Applied Spectroscopy Reviews

ISSN: 0570-4928 (Print) 1520-569X (Online) Journal homepage: http://www.tandfonline.com/loi/laps20

Nanophosphors synthesized by the water

assisted solid state reaction (WASSR) method:
Luminescence properties and reaction mechanism
of the WASSR method

Sun Woog Kim, Takuya Hasegawa, Mizuki Watanabe, Masaru Muto, Toshiya
Terashima, Yusuke Abe, Tatsuro Kaneko, Ayano Toda, Tadashi Ishigaki,
Kazuyoshi Uematsu, Kenji Toda, Mineo Sato, Emiko Kawakami, Junko Koide,
Masako Toda, Yoshiaki Kudo, Takaki Masaki & Dae Ho Yoon

To cite this article: Sun Woog Kim, Takuya Hasegawa, Mizuki Watanabe, Masaru Muto, Toshiya
Terashima, Yusuke Abe, Tatsuro Kaneko, Ayano Toda, Tadashi Ishigaki, Kazuyoshi Uematsu,
Kenji Toda, Mineo Sato, Emiko Kawakami, Junko Koide, Masako Toda, Yoshiaki Kudo, Takaki
Masaki & Dae Ho Yoon (2017): Nanophosphors synthesized by the water assisted solid state
reaction (WASSR) method: Luminescence properties and reaction mechanism of the WASSR
method, Applied Spectroscopy Reviews, DOI: 10.1080/05704928.2017.1390344

To link to this article: http://dx.doi.org/10.1080/05704928.2017.1390344

Accepted author version posted online: 11

Oct 2017.

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Nanophosphors synthesized by the water assisted solid state reaction (WASSR) method:

Luminescence properties and reaction mechanism of the WASSR method

Sun Woog Kim,a,b Takuya Hasegawa,a,c Mizuki Watanabe,a Masaru Muto,a Toshiya Terashima,a

Yusuke Abe,a Tatsuro Kaneko,a Ayano Toda,a Tadashi Ishigaki,a Kazuyoshi Uematsu,a Kenji

Toda,a,* Mineo Sato,d Emiko Kawakami,e Junko Koide,e Masako Toda,e Yoshiaki Kudo,e Takaki
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Masaki,f Dae Ho Yoon,f,*

a
Graduate School of Science and Technology, Niigata University, 8050 Ikarashi 2-nocho,

Niigata 950--2181, Japan

b
Department of Nanotechnology and Advanced Materials Engineering, Sejong University, 209

Neungdong-ro, Gwangjin-gu, Seoul 05006, Republic of Korea

c
Department of Marine Resource Science, Faculty of Agriculture and Marine Science, Kochi

University, 200 Otsu, Monobe, Nankoku City, Kochi 783--8502, Japan

d
Department of Chemistry and Chemical Engineering, Niigata University, 8050 Ikarashi 2-

Nocho, Niigata 950--2181, Japan

e
N-Luminescence Corporation, 8867-3 Ikarashi 2-nocho, Niigata 950--2101, Japan
f
School of Advanced Materials Science and Engineering, Sungkyunkwan University, Kyunggi-

do 400--746, Republic of Korea

* Corresponding authors: Professor Dr. Kenji Toda

E-mail: ktoda@eng.niigata-u.ac.jp, Tel.: +81-25-262-6771, Fax: +81-25-262-6771

Professor Dr. Dae Ho Yoon

E-mail: dhyoon@skku.edu, Tel: +82-31-290-7361, Fax:+82-31-290-7371

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Abstract

Ceramic materials have been widely used in various application areas and are significantly

important materials in our daily life. The various methods for synthesizing ceramics powder

materials have been already reported, and the synthesis method is known to considerably affect

the characteristics and particle morphology of ceramic powder materials. We have recently
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developed a novel soft chemical synthesis method, water assisted solid state reaction (WASSR)

method which can be synthesized at low temperatures below 100 ºC. We further demonstrated

the effect and availability of this method on the synthesis process for ceramic oxide materials. In

this paper, we review some results for nanophosphors synthesized by the WASSR method and

discuss the reaction mechanism of this method.

