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CHNG 4

KT QU V BN LUN: KHO ST MT S TNH

CHT QUANG CA VT LIU 10SnO2-90SiO2: xEr3+ CH TO

BNG PHNG PHP SOL-GEL.
4.1.

Ph nhiu x tia X (XRD).

Hnh 4.1: Ph XRD ca bt SnO2.

Cn c vo cc s liu trong ph nhiu x tia X (XRD) o t c ti
Vin Khoa hc Vt liu ng dng (s 1 Mc nh Chi, Q.1, Tp.HCM), chng ti
tin hnh tnh ton kch thc ht da theo phng trnh Scherrer:

(4.1)

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4.1.1.

nh hng ca nhit .

Hnh 4.2: Ph XRD ca vt liu 10SnO2-90SiO2: xEr3+ vi x = 0,4% mol c

nung cc nhit 120oC, 400oC, 600oC, 800oC v 1000oC.

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Hnh 4.3: Ph XRD ca vt liu 10SnO2-90SiO2: xEr3+ vi x = 0,8% mol c

nung cc nhit 120oC, 400oC, 600oC, 800oC v 1000oC.

Vt liu c sy 120oC ch yu cho peak c nh xung quanh 23 o c trng

cho vt liu SiO2 v nh hnh. Khi nung n cc nhit 400oC, 600oC, 800oC v
1000oC th ph XRD ca cc mu vt liu cho cc peak ti v tr 2 = 26.5o, 33.6o,
38.3o v 51.7o tng ng vi cc mt mng (110), (101), (200) v (210) c trng
cho tinh th SnO2 (theo phiu chun JPCD s 41-1445). Khi nhit tng, cng
cc peak tng tc tinh th ha ca SnO2 bn trong vt liu tng ln. Theo l

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thuyt, mt (110) u tin pht trin nht bi v mt nguyn t trn mt (110) ln

nht do n c nng lng b mt thp nht, tip theo l mt (101), (210) v (200).
T ph XRD ca vt liu 10SnO2-90SiO2: xEr3+ (hnh 4.2 v 4.3), chng ti chn
mt (101) tnh kch thc ht theo phng trnh Scherrer.

Bng 4.1: Kch thc ht SnO2:Er3+ trong vt liu 10SnO2-90SiO2: xEr3+ cc nhit
120oC, 400oC, 600oC, 800oC v 1000oC.
vt liu 10SnO2-90SiO2: xEr3+
x = 0.4%

Nhit
(oC)

Hng
mt mng
[hkl]

x = 0.8%

Kch thc

Kch thc

bn rng

ht theo

bn rng

ht theo

(FWHM)

phng trnh

(FWHM)

phng trnh

()

Scherrer (4.1)

()

Scherrer (4.1)

(nm)

(nm)

120

400

101

1.96

4.24

1.86

4.46

600

101

1.86

4.46

1.72

4.83

800

101

1.77

4.69

1,42

5.85

1000

101

1.53

5.43

1.31

6.34

Qua ph XRD theo nhit (hnh 4.3), ta thy cng mt nng pha tp ion
Er3+ (vi 0.4% v 0.8%), th kch thc ca ht SnO2: Er3+ tng theo nhit , nhng
tng chm.
Khi nhit tng, phn ln nng lng nhit dng loi b cc gc hu c
v to rn chc tinh th ha vt liu, dn ti hin tng kt m ca cc ht
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SnO2:Er3+, ng thi cng lm tng kh nng kt m ca cc ion Er3+ vi nhau trong

nn SiO2. Do , khi nhit tng th kch thc ht tng nhng tng tng i chm.

Hnh 4.4: S ph thuc kch thc ht SnO2:Er3+ vo nhit .

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4.1.2.

nh hng ca nng pha tp ion Er3+.

Hnh 4.5: Ph XRD ca vt liu 10SnO2-90SiO2: xEr3+ vi x = 0.2; 0.4; 0.6; 0,8
v 1.0% mol c nung nhit 1000oC.

