BO CO MN QUANG PH NG DNG

HVCH : TRN TH M HNH

CHUYN NGNH : Quang hc
NHM 3
I HC QUC GIA H CH MINH
TRNG I HC KHOA HC T NHI N
S 227 ng Nguyn Vn C Q.5, Tp. HCM
Tel : 38 353 193 Fax: 38 350 096
Tp. H Ch Minh Thng /2010
PHN I
Tn ca tp ch : Cu trc vt liu nano ( NanoStructured Materials)
S th t (Volume) : 11
S trang : 603 609
Nm ng bi : 1999
Nhm tc gi :
- T.R.Ravindran, Akhilesh K.Arora. Nhm khoa hc vt liu, trung tm nghin cu
nguyn t Indira Gandhi, Kalpakkam 603102, n .
- B.Balamurugan and B.R.Mehta. Phng th nghim mng mng, Khoa vt l, vin
cng ngh n , New Delhi 110016, n .
Tn bi bo :
INHOMOGENEOUS BROADENING IN THE PHOTOLUMINESCENCE
SPECTRUM OF CdS NANOPARTICLES
( S m rng khng ng nht trong ph pht quang ca ht nano CdS )
Mc ch chnh ca nghin cu ny :
Nguyn nhn gy ra s dn rng khng ng nht ca ht nano CdS c phi l do nh
hng ca s phn b kch thc ht hay khng.
Phng php to mu : phng php ph ha hc ( chemical capping )
- Cch to nh sau :
- Dung dch (a): 2.67 g cadmium acetate trong 80 ml methanol v 20 ml acetonitrile
- Dung dch (b): 0.8 g sodium sulphide trong 50 ml methanol v 50 ml n c.
- Dung dch (c): 1.1 ml thiophenol trong 100 ml acetonitrile
- Dung dch (a) v dung dch (c) c thm vo chm ri c khuy nh trong 30
pht.
- Sau dung dch (b) c thm vo chm trong hn hp trn ho trn , vn tip
tc khuy nh.
- Kt qu s thu c mt dung dch mu trng vng, chng t c ht nano CdS.
- Lc tch ht nano :
- Ht nano c phn tn trong chloroform v c tch ri bng my ly tm.
- Nhng mu nano sau c ra li trong methanol loi b phn tha khng
phn ng v sy kh.
- Kch thc ca ht nano c iu khin bng cch ph ln b mt ca ht
thiophenol v t s ca sulphur v thiophenol trong dung dch quyt nh kch thc
ca cc ht.
- Acetonitrile l lm tng s tn x ca cc ht nano trong mt mi trng phn cc
dimethyl formaldehyde ( DMF) .
BIN LUN KT QU
Cc kt qu :
1. ng vin vch ph ca mng a tinh th CdS phn b theo hm Gauss.
2. S dn rng khng ng nht ca ph c lin quan n s phn b kch thc ht. Ph
PL ca ht nano dch chuyn v dch chuyn v pha xanh so vi dang bulk.
3. Tnh cht tng qut ca phng trnh (8) .
, )
2
2.446 0.3031
E R = 2.43 + -
R R
(8)
1. ng vin vch ph ca mng a tinh th CdS phn b theo hm Gauss.
C s :
Xt s pht quang gy ra do s ti hp ca cc ht ti ti vng bin trong khi bn dn dch
chuyn trc tip vi rng vng cm E
0
th ng vin vch ph c th trnh by theo
dng phn b Guass :
, )
2
0
b 2
E-E A
g (E)= exp -
2

]
(1)
Thc nghim :
o ph quang pht quang ca mng a tinh th CdS thu c nh figure 3 ( ng ph
c xy dng l tp hp cc chm chm).
Nhn xt :
Kt qu ph quang pht quang
ca mng a tinh th thu c t
thc nghim c fit ph hp vi
hm gauss (1) trn.
Ph quang pht quang c nh ti
2,43 eV v c rng vch ph
(FWHM) 0,1eV.
rng vch ph ( FWHM) c hiu nh hnh v.
2. S dn rng khng ng nht ca ph c lin quan n s phn b kch thc ht.
Ph PL ca ht nano dch chuyn v dch chuyn v pha xanh so vi dang bulk
Thc nghim :
o ph quang pht quang ca cc ht nano CdS cc kch thc khc nhau thu c nh
figure 1
Nhn xt :
- Hnh ( a ) nh ph l 2,43 eV l ph ca CdS dng khi ( c chn lm chun )
- Hnh ( b) nh ph l 2,9 eV l ph ca ht nano CdS c bn knh 2nm. Nng lng
ca CdS dng ht nano dch chuyn so vi dng bulk khong l 2,9 2,43 = 0,46 eV.
- Hnh ( c) nh ph l 3,3 eV l ph ca ht nano CdS c bn knh 1.5nm. Nng
lng ca CdS dng ht nano dch chuyn so vi dng bulk khong l 3,3 2,43 =
0,89 eV.
Vy CdS khi dng ht nano c ph PL dch chuyn v dch chuyn v pha xanh ( v
. h c
E