Key words

Water assisted solid state reaction (WASSR) method, Low temperature synthesis method,

Functional ceramic powder material, Phosphor, Nano particle

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Introduction

Functional ceramic powder materials have typically been synthesized through the solid state

reaction method and the liquid phase reaction methods such as the co-precipitation method, sol-

gel method, hydrothermal processing, polymerized complex method, and others. Among these

synthesis methods, the solid state reaction method is the most widely used for producing the
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functional ceramic powder materials owing to its simplicity and ease. Since ionic diffusion in

solid is too slow at low temperature and is known to increase with increasing temperature, the

heat treatment at high temperature is necessary to accelerate the reaction between raw materials

(1, 2). However, the high temperature reaction usually results in the particle growth and irregular

particle morphology of the final production powder leading to the enhancement of processing

costs. Therefore, liquid phase reaction methods have been usually applied for obtaining ceramics

materials having fine particle size and homogeneous particle morphology (3-10). However, these

conventional methods require special chemical treatment using the strong acid or basic solutions

or organic solvents with a high concentration requiring a washing process to remove the acidic or

basic ligands or organic solvents adsorbed on the surface of the production particles (5). The

washing process generally leads to the production of the lattice defects, which is the cause of the

reduction of the crystallinity, owing to hydroxyl groups (OH)O• or organic carbonates

incorporated on O-sites or interstitial open spaces or both O sites and interstitial open spaces in

the crystal lattice (11-13). In addition, some conventional liquid phase reaction methods require

thermal or physical after-treatment to obtain a single phase with high crystallinity. The after-

treatment usually leads to irregular particle morphology and particle growth.

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To overcome these problems, we have recently developed a novel soft chemical synthesis

method, a water assisted solid state reaction (WASSR) method (in some our previous studies, we

recorded as a solid hydratethermal reaction (SHR) method) (14-19). This method is very simple

and can be easily synthesized the functional ceramic powder materials having a fine size particle

at low temperatures below 100 ºC without the special thermal, physical or chemical treatment. In
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this method, the addition of a small amount of water, which acts as a reaction accelerator, is

significantly important to ensure the reaction between the raw materials because the reaction in

this method is promoted by the presence of a small amount of water. In addition, this method

does not require a washing process, and the amount of water is quite minimal compared with

conventional liquid phase reaction methods, which contributes to enhance the crystallinity of the

final production particles owing to the suppression of the hydrogen interstitial in the lattice. In

our previous studies, we successfully synthesized the functional ceramic powder materials

having fine size particle and homogeneous particle morphology using the WASSR method.

Table 1 lists the chemical compositions of ceramics materials synthesized by the WASSR

method. In this paper, we mainly review the results for nanophosphors prepared by the WASSR

method and discuss the reaction mechanism of this method. Nanophosphors with high emission

intensity have recently attracted much attention due to their significant potential to obtain high

packing density and high emission efficiency in solid lighting system (20-23). Furthermore,

nanophosphors are considered to be promising candidates for spectral converters to enhance the

energy-conversion efficiency of silicon solar cells (24-26).

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Nanophosphor prepared by the WASSR method

RbVO3 white emission phosphor (14)

RbVO3 is a famous rare earth-free white emitting phosphor which shows a strong broad

optical absorption band in the range of UV to near UV spectra region and exhibits an unusual
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broad emission band from 400 to more than 700 nm (14, 20, 21). To synthesize the RbVO3

phosphor using the WASSR method, Rb2CO3 and V2O5 were used as starting materials and these

raw materials were mixed using a mortar for 1 min. A small amount of deionized water was

added to the mixture at a ratio of 10 wt% and mixed again for 1 min. The X-ray powder

diffraction (XRD) pattern of the RbVO3 sample prepared by the WASSR method is shown in

Figure 1. The standard XRD pattern of orthorhombic RbVO3 obtained from the inorganic crystal

structure database (ICSD) is also included as a reference. It is clear that a single phase of

orthorhombic RbVO3 structure with high crystallinity was successfully obtained and also that no

diffraction peaks with impurities are present in the pattern. Figure 2 shows SEM image of the

RbVO3 particles prepared by the WASSR method. Although particle aggregation was clearly

observed, RbVO3 particles have granular particle morphology, and the particle size was less than

100 nm.

