Noname manuscript No.

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Photoluminescence properties of YAG:Ce3+ ,Pr3+ phosphors synthesized via the Pechini method for white LEDs
Marin, R. Sponchia, G. Riello, P. Sulcis, R. Enrichi, F.

Received: date / Accepted: date

Abstract We describe a facile route for synthesize YAG nanophosphors via Pechini-type sol-gel process (PSG) for white light emitting diodes (LEDs) technology. The wet-type synthesis was followed by a heat treatment at 1000 C for 4 h. We carried out a study of the luminescent properties of the YAG:Ce,Pr system varying the concentration of praseodymium from 0.125% mol to 2% mol maintaining the quantity of cerium constant at 2% mol. The diractometric analysis conrmed the purity of the YAG phase. The luminescent analysis showed the typical Ce3+ emission arising from the 5d 4f transitions overlapped with the sharper Pr3+ emissions in the red region of the spectrum. The presence of energy transfer (ET) phenomenon was conrmed by PLE spectra of the samples and the appearance of concentration quenching at 0.5% mol Pr was observed thanks to the decrease both of the intensity of praseodymium emission and mean lifetime. Keywords Pechini-type sol-gel process (PSG) white light emitting diode (LED) YAG:Ce3+ ,Pr3+ energy transfer (ET) nanophosphors

LEDs as the best candidates for future applications. They have already been employed in numerous devices such as solid state lasers, automobile brake lights, trac lights, plasma display monitors, eld-emission displays and so on. LED lamps show a number of advantages with respect to conventional illumination sources, such as stability, high eciency, prolonged lifetime (about 100000 h) thus determining a pollution reduction (Jang et al, 2007; Lee et al, 2008). There are already commercial available white LEDs, but they show some limitations which justify the need for a deeper research in this eld. White-light emitting diodes can be produced exploiting the RGB technology: three phosphors are combined and excited by a near-UV (NUV) source (Zhang et al, 2011). This technique is rather expensive and may exhibit low eciency due to the absorption and re-emission processes occurring between the phosphors (Jang et al, 2007; Lee et al, 2008). A cheaper method to obtain a white light is to combine a blue-emitting LED, usually a GaN-based diode, with a yellow phosphor because of simpler and less expensive processing techniques of the phosphors (Pan, 2004; Katelnikovas et al, 2007; Lee et al, 2008; Zych et al, 2008). The combination of the transmitted light and the yellow component deriving from the excitation of the phosphor results in a bright white light (Yang et al, 2009a; Jang et al, 2007; Pan, 2004). The intermixing of the excitation and uorescence radiations is helped even by the scattering phenomena caused by the phosphors (Murai et al, 2010). The major problem of this technology is the usually poor color-rendering index (CRI) ( 80) of the so-produced LEDs arising from the lack of the red component in the emission. Actually the CIE coordinates are not in the usual white eld (x = 0.33

1 Introduction During the last decades the need for cheap, durable and energy saving illumination sources has pointed out
R. Marin G. Sponchia P. Riello Department of Molecular Sciences and Nanosystems Ca Foscari Universit` di Venezia, a via Torino 155/b, I-30172 Venezia-Mestre, Italy E-mail: riccardo.marin@hotmail.it R. Sulcis F. Enrichi Civen/NanoFAB, via delle Industrie 5, 30175 Venezia-Marghera, Italy E-mail: enrichi@civen.org

Marin, R. et al.

