LI CM N

Trc tin em xin trn trng by t lng bit n chn thnh v su sc n thy
gio TS.Trn Minh Thi, thy hng dn, gip v cung cp nhng kin thc ht sc
qu gi gip em hon thnh lun vn ny.
Em xin trn trng cm n cc thy gio, c gio trong t B mn Vt l Cht rn
in t, khoa Vt l Trng HSP H Ni trang b nhng tri thc khoa hc v to
mi iu kin thun li gip em trong qu trnh lm lun vn ti b mn.
Xin trn trng cm n n thy gio TS.ng Xun Th, TS.V Quc Trung v
TS.Trn Cng Vit, khoa Ha HcTrng HSP H Ni cho em nhiu kin ng
gp qu bu trong qu trnh thc nghim gip em hon thnh tt lun vn.
Xin trn trng cm n n thy gio TS.Phm Vn Bn, Khoa Vt l Trng
HKH T Nhin H Quc gia H Ni cung cp nhng kin thc khoa hc qu bu,
gip em nhiu php o hunh quang cho em hon thnh lun vn tt hn.
Ti xin gi li cm n n BGH Trng H Quy Nhn, to iu kin gip
ti trong sut thi gian qua.
Cui cng con xin gi li cm n chn thnh ti b m, xin cm n v, xin cm n
anh ch v hai em, bn b v ng nghip gn gi, ng vin v chia s, gip ti khc
phc kh khn trong qu trnh hc tp, nghin cu v hon thin lun vn.
Xin trn trng cm n!
H Ni, thng 11 nm 2008
Tc gi

Nguyn Minh Vng
i
MC LC
ii
M U
I- L DO CHN TI
Vi s pht trin ca khoa hc v k thut, ngi ta ch to c
nhng tinh th nhn to c kch thc nanomt. Hin nay, vic nghin cu vt
liu nano l mt trong nhng lnh vc nh cao si ng nht trong thi gian gn
y.
Mc tiu ban u ca vic nghin cu vt liu nano ng dng trong
cng ngh sinh hc, chng hn nh cc tc nhn phn ng sinh hc v hin nh
cc t bo. ng dng trong vt l, cc chm lng t c hng ti sn
xut cc linh kin in t nh cc diode pht quang (LEDs), laser chm lng t
c hiu sut cao hn v dng ngng thp. Trong vin thng, chm lng t
c dng trong cc linh kin khuch i quang v dn sng. Khng ch v
iu khin tp hp cc chm lng t l mt mc tiu ln dng cc vt liu
ny cho my tnh lng t.
Ngy nay, nhiu nh khoa hc phi dng n cm t nanoboom
din t s pht trin nh v bo ca cng ngh nano. S d cng ngh nano c
u t pht trin mnh m n nh vy l do nhng ng dng v cng to ln
ca n trong mi lnh vc ca i sng. Chng hn, ngi ta ch to ra cc
chip nano my tnh c tch hp rt cao v trin vng cho php dung lng b
nh my tnh tng ln rt cao; cc ng nano Cacbon cc k vng chc, c
bn c hc gp 10 ln thp v c bit c tnh bn nhit rt cao; nhng loi pin
mi c kh nng quang hp nhn to s gip con ngi sn xut nng lng
sch.Ngoi ra cng ngh nano cn nhiu ng dng quan trng trong nhiu
ngnh ngh khc nh y t, an ninh quc phng, thc phm.
Cc tnh cht mi bo hiu tinh th nano c kh nng ng dng to ln
trong cuc sng. Trong cc vt liu nano, ZnS l mt trong nhng vt liu c
1
nhiu nh nghin cu quan tm. N l hp cht c vng cm thng, rng
vng cm ln nht ( nhit phng l 3,68 eV) trong cc hp cht A
II
B
VI
, c
nhit nng chy cao (2103K). V vy m ZnS c ng dng trong nhiu
lnh vc khoa hc v i sng. Chng hn c th ng dng trong cc linh kin
quang in t nh ca s hng ngoi, laser pht quang, mn hnh hin th.
Mc khc ta c th iu khin rng vng cm cng nh mong mun
thu c di pht x khc trong vng nh sng nhn thy ca tinh th ZnS. Cc
ht nano c th c pha thm cc kim loi chuyn tip v cc kim loi t him
nh: Mn
2+
, Cu
2+
hoc Eu
3+
; thay i nng pha tp, bc ph Polymer, thay
i iu kin ch to mu nhm ci thin tnh cht quang ca chng.
Qua nhiu nghin cu cho thy vic bc ph polymer i vi cc ht nano
ZnS khng nhng c th thay i rng vng cm ca vt liu m cn c th
cch ly tt vt liu vi mi trng nhm trnh hin tng vt liu b oxy ha,
ngn cn s kt t ca cc ht li vi nhau cc tinh th nano khng ln ln
thnh tinh th mu khi. Ngoi ra cn hi vng tng hiu sut pht quang, tng
cng pht quang ca cc tinh th nano ZnS bc ph polymer so vi cc tinh
th nano ZnS khng bc ph polymer.
T nhng l do trn y v trn c s trang thit b sn c ca Trng i
hc S phm H Ni, chng ti chn ti nghin cu l: "Nghin cu ch to
v mt s tnh cht quang ca vt liu nano ZnS:Mn khng bc ph v bc
ph polymer"
II- MC CH NGHIN CU
Nghin cu ch to vt liu ZnS:Mn c kch thc nano khng bc
ph v bc ph polymer.
Nghin cu nh hng ca ch x l nhit ln cu trc v tnh cht
quang ca mu bt v mng ZnS:Mn khng bc ph polymer.
2
Nghin cu tnh cht quang ca mu mng ZnS:Mn bc ph polymer.
III- PHNG PHP NGHIN CU
Phng php nghin cu l lun.
Phng php thc nghim.
Phng php trao i v tng kt kinh nghim.
IV- CU TRC CA LUN VN
M u
Ni dung
Chng 1: Tng quan
Chng 2: Thc nghim ch to v phng php kho st mu
Chng 3: Kt qu v tho lun
Kt lun chung
Ph lc
Ti liu tham kho
3
NI DUNG
Chng 1
TNG QUAN
1.1. Vt liu nano
1.1.1. nh ngha
Vt liu nano l vt liu trong t nht 1 chiu c kch thc nanomet
(nm). Theo trng thi, ngi ta chia vt liu nano thnh trng thi rn, lng v
kh. Theo hnh dng vt liu, ngi ta chia vt liu nano thnh:
Vt liu nano khng chiu: l vt liu c ba chiu u c kch thc
nanomet. V d: m nano, ht nano.
Vt liu nano mt chiu: l vt liu trong hai chiu c kch thc
nanomet. V d: ng nano, dy nano.
Vt liu nano hai chiu: l vt liu trong mt chiu c kch thc
nanomet. V d: mng nano.
Ngoi ra cn c vt liu nanocomposit trong ch mt phn ca vt liu
c kch thc nano hoc cu trc ca n c nano khng chiu, mt chiu, v hai
chiu an xen nhau. V d: nanocomposit bc/ silica, bc/uretan.
1.1.2. c trng ca vt liu nano
Mt c im quan trng ca vt liu nano l kch thc ht v cng nh
b, ch ln hn kch thc ca nguyn t 1 hoc 2 bc. Do vy, t s gia s
nguyn t nm b mt trn s nguyn t tng cng ca vt liu nano ln hn
rt nhiu so vi t s ny i vi cc vt liu c kch thc ln hn.
4
Nh vy, nu nh vt liu thng thng, ch mt s t nguyn t nm
trn b mt, cn phn ln cc nguyn t cn li nm su pha trong, b cc lp
ngoi che chn th trong cu trc ca vt liu nano, hu ht cc nguyn t u
c "phi" ra b mt hoc b che chn khng ng k. Do vy, cc vt liu c
kch thc nano mt, mi nguyn t c t do th hin ton b tnh cht ca
mnh trong tng tc vi mi trng xung quanh. iu ny lm xut hin
vt liu nano nhiu c tnh ni tri, c bit l cc tnh cht in, quang, t, .
Kch thc ht nh b cn l nguyn nhn lm xut hin vt liu nano
ba hiu ng: hiu ng lng t, hiu ng b mt, hiu ng kch thc.
Hiu ng lng t
i vi cc vt liu v m gm rt nhiu nguyn t (1m
3
vt liu c
khong 10
12
nguyn t), cc hiu ng lng t c trung bnh ha cho tt c
cc nguyn t, v th m ta c th b qua nhng khc bit ngu nhin ca tng
nguyn t m ch xt cc gi tr trung bnh ca chng. Nhng i vi cu trc
nano, do kch thc ca vt liu rt nh, h c rt t nguyn t nn cc tnh cht
lng t th hin r hn v khng th b qua. iu ny lm xut hin vt liu
nano cc hin tng lng t k th nh nhng thay i trong tnh cht in v
tnh cht quang phi tuyn ca vt liu, hiu ng ng ngm....
Hiu ng b mt
vt liu nano, a s cc nguyn t u nm trn b mt, nguyn t b
mt c nhiu tnh cht khc bit so vi cc nguyn t bn trong. V th, cc hiu
ng c lin quan n b mt nh: kh nng hp ph, hot ng b mt...ca
vt liu nano s ln hn nhiu so vi cc vt liu dng khi. iu ny m ra
nhng ng dng k diu cho lnh vc xc tc v nhiu lnh vc khc m cc nh
khoa hc ang quan tm nghin cu.
Hiu ng kch thc
5
Cc vt liu truyn thng thng c c trng bi mt s cc i lng
vt l, ha hc khng i nh dn in ca kim loi, nhit nng chy,
nhit si, tnh axit....Tuy nhin, cc i lng vt l v ha hc ny ch l bt
bin nu kch thc ca vt liu ln (thng l ln hn 100 nm). Khi gim
kch thc ca vt liu xung n thang nano (nh hn 100 nm) th cc i
lng l, ha trn khng cn l bt bin na, ngc li chng s thay i theo
kch thc. Hin tng ny gi l hiu ng kch thc. Kch thc m , vt
liu bt u c s thay i tnh cht c gi l kch thc ti hn. V d: in
tr ca mt kim loi tun theo nh lut Ohm kch thc v m m ta thy
hng ngy. Nu ta gim kch thc ca kim loi xung nh hn qung ng t
do trung bnh ca in t trong kim loi (thng l t vi nanomet n vi trm
nanomet) th nh lut Ohm khng cn ng na. Lc in tr ca vt liu c
kch thc nano s tun theo cc quy tc lng t.
Cc nghin cu cho thy cc tnh cht in, t, quang, ha hc ca cc vt
liu u c kch thc ti hn trong khong t 1 nm n 100 nm nn cc tnh
cht ny u c biu hin khc thng th v vt liu nano so vi cc vt liu
khi truyn thng.
1.2. Cu trc mng tinh th ca vt liu ZnS
ZnS c 2 dng cu trc chnh l: cu trc lp phng gi km v cu trc
lc gic Wurtzite. Cu trc Wurtzite bn nhit cao, cu trc lp phng gi
km thng c hnh thnh nhit thp .
1.2.1. Cu trc lp phng gi km (Zinc blend).
Nhm i xng khng gian ca
tinh th A
II
B
VI
ng vi mng tinh th ny

