TP CH KHOA HC, i hc Hu, S 59, 2010

NGHIN CU C TRNG PHT QUANG CA VT LIU KMgSO4Cl:Ce3+,Tb3+

L Vn Tut Trng i hc Khoa hc, i hc Hu Nguyn Duy Linh Trng i hc Qung Nam

TM TT
Bi bo ny trnh by cc kt qu thu c trong vic p dng phng php ha t ch to vt liu pht quang nn halosulphate KMgSO4Cl n pha tp v ng pha tp Ce3+, Tb3+. Kho st ph quang pht quang cho thy: vt liu nn KMgSO4Cl c th pha tp, ng pha tp cc ion t him vi gi tr nng ln; ion Ce3+ gi vai tr l tm tng nhy, ion Tb3+ gi vai tr l tm pht quang; trong vng kh kin, ph PL ca tt c cc vt liu c bn nh ln lt khong 493, 546, 586 v 623nm ng vi cc chuyn di 5D4 - 7FJ (J=6,5,4,3) ca ion Tb3+; nh c bc sng khong 546nm - bc x mu xanh l cy - c cng mnh nht, rt cn thit ng dng vt liu trong k thut chiu sng v hin th.

1. Gii thiu Nh mt s u th nh quy trnh ch to tng i n gin, hiu sut quang pht quang cao, c th ng dng di dng vt liu pht quang nhp nhy... nn h vt liu pht quang nn halosulphate pha tp cc ion t him (RE), tiu biu l KMgSO4Cl:RE, ang c quan tm nghin cu hng ti ng dng trong k thut chiu sng v mt s ng dng khc. Kt qu ca cc nghin cu thu c cho thy vt liu KMgSO4Cl:Eu2+ cho bc x mu xanh lam, c cc i bc x gi tr bc sng 435 nm nh chuyn di c trng ca tm Eu2+ v vt liu KMgSO4Cl:Eu3+ pht bc x mu , c gi tr bc sng 612nm v 619nm nh chuyn di c trng ca tm Eu3+. C hai vt liu ny u c hiu sut pht quang cao [1], [2]. Nh vy, nu ch to c vt liu pht quang nn KMgSO4Cl pht bc x mu xanh l cy th chng ta c th thu c vt liu pht nh sng trng da trn s t hp ba vt liu thnh phn. ng thi, ta bit rng ng vin s mt v thch hp nht cho bc x xanh l cy l tm pht quang ion Tb3+. Chuyn di 5D4 - 7F5 ca ion Tb3+ cho bc x khong 545nm c dng ph bin trong cc ng dng cn n bc x xanh l cy c chi cao, c bit l khi n c ng pha tp vi ion Ce3+ [3]. T thc t , chng ti tin hnh cc nghin cu ch to vt liu nn KMgSO4Cl n pha tp ion
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Tb3+, ng pha tp cc ion Ce3+, Tb3+ v kho st cc c trng ph PL ca chng tm kim vt liu pht nh sng trng hng ti ng dng trong k thut chiu sng cng nh k thut hin th. Trong bi bo ny, chng ti s trnh by nhng kt qu thu c trong vic kho st s nh hng ca nng cc ion pha tp n s pht quang ca vt liu KMgSO4Cl n pha tp ion Tb3+, ng pha tp cc ion Ce3+, Tb3+ c ch to theo phng php ha t cng nh mt s nhn nh v vai tr ca cc tm tp Tb3+, Ce3+ trong s hnh thnh ph quang pht quang (PL) ca vt liu ny. 2. Thc nghim Cc vt liu pht quang KMgSO4Cl:Tb3+, KMgSO4Cl:Ce3+,Tb3+ c ch to bng phng php ha t. Cc cng on chnh ca phng php c m t bng s hnh 1 [1, 4, 5]. Kt thc qu trnh ta thu c cc vt liu KMgSO4Cl:Tb3+, KMgSO4Cl:Ce3+,Tb3+ dng bt v em bo qun trong mi trng khan.
KCl MgSO4 CeO2 Tb4O7 Sulphate ha v kh Mui khan RE2(SO4)3 (RE = Ce hoc Tb) Ha tan bng nc ct hai ln Dung dch KMgSO4Cl Dung dch RE2(SO4)3 (RE = Ce hoc Tb) Ha tan bng nc ct hai ln Dung dch KCl Dung dch MgSO4

Dung dch KMgSO4Cl:RE3+ Sy 800C, trong 8 gi Tinh th KMgSO4Cl:RE3+ Sy 1400C, trong 1 gi, nghin mn Bt tinh th KMgSO4Cl:RE3+

Hnh 1. Quy trnh ch to vt liu bng phng php ha t.