= khi E tng th gim ) so vi dng bulk.

Tuy nhin t hnh 1 ta cng c nhn xt nh tnh nh sau :
- rng ph ca ht nano CdS hnh (b) ng vi bn knh 2nm hp hn so vi
hnh (c) ng vi bn knh 1.5nm bn knh cng nh th ph cng rng.
- S m rng khng ng u, khng i xng hnh (b) v (c) s m rng ny
khng u v ph thuc vo s phn b kch thc ht.
Ph quang pht quang ca mu ht nano CdS
Ph t hnh 2 cho thy hai dy ph m rng c nh ti 2,56 eV v 3.00 eV.
- Ph dng cong u c nh 2,56 eV nt nh l ph do s ti hp ca cc khuyt tt
c rng vch ph l 0, 56 eV.
- Ph dng cong u c nh 3,00 eV nt nh l ph PL ca ht nano CdS c rng
vch ph l 0, 25 eV.
- C hai dy ny xut hin vi nng lng cao hn nng lng ca vng cm ca khi
CdS ( 2,43eV).
- ng ph cong, dy v m nt l tng hp ca hai ph nu trn.
- Ph c nh nhn 2,34eV, t v tr nh ny ( hnh 3 ) so vi ( hnh 2) ca ph PL ta
thy ph b dch chuyn 3,00 - 2,34 = 0,57 eV v pha xanh v rng ph PL ca
2,56eV
ht nano CdS ( 0,25eV ) dn r ng ra so vi rng nguyn thy ca CdS dng
khi (0,1 eV).
Nh vy ta thy c s gin rng ca vch ph v s gin rng ny l khng u v
ph thuc vo s phn b kch thc ht.Ngoi ra ph cn b dch chuyn v pha
xanh so vi dng bulk.
iu ny l hon ton ph hp v theo hnh 4 ht nano CdS hp th quang hc khong 0.53
3. Tnh cht tng qut ca phng trnh (8) .
C s tnh ton :
- Wu tnh ph hp th ca h thng bn dn lng t dng chm vi s phn b kch
thc hu hn., xp x mi chm lng t l mt ging th vi ro chn khng xc nh ti
bin gii, v b qua rng vch nguyn thy (ko c s m rng) ca chuyn di gia cc
mc trong dy ph bt ngun t lin kt dao ng.
- iu ny dn n ph hp thu hm delta cho nhng chm lng t tn sc n. Cng c
mt vi th nghim lm cho ph hp thu c tnh ton va khp vi d liu thc
nghim. lm c iu cn nhiu tham s ( khong 12 trong trng hp CdS), ly t
s tnh ton cu trc bng tn hoc t h thc kinh nghim, ch l xp x, lm cho s phn
b nh gi ko ng tin cy.
- Da vo lp lun, tnh ton ban u bqua s phn bkch thc ht th kt qucha
c khquan lm. Sau xt n s phn bkch thc ht.
- Nu kch thc ht khng ng u nhng c s phn b nht nh, ph ca h thng
chm lng t quan st c c th c xem nh s xp chng ln nhau ca tng ht mt
v mi ht s biu th im cao nht ti v tr ch ra trong ng knh ca n.
iu ny dn n s m rng ph PL khng ng nht.
ng vch ph c th c tnh da trn hm phn b kch thc PL
, ) , ) , )
qd
G E = P R .g E,R dR
}
(5)
tnh ton n gin, PL c xc nh theo phn b Gauss vi gi tr trung bnh R
o
v
lch tiu chun o
R
Vi , )
, )
R
2
0
2
R - R 1
P R = exp -
2 2