Hnh 1.1. Mohnh cau truc lap phng giakem

[100]
[010]
[001]
6
l T
2
d
F
43m
(216). y l cu trc thng gp ca ZnS iu kin nhit p
sut bnh thng.
Trong c s c 4 phn t ZnS c ta nh sau:
) 0 ,
2
1
,
2
1
( );
2
1
, 0 ,
2
1
( );
2
1
,
2
1
, 0 ( ); 0 , 0 , 0 ( : 4S
)
4
1
,
4
3
,
4
3
( );
4
3
,
4
1
,
4
3
( );
4
3
,
4
3
,
4
1
( );
4
1
,
4
1
,
4
1
( : 4Zn
Mi nguyn t Zn (S) c bao bc bi 4 nguyn t S (Zn) 4 nh ca
t din u vi khong cch a
4
3
, vi
) ( 410 , 5
o
A a
l hng s mng [ph lc
III]. Mi nguyn t S (Zn) cn c bao bc bi 12 nguyn t cn li, chng
ln cn bc hai nm trn khong cch a
2
2
. Trong c 6 nguyn t nm
nh ca lc gic trn cng mt phng ban u, 6 nguyn t cn li to thnh
hnh lng tr gm 3 nguyn t mt cao hn, 3 nguyn t mt phng thp hn
mt phng k trn. Cc lp ZnS nh hng theo trc [111] . Do tinh th c
cu trc lp phng gi km c tnh d hng. Cc hp cht sau y c cu trc
tinh th theo kiu lp phng gi km: CuF, CdS, InSb.
1.2.2. Cu trc Wurtzite
Nhm i xng khng gian tng ng vi cu trc ny l C
4
6V

P
63
mc(186). y l cu trc bn nhit cao ( nhit chuyn t cu trc lp
phng gi km sang cu trc Wurtzite xy ra 1020
o
C n 1150
o
C ). Trong
mt c s c 2 phn t ZnS, ta cc nguyn t nh sau:
)
2
1
,
3
2
,
3
1
( ); 0 , 0 , 0 ( : 2S
).
2
1
,
3
2
,
3
1
( ); , 0 , 0 ( : 2 u u Zn +
vi
8
3
u
Hnh 1.2: M hnh cu trc Wurtzite
7
Mi nguyn t Zn lin kt vi 4 nguyn t S nm trn 4 nh ca t din
gn u. Khong cch t nguyn t Zn n 4 nguyn t S mt khong bng
) . ( c u

cn 3 khong kia bng
2
2 2
2
1
3
1

,
_

+ u c a vi a v c l nhng hng s mng

c xc nh l
0 0
8 , 3 , 26 , 6 A a A c
.
C th coi mng lc gic Wurtzite cu to t 2 mng lc gic lng vo
nhau: mt mng lc gic cha cc nguyn t S v mt mng lc gic cha cc
nguyn t Zn. Mng lc gic th 2 trt theo trc z so vi mng lc gic th
nht mt on l
,
_

c
8
3
. Xung quanh mi nguyn t c 12 nguyn t ln cn bc
hai: 6 nguyn t nh lc gic nm trong cng mt phng vi nguyn t ban
u cch nguyn t ban u mt khong a v 6 nguyn t khc nh lng tr
tam gic cch nguyn t ban u mt khong
2 2
4
1
3
1
c a + .
1.3. Tnh cht quang
1.3.1. C ch hp th nh sng
H s hp th

c th xem nh xc sut hp th photon, nu trong bn

dn c mt s c ch hp th c lp vi nhau v mi c ch hp th c th c
trng bi mt xc sut
) (
i , th xc sut tng cng ca qu trnh hp th l:

i
i
) ( ) (
(1.1)
Nh vy, trong mt vng ph cho trc cn phi tnh n cc c ch hp
th ch yu, cho ng gp ln nht vo ph hp th. Qu trnh hp th nh sng
lin quan n s chuyn i nng lng ca photon sang cc dng nng lng
khc ca tinh th nn c th phn loi cc c ch hp th nh sau:
8
a. Hp th c bn (hp th ring)
Hp th c bn lin quan n chuyn mc ca in t gia cc vng cho
php ng vi chuyn mc 1 v 1a nh trn hnh 1.3 v 1.4. Chuyn mc 1
khng km theo s thay i vect sng k

nn gi l mc chuyn di thng.
Chuyn mc 1a km theo s thay i vect sng k

nn gi l mc chuyn di
xin.
Hnh 1.3: S chuyn mc in t khi vt liu
bn dn hp th nh sng
Hnh 1.4: Cc chuyn mc ca in t v trong
khng gian
k
Trong hp th c bn, chuyn mc xin nht thit phi c s tham gia ca
phonon. T hnh 1 v 1a ta thy hp th c bn khng th xy ra nu nng lng
ca photon nh hn b rng ca vng cm. V th ph hp th c bn phi c
mt di, h s hp th gim xung rt nhanh, chnh l b hp th c
bn. H s hp th cng nh dng iu ca b hp th ring ph thuc vo c
ch chuyn mc thng hay chuyn mc xin.
Mt s yu t lm chuyn dch b hp th c bn:
Nhit l yu t trc tin cn phi k n. Ta bit b rng vng cm
ca cc cht bn dn ph thuc vo nhit , khi nhit tng ln b
rng vng cm gim xung . T y ta thy khi nhit tng ln, b

1 (1a)
2
2a
3a
3b
3c
4
5
E
v
5a
3
E
a
E
d
E
c
E
exc
Hnh 1.3: S ochuyen mc ien tkhi vat lieu
ban dan hap thuanh sang.
2
1
(1a
)
2b
2c 2d
2a
E
c
E
v
Hnh 1.4: Cac chuyen mc ien t
vetrong khong gian k

)
9
hp th ring dch chuyn v pha tn s thp ca nh sng (v pha
nng lng photon nh hn).
Pha tp cht mnh cng l yu t dn n hin tng chuyn dch b
hp th c bn (hay cn gi l s dch chuyn Burstein - Moss). Chng
hn ta xt bn dn donor, do pha tp mnh bn dn donor tr thnh bn
dn suy bin c mc Fermi nm trong vng dn v cc mc nng
lng nm di mc Fermi c th xem l c in y hon ton.
Chuyn mc ca in t t vng ha tr ln vng dn khi hp th
photon c nng lng
) (
*
c n g
E F E +
l khng th v cc mc
nng lng tng ng trong vng dn b in y. Chnh v vy b
hp th c bn b dch chuyn v pha nng lng photon cao hn
b. Hp th Exciton
Hp th exciton lin quan n s hnh thnh hoc phn hy trng thi kch
thch c gi l exiton.
Exciton l trng thi lin kt gia mt electron c kch thch ln di dn
v mt l trng trong di ha tr thng qua tng tc Coulomb gia hai ht ny.
Ngi ta phn bit hai loi exciton Frenkel v exciton Wannier - Mott. Exciton
Frenkel (hay cn gi l exiton phn t) v trng thi rng buc ny gia electron
v l trng ch trong phm vi mt phn t (nguyn t). Exciton Frenkel cn
gi l exciton bn knh nh c th chuyn t phn t ny sang phn t khc v
(bng cch ) chuyn ng trong tinh th nhng khng tham gia dn in.
Exciton Frenkel thng xy ra trong cc tinh th phn t vi lin kt ha hc
Van der Waals. Khi in t v l trng trng thi lin kt vi bn knh gp
nhiu ln chu k mng tinh th nh trong cc cht bn dn th ta c exciton
Wannier. Exciton loi ny thng xy ra trong cc tinh th c s ph hm sng
ln nh trong tinh th ng ha tr.
10
Cch m t n gin nht cho trng thi exciton Wannier l dng m hnh
nguyn t Hydro. Trong l trng c khi lng hiu dng
*
p
m
ng vai tr
ht nhn nguyn t, cn electron c khi lng hiu dng
*
n
m
. Nu khng
n chuyn ng tm khi ca hai ht th nng lng exiton exc
E
(so vi
trng thi khi in t v l trng cch xa nhau v cc) s c dng:
) (
1
. . 6 , 13
2 2
*
eV
n m
m
E
exc
exc

(1.2)
Trong : 13,6eV l nng lng
Rydberg,

l hng s in mi ca bn dn
v
* *
* *
*
.
p n
p n
exc
m m
m m
m
+

l khi lng hiu dng

exciton.
Trong cng thc (1.2) nng lng c tnh bng eV v tnh t mc l
y vng dn. Chng ta nhn thy rng nng lng lin kt exciton gm mt
ph gin on, vi mc c bn
) 1 (
exc
E
khi n=1 v bng khng khi n