Figure 3 shows the excitation and emission spectra of the RbVO3 phosphor prepared by the

WASSR method. It is well known that the luminescence of the self-activated vanadate phosphor

is due to the charge transfer (CT) transition of an electron from O2 2p orbital to the V5+ 3d

orbital in the VO43 tetrahedron with Td symmetry (22-24). The excitation spectrum of the

RbVO3 phosphor consisted of two broad bands with peaks at around 314 and 364 nm, which

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were attributed to the partly spin-allowed 1A1 → 1T1 and 1T2 transitions, respectively (22-27).

The emission spectrum under excitation at 360 nm exhibited a broad white emission band from

400 to 700 nm, which corresponded to the 3T1 → 1A1 and 3T2 → 1A1 transitions of VO43 group

(28, 29). The Stokes shift (ΔS) of the phosphor is given by:

 S  E ex  E em
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where Eex is the energy of the the bottom of the excitation band and Eem is the energy of the

emission band of phosphor. The values of Eex and Eem of the RbVO3 nanophosphor are 27.0 ×

103 cm1 and 19.2 × 103 cm1, respectively, and the value of ΔS was estimated to be 7.8 × 103

cm1. The internal quantum efficiency of the RbVO3 phosphor obtained in this study at an

excitation wavelength of 360 nm was estimated to be 84%. Additionally, the internal quantum

efficiency of the CsVO3 phosphor prepared by the WASSR method, in which CsCO3 and V2O5

used as the raw materials, was estimated to be 91% under near-UV (λex = 360 nm) excitation.

The CsVO3 phosphor has same crystal structure to RbVO3 and is one of famous vanadate

phosphor.

Rb3V5O14 red emission phosphor (19)

We recently reported the Rb3V5O14, which showed a red emission and red body color, as an

environmentally friendly fluorescent pigment (19). Here, we mainly discuss the optical

properties of this material. Rb3CO2 and V2O5 are used as starting materials for synthesizing

Rb3V5O14 nanoparticles. These raw materials were mixed for 1 min in a stoichiometric ratio

using a mortar. The mixture was placed into a closed-polystyrene container after adding a small

amount of water and then the container was stored at 80 ºC for 6 h in an automatic oven. Figure 4

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presents the XRD patterns of the Rb3V5O14 sample prepared by the WASSR method. As a

reference, the standard XRD patterns of trigonal Rb3V5O14 and orthorhombic RbVO3 are also

plotted in Figure 4. Almost all of XRD peaks of the sample are well indexed to a single phase of

highly crystalline trigonal Rb3V5O14 structure, indicating that Rb3V5O14 structure was observed

as a main phase. Some weak peaks corresponding to orthorhombic RbVO3 structure and
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unknown phase appeared in the XRD pattern of the sample. In addition, the Rb3V5O14 sample

prepared by the WASSR method had a granular particle morphology and the particle size was

less than 100 nm.

Figure 5 depicts the photoluminescence spectrum and the UV-vis diffuse reflectance

spectrum of the Rb3V5O14 nanoparticle prepared by the WASSR method. The excitation

spectrum of Rb3V5O14 consisted of two broad optical absorption bands at 275 and 330 nm (Fig,

5(a)), which are attributed to the 1A1 → 1T1 and 1A1 → 1T2 transitions, respectively. This sample

exhibited an asymmetric broad red emission, which could be fitted into two Gaussian peaks at

610 and 650 nm corresponding to the 3T2 → 1A1 and 3T1 → 1A1 transitions of the [VO4]3 group.

An additional weak broad emission band with a peak at 500 nm was also obtained in the

emission spectrum, which may be due to the RbVO3 impurity. The Stokes shift (ΔS) of this

phosphor was estimated to be 14.3 × 103 cm1. As shown in Figure 5 (b), it is obvious that the

UV-vis spectrum showed a broader optical absorption band compared with that in the excitation

spectrum (Fig. 5 (a)). The reason for this phenomenon can be explained by the crystal structure

of trigonal Rb2V5O14, which is composed of an RbO10 polyhedron and VOn (n = 4 and 5)

polyhedra (Fig. 6). The optical absorption of vanadate materials is due to the energy transfer

from the O2 2p orbital to the V5+ 3d orbital and the position of optical absorption band strongly

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depends on the crystal field strength around the V5+ ions in the crystal lattice (30). Generally, the

crystal field strength in the VO5 square pyramid is known to be stronger than that in the VO4

tetrahedron. Therefore, the optical absorption in the green light region of the UV-vis spectrum is

considered to be due to the O2 → V5+ energy transition in the VO5 polyhedron.