Cu trc vt liu c kim tra bng php o nhiu x tia X (XRD) trn nhiu x k D8 ADVANCE ca hng Bruker (c), vi ch o: bc x K Cu, 40mV, 40mA, detector nhp nhy, 2=10-450, bc qut 0.030/0.3s (Trng i hc Khoa hc T nhin i hc Quc gia H Ni). Cc php o ph PL c thc hin ng thi trn hai h o: h o thng mi FL322, ngun kch thch s dng n Xenon cng sut 450W (Trng i hc Khoa hc T nhin i hc Quc gia H Ni) v h o t to, s dng n sc k SPM2
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vi cch t 651vch/mm, u thu nhn quang in loi M12FQS51, b khch i lockin SP510, h o c ghp ni v vn hnh bn t ng thng qua my tnh c nhn (Khoa Vt l, Trng i hc Khoa hc i hc Hu). Tt c cc php o c tin hnh vi mt lng mu bt nh nhau v vi cng mt ch kch thch v ghi nhn tn hiu pht quang. 3. Kt qu v tho lun 3.1. Kim tra cu trc vt liu Hnh 2 trnh by kt qu o gin XRD ca vt liu ch to c. Kt qu cho thy vt liu thu c c cu trc n pha, l bt tinh th KMgSO4Cl2.75H2O v c tn khong vt l Kainite. Cu trc tinh th thuc lp i xng n t (monoclinit-), nhm khng gian C2/m v cc thng s mng l a=19.72Ao, b=16.23Ao, c=9.53Ao, =90.00o, =94.92o, =90.00o. Cc thng s cu trc hon ton ph hp vi s liu ca th vin nhiu x k v cc nghin cu trc y v loi vt liu ny [4, 5]. ng thi, ging nh nhiu loi vt liu pht quang khc, s pha tp ion RE vi nng khng qu ln khng lm thay i cu trc ca mng tinh th nn.

Hnh 2. Gin XRD ca vt liu KMgSO4Cl:Tb3+

3.2. Kho st ph PL ca vt liu KMgSO4Cl:Ce3+ thay i theo nng pha tp Hnh 3 biu din ph PL ca vt liu KMgSO4Cl:Ce3+, kch thch bng bc x c bc sng 254nm, vi nng pha tp Ce3+ thay i t 1, 2, , 10 %mol. Ta thy tt c cc ph u c dng ging nhau, l ph m trong vng t ngoi, c hai nh vi cng kh mnh nm khong 345 nm v 325 nm, chng c xem l kt qu gy ra ca cc chuyn di tng ng t trng thi kch thch 5d v trng thi c bn
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F5/2 v 2F7/2 ca ion Ce3+. S thay i nng pha tp khng lm thay i cu trc ph m ch lm thay i cng bc x ca tm ion Ce3+. Khi tng nng pha tp Ce3+ th cng cc nh bc x u tng v cha c du hiu dp tt do nng ngay c khi nng pha tp Ce3+ t gi tr kh ln 10%mol, kt qu ny cng ph hp vi cc nghin cu cng b [1, 3, 5, 6].
1.4x10 1.2x10 Cng PL (vt) 1.0x10 8.0x10 6.0x10 4.0x10 2.0x10
7

10%mol Ce
7

3+

8%mol Ce
7 6 6 6 6

3+ 3+

6%mol Ce 3+ 4%mol Ce 2%mol Ce 3+ 1%mol Ce

3+

0.0 300
3+

350

400

450

Bc sng (nm) Hnh 3. Ph PL ca KMgSO4Cl:Ce thay i theo nng pha tp Ce3+, kch thch bng bc x c bc sng 254nm.

3.3. Kho st ph PL ca vt liu KMgSO4Cl:Tb3+ thay i theo nng pha tp Hnh 4 trnh by kt qu o ph PL ca vt liu KMgSO4Cl:Tb3+, kch thch bng bc x c bc sng 365 nm, vi nng pha tp Tb3+ thay i t 0.1 n 4%mol. Kt qu ny cho thy, ph PL ca vt liu n pha tp Tb3+ c bn di hp c lp nhau c nh khong 493, 546, 586 v 623 nm, chnh l bn bc x c trng ca tm ion Tb3+, tng ng vi cc chuyn di 5D4 - 7FJ (J=6, 5, 4, 3). Cc di ph ny c rng nh, trong mnh nht l di c nh khong bc sng 546 nm (chuyn di 5 D4 - 7F5), y chnh l yu t ion Tb3+ gi vai tr ch o trong cc ng dng cn n vt liu pht bc x xanh l cy [3, 7]. S thay i nng pha tp khng lm nh hng n cu trc ph m ch lm thay i cng cc bc x c trng ca ion Tb3+ theo cng mt quy lut: tt c u tng theo nng pha tp Tb3+. Ging nh i vi tp ion Ce3+, trng hp ny cng cha cho thy c du hiu dp tt nh sng pht quang v nng , ngay c khi nng pha tp Tb3+ t gi tr kh ln - 4%mol. iu a n nhn nh rng c th pha tp ion RE cho vt liu nn KMgSO4Cl vi gi tr nng cao hn thng thng.