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Bng 4.2: Kch thc ht SnO2:Er3+ trong vt liu 10SnO2-90SiO2: xEr3+ vi

x = 0.2; 0.4; 0.6; 0,8 v 1.0% mol c nung nhit 1000oC.
vt liu 10SnO2-90SiO2: xEr3+

x (%mol)

Hng mt mng
[hkl]

bn rng

Kch thc ht theo

(FWHM)

phng trnh

()

Scherrer (nm)

0.2

101

1.54

5.39

0.4

101

1.53

5.43

0.6

101

1.38

6.01

0.8

101

1.31

6.34

1.0

101

1.26

6.59

Qua ph XRD (hnh 4.5) v bng gi tr tnh ton c t ph ca vt liu

10SnO2-90SiO2: xEr3+ vi cc nng pha tp ion Er3+ khc nhau c nung cng
nhit 1000oC (bng 4.2), ta thy kch thc ht tng theo nng pha tp ca ion
Er3+, tuy nhin kch thc ht tng khng u. Kch thc ca ht tng rt t (t
5.39nm n 5.43nm) khi nng pha tp tng t 0.2% n 0.4%, tng nng pha tp
n 0.6% th kch thc ht tng tng i nhanh hn (6.01nm) v sau tip tc tng
u khi nng pha tp tng n 0.8% v 1.0%. iu ny cho thy, khi nng pha
tp ion Er3+ tng, th mt phn tn ca ion Er3+ vo trong nn SnO2-SiO2 nhiu hn,
kh nng kt m ca chng cng hiu dng nhit cao, t lm cho kch thc
ht tng ln.

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Hnh 4.6: S ph thuc kch thc ht SnO2:Er3+ vo nng phn trm pha tp ion
Er3+.

4.2.

Ph hp th UV Vis.
Chng ti nhn thy rng, vt liu 10SnO2-90SiO2: xEr3+ m chng ti tng

hp l vt liu trong sut (c kh nng cho nh sng truyn qua), v vy chng ti tin
hnh o ph hp th vng t ngoi kh kin (UV-Vis) b sung thm vic xc nh
kch thc trung bnh ca ht SnO2: Er3+ c kch thc c nano mt c pha tp trong
nn SiO2, ng thi kho st thm tnh cht quang ca vt liu thng qua vic kho
st s thay i rng vng cm ca ht nano tinh th.
Theo c s l thuyt ca hiu ng suy gim kch thc lng t cho thy b
hp thu dch chuyn v bc sng ngn khi kch thc ht tinh th gim (c nm). S
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dch chuyn b nng lng lin quan n kch thc ht c tnh theo phng trnh
Kayanuma trong trng hp i vi tinh th SnO2:
(4.2)

Eg0 = 3.6eV: rng vng cm tng ng dng khi ca tinh th SnO2.

= 13.5: hng s in mi ca vt liu SnO2.

= (1/m*e + 1/m*h)-1= 0.3mo: khi lng hiu dng rt gn.

m*e v m*h : khi lng hiu dng ca in t v l trng vi m*e<< m*h ;

mo: khi lng tnh ca in t t do.

R: bn knh ht tinh th.

D = 2R: kch thc ht tinh th.

Hnh 4.7: th biu din s ph thuc ca nng lng rng vng cm Eg(R) theo
bn knh ht tinh th.

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Cn c vo kt qu tnh ton kch thc trung bnh ca ht SnO2: Er3+ pha tp

trong nn SiO2 da theo ph XRD ca vt liu 10SnO2-90SiO2: xEr3+ vi x = 0.2; 0.4;
0,8 v 1.0% mol nhit 1000oC, chng ti nhn thy kch thc trung bnh ca ht
o c khong t 5-7nm. Tng ng vi kch thc ny, th ht SnO2: Er3+ nm trong
vng suy gim kch thc lng t trung bnh, do chng ti vn c th p dng hiu
ng suy gim kch thc lng t tnh nng lng rng vng cm ca ht nano
SnO2: Er3+ pha tp trong nn SiO2 1000oC theo phng trnh Kayanuma . T ,
chng ti tin hnh o ph hp th UVVis ca vt liu 10SnO2-90SiO2: xEr3+ (vi x =
0.2; 0.4; 0,8 v 1.0% mol) nhit 1000oC bng my HALO RB-10 t ti phng
Vt L ng Dng, trng i hc Khoa hc T nhin TP.HCM.

Hnh 4.8: Ph hp th UVVis ca vt liu 10SnO2-90SiO2: xEr3+ vi x = 0.2; 0.4;

0,8 v 1.0% mol c nung nhit 1000oC.