and y = 0.33 (Pan, 2004)), but they fall in a greenish region of the cromaticity diagram. Among various phosphors those based on yttrium aluminium garnet (YAG) have been intensively studied along several years. They show unique chemical and thermal stability, extremely low phonon energy, transparency in the UV to IR region, and they allow a prolonged exposure to electron beams (Lee et al, 2008; Murai et al, 2010; Hassanzadeh-Tabrizi, 2011; Fu, 2006). YAG is used in a plethora of applications: lasers, refractory coating for electronic devices, cathode ray tube, and backlight source (Cinibulk, 2000; Kasuya et al, 2006; Zhou, 2002; Yang et al, 2009a). Furthermore this garnet phase (Y3 Al5 O12 ) of the alumina-yttria (Al2 O3 Y2 O3 ) system can host a number of lanthanide ions, Y3+ being vicariant with Ln3+ (Yang et al, 2009b). Considering the eld of white-LED technology, the YAG:Ce3+ system is one of the most utilized yellow phosphor. It exhibits a broad band between 450nm and 700nm with its maximum at about 540nm. This emission arises from the transitions of the single outer electron from the excited 5d states of the Ce3+ to the lower 4f states. The broadening of the emission is determined by the splitting of energy levels of the lanthanide ions induced by the crystal eld of YAG and is very sensitive to the impurities and dopants introduced in the lattice (Katelnikovas et al, 2007; Dorenbos, 2002). In order to overcome the obstacle of the poor CRI index of the white LEDs some strategies have been investigated. Many groups reported the eect of the substitution of Y and Al ions in the YAG structure with smaller or larger ions: the substitution of Y3+ in its dodecahedrally coordinated site with larger Gd3+ or smaller Lu3+ leads to a red- and blue-shift respectively. By substituting the octahedrally coordinated Al3+ with larger Ga3+ or In3+ again a blue-shift in the cerium emission can be achieved (Yang et al, 2009a; Mukherjee et al, 2009). Even an increment in the concentration of Ce3+ can tailor in the red region the emission of the phosphor, but above 4%mol quenching eects appear. The introduction in the lattice of a co-dopant acting as a secondary luminescence source in the red spectral range is an alternative to those methods. Pr3+ and Eu3+ are the more common lanthanide ions used in the luminescent technology to produce red phosphors. Lee et al. (Lee et al, 2008) reported the synthesis of Ce3+ ,Eu3+ -codoped YAG phosphors via a continuous supercritical water (SCW) method. Yangs group (Yang et al, 2009a) synthesized nano-phosphors through a modied polyol process combining the red shift induced by the introduction of lattice-softening ions and the presence of red emitting Pr3+ .

These systems take advantage of the energy transfer (ET) phenomena occurring between neighboring Ce3+ ions (sensitizer ) and codopant ions. Actually cerium has a relatively large absorption cross section and thanks to its broad emission band can eciently transfer part of the absorbed energy to a nearby luminescent center which can emit in the red region, thus leading to an enhanced CRI value. Lately Hassanzadeh-Tabrizi (Hassanzadeh-Tabrizi, 2011) proposed the Pechini-type sol-gel process (PSG) (Pechini, 1967) as an alternative in producing YAG:Ce nanophosphors due to the capability of this process technology to control the product stoichiometry and dimensions of the particles. The PSG is a very useful and common method for the synthesis of metal oxide materials with the aid of organic polymer, such as ethilenglycole (EG), and an chelating agent to obtain metal complex, such as citric acid (CA). These organics compounds form a polyesteric network which can be eliminated through a thermal treatment. On the whole this process is considered enough friendly and economic. Our group has already worked on rare-earth doped luminescent silica and zirconia nanoparticles for different applications (Enrichi, 2008; Enrichi et al, 2008, 2010b,a; Parma et al, 2010; Sivestrini et al, 2010). In this work we synthesized co-doped YAG:Ce,Pr nanophosphors through the PSG method for white-LED application. Their luminescent properties were investigated and a systematic study of the eect of Pr concentration on the emission intensity was carried out.