MgV2O6·2H2O yellow emission phosphor

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Mg(OH)2 and V2O5 are used as starting raw materials for synthesizing the single phase of

the MgV2O6·2H2O nanophosphor. These raw materials were mixed for 5 min using a mortar, in

which the molar ratio of Mg(OH)2:V2O5 was 2:1. Then, a small amount of deionized water was

added to the mixture of Mg(HO)2 and V2O5, and the mixture was placed into a closed

polystyrene container and stored at 80 ºC for 24 h in an automatic oven. The sample was dried at

80 ºC for 72 h, and then the sample was washed and filtered with deionized water for removing

the excess amount of Mg(OH)2. Finally, the filtered sample was dried again at 80 ºC for 24 h and

was reground using a mortar. The XRD pattern of the MgV2O6·2H2O nanophosphor prepared by

the WASSR method was in good agreement with the single phase of highly crystalline

orthorhombic MgV2O6·2H2O structure (JCPDS No. 52--0478), as shown in Figure 7. The

nanophosphor had a granular particle morphology having small size particles less than 200 nm

(Fig. 8).

Figure 9 depicts the photoluminescence excitation and emission spectra of the

MgV2O6·2H2O nanophosphor synthesized by the WASSR method. Upon the monitoring the

wavelength at 562 nm, the MgV2O6·2H2O nanophosphor exhibited a two broad optical

absorption bands from 300 to 430 nm corresponding to the charge transfer (CT) transition in

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ligand-metal localized tetrahedral coordinated [VO4]3 group with Td symmetry (22-24). The

emission spectrum of the MgV2O6·2H2O nanophosphor with excitation at 375 nm showed an

asymmetric broad yellow emission peaked at 562 nm. In addition, the emission band can be

decomposed to two Gaussian peaks at 563 nm and 641 nm, which are attributed to the intrinsic

transitions in VO4 tetrahedron of 3T1 → 1A1 and 3T2 → 1A1 transition (28, 29). The Stokes shift
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(ΔS) of this phosphor calculated by following equation, ΔS = Eex ‒ Eem, was estimated to be 9.4

× 103 cm1. The absorbance and internal quantum efficiency of the MgV2O6·2H2O nanophosphor

at an excitation wavelength of 380 nm were estimated to be 83.5% and 1.6%, respectively.

LaPO4:Ce3+, Tb3+ green emission phosphor (16)

Ce3+ and Tb3+ co-doped lanthanum orthophosphate LaPO4, which has high luminescence

efficiency and excellent chemical and thermal stability, has been often used as a commercial

green emission phosphor in the tricolor fluorescent lamps and PDP display (31-34). A mixture of

La(NO3)3·6H2O, TbCl3·6H2O, CeCl3·7H2O and NH4H2PO4 was ground using a mortar for 1 min,

wherein the Ce3+ and Tb3+ contents are fixed at 32 and 17 mol% which is similar to that of a

commercial LaPO4:Ce3+, Tb3+ green emission phosphor. The mixture was placed into an

autoclave without water and stored at 100 ºC for 6 h in constant temperature oven. In this case,

the water layer, which is required for the reaction between raw materials, on surface of raw

material particles is formed by the crystal water included in raw materials. Finally, the sample

was washed with de-ionized water to remove the nitrate ligand and chlorine ions remaining as

impurities on the surface of the particles and then dried at 80 ºC for 24 h. Figure 10 shows the

XRD pattern of the LaPO4:Ce3+, Tb3+ phosphor prepared by the WASSR method. The standard

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XRD pattern of hexagonal lanthanum orthophosphate, LaPO4 obtained from the ICSD (#31564)

is also included as a reference. The XRD pattern of the sample was in good agreement with a

single phase of highly crystalline hexagonal lanthanum orthophosphate, LaPO4, and no impurity

phase was observed in the pattern. This result indicates that Ce3+ and Tb3+ ions successfully

substituted La3+ site in host LaPO4 lattice to form solid solutions.