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Bng 4.3: Kch thc trung bnh ca ht SnO2:Er3+ trong vt liu 10SnO2-90SiO2:
xEr3+ vi x = 0.2; 0.4; 0.6; 0,8 v 1.0% mol c nung nhit 1000oC.
Kch thc ht

Kch thc ht

(2R) tnh theo

Eg tnh theo

Eg tnh t ph

(2R) tnh theo

phng trnh

phng trnh

hp th

phng trnh

(%mol)

Scherrer (4.1) t

Kayanuma (4.2)

1000oC (hnh

Kayanuma (4.2)

ph XRD

(eV)

4.8) (eV)

t ph hp th

1000oC (nm)

1000oC (nm)

0.2

5.39

3.708

4.254

2.62

0.4

5.43

3.704

4.046

3.10

0.8

6.34

3.666

3.906

3.65

1.0

6.59

3.656

3.670

6.53

Theo kt qu tnh ton c t bng 4.3 cho thy kch thc ht SnO2:Er3+ suy
ra t phng trnh c s sai lch tng i ln so vi kt qu tnh ton da theo ph
XRD ca vt liu khi nng pha tp Er3+ tng t 0.2-0.8% mol, v khi nng pha
tp Er3+ bng 1.0% mol th kt qu thu c trong 2 trng hp gn nh bng nhau.
iu ny c th c gii thch l do vt liu m chng ti tng hp l hn hp gm
nano tinh th SnO2, ion Er3+ v vt liu nn SiO2, trong khi cng thc Kayanuma c
dng tnh ton cho vt liu thun SnO2.

4.3.

nh hin vi in t truyn qua (TEM).

kho st chnh xc hn v s phn b, hnh thi v kch thc ca ht

SnO2:Er3+ trong vt liu 10SnO2-90SiO2: xEr3+, sau khi tnh ton kch thc ht da
trn nn ph XRD v ph hp th UV-Vis, chng ti tin hnh o kch thc ht
bng knh hin vi in t truyn qua TEM 1400 ti Trng i Hc Bch Khoa,
HQG TP.HCM. Vt liu chng ti s dng l vt liu 10SnO2-90SiO2: xEr3+ vi:
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Mu 1: x = 0.8% c nung nhit 800oC.

Mu 2: x = 0.8% c nung nhit 1000oC.
Mu 3: x = 1.0% c nung nhit 1000oC.

Do vt liu m chng ti tng hp dng khi, nn chng ti khng th thc

hin qu trnh o. V vy chng ti tin hnh nghin vt liu thnh dng bt mn v
sau ha tan bng dung dch CH3COOH long, sau nh git ln trn li ng ri
mi tin hnh o TEM.

Hnh 4.9: nh TEM ca vt liu 10SnO2-90SiO2: 0,8%Er3+ c nung nhit

800oC.

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Hnh 4.10: nh TEM ca vt liu 10SnO2-90SiO2: 0,8%Er3+ c nung nhit

1000oC.

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Hnh 4.11: nh TEM ca vt liu 10SnO2-90SiO2: 1.0%Er3+ c nung nhit

1000oC
Bng 4.4: Kch thc trung bnh ca ht SnO2:Er3+ trong vt liu 10SnO2-90SiO2:
xEr3+ o t c da vo nh TEM.
vt liu 10SnO290SiO2: xEr3+
Nhit nung (oC)
Kch thc trung
bnh ca ht (nm)

x = 0.8%

x = 0.8%

x = 1.0%

800oC

1000oC

1000oC

3.5 n 6.0

4.0 n 7.0

5.0 n 8.0

Nhn xt: Kt qu thu c tng i ph hp vi kt qu tnh ton kch

thc trung bnh ca ht SnO2:Er3+ trong vt liu 10SnO2-90SiO2: xEr3+ (vi x = 0.8%
v 1.0% mol) c nung 800oC v 1000oC da theo ph nhiu x XRD mc 4.1.

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4.4.

Ph Raman theo nhit .