2 Experimental 2.1 Materials The reagents used in this experience are yttrium nitrate (Y(NO3 )3 6 H2 O, Acros Organics 99.9%), aluminium nitrate (Al(NO3 )3 9 H2 O, Carlo Erba 98%), cerium nitrate (Ce(NO3 )3 6 H2 O, Aldrich 99.99%), praseodymium nitrate (Pr(NO3 )3 5 H2 O, Acros Organics 99.9%), citric acid (CA, Carlo Erba 99.5%), ethilenglycole (EG, Acros Organics 99.96%), and nitric acid (HNO3 , SigmaAldrich 69%)

2.2 Synthesis of the phosphors For the synthesis of YAG we used the PSG method (Pechini, 1967). Briey the nitrates and acids were stirred directly in a crucible while heating at 100 C. Batch solutions of lanthanides (Ce 24mM and Pr 6mM) were prepared by dissolving the precursors in a solution of HNO3 :H2 O= 1:1. After complete dissolution of the salts

Photoluminescence properties of YAG:Ce3+ ,Pr3+ phosphors synthesized via the Pechini method for white LEDs Table 1 Samples stoichiometry %Ce C0 C1 C2 C3 C4 C5 C6 0 2 2 2 2 2 2 %Pr 1 0 0.125 0.25 0.5 1 2 Formula
1 0 0

-10

(Y2.97 Pr0.03 )Al5 O12 (Y2.94 Ce0.06 )Al5 O12 (Y2.93625 Ce0.06 Pr0.00375 )Al5 O12 (Y2.9325 Ce0.06 Pr0.0075 )Al5 O12 (Y2.925 Ce0.06 Pr0.015 )Al5 O12 (Y2.91 Ce0.06 Pr0.03 )Al5 O12 (Y2.88 Ce0.06 Pr0.06 )Al5 O12

-20

DTA (uV/mg)

2 -30 3 -40

-50

EG was added and stirred until gelication. Then the reaction mixtures were left on the hot plate overnight. Finally the samples were calcined at 1000 C for 4 h. The quantities of reagents are calculated according to the following reaction:

5 100 200 300 400 500 600 700 800 900

-60 1000

Temperature (C)

Fig. 1 TG and DTA curves of the sample C1 before thermal treatment.

xY(NO3 )3 + 5 Al(NO3 )3 + yLn(NO3 )3 + EG + CA Yx Al5 O12 :Lny 3

H2 O HNO

(1)

The nitrates molar proportions are selected by the stoichiometry of samples show in Table 1. The molar proportion between all salts, CA and EG is 1:3:4.5, while the aqueous HNO3 solution is added in 20mL for every 10mmol of salts.

Ce3+ and ex = 287nm for Pr3+ . For lifetime (LT) measurements two dierent methods were used. For Ce3+ TCSPC method was chosen and as radiation source a Nanoled (ex = 454nm) with pulse of 1.3ns was used. For Pr3+ we used the MCSPC method with a Spectraled (ex = 445nm). Both analysis required a lter at 500nm.

3 Results 2.3 Characterization For the thermogravimetry (TG) a Netzsch STA 409 PC was used. For the X-ray diractometry (XRD) analysis a Philips diractometer with PW 1319 goniometer was used with an applied voltage of 40 kV. The TEM images were collected using a JEOL JEM 3010 microscope. Before the imaging the sample was dispersed in ethanol with the aim of sonication and then deposited on a carbon-coated copper grid. For the photoluminescence (PL), excitation photoluminescence (PLE), multi channel scaler photon counting (MCSPC), and time correlated single photon counting (TCSPC) lifetimes a Fluorolog TCSPC Horiba Jobin Yvon was used. A Xenon arc lamp was used as a continuous-spectrum source (450W) selecting the excitation wavelength with a double Czerny-Turner monochromator. All the samples were mildly ground before the analysis and put in a sample holder 1.8mm deep, so we can be condent that the incident beam is entirely absorbed by the sample. The actual power impinging on the sample is of the order of 0.1mW. For PLE measurements we selected em = 580nm for Ce3+ and em = 609nm, for direct excitation of Pr3+ . For PL measurements we chose ex = 430nm for 3.1 Thermogravimetric analysis Fig. 1 shows the TG and DTA curves of sample C1. The sample was washed several times with water to neutral pH and then dessicated for ve minutes at 100 C. The analysis was carried out in an air ux, scanning from 30 to 1000 with a heating rate of 20 /min. From the TG curve and its derivative we can individuate four major weight losses: the rst, around 130 C, can be attributed to the loss of water and moisture still absorbed and is an endothermic process according to the DTA curve. A second loss is around 325 C and there is another preponderant one at 435 C. Both have a correspondent small exothermic peak in the DTA curve. These can be attributed to the collapse of the organic structure and carbonization of it. Finally there is an exothermic peak at about 600 C which can be associated with the nal combustion of the carbon residue. The total weight loss is of 55%. Above 750 C the weight remains unchanged and a slow increase in the slope of the DTA curve can be noted. This increment is in connection with the appearance of the crystalline phase. Actually in previous studies we noted that a heat treatment of 800 C was not enough to obtain a well crystallized single phase YAG even if the crystallization was