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The excitation and emission spectra of the LaPO4:Ce3+, Tb3+ phosphor synthesized by the

WASSR method are shown in Figure 11. The excitation spectrum was obtained for emission at

543 nm, and the emission spectrum was obtained for excitation at 273 nm. The phosphor

obtained in this study showed similar luminescence behavior to that of the commercial and

previously reported LaPO4:Ce3+, Tb3+ phosphors (31-34). The excitation spectrum of this

phosphor consisted of a strong broad optical absorption band from 220 to 320 nm, which

corresponds to the 4f1 → 4f05d1 allowed transition of Ce3+ ions. The phosphor exhibited a well-

known characteristic Tb3+ emission. The emission peaks at 489, 543, 585, and 620 nm

corresponded to the transition from 5D4 excited state to the 7F6, 7F5, 7F4, and 7F3 ground states of

Tb3+, respectively.

YVO4:Eu3+ red-emission phosphor (18)

YVO4:Eu3+ is considered a promising red emission phosphor for use in cathode ray tube and

field emission display devices due to their high thermal stability and high luminescence

efficiency (35-37). A small amount of deionized water was added to a stoichiometric mixture of

Y2O3, V2O5, and Eu2O3, in which the Eu3+ concentration was fixed at 10 mol%, and then the

mixture was mixed for 1 min using a mortar. The mixture was placed into the closed polystyrene

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container and stored at 80 ºC for 6 h in a constant temperature oven. The XRD patterns of the

YVO4 host material and YVO4:Eu3+ phosphor prepared by the WASSR method are shown in

Figure 12. The standard XRD pattern of tetragonal yttrium orthovanadate, YVO4 obtained from

the ICSD (#246708) is also included as a reference. Although an impurity phase corresponding

to cubic Y2O3, which is the raw material used in this study, was observed, most peaks of both
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YVO4 and YVO4:Eu3+ were in good agreement with that of tetragonal YVO4 obtained from the

ICSD. A peak shift to a lower diffraction angle was observed with Eu3+ doping into the host

YVO4 lattice, which indicates that larger Eu3+ ions (ionic radius: 0.1066 nm for 8-fold

coordination (38)) are successfully substituted into the Y3+ ion (ionic radius: 0.1019 nm for 8-

fold coordination (38)) site in the YVO4 lattice to form solid solutions. Figure 13 shows the SEM

images of YVO4:Eu3+ phosphor synthesized by the WASSR method. It is abundantly clear that

the phosphor showed granular particle morphology and the average particle size was less than

100 nm.

Figure 14 shows the excitation and emission spectra of the YVO4:Eu3+ phosphor synthesized

by the WASSR method. The excitation spectrum consisted of a strong broad band from 220 to

340 nm, which is attributed to a charge transfer transitions from O2− to V5+, followed by an

energy transfer to Eu3+ (39). Some weak peaks between 340 and 500 nm were due to the 4f-4f

transitions of Eu3+. All emission peaks corresponded to the transition from the 5D0 excited level

to 7FJ (J = 0, 1, 2, 3, and 4) ground levels of Eu3+. This result is similar to that of a previous

report for YVO4:Eu3+ red emission phosphor. In addition, the internal quantum efficiency of the

phosphor prepared by the WASSR method was 32% under the excitation wavelength at 300 nm.

This value is relatively high value for the previously reported YVO4:Eu3+ nanophosphor (40, 41).