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2.5x10 Cng PL (vt) 2.0x10 1.5x10 1.0x10 5.0x10

4%mol Tb 3%m ol Tb 2%mol Tb

3+

3+

3+

1%mol Tb

3+ 3+ 3+

0.5%m ol Tb
6

0.1%m ol Tb

0.0 450

500

550 Bc sng (nm )

600

650

Hnh 4. Ph PL ca KMgSO4Cl:Tb3+ thay i theo nng pha tp Tb3+, kch thch bng bc x c bc sng 365nm.

3.4. Ph PL ca vt liu KMgSO4Cl:Ce3+,Tb3+ thay i theo nng pha tp Ce3+ kho st vai tr v nh hng ca nng pha tp ion Ce3+ i vi s hnh thnh ph PL ca vt liu ng pha tp KMgSO4Cl:Ce3+,Tb3+, mt lot mu c ch to vi cng nng 0.5%mol Tb3+ v nng Ce3+ thay i t 0 ti 10%mol. Hnh 5 biu din kt qu cc php o ph PL ca lot mu trong cng mt iu kin.
0.5%m ol Tb ,10%m ol C e 3+ 3+ 0.5%m ol Tb 3+,8%m ol C e 3+ 0.5%m ol Tb ,6%m ol C e 0.5%m ol Tb ,4%m ol C e
3+ 3+ 3+ 3+ 3+

8.0x10

Cng PL (vt)

6.0x10 4.0x10 2.0x10

0.5%m ol Tb ,2%m ol C e 3+ 3+ 0.5%m ol Tb ,1%m ol C e

3+

0.5%m ol Tb

3+

0.0 450

500

550

600

650

700

B c sng (nm ) Hnh 5. Ph PL ca KMgSO4Cl:Ce3+,Tb3+ thay i theo nng pha tp Ce3+, kch thch bng bc x c bc sng 254nm.

Ta thy, tt c cc ph u th hin cc bc x c trng ca tm Tb3+, s gia tng nng pha tp Ce3+ khng lm thay i cu trc ph m ch lm gia tng cng cc bc x v so vi tt c cc mu ng pha tp, cc bc x c trng ca mu n pha tp Tb3+ c cng yu nht. iu c ngha l, vic ng pha tp Ce3+ lm gia tng r rt hiu sut pht quang ca tm Tb3+, v l minh chng r rng cho
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vai tr tm tng nhy ca ion Ce3+ i vi tm pht quang ion Tb3+. Nh vy, c tn ti mt qu trnh truyn nng lng kch thch t tm tng nhy Ce3+ n tm pht quang Tb3+ trong qu trnh pht quang ca vt liu KMgSO4Cl:Ce3+,Tb3+, ni cch khc bc x pht quang ca tm Ce3+ lm gia tng hiu qa pht quang ca tm Tb3+. Qu trnh ny xy ra hon ton tng t nh trong vt liu KMgSO4Cl:Ce3+,Eu2+ cng nh cc vt liu khc ng pha tp ion Ce3+ vi cc ion t him khc [1, 3, 5]. 3.5. Ph PL ca vt liu KMgSO4Cl:Ce3+,Tb3+ thay i theo nng pha tp Tb3+ Hnh 6 trnh by kt qu o ph PL ca vt liu KMgSO4Cl:Ce3+,Tb3+ vi nng pha tp Ce3+ khng i l 10%mol v nng pha tp Tb3+ thay i tng ng l 0.1, 0.5, 1, 2, 3 v 4%mol. Ta thy, cng ging nh trng hp kho st trn vi vt liu KMgSO4Cl:Tb3+, khi nng tm tng nhy Ce3+ khng i, cng cc bc x c trng ca Tb3+ trong vt liu KMgSO4Cl:Ce3+,Tb3+ cng tng dn theo nng tm Tb3+, cha c du hiu dp tt nh sng pht quang v nng trong khong nng kho st.
3 .0 x10 2 .5 x10 Cng PL (vt) 2 .0 x10 1 .5 x10 1 .0 x10 5 .0 x10
7

10% m ol C e , 4%m o l Tb

3+

3+

10%m o l C e , 3%m ol T b 10%m o l C e , 2% m ol T b

3+

3+

3+

3+

10%m o l C e , 1% m ol T b
7
3+

3+

3+

10%m o l C e , 0.5%m o l T b
6

3+ 3+

10%m o l C e , 0.1%m ol T b

3+

0.0 45 0

500

550

6 00

6 50

70 0

B c sng (nm )
Hnh 6. Ph PL ca KMgSO4Cl:Ce3+,Tb3+ thay i theo nng pha tp Tb3+, kch thch bng bc x c bc sng 254nm.