Mass loss (%)

Marin, R. et al.

Fig. 3 XRD spectrum of the sample C1 after annealing at 1000 C. The peaks can be attributed to pure phase YAG.

3.4 Luminescence analysis In Fig. 4 a schematic energy level of Ce3+ and Pr3+ ions is presented. The transitions schematized here are consistent with the analysis of the luminescent spectra in Fig. 5 and Fig. 6.

Fig. 2 TEM image of the sample C1 acquired at a magnication of x50k. In the inset the crystalline planes are well distinguishable.

already taking place. That is why an annealing temperature of 1000 C was chosen along with the fact that Harada and Goto (Harada and Goto, 2006) reported that in order to obtain a pure phase YAG with samples prepared via PSG method a temperature of at least 900 C is needed.

3.2 Transmission electron microscope observations In Fig. 2 we can observe the morphology of the sample C1 to be rather irregular. The sample seems to be constituted by two population of particles: small crystals some tens of nanometers large and bigger particles of at most 200nm. These crystals display a good degree of crystallinity as can be seen by the inset which shows the presence of well ordered large domains of crystalline planes.

3.3 X-ray diraction analysis Fig. 3 reports the XRD spectrum of sample C1 annealed at 1000 C for 5 hours. The spectrum shows well dened peaks. Each of the reection has been attributed to a crystallographic plane of the YAG, which has a cubic structure. No secondary phase such as the orthorombic perowskitelike YAP (Y4 Al2 O9 ) or the monocline YAM (YAlO3 ) is present.

Fig. 4 Schematic energy level of Ce3+ and Pr3+ ions. Full, bold, dashed and curly arrows correspond respectively to absorption, emission, energy transfer and multiphonon relaxation mechanisms.

Photoluminescence properties of YAG:Ce3+ ,Pr3+ phosphors synthesized via the Pechini method for white LEDs

In Fig. 5 we reported the excitation and emission spectra of the singly doped sample C1 (YAG:2%Ce). The absorption of the cerium-doped sample arises from the transition from the ground state 2 F5/2 to the upper 5d band split by the crystal eld in 2 D3/2 and 2 D5/2 . A much less intense band appear at about 345nm (29000cm1 ) due to the transitions to the upper 5d band as depicted in Fig. 3. The asymmetric emission peak centered at around 550nm is the sum of the two transitions from the phonon-relaxed 5d states (2 A1g ) to the spin-orbit coupling split levels of the ground state 2 F7/2 and 2 F5/2 (Pan, 2004; Kasuya et al, 2006; Murai et al, 2010).