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Reaction mechanism of the WASSR method

The WASSR method was recently developed by our research group as a novel synthesis

method for obtaining fine ceramic nanomaterials at low temperatures below 100 ºC without

thermal and physical after-treatment. This method is also did not require a chemical treatment

using basic or acid solution or organic solvents during synthesis processing. Figure 15 (a) and (b)
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show the photographs for real time reaction between Rb2CO3 and V2O5, which are raw materials,

during the synthesis processing of the RbVO3 white emission phosphor using the WASSR

method in the absence and in the presence of the water. To investigate the reaction between

Rb2CO3 and V2O5, we checked the real time reaction under UV light irradiation because RbVO3

shows a strong white emission under UV excitation when RbVO3 successfully synthesized. As

shown in Figure 15 (a), the white emission began to be observable at the contact points between

particles, and the emitted area and emission intensity become greater and stronger with increased

reaction time. The XRD pattern of the emitted powder was in good agreement with a single

phase of highly crystalline orthorhombic RbVO3. On the other hand, no emission or reaction was

observed in the sample prepared in the absence of the water (Fig. 15(b)). These results indicate

that a single phase of RbVO3 white emission phosphor was successfully synthesized by the

addition of water.

Figure 16 shows the thermogravimetric-differential thermal analysis (TG-DTA) curves of

the mixture of Cs2CO3 and V2O5, which are raw materials for synthesizing the CsVO3 phosphor.

TG-DTA was analyzed at 25 ºC for 3 h in a flow of water vapor, and Fig. 16 plotted the TG-

DTA curves in the time range of 0 – 100 min.. In TG curve, the mixture showed weight gain in

the time range of 0 – 30 min., which was caused by the adsorption of water vapor. In addition,

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the mixture showed the weight loss in the time range of 30 – 50 min. and the exothermic and

endothermic peaks in the DTA curve also appear at 32 and 35 min., respectively. Additionally,

after 50 min. from the start of TG-DTA analysis, the exothermic and endothermic peaks or

weight loss were not observed. These results indicate that the weight loss is considered to be due

to the evaporation of CO2, and the decomposition of Cs2CO3 and the reaction between Cs2CO3
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and V2O5 occur simultaneously. In addition, the reaction of Cs2CO3 and V2O5 started when the

water layer is formed on the surface of the particles of raw materials, and the reaction was

completed in about 10 min..

From the above results, we understood that the water addition is significantly important to

promote the reaction between raw materials in the WASSR method. The dependence of an

amount of water on the reaction rate of the WASSR method was investigated using Y2O3 and

V2O5, which are raw materials for synthesizing YVO4. Figure 17 shows the XRD patterns of the

YVO4 prepared by the WASSR method in the absence and in the presence of different amounts

of water. In this case, Y2O3 and V2O5 were mixed using a mortar for 3 h after the addition of a

small amount of deionized water. Although secondary phases corresponding to raw materials,

Y2O3 and V2O5 were observed as extremely small peaks in the sample mixed in the presence of

the 0.05 g water, most of XRD peaks are well indexed to the standard XRD pattern of tetragonal

yttrium orthovanadate, YVO4 structure. In contrast, the sample mixed with 0.1 g water resulted

in a three-phase mixture of Y2O3, V2O5, and YVO4, in which the peak intensity of YVO4 is

extremely low. In addition, the XRD peaks of the sample mixed without water corresponded to

the Y2O3 and V2O5 raw materials, and the diffraction peaks evident of YVO4 phase was not

presented in the pattern (17). These results suggest that the control of an amount of the added

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water is significantly important for proceeding the reaction in the WASSR method. An excess

amount of water suppresses the reaction between the raw materials particles because the excess

water leads to a reduction of the contact point between the particles. Since the solubility of both

Y2O3 (0.018 g/l) and V2O5 (0.700 g/l) is too low (42), the dissolution of these materials is

negligible in the reaction of the WASSR method. The amounts of dissolved Y2O3 and V2O5 in
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water (approximately 0.05 g) are 9.0  106 g and 3.5  105 g, respectively. This result indicates

that the WASSR method is different from the solution reaction.

To determine the reaction mechanism of the WASSR method, we investigated the solid

acid-base reaction using MoO3 and NaOH, which are raw materials, to obtain Na2Mo2O7·2H2O.