Chng ti tin hnh chp ph Raman ca vt liu 10SnO2-90SiO2:

0,8%Er3+ c nung cc nhit 400oC, 600oC, 800oC v 1000oC. Ph c chp

bi my quang ph Micro-Raman, s dng ngun laser kch thch c bc sng l
632.81 nm, t ti PTN. Cng ngh Nano, i hc Quc gia TP.HCM.

Hnh 4.12: Ph Raman ca vt liu 10SnO2-90SiO2: 0,8%Er3+ c nung cc nhit

400oC, 600oC, 800oC v 1000oC.

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14
Nh bit, tinh th SnO2 thuc nhm D4h
(P42/mnm) v c cu trc t din

(pha Rutile). Vt liu khi SnO2 c 4 mode dao ng xut hin trong ph Raman: 123
cm-1 (B1g) , 476 cm-1 (Eg), 638 cm-1 (A1g) v 782 cm-1 (B2g). Cng Raman ca B1g
rt yu. Cc mode A2u , Eu v B1u l cc mode ch xut hin trong ph hng ngoi.

Bng 4.5: Bng tng quan gia cc dao ng v s sng ca vt liu 10SnO2-90SiO2:
0,8%Er3+ c nung cc nhit 400oC, 600oC, 800oC v 1000oC.
Nhit

(Si-O-Si )

D1

D2

vs Sn-O

-1

(cm )

( C)

vs Si-O-Si
-1

(cm-1)

(cm-1)

A1g (cm )

-1

(cm )

vs C-C ,
vs C-O

(cm-1)

vs Si-OH

(cm-1)

400

453

483

809

972

600

486

626.5

796

975

800

483

596

630

783

975

1000

453

486.5

603

630

786

972

Trong cc mu khi c nung cc nhit khc nhau t 400oC n 1000oC

th hu nh khng xut hin cc mode dao ng s(C-C) v s(C-O), m ch yu l cc
mode dao ng c trng cho cu trc v nh hnh ca SiO2 nhit cao nh: 453
cm-1 (Si-O-Si), 483 cm-1 D1, 596 cm-1 D2, 809 cm-1 s(Si-O-Si), 972cm-1 s(Si-OH) v
c bit l mode dao ng 630cm-1 A1g(s(Sn-O)) c trng cho vt liu nano SnO2.
Khi nhit tng, cng nh ph 972 cm-1 s(Si-OH) gim rt nhanh,
l do nhit cao, cc gc OH trong mu b bay hi gn nh hon ton, kt qu ny

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ph hp vi ti liu tham kho s [7]. Ngc li, khi nhit tng, th cng ca
peak 630 cm-1 A1g(s(Sn-O)) cng tng theo. Theo kt qu tnh ton kch thc ht thay
i theo nhit da vo ph XRD (phn 4.1.1) th chng ti c th kt lun: nhit
cng tng th kch thc ht SnO2 cng tng, do cng dao ng A1g ca nano
tinh th SnO2 trong nn SiO2 cng tng theo.

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4.5. Ph pht quang (PL).

4.5.1.

Ph pht quang (PL) vng bc x kh kin theo nhit v theo

nng pha tp Er3+.

Ph pht quang (PL) vng bc x kh kin ca vt liu 10SnO290SiO2: xEr3+ nung cc nhit v pha tp Er3+ khc nhau c chng ti
tin hnh o t vi bc sng kch thch 325nm, thc hin ti phng th nghim
Vt L ng Dng thuc khoa Vt L, trng i hc Khoa hc T nhin
TPHCM, a ch 227 Nguyn Vn C, Q.5, Tp.HCM.

Hnh 4.13: Ph PL thuc vng kh kin ca vt liu 10SnO2-90SiO2: 0.4%Er3+

c nung cc nhit 120oC, 400oC, 800oC v 1000oC.

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Hnh 4.14: Ph PL thuc vng kh kin ca vt liu 10SnO2-90SiO2: x%Er3+ vi

x = 0.2%, 0.4%, 0.8% v 1.0% mol c nung nhit 1000oC.