PLE
3

H -> 4f5d
4

-> H

PL
4

Normalized Intensity

H -> 4f5d
4

H ->
4

0 3 3 3

-> H

1 6

-> H

350

-> H

5 3

-> F

250

300

350

400

450

500

550

600

650

700

750

Wavelenght (nm) PLE

2

5/2

-> 5d

PL

Fig. 6 PL (ex = 287 nm) and PLE (em = 609nm) spectra of the Pr3+ ions
%Pr

5/2

-> F

5/2 2

Normalized Intensity

3/2

-> F

5/2

0.5
2

5/2

-> 5d

0.25

300

350

400

450

500

550

600

650

700

750
0.125

Wavelenght (nm)

Fig. 5 PL (ex = 430nm) and PLE (em = 580nm) spectra of the Ce3+ ions
500 550 600
Wavelenght (nm)

650

700

750

In Fig. 6 we reported the PL and PLE spectra of the singly doped sample C0 (YAG:1%Pr). They are normalized at their maxima to allow a proper comparison of the spectral shape. The absorptions derive from the transitions from the 3 H4 ground state to the upper triply split 3 P0 level and the 1 I6 level which determine the four-peaks structure of the absorption between 430 500nm. Another absorption peak appears at 287nm (350000 cm1 ) due to the electronic transitions from the 3 H4 level to the 4f 1 5d band (Piramidowicz et al, 2008). In the emission spectrum the transitions arise from the decay of the electron from the two metastable states 3 P0 and 1 D2 , the latter usually populated through a multiphonon relaxation process, to the lower lying levels. The strongest of them is that centered at 609nm which corresponds to the 1 D2 3 H4 transition (Murai et al, 2010). Fig. 7 shows the PL spectrum of the co-doped samples C2-C6. Changing the concentration of Pr3+ in the

Fig. 7 PL spectra of the co-doped samples C2-C6. The spectra are recorded with ex = 430nm, a wavelength at which the praseodymium absorption is minim.

crystal we note a non-linear variation of the intensity of the peak centered at 609nm: there is a correspondence between the increase of the concentration of Pr and the decrease of the emission intensity of Ce. In particular, as reported elsewhere (Yang et al, 2009a), in the co-doped samples the transitions of praseodymium can take place thanks to the ET from the 5d states of a cerium ion and the 3 P0 level of a nearby Pr3+ (Zhang et al, 2011). When the concentration of Pr3+ grows to 0.5% mol there is a maximum in the emission 1 D2 3 H4 In Fig. 8 the normalized intensities of the Pr3+ and 3+ Ce emissions in the co-doped samples C2-C6 are reported. The intensities were evaluated through the integration of the band peaked at 530nm for cerium and

Marin, R. et al.

the peak at 609nm for praseodymium. The intensities of both cerium and praseodymium are normalized to the most intense in the series, in order to highlight the trend. There is an initial increase of the emission intensity of Ce3+ when passing from a content of Pr3+ of 0% to 0.0125%. That is an evidence of the possible energy transfer from praseodymium to cerium as well. As we noted before the emission of praseodymium has a maximum when its concentration reaches 0.5% mol. Above this threshold there is a decrease of the intensity even though the ET process is still present, as can be guessed by the trend of the cerium intensity, which decreases monotonically. An interpretation of this phenomenon is the appearance of the concentration self-quenching among Pr neighboring ions, as was already observed by Zhang et al. (Zhang et al, 2011) in the praseodymium system.

Ce 2%, Pr 0.125%

Ce 2%, Pr 0.25%

PLE Intensity (a.u.)

Ce 2%, Pr 0.5% Ce 2%, Pr 0%

Ce 2%, Pr 1%

Ce 2%, Pr 2%

Ce 0%, Pr 1%

320

340

360

380

400

420

440

460

480

500

520

Wavelenght (nm)

Fig. 9 PLE spectra of the samples C0-C6. The spectra are recorded with em = 580nm, a wavelength at which the praseodymium emission is negligible.

1,0

Ce 2%, Pr 0% Ce 2%, Pr 0.25%

PL Intensity normalized

0,8

Ce 2%, Pr 2%
e
-1

0,6

0,4

-2

0,2

-3

0,0 0,00 0,25 0,50 0,75 1,00 1,25 1,50 1,75 2,00

Quantity of Pr (%)
0 20 40 60 80

Fig. 8 Normalized intensity of the the emission of the two lanthanide ions under excitation at = 430nm. Fig. 10 Cerium excited states decay in samples C1, C3 and C6 exciting at ex = 454nm and recording the emission at em = 580nm.