R




]
(6)
V , )
2
2.446 0.4547
E R = 2.43 + -
R R
(7)
Khi phn tch nh lng ng ph PL theo phng trnh (5) th ph hp ( fit) vi dy c
nh ph 3,00 eV hnh 2 (khi kho st cc tham s bn knh trung bnh R
o
v lch
chun
R

ca phn b), kt qu thu c rt chnh xc khi bn knh Ro = 1,8 nm

v
R

= 0,1 nm vi s tn x tng ng l 6 %Kt qu tnh ton ph hp thc nghim.

iu ny chng t s dn rng khng ng u ca ph PL ca ht nano CdS l do
s phn b kch thc ht.
Mt khc, c th so snh vi kt qu t c t phng php xc nh rng ca nh
ph XRD l 4,2 nm so vi thc nghim v tnh ton l 3,6nm.
y c s sai lch l do khi tnh ton dng gn ng khi lng hiu dng.( i vi ht
c ng knh rt nh khi dng gn ng khi lng hiu dng th kt qu km chnh xc
(less accurate).
- Nng lng dch chuyn trc tip gia cc bng tn thp nht ca mt chm lng t dng
hnh cu bn knh l R0 c xc nh bi Brus l
2n
2 2 2 2
0 0 n 2
n=1
e h 0 2 0 0 0
h
1 1 1 1.8e 1 e S
E(R )=E + + - . +

2 m m R
R R R
| |
| |
' '
_
(2)
m
e
l khi lng e
m
h
l khi lng l trng
e l in tch e
c
2
l hng s in mi ca mi trng
o
n
l hm ca hng s in mi
S l khong cch gia e v l trng
S hng th hai v bn phi PT(2) biu th nng lng nh v lng t.
S hng th ba ng vi th nng Coulumb
S hng th t ng vi nng lng phn cc
- Nh ch ra trc cc mc nng lng e ca chm lng t b dch chuyn so vi cc
mc nng lng e ca dng khi v dch chuyn v pha xanh
, ) , )
0 0 0
E R =E R - E (3)
- Ph PL ca chm lng t bn knh R
o
c th c a ra bi
, )
2
0
qd 0 2
E - E(R ) A
g (E,R )= exp -
2