. V bn
cht vt l ta c th quan nim rng mc c bn exciton nm thp hn y ca
vng dn E
c
mt khong nng lng l
) 1 (
exc
E
, trng thi kch thch tip theo thp
hn E
c
nhng lng tng ng l
4 /
) 1 (
exc
E
,
9 /
) 1 (
exc
E
. Chng ta nhn c v s
mc gin on cho n tn ph lin tc khi n

(hnh 1.5).
Khi kch thch to ra exciton bng chiu sng, in t t vng ha tr
chuyn ln mc exciton, iu c ngha l nng lng photon phi tha mn
iu kin sau y:

2 ) 1 (
/ n E E
exc g n

vi n=1, 2, 3. (1.3)

c
E
) 1 (
exc
E
Hnh 1.5: Phonang lng exiton
g
E
Hnh 1.5: Ph nng lng exiton [2]
11
V vy ph hp th exiton phi l ph gin on, gm mt dy vch nh
ph hp th ca hyro, nm gn b hp th c bn v tip gip vi ph hp th
c bn ti g
E
. Tuy nhin do nh hng ca dao ng nhit ca mng tinh
th v cc sai hng khc m cc vch ph thng b rng (nhe) ra, trong nhiu
trng hp thm ch b ln vo ph hp th c bn.
c. Hp th do tp cht
Cc tp cht donor, acceptor c xt theo m hnh nguyn t hyro
thng cho cc mc nng lng gn y vng dn (mc donor) v gn nh
vng ha tr (mc acceptor) nn gi l cc mc nng. Bn cnh nhng mc tp
cht nng trong vng cm ca cht bn dn cn gp nhiu trng thi nh x c
mc nng lng cch xa hai b vng, ngha l nm khong gia hai vng cm,
l cc tm su. gii thch s tn ti ca cc mc nng lng su, ngi ta
s dng mt trng th b chn vi gi thit rng in t trong cc nguyn t tp
cht tng tc rt yu vi cc nguyn t c bn, qu o ca in t c bn
knh rt nh. Ngoi ra, cc dng khuyt tt khc ca tinh th nh nt khuyt,
lch mngcng c th gy nn nhng nhiu lon trng tinh th v v th sinh
ra cc trng thi nh x trong tinh th. Cc trng thi cng c th l ngun
cung cp cc in t hay l trng, ngha l c th l cc mc donor, acceptor hay
l cc tm su.
Cc chuyn mc trong qu trnh hp th tp cht (3, 3a, 3b, 3c) v cc
chuyn mc gia cc mc tp cht (4) trn hnh 1.3 ng vi trng hp nguyn
t tp cht chuyn t trng thi trung ha sang trng thi ion (3, 3a) hoc ngc
li (3b, 3c). Ph hp th vi chuyn mc 3, 3a, 3b, 3c i vi cc trng thi tp
cht nng nm cch nhau rt xa. Chuyn mc 3, 3a nm trong vng hng ngoi
xa, chuyn mc 3b, 3c v 4 nm gn b hp th c bn. Nu nhng chuyn mc
12
ny xy ra gia cc tm su th nhng ng gp ca chng cho ph hp th nm
xa b hp th c bn, dch v pha sng di.
i vi cc trng thi nng, khi gii bi ton ging nguyn t hyro
chng ta nhn c mt dy mc nng lng tp cht di dng:

2
2
*
1
.
1
. . 6 , 13
n m
m
E
n
d

,
_

vi n=1, 2, 3. (1.4)
Nng lng photon hp th vi chuyn mc acceptor donor c dng:

r
e
E E E
a d g
0
2
4
+
(1.5)
Trong s hng cui cng trong (1.5) m t nng lng tng tc
Coulomb gia ion donor v ion acceptor nh v cch nhau mt khong r.
d. Hp th do ht dn t do
Cc mc chuyn 2, 2a, 2b, 2c, 2d hnh 1.4 l cc chuyn mc ca ht
dn t do trong vng nng lng cho php (2, 2a) v gia cc vng con cho
php (2b, 2c, 2d). Ph hp th vi chuyn mc ca ht dn t do trong vng cho
php c dng mt ng cong thay i n iu ch khng c dng mt cc
i, l hp th khng chn lc do cc ht dn t do. Ngc li ph hp th
vi chuyn mc gia cc vng con cho php trong vng nng lng cho php
thay i c quy lut tn sc, bao gm cc cc i v cc cc tiu xen k nhau,
l hp th c chn lc do ht dn t do. Hp th chn lc do ht dn t do c
th do cc chuyn mc thng khng c s tham gia ca phonon. Thc nghim
cho thy hp th do cc ht dn t do tng rt mnh trong vng ph hng ngoi.
e. Hp th do phonon
Cc bn dn hp cht c cu to t cc nguyn t khc loi, c th
c coi nh l mt tp hp cc lng cc in. Cc lng cc c th hp
th nng lng ca trng in t trong nh sng. S hp th l mnh nht khi
13
tn s bc x in t bng tn s dao ng ring ca lng cc. l cc tn s
ng vi nh sng trong vng hng ngoi xa. Thng th ph l phc tp, bao
gm nhiu loi dao ng chun. tha mn nh lut bo ton xung lng, cn
c s tham gia (hp th hay pht x) ca mt hay nhiu phonon.
Trong cc bn dn ng cc (ch c mt loi nguyn t), th khng c
mmen lng cc, nhng vn c hp th do dao ng mng. l v trng
in t gy nn cc lng cc cm ng, v cc lng cc ny tng tc mnh
vi trng in t.
1.3.2. C ch chuyn di
Bc x l qu trnh ngc vi hp th. Cc electron chuyn ln mc nng
lng cao do nhn c nng lng t bn ngoi (chng hn do s hp th nh
sng). Tuy nhin trng thi kch thch l khng bn, sau mt khong thi gian
no gi l thi gian sng kch thch, electron chuyn v mc nng lng thp
hn, v gii phng nng lng. Nu nng lng c gii phng ra di dng
nh sng, th ta gi l s pht x (pht quang). Nh vy, s pht quang gn
lin vi qu trnh ti hp ht dn. Nu ch v gin nng lng b qua vect
sng k

c th minh ha cc kh nng pht quang trong bn dn nh sau:

Hnh 1.6. Cc qu trnh pht quang trong tinh th bn dn
14
Trong mi trng hp, khi iu kin cn bng b vi phm u xy ra qu
trnh hi phc nhm a trng thi khng cn bng v trng thi cn bng. Qu
trnh ti hp trong bn dn c bn cht ngc li so vi qu trnh hp th. N
lm gim nng ht ti trong bn dn. Qu trnh ti hp c phn loi theo
nhiu phng din khc nhau.
Theo cch gii phng nng lng ca qu trnh ta c th k mt s
dng ti hp sau:
Ti hp bc x (hay ti hp photon):l qu trnh ti hp m nng
lng gii phng ra di dng cc photon. Qu trnh ti hp bc x
gi l hunh quang.
Ti hp khng bc x (hay ti hp phonon): l qu trnh ti hp m
nng lng gii phng ra c truyn cho dao ng mng tinh th,
ngha l lm pht sinh cc phonon.
Ti hp Auger ( l dng ti hp khng bc x): khi nng lng c
truyn cho ht th ba lm cho ht dn ny "nng" ln. Ht dn
"nng" ny qua s ln tn x trn cc ion nt mng truyn ht nng
lng cho mng tinh th. Xc sut ca ti hp Auger thng khng
ln v i hi ca s "gp g" cng mt lc ba ht dn.
Theo c ch vt l ca qu trnh c th chia thnh cc dng sau:
a. Ti hp vng - vng (ti hp c bn hay ti hp trc tip)
Mt in t t do trc tip "gp" mt l trng v ti hp vi nhau. Thc
cht l mt in t trn vng dn chuyn mc xung mt trng thi trng
trong vng ha tr.
Nu bn dn c vng cm thng (cc tiu ca vng dn v cc i ca
vng ha tr cng mt gi tr ca vect sng) th qu trnh ti hp khng i
hi c s tham gia ca phonon. Xc sut ca s chuyn mc thng ny thng
15
ln. Ti hp thng vng-vng c trng bi s m rng ph v pha nng lng
thp khi nhit tng, trong khi pha nng lng thp ph b chn bi
g
E
.
Nu bn dn c vng cm xin (cc tiu ca vng dn v cc i ca
vng ha tr khng cng mt gi tr ca vect sng), th qu trnh ti hp i
hi c s tham gia (pht x hay hp th) ca phonon. Xc sut ca s chuyn
mc xin thng nh hn xc sut ca s chuyn mc thng.
Nu trong bn dn ng thi xy ra cc chuyn di thng ln chuyn di
xin th ph hunh quang s quan st c hai di: di sng di do chuyn di
xin v di sng ngn do chuyn di thng.
b. Ti hp qua tm (ti hp gin tip)
Qu trnh ti hp thng qua s "mi gii" ca mt tm bt (tm ti hp).
Cc tm ti hp thng c mc nng lng nm gn gia vng cm v c kh
nng tng tc vi vng dn v vng ha tr nh nhau.
Nhng qu trnh c th xy ra i vi cc tm c biu din nh hnh
1.7, bao gm:
{a}- Khuyt tt trung ha bt mt in t t do.
{b}- Khuyt tt tch in m th in t vo vng dn.
{c}- Khuyt tt trung ha bt mt l trng t vng ha tr.
{d}- Khuyt tt tch in dng "th" mt l trng vo vng ha tr
(ngha l bt mt in t t vng ha tr).
{e}- Khuyt tt bt mt in t t vng dn, tch in m v bt mt l
trng t vng ha tr (th in t vo vng ha tr) lm cho mt cp in t - l
trng ti hp.
16
{f}- Khuyt tt bt l trng t vng ha tr, tch in dng v bt in t
t vng dn v lm cho mt cp l trng - in t ti hp vi nhau.
Hnh 1.7: M t cc qu trnh bt ht dn v ti hp ht dn
1.3.3. Mt s kt qu nghin cu v cu trc v tnh cht quang ca tinh
th ZnS v ZnS:Mn.
a. nh hng ca nhit nung ln tch cht ca mu.
Theo nhm nghin cu , cc ht nano ZnS:Mn c tng hp bng
phng php lng ng ha hc t pha lng. Kt qu nghin cu cho thy khi
nung cc ht tinh th n nhit 230
o
C trong khong thi gian 2h th cc thng
s mng khng b nh hng, tuy nhin kch thc ht tinh th trung bnh tng
ln t 5 n 8nm. ng thi khi nhit nung tng ln n 320
o
C th mu xut
hin cu trc wurtzite.
Trong ph hunh quang ca cc ht nano ZnS:Mn (hnh 1.8), nhit
thp hn 200
o
C, c mt nh pht x xanh (440nm) v mt nh pht x mu da
cam (590nm). Pht x cam c gn cho s dch chuyn mc
4
T
1