The increase in the rate of the energy transfer phenomenon is conrmed by the PLE spectra of the samples C0-C6 (Fig. 9). These spectra were recorded at em = 580nm. Here praseodymium has a little uorescence (see Fig. 5) so most of the intensity can be ascribed to cerium. It is worth noting that the re-emitted radiation has an abrupt fall in sample C4 (0.5% mol). That is in accordance with the interpretation given before about the ET process, which can occour more frequently as the number of neighboring Ce3+ and Pr3+ increases, thus killing the emission of cerium. Actually the two ions have overlapping emissions, as can be seen by comparing the emission of the singly doped samples C0 (1% Pr) and C1 (2% Ce), so the signal cannot be exactly discern either coming from cerium or from

praseodymium, and the quantity of energy which is really transferred to Pr is underestimated. When the concentration of Pr3+ increases the intensity of the Ce3+ band diminishes even though the content of this lanthanide is constant in every sample. This is again an indication that the phenomenon of energy transfer strongly aects the properties of the system YAG:Ce,Pr. In Figs. 10 and 11 we reported the lifetimes of some selected samples in order to exemplify the trend of the decay of both cerium and praseodymium with respect to the increase of the doping degree. To t the decay of the ions the general function is:

Photoluminescence properties of YAG:Ce3+ ,Pr3+ phosphors synthesized via the Pechini method for white LEDs
e
0

Ce 0%, Pr 1% Ce 2%, Pr 0.5% Ce 2%, Pr 2%

45

-1

40

Normalized Intensity

-2

Lifetime (ns)

35

-3

30

25

-4

20

100

200

300

400

500

0,00

0,25

0,50

0,75

1,00

1,25

1,50

1,75

2,00

Time (

Quantity of Pr (%)

Fig. 11 Praseodymium excited states decay in samples C0, C4 and C6 exciting at ex = 445nm and recording the emission at em = 609nm.

Fig. 12 Mean lifetimes of cerium in samples C1-C6. There is an initial increase probably due to an energy absorption and transfer from praseodymium to cerium. Then the slope of the curve remains unchanged with a monotonic decrease in Ce lifetime.

I(t) = f +
i=1

Ai e

We used a double exponential form (n = 2) because of the ET phenomena which occur from cerium to praseodymium, and vice versa the energy transfer process may occur even from Pr to Ce, as can be guessed by the previous observations about the emission of cerium alone or in presence of praseodymium (see Fig. 8), along with the direct emission of the excited ion. Finally the mean lifetime has been evaluated using the formula:
n

Ai i2 =
i=1 n

Ai i
i=1

The data obtained from the tting procedure are reported in Tables 2 and 3 From Fig. 12 we can see how the mean lifetime of cerium varies by increasing the concentration of Pr. The lifetime of cerium varies from 24ns to 45ns, smaller than the values ranging from 60ns to 90ns reported in literature for micro-sized crystals (Zych et al, 1997; Katelnikovas et al, 2007) but in fair accordance with Zhou et al. (Zhou et al, 2006) who reported a mean lifetime of 30ns for nanophosphors. There is an initial increase when passing from 0%Pr to 0.125%Pr probably because of the occurrence of energy transfer processes. Actually praseodymium does absorb at 454nm. Then we see a monotonic decrease of the lifetime, due to the increasing importance of the phenomenon of energy transfer. The small value of the lifetime of cerium is determined by the allowed nature of the dipole transition, practically independent from the crystal-eld eects (Elias et al, 1973). In Fig. 13 we reported the mean lifetimes of praseodymium. These are in the microsecond range