Nh vy, c th kt lun rng i vi vt liu nn KMgSO4Cl c th pha tp, ng pha tp cc ion t him vi gi tr nng kh ln. Tuy nhin, kt qu thu c y cho thy, vi nng pha tp 10%mol Ce3+ v 4%mol Tb3+ vt liu cho bc x pht quang c cng mnh thc hin cc kho st, nghin cu khc v c trng quang ph cng nh nh hng ng dng ca n. V vy, hin ti cha cn thit thc hin tip cc php kho st tng t vi vt liu pha tp, ng pha tp ion Ce3+, Tb3+ vi cc gi tr nng ln hn na.

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4. Kt lun ch to thnh cng vt liu KMgSO4Cl pha tp v ng pha tp cc ion Ce3+, Tb3+ bng phng php ha t. Ph PL trong vng kh kin ca vt liu mang c trng cho cc chuyn di ca ion Tb3+, c th gm bn bc x c nh ln lt khong 493, 546, 586 v 623 nm ng vi cc chuyn di 5D4 - 7FJ (J=6,5,4,3) ca ion Tb3+. Cng mnh nht l bc x c bc sng khong 546 nm, l bc x mu xanh l cy (green) c chi cao, c bit cn thit trong k thut chiu sng v hin th bn cnh cc bc x xanh lam (blue) v (red). Trong vt liu ng pha tp, ion Ce3+ ng vai tr tm tng nhy cho tm pht quang Tb3+. C th dng vt liu KMgSO4Cl:Ce3+, Tb3+ vi nng pha tp: 10%mol Ce3+ v mt vi %mol Tb3+ cho cc cng vic kho st, nghin cu v c trng quang ph cng nh hng ng dng ca loi vt liu pht quang ny.

TI LIU THAM KHO

1. Gedam S.C., Dhoble S.I., Moharil S.V. Eu2+ and Ce3+ emission in sulphate based phosphor, Journal of Luminescence, (128), (2008), 1 6. 2. Dhoble S.I., Gedam S.C., Nagpure I.M., Godbole S.V. and Bhide M.K. Photoluminescence and thermoluminescence characteristics of KXSO4Cl: Eu (X = Zn or Mg) halosulfate phosphor, Journal of physics, (40), (2007), 6039 6043. 3. Blasse G., Grabmaier B.C. Luminescent materials, Springer Verlag, Berlin Heidelberg, (1994). 4. Gedam S.C., Dhoble S.I., Moharil S.V. Dy3+ and Mn2+ emission in KMgSO4Cl phosphor, Journal of Luminescence, (124), (2007), 120 126. 5. Gedam S.C., Dhoble S. I., Moharil S.V. 5d 4f transition in halosulphate phosphor, Journal of Luminescence, (126), (2007), 121 129. 6. I.V. Berezovskayaa, V.P. Dotsenkoa, N.P. Efryushinaa, A.S. Voloshinovskiib, C.W.E. van Eijkc, P. Dorenbosc, A. Sidorenkoc. Luminescence of Ce3+ ions in alkaline earth borophosphates. Journal of Alloys and Compounds 391 (2005), 170176. 7. Chaofeng Zhu, Xiaoluan Liang, Yunxia Yang, Guorong Chen. Luminescence properties of Tb doped and Tm/Tb/Sm co-doped glasses for LED applications. Journal of Luminescence 130, (2010), 7477

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STUDY LUMINESCENCE PROPERTIES OF KMgSO4Cl:Ce3+,Tb3+ MATERIALS

Le Van Tuat College of Sciences, Hue University Nguyen Duy Linh Quang Nam University

SUMMARY
This paper reports the results of applying the wet chemical method to synthesize the phosphors based on KMgSO4Cl host doped and co-doped Ce3+, Tb3+ ions. The photoluminescent spectra shows that: we can dope and co-dope the rare earth ions with a rather high concentration for the KMgSO4Cl materials; the Ce3+ ion plays the role of sensitizer center and the Tb3+ ion is the luminescent center. In addition, in the visible spectra band, the photoluminescent spectra from all of received phosphors present four peaks, at the wavelength of 493, 546, 586 and 623nm, corresponding to the 5D4 - 7FJ (J=6,5,4,3) transitions of Tb3+ ions, among them the intensity of the 546nm peak (green-color radiation) is the strongest. This radiation is necessary factor for applications in the indicators and light sources.

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