172], where the XPS spectrum of the synthesized
specimen indicates the presence of both oxygen and fluorine in the comparable amounts. It is
lP

very likely that the latter “cubic YF3” is a well-known cubic yttrium oxofluoride (cubic rare-
earth oxofluorides are widely known and have been thoroughly described in the literature [41]).
Also, a similar story has been documented for the “cubic BiF3” [53].
na

Phase formation as a result of chemical reactions usually occurs at high values of driving
forces. The latter factor usually results in the formation of the crystals according to the non-
ur

classical mechanism of cooperative agglomeration of nanoparticles when reaction occurs at the

relatively low temperatures [224-228]. Such scenarios have been observed for both MSS and
ILs-syntheses by TEM, e.g., for the self-assembly of small nanoparticles of GdF3 [212], LaF3
Jo

[201], CaF2 [185], YF3 [178], cubic [181, 169] and hexagonal [150] NaYF4 (Fig. 7). The
formation of LiLnF4 skeletal forms (MSS technique) followed by their further growth has been
observed in [142]. The lack of faceting for nano-and microcrystals can also be considered as a
sign of the processes of agglomeration of primary particles.

29
 of
ro
Fig. 7. Images of particles aggregates, testified to non-classical cooperative mechanism of
crystal formation: (a) SrF2 [126], (b) LaF3 [201], (c) and (d) NaYF4:Yb,Er [150].
-p
For NaLnF4 formation, the typical non-classical phase formation mechanism has been
documented in [141, 200]. It included the initial formation of seed crystal nanoparticles of the
re
smaller size of the metastable cubic NaLnF4 followed by the merge of these nanoparticles and
formation of the equilibrium hexagonal phase. Such transformations occurred in the
lP

precipitations from aqueous solutions as well as in IL [200] and MSS [141] syntheses. These
observations are in a full agreement with the Ostwald’s rule of stages [229]. Various
combinations of cubic and hexagonal NaLnF4 phases were obtained for ILs-syntheses [169, 184,
na

191, 204, 215], whereas MSS techniques provided stable hexagonal products due to the higher
rates of the phase formation processes [141].
ur

Reaction temperatures affect the possibility of obtaining equilibrium phases. It can be

easily illustrated for the rare earth trifluoride series, where equilibrium polymorphism and
morphotropy have been thoroughly studied [41, 42, 52, 230-234]. La-Nd trifluorides and the
Jo

higher temperature Sm, Eu, Gd trifluoride polymorphs are the hexagonal tysonite-type
structures; and Tb, Dy, Ho trifluorides along with the lower temperature Sm – Gd, Er-Lu, Y
trifluoride polymorphs are orthorhombic β-YF3-type (Pnma space symmetry group, SSG). The
higher temperature polymorphs of LnF3 (Ln = Er-Lu, Y) belong to the α-YF3 (α-UO3)-type
structures, but they could not be quenched down to the room temperature [235-236]. It is known
[230, 231, 237] that the tysonite structure of the rare earth trifluorides can be stabilized by the
introduction of anionic vacancies in their crystal lattices. This can be done either by oxygen

30
admixture or by substitution of the rare earth ions by divalent metals. Thus, the formation of
both intrinsic and doped La-Nd trifluorides is a natural process, for they do not exhibit the other
type polymorphs [174, 199, 201]. The verification of the space symmetry group (SSG) of the
corresponding nanoparticles is of interest. It is the other rare earth trifluoride nanoparticles that
should be verified. It is worth noting that the frequent appearance non-equilibrium tysonite
modifications of the corresponding rare earth fluorides for dimorphic SmF3 [178, 199, 201],
EuF3 [199, 211], as well as mixtures of equilibrium and non-equilibrium phases for EuF3 [171]
and GdF3 [170, 201] in the IL-synthesized trifluoride specimens (phase transitions temperatures
for SmF3, EuF3, GdF3 are 480, 852, 1065 °C, respectively [233]). EuF3 [178] and GdF3 [175,
178] may also be crystallized as the stable orthorhombic phases.
The addition of ethanol to the Eu(NO3)3 and [Bmim]BF4 reaction mixture may have

of
caused transition from the stable orthorhombic EuF3 polymorph to the non-equilibrium
hexagonal form [183].