6
A
1
ca ion
Mn
2+
. Bt nano ZnS:Mn c nung trong 2h vi nhit t 100300
o
C. Thnh
phn hp cht hu nh khng thay i khi nhit nung thay i t 100 n
200
o
C. Ngc li c th thy rng, vi nhit nung cao hn 200
o
C, hu ht cc
ion Mn
2+
thot khi cht nn ZnS, pht x ti nh 590nm khng cn na v ph
hunh quang tr nn m rng ra. Cc nh m rng l c trng ca cc tm sai
hng khc nhau trong vng cm ca cc ht nano ZnS cng vi lng tng ca
{a}
E
c
E
v
E
t
{b} {c} {d} {e} {f}
17
s mt trt t ca cht nn ZnS khi cc ion Mn
2+
di chuyn ra b mt. nhit
trn 280
o
C, s pht x di rng khng cn na, iu ny c ngha l cc ht nano
ZnS:Mn b oxy ha.
Tuy nhin, theo nhm tc gi , h khng thy c s dp tt hunh quang
khi mng ZnS ch to bng phng php lng ng nung n c 500
o
C. Kt qu
kho st ph hunh quang cho thy cng nh ca mu x l nhit
500
o
C thp hn so vi mu cha x l nhit v iu ny h cho rng nguyn
nhn l do cc trng thi sai hng b mt ca mu. Khi nung, kt qu ca s ln
ln cc ht lm b mt mu phng hn, do kh i cc trng sai hng b
mt mu v dn n nh pht x c cng thp hn.

C

n
g

o

h
u
y
n
h

q
u
a
n
g

(

.
v
.
t
.
y
)

Bc song (nm)
Hnh 1.8: Ph hunh quang ca mu ZnS:Mn nung
cc nhit khc nhau
Hnh 1.9: Ph hunh quang ca mu ZnS:Mn,
%Mn=8, 9,10, 11, 12%
b. nh hng ca nng tp cht Mn
Theo cc tc gi th h nghin cu nh hng ca hm lng Mn thay
th ZnS ln ph hunh quang ca h bt nano ZnS. Cc mu ZnS:Mn c ch
to bng phng php ha t c hm lng Mn thay th cho Zn c thay i
t 0%, 0,25%, ti 12% nguyn t. Kt qu nghin cu cho thy cc mu u
pht quang mnh trong vng c bc sng t 361752nm.
18
c bit tt c cc mu u xut hin nh ng vi bc sng 484nm,
ng vi nng Mn l 2,5% th ph hunh quang ca mu xut hin thm mt
nh ti bc sng 596(nm). Khi nng Mn tip tc tng ln th cng ca
bc x xanh do ZnS pht ra gim dn, cn bc x c trng do s ng gp ca
Mn tng dn. ng vi nng Mn l 9% cng hunh quang tng mnh
vng bc x cam, tuy nhin cng hunh quang ti vng bc x xanh vn rt
mnh (hnh 1.9).
Chnh v l trong lun vn ny, chng ti chn hm lng Mn thay th
cho Zn trong mu ZnS l 9% ch to v kho st mu.
c. nh hng ca Polymer i vi vt liu nano
Nhm tc gi tng hp vt liu ZnS bc ph Polystyrene (PS) bng
phng php lng ng ha hc t pha lng. Kt qu o ph nhiu x tia X i
vi cc ht ZnS v cc ht PS@ZnS (k hiu ca tc gi i vi ht ZnS bc
ph PS) cu trc li - v vi b dy v polystyrene l 200nm v 2m c so
snh nh trong hnh 1.10. Cc nh ca cc mu c cu trc li v tng ng
vi cc mt phn x (111), (220) v (311) ca cu trc tinh th sphalerite. V tr
nh, ng cong fit, v tnh ton t bn rng ca nh nhiu x cho ta kch
thuc ht tinh th ln lt l 6,6; 4,7 v 3,3nm tng ng vi cc ht ZnS sch,
PS@ZnS cu trc li v vi chiu dy v l 200nm v 2m. Nh vy ta thy
hm lng PS khi tng hp mu cng tng th kch thc ht cng gim.
19

2 (o)
C

n
g

o

(

.
v
.
t
.
y
)

Hnh 1.10: Gin nhiu x tia X: (a) ZnS sch,
(b) PS@ZnS vi li 2 m polystyrene, (c) PS@ZnS vi li 200nm polystyrene
Theo nhm tc gi , nghin cu s nh hng ca polymer ln hiu
sut lng t, cc tc gi tin hnh bc ph cc mu vi cc loi polymer l
polyvinyl butyral (PVB), polyvinyl alcohol (PVA), methacrylic acid (MA),
sodium polyphosphate (PP). Cc mu khng bc ph polymer cng c
tng hp. tm nng Mn ti u, nhm tc gi thay i dung dch hm
lng Mn dng trong qu trnh tng hp, gi khng i mt loi polymer bc
ph. i vi mi polymer, mu vi hiu sut lng t cao nht c phn tch
dng cng ngh ICP (inductively coupled plasma analysis). Bng 1.1 hin th
kt qu ca vic phn tch ICP, kch thc ht trung bnh (xc nh t gin
nhiu x tia X) v hiu sut lng t ca cc mu c k n trn.
Bng 1.1: Hiu sut lng t, kch thc trung bnh, t l Mn/Zn thc t c trong ht v
c dng trong qu trnh tng hp i vi cc mu c hiu sut lng t cao nht
Polymer
T l Mn/Zn dng
trong tng hp
(%nguyn t)
T l Mn/Zn thc t
trong ht nano
(%nguyn t)
Kch thc ht
trung bnh
(nm)
Hiu sut
lng t
(%)
PVB 10 2,38 3,2 3,5
PVA 1,5 0,96 3,7 2,7
Khng bc 1,5 0,48 4,3 1,6
MA 1,5 0,35 4,1 1,0
PP 0,7 0,13 3,0 4,5
20
Kt qu trong bng 1.1 cho thy rng khi thay i polymer th dn n
nhiu yu t khc cng thay i theo, chng hn nh kch thc ht trung bnh
v hm lng Mn thc t i vo trong ht nano. Chnh v vy, tht kh c th
ch nghin cu nh hng ca polymer, v rng nhng thay i v kch thc
ht, nng Mn v nhng sai hng b mt lm nh hng n hiu sut lng
t ca cc ht nano.
Ta thy lng Mn
2+
trong ht nano t hn nhiu so vi lng Mn
2+
s
dng tng hp. Ngoi ra, s khc nhau gia phn trm Mn
2+
dng tng
hp v phn trm Mn
2+
c trong mu th ph thuc vo polymer s dng.
i vi mu ph PVA, MA v mu khng c polymer, nng Mn
2+
ban
u s dng l nh nhau (1,5%) nhng lng Mn
2+
trong mu li nm trong
khong t 0,35% nguyn t i vi mu ph MA ti 0,96% nguyn t i vi
mu ph PVA. Do , khi thay i polymer cng lm nh hng n hm lng
Mn
2+
thc t i vo trong ht nano.
Kch thc trung bnh ca ht trong khong 34,5nm. Nu khng c s
c mt ca polymer, kch thc trung bnh ca ht ln hn. C hng lot cc
kin cho rng cc ht ln ln trong khi c bao quanh bi polymer. S kt hp
ca polymer cng mnh th ht ln ln cng chm v kch thc trung bnh ca
ht s cng nh.
D liu trong bng 1.1 gi v mi quan h t l nghch gia kch thc
ht v hiu sut lng t: ht cng nh c hiu sut lng t cng ln. S ph
thuc ca hiu sut lng t vo kch thc ht cng c bo co trc v
c gn cho hiu ng kch thc lng t. i vi nhng ht cng nh, xc
sut mt ht khng cha tm dp tt no tng ln. Hiu sut lng t cao ny
ch c th thu c trong nhng mu tinh th kch thc nano m nhiu ht
21
"hon ho" vi hiu sut lng t gn hp nht c th hnh thnh. Do vi kch
thc nh, xc sut vi tinh th sai hng t do cao.
----- -----
Chng 2
THC NGHIM CH TO V PHNG PHP KHO ST MU
2.1. Thc nghim ch to mu
2.1.1. Mt s phng php ch to vt liu nano
Hin ti c rt nhiu phng php ch to mu ZnS di dng khi v
mng. Cc phng php ny c chia lm hai nhm chnh: nhm cc phng
php vt l v nhm cc phng php ha hc.
Nhm cc phng php vt l bao gm: bc bay nhit trong chn khng,
phn x cao p cao tn, bay hi chm in t, epitaxi chm phn t, lng ng
bng xung Laser,. u im ca nhm phng php ny l ch to c mu
vi tinh khit cao, ng nht v quang hc v mt ht cao. Tuy nhin cc
22
phng php ny i hi cao v cng ngh ch to nh phi thc hin trong cc
mi trng chn khng cng vi cc thit b phc tp.
Nhm cc phng php ha hc bao gm: Phng php Sol-gel, nhng
keo, phng php phun tnh in, lng ng in ha, phng php ng kt
ta, phng php cy ion, phng php ha t.u im ca phng php l
d p dng, gi thnh thp, c th thay i d dng nng pha tp v c kh
nng a vo ch to hng lot. Nhc im ca phng php ny l tinh
khit ca mu khng cao, ph thuc vo mi trng nn khng n nh.
Trong cc phng php trn, phng php ha t (wet chemical method)
c nhng u im ring v mt cng ngh, gi thnh cng nh trin vng trong
ch to mu. Trong lun vn ny chng ti ch to mu ZnS:Mn
2+
bng phng
php ha t. S hp tc cht ch trong cng tc nghin cu khoa hc ca cn
b khoa Vt l v khoa Ha hc cng l iu kin rt thun li gip chng ti c
th tin hnh cc th nghim ch to mu theo phng php ny phng th
nghim ca c hai khoa.
2.1.2. Ha cht v thit b ch to mu
Ha cht
Mui Zn(CH
3
COO)
2
.2H
2
O; Mn(CH
3
COO)
2
.4H
2
O; Na
2
S.9H
2
O.
Axit CH
3
COOH; HCl.
Dung dch CH
3
COONa.
Nc ct
Polymer: Poly vinyl alcohol (PVA _ [C
2
H
4
O]
n
); Poly acrylic (PA _
[C
8
H
8
]
n
); Poly styrene (PS_C
3
H
4
O
2
)
n
.
Xylen [C
8
H
10
]_M
w
=106,17 g/mol.
Dng c
23
Cc loi pipt 2ml, 10ml, bnh nh mc 100ml, 250ml, 500ml.
Cc cc cn, a v tha thy tinh, qu bp, bnh xt nc ct.
thy tinh c vi kch thc 22220.25mm
3
.
Thit b
My o pH: HM-5S.
Cn phn tch (BP-1218): max 120g; chnh xc 10
-4
g (0,1mg);
ch ngun 12-30V(DC).
My khuy t Jenway 1000: U=230(V); f=50(Hz); P=500(W).
My li tm Hettich EBA 8S: max=6000(vng/pht);
U=230(V); f=50-60(Hz); I=0,35(A).
T sy chn khng (VT 6025): Pmax=1000(mbar); P=180W;
U=230V; I=1,6(A); f=50-60Hz.
L nung.
2.1.3. Ch to mu
a. Dung dch mui tng hp mu
Dung dch 1 [Zn(CH
3
COO)
2
0,1M]: cn 21,95(g) Zn(CH
3
COO)
2
.
2H
2
O, ha tan trong cc ong bng CH
3
COOH long. Chuyn vo
bnh nh mc 1 lt, nh mc ti vch bng dung mi nc ct 2 ln
v CH
3
OH (1:1).
Dung dch 2 [Mn(CH
3
COO)
2
0,1M]: cn 6,1275(g) Mn(CH
3
COO)
2
.
4H
2
O, ha tan trong cc ong bng CH
3
COOH long. Chuyn vo
bnh nh mc 250ml, nh mc ti vch bng dung mi nc ct 2
ln v CH
3
OH (1:1).
24
Dung dch 3 [Na
2
S 0,1M]: cn 24,018(g) Zn(CH
3
COO)
2
.2H
2
O, ha
tan trong cc ong bng nc ct 2 ln. Chuyn vo bnh nh mc 1
lt, nh mc ti vch bng dung mi nc ct 2 ln.
b. Ch to mu ZnS:Mn khng bc ph Polymer
Cc mu ZnS:Mn c ch to vi hm lng Mn dng thay th (theo
s mol) cho Zn l 9% (
% 9
Zn
Mn
n
n
). Vi nng mol ca cc dung dch mui
dng tng hp mu nh trn, ta c quy tc dng pha trn t l dung dch 1
v 2 nh sau:

2 1
.
100
9
dd dd
V V (2.1)
(Vi V
dd1
, V
dd2
ln lt l th tch dung dch 1 v 2)
S d chng ti chn t l Mn thay th 9% l v theo cc nhm nghin cu
, khi thay i hm lng pha tp Mn trong bn dn ch ZnS ch to bng
phng php ha t, cc tc gi nhn c mu bt ZnS:Mn vi hm lng
9%Mn cho nh pht x bc sng 600nm mnh nht. Kt qu cho thy vt
liu ny c ng dng trin vng cho cc ngun sng pht x nh sng ti bc
sng 600nm.
Chng ti iu chnh pH ca cc dung dch trn bng 5 trc khi cho
phn ng xy ra. S d nh vy l v theo nhm tc gi nghin cu s nh
hng ca pH n tnh cht ca mu ZnS, kt qu nghin cu cho thy cc
mu ZnS c pH=5 mu kt tinh n pha v cho ph pht quang tt nht.
Ch to mu bt ZnS:Mn khng bc ph Polymer
Bc 1: Cc dung dch 1 v 2 c trn u vo nhau bng my
khuy t nhit phng vi t l thch hp nhm to ra vt liu
25
ZnS:Mn_9%. Sau hn hp dung dch c chnh vi pH=5 bng
dung dch Axit axetic (CH
3
COOH) v Natri axetat (CH
3
COONa).
Bc 2: Nh t t dung dch 3 ( iu chnh pH=5) vo hn hp trn.
Thi gian phn ng ht dung dch vo khong 30 pht. Khi trong
dung dch xy ra phn ng:
Zn(CH
3
COO)
2
+ Na
2
S ZnS + 2CH
3
COONa
Mn(CH
3
COO)
2
+ Na
2
S MnS + 2CH
3
COONa
Bc 3: Quay ly tm v ra kt ta
Chng ti tch kt ta bng cch cho ton b dung dch sau phn ng vo
my quay ly tm, quay khong 5 pht li gn b lp dung dch pha trn kt ta,
tip tc ra kt ta bng dung mi CH
3
OH:H
2
O (1:1) sau vi ln chng ta thu
c kt ta sch.
Buc 4: X l nhit
Kt ta c sy 50
O
C bng t sy chn khng. Sn phm thu c
dng bt mn mu trng.
Quy trnh ch to mu bt trong lun vn c th tm tt theo s hnh 2.1
26
Hnh 2.1: S tm tt quy trnh tng hp bt nano tinh th ZnS:Mn
Ch to mu mng ZnS:Mn khng bc ph polymer
ch to mu mng ZnS:Mn, cc kt ta ZnS:Mn (cha sy) c phn
tn vo trong dung mi CH
3
OH:H
2
O (t l 1:1). Mng c ch to bng
phng php quay ph thng thng. Qu trnh quay ph c thc hin theo 4
bc: (a) nh dung dch cn ph ln , (b) bt u xoay ly tm, (c) kt thc
xoay ly tm, (d) bay hi dung dch. Thi gian thc hin gia bc (b) v bc
(c) khng 30s. Tc xoay ly tm l 3000(vng/pht). c s dng to
mng l lam knh thy tinh c vi kch thc 22220.25mm
3
.
Cc mu bt v mng ZnS:Mn c x l cc nhit 80
o
C, 200
o
C,
300
o
C v 400
o
C trong mi trng kh Nit bng l c iu khin nhit theo
quy trnh nh sau: tng nhit ln n gi tr mong mun vi tc tng nhit
Zn(CH
3
COO)
2
.2H
2
O
0,1M
(dd1)
Mn(CH
3
COO)
2
.4H
2
O
0,1M
(dd2)
Na
2
S.9H
2
O
0,1M
(dd3)
pH=5
Khuy u, t
o
=300K, 30 pht
Zn(CH
3
COO)
2
+ Na
2
S ZnS + 2CH
3
COONa
Mn(CH
3
COO)
2
+ Na
2
S MnS + 2CH
3
COONa
Sy kh p sut thp (200mbar)
t
o
=50
o
C, 48h
Sy kh p sut thp (200mbar)
t
o
=50
o
C, 48h
Tch kt ta bng my quay li tm
Ra vi ln vi CH
3
OH:H
2
O(1:1)
27
l 6
o
C/pht, duy tr nhit ny trong vng 1 gi, sau h nhit l n
nhit phng.
Vi quy trnh nh trn chng ti ch to c 8 mu (4 mu bt v 4
mu mng ) vi tn ln lt cc mu l: B-80, B-200, B-300, B-400 v M-80,
M-200, M-300, M-400.
c. Ch to mu mng ZnS:Mn bc ph Polymer
Ch to mu mng ZnS:Mn bc ph PVA vi hm lng thay i
Ha tan ln lt 2g, 4g, 5g PVA (polyvinyl alcohol) vo hn hp dung
dch 1 v 2 sau khi pha trn vi t phn thch hp v iu chnh
pH. Gia nhit hn hp n khong 80
o
C cho lng PVA tan ht, sau
cho nhit dung dch gim xung nhit phng. Tip , nh
t t tng git dung dch 3 ( chnh pH) vo hn hp dung dch trn.
Thi gian phn ng ht dung dch khong 30 pht. Khi cc phn
ng xy ra nh trong bc 2 trn.
ch to mu mng ZnS:Mn bc ph PVA, chng ti dng cc sn
phm dung dch sau phn ng v phn tn chng vo trong dung mi
CH
3
OH:H
3
O (1:1). c s dng l lam knh thy tinh ca c vi
kch thc 22220.25mm
3
. Mng c ch to bng phng php
quay ph ging nh phng php ch to mng ZnS:Mn khng bc
ph polymer nh trn.
Vi quy trnh nh vy chng ti ch to c 3 mu mng ln lt c
tn tng ng l M-PVA2, M-PVA4, M-PVA5.
Mu mng ZnS:Mn bc ph cc loi Polymer PVA, PA, PS.
Dng mu bt ZnS:Mn thu c trong qu trnh ch to trn (s hnh
2.1) phn tn vo trong dung mi thch hp. C th, dung mi tng ng vi cc
loi polymer dng bc ph mu ZnS:Mn c cho trong bng 2.1.
28
Bng 2.1: Dung mi tng ng i vi cc loi polymer
Polymer
Dung mi
Tn Cng thc ha hc
Tn Cng thc ha hc
Phn t gam
(g/mol)
Polyvinyl alcohol - PVA (C2H4O)n Nc ct H2O 18,02
Poly acrylic - PA (C3H4O2)n Xylen C8H10 106,17
Poly styren-PS (C8H8)n Xylen C8H10 106,17
Sau cho polymer vo trong hn hp dung dch phn tn bt trn
vi t l polymer:bt = 1:1. C th trong lun vn dng t l hn hp nh sau:
Bt (0,15g) + Polymer (0,15g) + Dung mi (3ml). i vi polymer PVA, cn
phi gia nhit nhit khong 80
o
C PVA c th tan ra. Dng my khuy t
khuy lin tc hn hp trong thi gian 2h. Sau ch to mu mng bng
phng php nhng ph thng thng.
Vi quy trnh nh trn chng ti ch to c 3 mu mng ln lt c
tn tng ng l M-PVA(1:1), M-PA(1:1), M-PS(1:1).
2.2. Mt s phng php kho st mu
2.2.1. Php o nhiu x tia X
Nhiu x tia X l hin tng cc chm tia X nhiu x trn cc mt tinh th
ca cht rn. Do tnh tun hon ca cu trc tinh th to nn cc cc i v
cc tiu nhiu x. K thut nhiu x tia X c s dng phn tch cu trc
ca vt liu . i vi cc tinh th nh c kch thc nanomet, ngoi vic cho
bit cu trc pha ca nano tinh th, k thut ny cn cho php ta c lng kch
thc ht tinh th ca mu.
Nguyn l chung ca phng php nhiu x tia X: Chiu chm tia X n
sc vo tinh th, khi cc nguyn t b kch thch v tr thnh cc tm pht
sng th cp. Cc sng th cp ny trit tiu vi nhau theo mt s phng v
tng cng vi nhau theo mt s phng to nn hnh nh giao thoa. Hnh nh
ny ph thuc vo cu trc ca tinh th. Phn tch hnh nh ta c th bit
29
c cch sp xp cc nguyn t trong mng. Qua ta xc nh c cu
trc mng tinh th, cc pha cu trc trong vt liu, cu trc mng c s .
Phng trnh nhiu x Bragg: Ta xem mng tinh th l tp hp ca cc
mt phng song song cch nhau mt khong d. Khi chiu tia X vo b mt, do
tia X c kh nng m xuyn mnh nn khng ch nhng nguyn t b mt m
c nhng nguyn t bn trong cng tham gia vo qu trnh tn x.
Hnh 2.2: S nguyn l ca nhiu x tia X
Nu ta quan st cc chm tia tn x theo phng phn x th hiu quang
trnh gia cc tia tn x trn cc mt l:
sin . . 2 d L (2.2)
Nh vy c cc i nhiu x th gc ti phi tha mn iu kin:

. sin . . 2 n d L
(2.3)
Trong :
n
l bc phn x (
... , 3 , 2 , 1 n
),

l gc ti,
d
l khong cch
gia cc mt phng mng.
y chnh l nh lut Vulf-Bragg m t hin tng nhiu x tia X trn
cc mt tinh th. Nu tm c cc gc ng vi cc i s tm c d theo
iu kin Vulf-Bragg. Cc nh nhiu x trn gin nhiu x tia X c trng
cho cu trc ca vt liu. Da vo s lng, bn rng, v tr cc nh nhiu
x ta c th suy on c kiu mng, xc nh bn cht mu.
2.2.2. Chp nh hin vi in t qut (SEM)
SEM l mt trong nhng k thut phn tch tin li v nhanh chng nht,
cho php quan st trng thi b mt mu c phng i ln rt nhiu ln.
30
in t c pht ra t sng phng in t, sau c tng tc v hi t
thnh mt chm in t hp, nh h thng thu knh t, sau qut trn b mt
mu nh cc cun qut tnh in. Khi in t tng tc vi b mt mu vt s c
cc bc x pht ra. Cc bc x pht ra ch yu gm: in t th cp, in t tn
x ngc, tia X, in t Auger. Mi loi bc x thot ra mang mt thng tin v
mu phn nh mt tnh cht no ch tia in t ti p vo mu, cc in
t thot ra ny c thu vo u thu kt ni vi my vi tnh (c ci t
chng trnh x l), kt qu thu c l thng tin b mt mu c a ra mn
hnh.
S cu to v nguyn tc hot ng ca SEM c m t trn hnh 2.3.
N g u n c p
e l e c t r o n
V t k n h
T r n g q u t
M u
P h n x
T h c h i n
q u t r n h
q u t n g b

n h

n g t i a c a t t
C h u y n t h n h t n h i u
i n v k h u y c h i
D e t e c t o r
Hnh 2.3: Cu to my o SEM
2.2.3. Php o ph hp th
Ph hp th l mt cng c hu ch trong vic nghin cu s tng tc
ca vt liu vi nh sng chiu vo, qua c th bit c thng tin v cc qu
trnh hp th xy ra tng ng vi cc chuyn di quang hc t mt s trng
thi c bn m
j
n mt s trng thi kch thch n
i
, t c th xc nh c
bc sng kch thch hiu qu cho qu trnh quang hunh quang (j - i) m ta
quan tm.
31
Mi trng vt cht hp th nh sng tun theo nh lut Beer - Lambert:

d
e I R I
) (
0
). ( ). 1 ( ) (




(2.4)
()=
]
) (
) 1 ).( (
ln[ .
1

I
R I
d
o

(2.5)
Trong :
) (
0
I
l cng ca chm tia sng ti,
) ( I
l cng ca
chm tia sng sau khi i qua mi trng, () l h s hp th ca vt liu i
vi photon c nng lng h , d l qung ng nh sng truyn qua mu, R l
h s phn x ca mu.
Nu coi h s phn x R ca mu l rt nh, khi ta c:

d
e I I
) (
0
). ( ) (

(2.6)
()=
]
) (
) (
ln[ .
1

I
I
d
o
(2.7)
Nu nh sng b hp th bi cc phn t, ion hoc l cc tm quang no
trong vt rn th h s hp th () l c trng cho nhiu qu trnh hp th
xy ra ng thi trong mu, trn cc tm khc nhau. Trong thc t, theo thi
quen v d hnh dung v mc suy gim nh sng khi i qua mt vt liu,
ta thng bin i cng thc trn nh sau:

A I I I I d . 3 , 2 )] ( / ) ( lg[ . 10 ln ) ( / )) ( ln( ). (
0 0

(2.8)
)] ( / ) ( lg[
0
I I A
c gi l hp th (hay mt quang hc), l i
lng khng th nguyn, lin h vi h s hp th () bng biu thc:

d A ). ( . 3 , 2
(2.9)
Ph hp th l th biu din s ph thuc ca h s hp th () (hay
hp th A) theo bc sng hay nng lng ca photon i qua vt cht.
2.2.4. Php o ph hunh quang
C ch ca hin tng hunh quang
32
Khi chiu vo vt liu mt bc x kch thch c bc sng thch hp,
cc in t b kch thch ln trng thi c nng lng cao hn. Khi trng thi
c nng lng cao, cc in t li c xu hng chuyn xung trng thi c nng
lng thp hn v truyn nng lng ca n cho dao ng mng hoc pht x ra
photon. S chuyn mc nng km theo hin tng pht x photon nu n xy
ra gia cc mc nng lng c khong cch ln. l hin tng hunh
quang hay pht x t pht. Tm li hunh quang l hin tng pht x ra photon
khi vt liu tng tc vi cc bc x kch thch hoc cc ht.
Phng php o ph hunh quang
Trong thc t c nhiu php o hunh quang ph thuc vo kiu kch
thch. Nu vt liu c kch thch bng bc x in t ta c ph quang hunh
quang. Hunh quang kch thch bng tia X ta c ph hunh quang tia X. Khi
kch thch bng in trng ta c in hunh quang. Nu kch thch bng phn
ng ha ha hc th ta c ph ha hunh quang.
Ph hunh quang biu din s ph thuc ca cng hunh quang vo
bc sng (hoc tn s) di mt bc sng nh sng kch thch nht nh.
S khi ca mt h o hunh quang c minh ha nh hnh 2.4.
Hnh 2.4: S khi ca h o ph hunh quang
Kt qu o ph hunh quang s cung cp cc thng tin v cc mc nng
lng ca tm quang hc. Trong trng hp mu c cha nhiu loi tm tch
cc quang th ph hunh quang c th s l chng chp ca cc nh hunh
quang c ngun gc t cc tm khc nhau.
NGUN KCH NGUN KCH
THCH THCH
MU MU MY N SC MY N SC
MY VI TNH MY VI TNH
NG NHN QUANG NG NHN QUANG
iN iN
33
2.2.5. Php o hunh quang phn gii thi gian
Php o hunh quang phn gii theo thi gian gip ta c th d on c
ch ti hp tng ng vi cc bc x pht ra. ng thi php o ny cn cho ta
xc nh c thi gian sng hunh quang ng vi cc bc x v mt cch nh
tnh c th so snh thi gian sng hunh quang ca cc bc x vi nhau.
Php o phn gii thi gian thng yu cu ngun kch xung lp li v
nhiu gi tr thi gian tr sau khi ly mu. Thi gian tr c t mt gi tr
theo yu cu, bc sng c qut chm tng ng vi tc lp li ca xung
kch thch. Tuy nhin c th phn gii thi gian tt, cn thit phi c s tr
n nh v khong thi gian gia hai ln ly mu l ngn. Do cng kch
thch thng ln trong khi bc x tr l kh yu nn u thu cn phi c bo
v trnh nh sng tn x t ngun kch thch.
Ngun nh sng xung truyn thng (nh n Xenon) pht ph lin tc c
th gy ra nh sng tn x ln. Ngun xung Laser c th khc phc c nhc
im ny ng thi cho cng kch thch cao hn.
Mayn sac
Heghi
Henhthi
Bocam
bien
Bocam bien Si
LED
ieukhien
toc oMotor
Motor
Mau
Nguon sang
Hnh 2.5: S khi ca h o ph hunh quang phn gii thi gian s dng Chopper kp
2.2.6. Php o thi gian sng hunh quang (bng phng php xung)
Php o thi gian sng hunh quang s cho bit thi gian trung bnh m
nguyn t hay in t nm trng thi kch thch trc khi tr v trng thi c
bn. C hai phng php o thi gian sng hunh quang: phng php xung v
phng php iu bin (bin iu pha).
34
Trong phng php xung th mu c kch thch bi nh sng di dng
xung v s suy gim cng hunh quang ph thuc theo thi gian s c
o. Nguyn l ca phng php xung o thi gian sng hunh quang c trnh
by nh sau: Xt mt mu c kch thch bi nhng xung nh sng ngn. Gi
s mt tm hunh quang ban u trng thi kch thch l N(0) v tc
gim ca mt tm hunh quang trng thi kch thch c xc nh bi
cng thc: ) ( ) (
) (
t N k g
dt
t dN
+ (2.10)
Trong : N(t) l mt tm hunh quang nm trng thi kch thch
thi im t sau khi tt xung kch thch, g l tc pht x v k l tc phn
hy khng bc x. Nh vy, ti thi im t=0 th N(t)=N(0) , tch phn hm
2.10 ta c:
t
e N t N