The sample was prepared in the following steps: 1) the MoO3 particles were dispersed in methyl

red solution to adsorb the methyl red on the surface of the MoO3 particles, 2) the particles were

dried at 80 ºC for 12 h and mixed with the NaOH particles and 3) finally, a small amount of

deionized water was added dropwise into a mixture of the methyl red adsorbing MoO3 particles

and NaOH particles. The color of the methyl red adsorbing particles is known to change from red

to yellow when the acidity of particle changed from the acid to the neutral state. As shown in

Figure 18, the mixture of the methyl red adsorbing MoO3 particles and the NaOH particles,

which is known to be a strong basic material, had red body color that is due to methyl red. When

a small amount of deionized water was added, the body color of the mixture changed to the

yellow. Furthermore, small peaks evident of Na2Mo2O7·2H2O are observed in the XRD pattern

of the mixture. This result confirms that the reaction between raw materials in the WASSR

method occurs due to the solid acid-base reaction.

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Considering the aforementioned results, we hypothesized the reaction mechanism of the

WASSR method as illustrated in Figure 19. As mentioned above, the reaction between the raw

materials occurred rapidly when a small amount of water was added to the mixture of raw

materials and the reaction rate was strongly depended on an amount of addition water. Namely,

the addition of a small amount of water, which acts as a reaction accelerator, is significant to
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ensure the reaction between raw materials in this method. The added water, which covers the

surface of the raw material particles as shown in Figure 19, activates the surface reaction of the

raw material particles resulting in the acceleration of the solid acid-base reaction of raw materials

at particle-particle contact points. Consequently, this method presented unusually fast reaction

between the solid state raw material particles at a temperature below 100 °C.

We investigated the reactivity of Rb2CO3 and V2O5 in solvents other than water such as

acids, alcohols, and organic solvents, and these results are listed in Table 2. Although a partial

reaction between raw materials has occurred in ethanol, the reaction does not occur in these

solvents. This result indicates that the water has a decisive effect on the reaction between the raw

materials in the WASSR method.

Conclusion

We recently developed a water assisted solid state reaction (WASSR) method, which is a

novel soft chemical synthesis method to synthesize fine functional ceramic powder materials

having nano size particles at low temperatures below 100 ºC without thermal and physical after-

treatment and without a chemical treatment using organic solvents or basic or acid solutions.

Using this method, we successfully synthesized many kinds of functional ceramic powder

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materials. The phosphors synthesized by this method were obtained nano size particles less than

100 nm with high crystallinity and these phosphors exhibited high emission efficiency.

Furthermore, besides phosphors, the most of the functional ceramics materials synthesized by the

WASSR method have granular particle morphology and the particle size was less than 100 nm

without reference to the particle size of raw materials. Since this method does not require a
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special experiment and special chemical treatment for producing functional ceramic powder

materials, it can reduce the material costs. In view of this, our developed novel soft chemical

synthesis technique, WASSR method is promising for the industrial applications for functional

ceramic powder materials synthesis processing.

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Table 1 List of the ceramics materials synthesized by the WASSR method

Raw materials Obtained material Amount of Synthesis condition

water

Y2O3, V2O5, Eu2O3 YVO4:Eu3+ 10 wt% Mixing, 25 ºC, 3 h

Storing, 80 ºC, 6h
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La(NO3)3∙6H2O, NH4H2PO4, LaPO4:Ce3+,Tb3+ Crystalline Storing, 100 ºC, 6 h

TbCl3∙6H2O, Ce(NO3)3∙6H2O water

Li2CO3, MoO3 Li2MoO4 10 wt% Storing, 80 ºC, 6h

Li2CO3, NH4H2PO4 Li3PO4 10 wt% Storing, 80 ºC, 6h

LiOH∙H2O, SiO2 Li2SiO3 10 wt% Storing, 80 ºC, 6h

M2CO3 (M = Rb, Cs), V2O5 MVO3 (M = Rb, Cs) 10 wt% Mixing, 25 ºC, 1min

MCO3 (M = Ca, Sr), MoO3 MMoO4 (M = Ca, Sr) 10 wt% Mixing, 25 ºC, 3 h

LiOH∙H2O, Al2O3 LiAl5O8 10 wt% Storing, 80 ºC, 6h

LiOH∙H2O, Nb2O5 LiNb3O8 10 wt% Storing, 80 ºC, 6h

LiOH∙H2O, GeO2 Li2GeO3 10 wt% Storing, 80 ºC, 6h

Ca(OH)2, V2O5 CaV2O6 10 wt% Storing, 80 ºC, 6h

Ca(OH)2, WO3 CaWO4 10 wt% Storing, 80 ºC, 6h

M(OH)2∙8H2O (M = Sr, Ba), MTiO3 (M = Sr, Ba) 10 wt% Storing, 100 ºC, 6h
TiO2 (anatase)