]
(4)
tnh nh hng ca phn b kch thc ht ln ph PL ca cc ht nano CdS, E(R) u
tin c xc nh vi E
o
= 2,43 eV, m
e
= 0,19 v m
h
= 0,8 v c2 = 5,7
Tnh ton ca s hng phn cc cui cng trong PT th khng c tnh thng. B qua gi
tr ca s hng cui cng chng ta c th vit PT (2) nh sau
, )
2
2.446 0.4547
E R = 2.43 + -
R R
(7)
Trong thc t tnh ton s hng phn cc c xc nh bng php xp x.
T kt qu ca cc bi bo trc nhn thy rng cc ht nano CdS c bn knh t 1 n 4
nm s hng phn cc c khong 1/3 s hng couloumb vi du ngc li.
V vy chnh xc ha khi xt n s hng phn cc ta phi thay i h s ca s hng
couluomb. Sau khi thay i PT E(R) l :
, )
2
2.446 0.3031
E R = 2.43 + -
R R
(8)
Ph PL chm lng t c tnh ton t PT (4) bng cch thay E(R
o
) t PT (8).
Tnh ton ny c tin hnh i vi kch c ht trung bnh khc nhau R
0
v chiu rng
khc nhau o
R
. rng ni ti o c ly t ph PL ca mt mng CdS dng khi
( FWHM = 0,1 eV )
T c s l thuyt trn hon ton ph hp vi thc nghim thu c nn phng trnh (8)
c tha nhn v xem nh tng qut.
Kt qu chnh nhm tc gi t c :
- Khng nh s m rng khng ng nht ca ph quang pht quang m nguyn nhn
chnh l do nh hng ca s phn b kch thc ht.
- Ph PL ca ht nano dch chuyn v dch chuyn v pha xanh so vi dang bulk.
- tin cy ca s liu tnh ton l ph hp m cha c nghin cu no trc y lm
c.
PHN II
Vt liu TiO
2
c hiu ng quang xc tc rt cao trong vng t ngoi (UV) nhm ng dng
trong s l mi trng. Tuy nhin c hiu ng quang xc tc mnh trong vng nh sng
kh kin th hin nay c rt nhiu nghin cu pha tp SnO
2
vi TiO
2
. T ph hp thu cu
dung dch, mngSnO
2
:TiO
2
( 5 % , 10%, 20 % ) v ph PL o ti B mn VLD.Bin lun.
1. Bin lun ph hp th ca mng TiO
2
/SnO
2
380 400 420 440 460 480 500
0.0
0.5
1.0
1.5
2.0
2.5
3.0
A
b
s
nm
Sol TiO2
Sol SnO2
Sol 5%
Sol 10%
Sol 20%
Sol 30%
Ph UV-VIS ca mng ng vi cc nng
Cha pha tp :
- Mng TiO2 ( vin en )c nh ph nhn trong vng c bc sng nh hn
380nm nn TiO2 hp thu mnh trong vng t ngoi.
- Mng SnO2 c dng ng thng nm ngang ( ko c nh ph ) nn n khng
hp thu trong min t ngoi gn v kh kin hay c th hiu l mi trng trong sut.
Khi pha tp :
- Bnh thng TiO2 hot ng mnh ch trong vng t ngoi nhng khi pha tp SnO2 vo
th ta thy c s dch chuyn cc v tr nh ph v pha bc sng trong vng kh kin.
- Theo th ph, ta thy nng pha tp cng tng ( 5%, 10%, 20%, 30% ) th nh ph
cng dch chuyn v pha bc sng trong vng kh kin. Tuy nhin n vn c hiu ng
quang xc tc trong vng t ngoi v ngoi nh ph cng dch chuyn v pha bc sng
trong vng kh kin cn c nh ph trong vng t ngoi.
- Mt cch gn ng ta thy v tr cc nh ph nh sau
Nng
(%)
Bc sng
(nm)
0
5
10
20
30
370
380
390
400
410
Nh vy: khi nng tp cht pha vo tng th nh ph UV-VIS dch cng nhiu v pha
nh sng kh kin .
Ngoi ra ta thy cng hp thu thay i khi c s pha tp, v s thay i l khng
u v khi nng pha tp tng th cng hp th tng.
390 400 410 420 430 440 450 460 470 480
0.0
0.1
0.2
0.3
A
b
s
nm
TiO2
5
10
20
30
Ph hp thu ca cc mng TiO
2
-SnO
2
pha tp vi cc nng khc nhu ti 500
0
C
- nhit cao 500
0
C cng pht quang gim mnh trong vng kh kin cng
nh hn 0,3 Abs.
- Cc ng ph khng u v t c s sai khc v nh ph nn s pha tp SnO
2
vo
TiO
2
khng cn tc dng thay i hiu ng quang xc tc ca TiO
2
.
2. Bin lun ph quang pht quang ca TiO
2
pha tp SnO
2
10%
200 400 600 800 1000 1200 1400
0
500
1000
1500
2000
2500
3000
s
o
l

1
0
%

(
C
o
u
n
t
s
)
X ( nm)
sol 10%
f 10%
Tt inh
So snh ph quang pht quang ca TiO2 pha tp SnO2 10% dng mng v dng dung
dch :
- ng mu xanh : biu din ph PL ca thy tinh.
- ng mu : biu din ph PL ca TiO2 /SnO2 dng mng pht quang bc
sng khong 520 nm v 710 nm.
- ng mu en : biu din ph PL ca TiO2 /SnO2 dng dung dch pht quang
bc sng khong 520 nm v 710 nm.
- C hai u pht quang mnh bc sng khong 710nm trong vng kh kin, v pht
quang yu hn bc sng 510nm, khng c s thay i dng mng hay dng dung dch.
- Cng pht quang dng mng ln hn dng dung dch do b nh hng bi thy
tinh.
Khi tin hnh o cc nng khc nh 5%, 20% ta cng thu c mt kt qu tng t
nh trn
200 400 600 800 1000 1200 1400
0
1000
2000
3000
4000
5000
6000
7000
s
l
o

2
0
%

(
C
o
u
n
t
s
)
X (nm)
slo 20%
f 20%
Ttinh
200 400 600 800 1000 1200 1400
-500
0
500
1000
1500
2000
2500
3000
3500
s
o
l

5
%

(
C
o
u
n
t
s
)
X (nm)
sol 5%
film 5 %
ttinh