ro
In the case of the synthesis of functional materials, the formation of non-equilibrium
polymorphs can be accompanied by the transformation of the latter to the equilibrium state with
-p
the evolution of a significant amount of energy (e.g., as a heat) and changes in the physical and
chemical properties of such materials in the course of their utilization [238], and, thus, shall be
considered and controlled properly when such materials are in use. Such caution can be omitted
re
for rare earth trifluorides of yttrium subgroup, for they always form stable orthorhombic low-
temperature β-YF3–type (Pnma SGG) polymorphs [175, 201, 213], and high-temperature α-YF3
lP

polymorph formation has hardly been observed.

MSS syntheses at or above 300°C allow one to obtain equilibrium phases. This opens up
great opportunities for refining the low-temperature regions of the phase diagrams of fluoride
na

systems, as well as for obtaining low-temperature ordered phases, such as rhombohedral

Ba4Ln3F17, tetragonal M2LnF7, rhombohedral Ca13Ln6F44, rhombohedral M8Ln5F31, etc. (see, for
ur

example [42, 239, 240]), many of which have yet to be studied as functional materials. Also, the
series of unidentified ordered fluorite-type phases have been obtained at the attempted
BaCaLu2F10:Ln preparations [214]. However, the syntheses in IL, apparently, led systematically
Jo

to the formation of non-equilibrium phases.

Note that the fluoride flux of complex chemical composition was used to determine the
low-temperature pattern of phase equilibria in refractory oxide systems [241].
There is a serious problem regarding identification of the phases obtained by lower
temperature syntheses. A significant majority of the corresponding publications lack chemical
analysis for the formed phases, and phase identification is based solely by comparison of the
obtained X-ray powder diffraction data with the existing database records for the known powder

31
materials (the value of the chemical analysis data for the multi-phase specimens, of course, is a
separate problem, and the use of such data unequivocally has its own limitations and
applicability). As a result, there is a wide-spread tendency to assign the certain stoichiometric
chemical formulas to the nonstoichiometric phases of variable compositions for the synthesized
samples. One of the most striking examples is the case of so-called “NaLnF4” compounds: we
are using the latter label because of its common application [151]. Cubic “α-NaLnF4” are
actually fluorite-type Na0.5-xLn0.5+xF2+2x solid solutions. For example, according to the NaF-LuF3
system phase diagram [242], the area of homogeneity of the Na0.5-xLu0.5+xF2+2x phase is about 44
- 65 mol% LuF3, and the area of homogeneity of the Na0.5-xY0.5+xF2+2x phase is about 47–64
mol% YF3 for the NaF-YF3 system [87, 100], respectively (Fig. 1c). The Na0.5-xLn0.5+xF2+2x
phases contain Ln6F36 clusters [243-244], i.e., the same clusters as in M1-xLnxF2+x solid solutions

of
and cubic KY3F10 crystals (the latter comprises aforementioned Ln6F36 clusters in an orderly
manner). Hexagonal “β-NaLnF4” phases are actually solid solutions based on the unstable LnF3

ro
polymorphs (UCl3-type structure) of general Ln2-xNa3xF6 formulas. Areas of homogeneities of
Ln2-xNa3xF6 phases are more narrow than those of the fluorite-type phases in the corresponding
-p
systems, but in the NaF-GdF3 system, the area of homogeneity is about 52-56 mol% GdF3 [99],
even if the corresponding lattice parameters exhibit significant value changes when solid
solution composition changes.
re
We are unaware about publications disclosing influence of Na:Ln on the luminescent
spectral properties of the “NaLnF4”-type phases. However, because nanoparticles of almost
lP

stoichiometric compositions like aluminoyttrium garnet (YAG), synthesized at the lower

temperatures, can undergo transformations to the variable composition phases with wide areas of
homogeneity [245] it could be quite interesting to check stoichiometry of the synthesized LiLnF4
na

[142, 145] powders.