Table 2 Values of coecients of the exponential tting for Ce3+ decay. Sample C1 C2 C3 C4 C5 C6 A1 (%) 27 30 34 27 27 25 1 (ns) 53.03 59.31 57.15 56.56 52.15 32.72 A2 (%) 73 70 66 73 73 75 2 (ns) 9.86 10.53 11.24 9.72 8.42 5.31 (ns) 38.46 44.89 44.43 41.49 38.90 23.85 Table 3 Values of coecients of the exponential tting for Pr3+ decay. Sample C0 C2 C3 C4 C5 C6 A1 (%) 42 72 68 57 56 45 1 (s) 240.57 256.39 236.08 265.91 192.81 134.20 A2 (%) 58 28 32 43 44 55 2 (s) 79.64 111.82 95.73 99.23 62.38 42.05 (s) 190.73 235.17 213.55 229.44 166.11 108.62

8
240

Marin, R. et al.
Ce2%

4 Conclusions In this work we have synthetized and analyzed YAG:Ce,Pr co-doped phosphors. These are a promising development in the white LEDs technology by covering of GaN blue LEDs, which is an alternative to the much more expensive RGB-LED technology. YAG:Ce system is just used for this purpose, but the resultant light is cold. By the ET phenomenon between lanthanides ions it is possible to transfer part of cerium green emission (485nm) to praseodymium red emission (609nm) with a nonradiative process. For optical use both emissions can add to a residual blue emission (460nm) of the common LEDs giving a warmer white light with higher CRI. From observations of the photoluminescence data we can conclude that the three phenomena governing the optical behavior of these systems are: a) the ET between Ce3+ and Pr3+ which increases with the quantity of co-dopant and is visible by the monotonic decrease of emission band of cerium; b) the energy transfer can occur even from praseodymium to cerium due to the almost resonant levels 2 D3/2 ,2 D5/2 of Ce3+ and the split 3 P0 level of Pr3+ that can be guessed from the increase in the emission intensity of cerium when also praseodymium is present; c) the eciency of Pr emission have a maximum at 0.5% mol, then a concentration quenching phenomenon is present. Future eorts will be made to determine the nanostructure of these systems and better understand the energy transfer phenomenon.
Acknowledgements The authors would like to thank Ph.D. R. Ricc` for the help given with the synthesis and Mr T. o Finotto for the XRD measurements. The reaserch projects of CIVEN are fully nanced by the Veneto Region Government.

220

200

Lifetime ( s)

180

160

140

120

100 0,125 0,25 0,5 1 2

Quantity of Pr (%)

Fig. 13 Mean lifetimes of praseodymium in C0 and C2-C6. There is an evident change in slope at the concentration of 0.5% mol.When both Ce and Pr are present the lifetime of Pr is smaller probably because of back energy transfer phenomena.

(108 240s) as reported by Liu (Liu and Jacquier, 2005) and Moune (Moune et al, 2002). Accordingly with previous observations we note a change in slope at 0.5% mol. This is due to the appearance of the concentration quenching between Pr centers. Comparing the lifetime of the two samples containing 1% mol of praseodymium we note a dierent behavior either the sample is singly or co-doped: when both cerium and praseodymium are present the lifetime is shorter. That is an eect of the transfer of the energy between ions. In the sample singly doped the mean distance between Pr3+ and another luminescent center is longer than that in the co-doped sample: in the former only the transfer between two Pr3+ can take place, in the latter there can be a transfer even between Pr3+ and Ce3+ . The real process, however, is not really clear because of the overlapping emission and absorption of the lanthanide ions and the diculties of singly exciting one of them. The lifetime curves show a non exponential decay, which was conveniently tted using a double exponential function. However, the similar trend observed in the two components 1 and 2 of both the lifetimes of cerium and praseodymium does not allow to make speculations about the attributions of these two decay components to single specic processes. Indeed, it is more likely that in these nanostructured materials the non exponential decay of lanthanide ions could be due to their dierent surroundings, since they can be closer to the surface of the particles or in the bulk. In this situation the use of a mean lifetime allows to take into account the diversity of the occupied sites, averaging the dierent contributions.

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Photoluminescence properties of YAG:Ce3+ ,Pr3+ phosphors synthesized via the Pechini method for white LEDs

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