Nhn xt:
Kt qu nhn c t ph PL thuc vng kh kin (hnh 4.13, 4.14)
ca vt liu 10SnO2-90SiO2: 0.4%Er3+ cc nhit khc nhau v ca vt liu
10SnO2-90SiO2: xEr3+ vi nng pha tp khc nhau c nung ti nhit
1000oC cho thy: Khi mu 10SnO2-90SiO2: 0.4%Er3+ cha c x l nhit (sy
120oC) hoc khi c nung nhit thp (400oC) th vt liu ch yu pht x
vng ln cn 550nm vi nh ph c rng tng i ln. Nguyn nhn l do
hin tng dp tt hunh quang gy ra bi cc gc OH- cn tn ti nhiu trong
vt liu do nhit x l mu cn thp. Vi nhit x l cao (800oC v 1000oC),
th c xut hin mt s nh ph tng i r i vi c 2 loi vt liu trn:

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+ nh ph hp ti 555.5nm vi cng rt mnh.

+ nh ti 664nm c rng tng i v cng thp.
Hai bc x ny c gy ra do s chuyn mc nng lng tng ng
4

S3/2 4I15/2 v 4F9/2 4I15/2 ca ion Er3+, cng ca hai bc x ny ph

thuc vo c nhit v nng pha tp. Kt qu ny chng t rng, s pht x

ca vt liu ch yu l do cc ion Er3+ ha tan trong tinh th SnO2 (cc ion Er3+
ny nhn c nng lng truyn n t cc tinh th nano SnO2) v cc ion Er3+
kt m trong nn SiO2; nng lng ny hoc c truyn trc tip t cc sai
hng ca cu trc mng, hoc c truyn gin tip qua s kt hp ca cc l
trng vi cc ion Er3+.
+ Ngoi ra cn c 2 nh ph c cng rt thp ti 572nm v 690nm.
Cng nh ti bc sng 572nm gn nh khng ph thuc vo nhit mu
v nng pha tp ca ion Er3+. Bc x ny c bit nh s kt hp cc mc
nng lng khuyt tt trong phm vi vng nng lng ca SnO2 (khng ha tan
ion Er3+) do s kt hp ca cc nt khuyt O, cc nt Sn hoc d lin kt trong
mng SnO2 v cc khuyt tt ny c hnh thnh trong sut qu trnh tng hp
vt liu. i vi nh ph ti bc sng 690nm, th cng bc x ch yu chu
nh hng ca nng pha tp ion Er3+ hn l nhit nung mu. Bc x ny l
do s chuyn mc 4F9/2 4I15/2 ca cc ion Er3+ kt m trong nn SiO2. iu
ny chng t, khi nng pha tp ion Er3+ tng, th s kt m ca chng trong
nn SiO2 cng nhiu, ngha l ch c mt lng nh ion Er3+ pha tp l c ha
tan vo tinh th nano SnO2.

4.5.2. Ph pht quang (PL) vng bc x hng ngoi theo nng pha tp
ion Er3+.

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Ph pht quang (PL) vng bc x hng ngoi vt liu 10SnO2-90SiO2:

x%Er3+ theo nng pha tp ion Er3+ khc nhau c thc hin o t ti phng
phn tch quang ph v phn tch Raman,i hc Lille, nc Php, vi bc sng
kch thch l 351nm.

Hnh 4.15: Ph PL ca vt liu 10SnO2-90SiO2: x%Er3+ vi x = 0.2%, 0.4%,

0.8% v 1.0% mol c nung nhit 1000oC.

i vi ph pht quang (PL) vng bc x hng ngoi ca vt liu

10SnO2-90SiO2: x%Er3+ (vi x = 0.2%, 0.4%, 0.8% v 1.0% mol) nhit
1000oC, c xut hin mt s nh ph c trng:
+ nh ti 1551nm c cng ln nht, cng nh tng chm theo
nng pha tp ion Er3+.

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+ Cc nh ti bc x 1522.5nm, 1533nm v 1571.5nm c cng thp

hn, cng cc nh ny cng tng kh chm theo nng pha tp ion Er3+.
Cc bc x ny c gy ra do s chuyn mc nng lng tng ng
4

S3/2 4I9/2 v 4I13/2 4I15/2 ca ion Er3+. Kt qu ny cng chng t c rng,

c mt phn nh ion Er3+ trong lng pha tp ha tan vo cc tinh th nano

SnO2, cn li hu ht chng b kt m trong nn SiO2, s kt m ny xy ra
cng mnh khi nhit nung mu cng tng. iu ny l ph hp i vi nhng
vt liu tng hp bng phng php Sol-Gel.

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