Almost completely absent in the literature are reports of analyses of such anionic
ur

admixtures as oxygen.
We think that this is wrong that authors of the publications do not calculate lattice
parameters for the obtained phases when they present their X-ray diffraction patterns as figures
Jo

only and just refer their readers to the corresponding database entries for the polycrystalline
specimens. This is a very questionable venue, especially, in light of the aforementioned
databases containing several outdated entries related to incorrect experimental results and/or
erroneous data interpretations such as BaGdF5, JCPDS card # 24-0098; Na5Y9F32 JCPDS cards #
27-1428, 30-1263 etc. Using these data, authors [148] mistakenly reported “BaCeF5” synthesis
making an analogy with non-existent BaGdF5 compound.

32
 In some cases, when the aforementioned crystal lattice parameters have been calculated,
analysis of the obtained values is omitted despite the opportunity to extract from them a plethora
of important information. Correlations between said lattice parameters and the compositions of
the corresponding fluorite-type solid solutions are widely known [42]. Use of the general
equation [246], which includes ionic radii of cations, allows calculation of the lattice parameters
of the M1-xLnxF2+x solid solutions within ± 0.005 Å accuracy for the multicomponent specimens:
a = 2.2975 +2.502r2 + [2.480(r3 – r2) + 0.794r2–2.094]x Å , (13)
where r2 and r3 are the crystal radii (CR) of M2+ and Ln3+ cations according to Shannon
system [247] for coordination number 8. Similar equation is known for Na0.5-xLn0.5+xF2+2x cubic
phases [248]:
a = 4.454 + 0.874r3 + (6.7238r3 – 7.259)x Å. (14)

of
For example, authors [186] reported crystal lattice parameters for the samples of BaF2-
15%LaF3 and CaF2-15%LaF3 nominal compositions (a = 6.131 and a = 5.501 Å, respectively).

ro
According to the above equation (13), compositions of these specimens should be
Ba0.79La0.21F2.21 and Ca0.94La0.06F2.06, respectively, i.e., quite different from nominal ones BaF2-
-p
15%LaF3 and CaF2-15%LaF3. Attempts to introduce 15% NaF in BaF2 and CaF2 crystal lattices
[186] did not cause any significant changes in the unit cell parameters of the intrinsic difluorides
and, thus, nominal compositions did not reflect reality: studying phase formation in the CaF2-
re
NaF system [125] revealed the very low solubility of NaF in CaF2.
It should be noted that the use of low-temperature fluxes allows to conduct crystallization
lP

processes in a stable mode, as opposed to high-temperature growth from melts [249].

Conclusions
na

The potential of MSS and ILs synthesis methods are very bright and there are broad
opportunities for their use, both for obtaining functional fluoride materials and for fundamental
ur

research. Synthesized powders can be utilized as efficient luminescent materials, including

phosphors for white light emitting diodes, up- and down conversion materials, fluoride cathode
materials for lithium batteries with cations of variable valence, etc. [195]. Low-temperature
Jo

syntheses in nitrate fluxes allow potential access to easily hydrolyzed fluorides, such as InF3,
GaF3, ZrF4, etc.
Acknowledgements
Authors thank S.V. Kuznetsov, M.N. Mayakova and I.V. Morozov for valuable
discussion of the presented materials, А.Е. Baranchikov for electron microscopy experiments,
A.I. Popov and R. Simoneaux for his help in preparation of the present paper. This work was
partially supported by Russian Foundation for Basic Research grant number 18-29-12050 mk.

33
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