Mg(OH)2, V2O5 MgV2O6·2H2O 100 wt% Storing, 80 ºC, 24h

Rb2CO3, V2O5 Rb3V5O14 10 wt% Storing, 80 ºC, 6h

Na2CO3, MoO3, Eu2O3 NaEu(MoO4)2 Humidity Storing, 80 ºC, 10h

Bi(NO3)3, V2O5 BiVO4 Humidity Storing, 30 ºC, 6h

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Table 2 List of the results for synthesis of RbVO3 by the WASSR method as a function of

solvents. Rb2CO3 and V2O5 were mixed for 3 min. after adding a small amount of the solvents.

The crystal phase of the obtained materials was confirmed using the XRD.

Solvent Crystal phase Solvent Crystal phase

de-ionized water RbVO3 acetylacetone Rb2CO3, V2O5

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ethanol (purity 98%) RbVO3, Rb2CO3, V2O5 2-butanone Rb2CO3, V2O5

methanol Rb2CO3, V2O5 cyclohexane Rb2CO3, V2O5

acetone Rb2CO3, V2O5 toluene Rb2CO3, V2O5

hexanol Rb2CO3, V2O5 xylene Rb2CO3, V2O5

1-butanol Rb2CO3, V2O5 tetrachloroethylene Rb2CO3, V2O5

benzyl alcohol Rb2CO3, V2O5 chlorobenzene Rb2CO3, V2O5

ethylene glycol Rb2CO3, V2O5 dimethyl carbonate Rb2CO3, V2O5

1,4-butanediol Rb2CO3, V2O5 propylene carbonate Rb2CO3, V2O5

diethylene glycol Rb2CO3, V2O5 formic acid Rb2CO3, V2O5

polyethylene glycol Rb2CO3, V2O5 oleic acid Rb2CO3, V2O5

chloroform Rb2CO3, V2O5 phosphoric acid Rb2CO3, V2O5

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Figure 1. XRD pattern of the RbVO3 nanophosphor.

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Figure 2. SEM image of the RbVO3 nanophosphor.

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Figure 3. Excitation and emission spectra of the RbVO3 nanophosphor.

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Figure 4. XRD pattern of the Rb3V5O14 sample prepared by the WASSR method.

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Figure 5. Photoluminescence spectrum and UV-vis diffuse reflectance spectrum of the Rb3V5O14

nanoparticle prepared by the WASSR method.

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Figure 6. Crystal structure of Rb3V5O14.

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Figure 7. XRD pattern of the MgV2O6·2H2O nanophosphor.

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Figure 8. TEM image of the MgV2O6·2H2O nanophosphor.

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Figure 9. Excitation and emission spectra of the MgV2O6·2H2O nanophosphor.

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Figure 10. XRD pattern of LaPO4:Ce3+,Tb3+ nanophosphor.

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Figure 11. Excitation and emission spectra of LaPO4:Ce3+,Tb3+ nanophosphor.

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Figure 12. XRD patterns of YVO4 host materials and YVO4:Eu3+ nanophosphor.

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Figure 13. Excitation and emission spectra of the YVO4:Eu3+ nanophosphor.

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Figure 14. SEM image of the YVO4:Eu3+ nanophosphor.

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Figure 15. Photographs for real time reaction between Rb2CO3 and V2O5 in a flow of water

vapor (humidity 80%) (a) and in a flow of Ar gas (b). The photographs observed under UV light

irradiation.

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Figure 16. TG/DTA curves of the mixture of Cs2CO3 and V2O5.

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Figure 17. XRD patterns of the YVO4:Eu3+ nanophosphor as function of an amount of water.

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Figure 18. Photographs of the solid acid-base reaction test for the reaction between MoO3 and

NaOH particle using methyl red.

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Figure 19. Schematic diagram of hypothetical reaction mechanism for the WASSR method.

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