) 0 ( ) (
(2.11)
Trong :
1
) (

+ k g l thi gian sng ca tm hunh quang trng thi
kch thch. Chng ta coi cng hunh quang I(t) t l vi mt trng thi
kch thch I(t)gN(t) v suy gim theo quy lut hm m. Thi gian sng hunh
quang c coi l thi gian cn thit cng hunh quang gim n cn
1/e ln so vi cng hunh quang ban u.
35
Hnh 2.6: th m t kt qu php o thi gian sng hunh quang bng phng php xung
Kt qu ch to mu v cc php o kho st c trnh by trong bng 2.2.
Bng 2.2. Kt qu ch to mu v cc php o kho st mu
Tn mu XRD SEM Abs PL PLEPD TRP PLD
Mu
khng
bc
ph
polymer
1 B-80 x x
2 B-200 x x
3 B-300 x x
4 B-400 x x
5 M-80 x x
6 M-200 x x
7 M-300 x x
8 M-400 x x

1
) ( + k g tg
LnI(t)
{LnN(t)}
t
I(t)
{N(t)}
t
) 0 (
1
I
e

36
Mu
bc
ph
polymer
9 M-PVA2 x x x x x
1
0 M-PVA4 x x x
11 M-PVA5 x x
1
2 M-PVA(1:1) x x x x
1
3 M-PA(1:1) x x
1
4 M-PS(1:1) x
Ch thch: cc k hiu dng trong bng.
o XRD: (X-ray diffraction) php o nhiu x tia X.
o SEM: (Scan electron microscopy) php o knh hin vi in t qut.
o Abs: (Absorption) php o ph hp th.
o PL: (Photoluminescence) php o ph hunh quang.
o PLEPD : (Photoluminescence with different exciting power density)
php o ph hunh quang vi mt cng sut kch thch khc nhau.
o TRP : (Time resolved Photoluminescence) php o hunh quang phn
gii thi gian.
o PLD: (Photoluminescence decay): php o ph hunh quang tt dn.
----- -----
Chng 3
KT QU V THO LUN
3.1. Nghin cu nh hng ca ch x l nhit ln mt s tnh cht ca
mu bt v mng ZnS:Mn.
3.1.1. Kt qu nghin cu mu bt ZnS:Mn
a. Kt qu o nhiu x tia X
37
Gin nhiu x tia X (gin XRD) ca cc mu c o ti khoa Ha,
trng i hc Khoa hc T nhin. Mu c kch thch bng bc x CuK

vi
bc sng =1,5406.
Hnh 3.1 trnh by gin XRD ca cc mu bt ZnS:Mn x l cc
nhit khc nhau 80, 200, 300 v 400
o
C trong mi trng kh Nit. Hnh 3.2a
v 3.2b trnh by kt qu i chiu ph XRD ca mu ZnS:Mn nung 80
0
C v
300
o
C vi th chun ca ZnS.
T gin XRD, v kt qu so snh vi th chun ta c nhn xt sau:
Cc mu ZnS:Mn c v tr cc nh nhiu x ph hp vi cc nh
nhiu x ca th chun ca vt liu ZnS. iu ny khng nh cc mu
ch to u kt tinh.
Trn ph nhiu x ca cc mu khc nhau u xut hin cc nh
tng ng, cc mu ny u c chung mt loi cu trc lp phng gi
km (sphalerite) thuc nhm khng gian
m d
F T
43
2

(216).
Khi nhit x l mu t 300
o
C tr ln, ngoi cu trc sphalerite c
trng ca bn dn ZnS cn xut hin cu trc lc gic (hexagonal) c
trng ca ZnO. iu ny c th l do bung mu cha kn, kh Nit
cha sch hoc c th l do vi pH cao (pH=5) sn phm to thnh
sau phn ng c xut hin km hydroxit Zn(OH)
2
. Chnh Zn(OH)
2
khi
nung nhit cao to thnh ZnO [Zn(OH)
2

o
t

ZnO + H
2
O].
38
Hnh 3.1: Gin XRD ca mu ZnS:Mn x l cc nhit khc nhau
lm r hn cc nhn xt trn, chng ti tin hnh tnh ton hng s
mng v kch thc ht ca cc mu ny.
Tnh hng s mng
p dng phng php dy t s

2
sin
xc nh cc ch s Miller
(h,k,l) v hng s mng ca cc mu. Ni dung cc bc tnh ton nh sau:
Bc 1: T gin nhiu x tia X, xc nh cc gi tr ca gc 2 ,
sau tnh d
hkl
theo phng trnh Vulf-Bragg:
sin . d 2. n
(
5406 , 1
).
39
Hnh3.2a: Kt qu so snh gin XRD ca mu B-80 vi th chun
Hnh3.2b: Kt qu so snh gin XRD ca mu B-300 vi th chun
Bc 2: Lp bng tnh ton cc gi tr
2
sin , sin .
40
Bc 3: Tnh gi tr ca dy t s
1
2
2
sin
sin

i
i
K
, tra bng chun tm
h, k, l t suy ra cu trc [Ph lc I].
Kt qu tnh ton c th ca mu c trnh by trong bng 3.1. Cc mu
cn li cng tnh ton hon ton tng t.
Bng 3.1: Kt qu tnh ton cc h mt phn x ca mu B-80
STT nh d
hkl
() 2 sin Sin
2
K
i
h k l
1 3,098 28.8 0.25 0.06 1 1 1 1
2 1,88 48.4 0.41 0.17 2.71 2 2 0
3 1,616 56.9 0.48 0.23 3.67 3 1 1
Bc 4: p dng cng thc lin h gia khong cch cc mt mng
d
hkl
vi cc ch s Miller v hng s mng:

2
2
2
2
2
2
2
1
c
l
b
k
a
h
d
+ + (3.1)
p dng biu thc trn cho mng lp phng (a=b=c) ta c:

2 2 2
. l h k d a
hkl
+ + (3.2)
Tnh sai s:
g a a cot . .
(3.3)
Kt qu tnh hng s mng ca cc mu ZnS:Mn c cho trong bng 3.2
Bng 3.2: Hng s mng ca cc mu bt ZnS:Mn
2+

Mu Hng s mng a () Sai s a ()
B-80 5,360 0,005
B-200 5,358 0,003
B-300 5,322 0,002
B-400 5,352 0,004
Nh vy, qua tnh ton trn ta c th kt lun: mu ZnS:Mn cho cc
nh nhiu x ng vi cc h mt phng mng (111), (220) v (311) . Tinh th c
41
cu trc lp phng tm mt. Hng s mng ca cc mu ZnS:Mn vo khong
t 5,325,36() v hu nh trong phm vi nhit x l mu nh trn khng
nh hng n hng s mng ca tinh th. Cc kt qu v cu trc tinh th,
hng s mng m ta va xc nh c ph hp vi cc nghin cu ca cc tc
gi .
Tnh kch thc ht bng cng thc Scherrer
Da vo gin nhiu x XRD ta c th tnh kch thc ht tinh th bng
cng thc Scherrer:

cos .
. 9 , 0
L
(3.4)
Trong : L l ng knh ht tinh th,

(rad) l rng Scherrer ti

2
max
I
ca nh,

() l gc ng vi v tr nh.
Kt qu tnh kch thc ht c trnh by trong bng 3.3.
Bng 3.3. Kt qu tnh kch thc ht t cng thc Scherrer
Tn mu (nm) 2() (rad) L(nm) Li/L1
B-80 0,15406 28.81 0,06 2,6 1
B-200 0,15406 28.92 0,05 2,7 1,04
B-300 0,15406 29.28 0,04 3,9 1,5
B-400 0,15406 28.87 0,03 4,9 1,88
Kt qu cho thy khi nhit x l mu cng cao th kch thc ht
cng ln. iu ny c gii thch l do khi tng nhit x l mu, cc ht s
b kt m li v hnh thnh nn ht c kch thc ln hn . Kt qu v s thay
i kch thc ht tinh th theo nhit x l mu trn hon ton ph hp vi
kt qu ca cc nhm nghin cu .
42
b. Kt qu o ph hunh quang
Ph hunh quang ca cc mu B-80, B-200, B-300 v B-400 c o ti
Vin Vt liu - Vin Khoa hc v Cng ngh Vit Nam.
Hnh 3.3 l ph hunh quang ca mu bt tinh th nano ZnS:Mn_9% vi
pH=5 x l cc nhit 80, 200, 300, 400
o
C khi kch thch mu bng bc
sng 325nm nhit 300K. Khi o ph hunh quang, chng ti c gng gi
cho khi lng mu trong cc ln o l xp x nh nhau.
Hnh 3.3: Ph hunh quang ca mu ZnS:Mn theo ch x l nhit (
kt
=325nm)
Da vo ph hunh quang hnh 3.3 ta c nhn xt sau:
Cc mu ZnS:Mn pht quang mnh trong vng kh kin v quan st
thy c ba nh hunh quang D1 (bc x xanh lam), D2 (bc x da
cam-vng) v D3 (bc x ).
Ngun gc ca bc x mu xanh lam theo nhm tc gi lin quan n s
kch thch ca ion Mn
2+
trn nn bn dn ch ZnS thng qua s dch chuyn ca
in t t mc
4
A
1
+
4
E(G) xung mc
6
A
1
(S). Tuy nhin, theo cc nghin cu
43
ca nhm tc gi cho thy khi mu ZnS khng pha tp Mn th nh hunh
quang cng xut hin ti v tr ny. iu ny cho thy nh hunh quang ti
bc sng ny c th l do sai hng ca bn dn ch ZnS. C th ngun gc ca
bc x ny l do s chuyn di trn mc nng lng ca cc mc khuyt tt S
2-
(ng vai tr tm donor ) v ca cc mc khuyt tt Zn
2+
(ng vai tr tm
acceptor) .
Ngun gc ca bc x mu da cam l do s chuyn ca in t t mc
4
T
1

6
A
1
(trong trng tinh th ca mng lp phng) ca ion Mn
2+
. Ta bit rng
Mn v Zn c bn knh ion khc nhau (
pm r
Zn
74
2

+ ,
pm r
Mn
67
2

+

v
pm r
S
184
2

). Khi Mn
2+
i vo trong mng tinh th ch ZnS, n s lm mng
tinh th b bin dng, ng thi cc trng thi electron lp d ca ion Mn
2+
tng tc rt mnh vi cc trng thi electron s-p ca tinh th nano ZnS, v th
n nh hng n cu trc mc nng lng ca ZnS. C th l dn n s tch
cc mc nng lng ca ion Mn
2+
trong trng tinh th lp phng .
m pht quang mu v tr nh D3 c th lin quan n tp cht
khng mong mun m cha th kim tra c c trong tinh th ZnS:Mn.
Trong mu ch to trn, chng ti khng nh cc ion Mn
2+
khuch tn
trong mng tinh th ca bn dn ch ZnS. Bi theo cc nhm nghin cu cho
thy nu cc ion Mn
2+
c phn tn vo bn trong tinh th ZnS:Mn th trong
ph hunh quang ca mu ta thu c di pht x mu da cam, nhng nu cc
ion Mn
2+
phn tn nhng bn ngoi mng tinh th ZnS th ta khng thu c
di pht x trn trong ph hunh quang ca n.
Cng pht x ca cc nh D1, D2, D3 gim mnh, ng thi v
tr nh ph pht x mu xanh lam D1 dch chuyn v pha sng di
khi nhit x l mu tng ln.
44
iu ny c th gii thch nguyn nhn l do khi nhit x l mu tng
ln, dn ti rng vng cm hp li. ng thi cc ht ln ln lm b mt mu
phng hn, cu trc ca tinh th tr nn n nh v hon ho hn, do kh i
cc trng thi sai hng ca mu. Khi , bc x hunh quang ch yu do s ti
hp ca cc in t vng dn, cng nh cc in t b by cc mc donor
nh x nm ngay di vng dn vi mc nng lng thp hn cng nh vi
di ha tr ca bn dn ch ZnS s gim. Cc mc by donor ny hnh thnh do
cc trng thi khuyt tt, lch mng ca tinh th cng nh do cc tp cht c
trong mu .
Mc khc ta cn nhn thy v tr nh ph pht x mu da cam D2 dch
chuyn nh v pha bc sng ngn. iu ny c th gii thch nguyn nhn l
do khi nhit x l mu tng ln nhit 300
o
C v 400
o
C xut hin cc vch
c trng ca pha ZnO (theo phn tch XRD hnh 3.3). S c mt ca ZnO trong
nn bn dn ch ZnS cng c th l nguyn nhn gy nn s dch nh ph D2
v pha sng ngn.
khng nh nhn xt trn, t s bt i xng ph hunh quang ca cc
mu ZnS:Mn, c th d on l do chng chp rt nhiu nh hunh quang. Ta
tch nh hunh quang ca h mu B-80, B-200, B-300, B-400 bng phng
php Gaussian (Fit 4 nh hunh quang) nh hnh 3.4, ta thu c s liu v v
tr v cng tng i nh hunh quang nh trong bng 3.4.
Hnh 3.5 m t s thay i ca cng hunh quang v v tr ca cc
nh ph theo nhit x l mu xut pht t bng s liu 3.4.
45
Hnh 3.4: th tch nh hunh quang ca cc mu B-80, B-200, B300 v B400 bng
phng php Gaussain
Bng 3.4: So snh tng i cng hunh quang v v tr cc nh ph i vi
h mu ZnS:Mn_9%, pH=5 x l cc nhit khc nhau khi thc hin vic tch nh
hunh quang bng phng php Gaussian.
Tn mu
D1(xanh) D2(Cam) D3() D4()

(nm)
I
(.v.t.y)

(nm)
I
(.v.t.y)

(nm)
I
(.v.t.y)

(nm)
I
(.v.t.y)
B-80 470 21457 595 11693 685 7523 730 2186
B-200 492 14926 591 7112 685 6059 744 1547
B-300 492 194 579 639 675 271 752 64
B-400 485 22 580 200 656 76 706 20
46
Hnh 3.5: th m t s thay i ca cng hunh quang (a) v v tr ca nh ph
(b) theo nhit x l mu
T hnh 3.3 v 3.5a ta thy rng mu ZnS:Mn_9% (pH=5) nhit
80
o
C cng ca nh D1 (m xanh lam) ln hn rt nhiu
cng ca nh D2 (m da cam).
Kt qu ny cha tng ng vi kt qu m cc nhm nghin cu
cng b. iu ny c th gii gii thch nguyn nhn l do nh hng ca pH
ca dung dch trc khi cho cc cht tham gia phn ng. Ngoi ra cn c th l
do cht lng ca ngun ha cht ban u cng nh mt s iu kin, k thut
ch to mu khc nhau. Nh vy s thay i cng pht quang rt nhy vi
iu kin tng hp. Trong qu trnh tng hp mu, mt s thay i d rt nh
cng s gy nh hng ln n cng pht quang .
3.1.2. Kt qu nghin cu mu mng ZnS:Mn
a. Kt qu o ph hunh quang
Hnh 3.6 l ph hunh quang ca mu mng ZnS:Mn ch to bng
phng php quay ph vi cc iu kin ch to nh nhau x l cc nhit
80, 200, 300 v 400
o
C. Kt qu cho thy i vi mu x l nhit 80
o
C cng
pht quang mnh trong vng nh sng nhn thy v xut hin ba nh hunh
50 100 150 200 250 300 350 400 450
460
480
500
520
540
560
580
600
B
u
o
c

s
o
n
g

(
n
m
)
Nhiet do (
o
C)




D1
D2
50 100 150 200 250 300 350 400 450
-2000
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
22000
24000


C
u
o
n
g

d
o

h
u
y
n
h

q
u
a
n
g

(
d
.
v
.
t
.
y
)
Nhiet do (
o
C)
D4
D3
D2
D1
(a)
(b)
47
quang D1, D2, D3. Ging vi kt qu mu bt trn, nh D1 dch chuyn v
bc sng di cn nh D2 dch chuyn nh v bc sng ngn hn.
300 400 500 600 700 800 900 1000
0
500
1000
1500
2000
2500
3000
D3
D2
D1
a M-80
b M-200
c M-300
d M-400
e glass
d
c
b
a


C
u
o
n
g

d
o

(
a
.
u
)
Buoc song (nm)
Hnh 3.6: Ph hunh quang ca cc h mu mng ZnS:Mn
Nhm d on s thay i rng vng cm ca cc mu mng trn,
chng ti tin hnh o ph hp th i vi h mng ny.
b. Kt qu o ph hp th
Hnh 3.7 l ph hp th ca cc mng mng ZnS:Mn nung cc nhit
khc nhau o nhit phng vi bc sng trong khong t 300850nm.
Ph hp th cho thy cc b hp th v s dch chuyn ca chng tng i r.
B hp th cung cp cho chng ta thng tin kh chnh xc v b rng vng cm
ca h.
Mi quan h gia h s hp th vi nng lng ca photon ti c biu
din bi phng trnh sau :

h
E h K
n
g
2
) (
(3.5)
Trong : K l hng s, E
g
l nng lng di cm v n l hng s bng 1
i vi vt liu c vng cm thng.
48
T phng trnh (2.9) v (3.5) ta suy ra i vi vt liu c b rng vng
cm thng, ta c phng trnh:
) (
3 , 2
) (
2
2
g
E h
Kd
Ah (3.6)
300 400 500 600 700 800 900
0.00
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2.00
2.25
2.50
a M-80
b M-200
c M-300
d M-400
d
c
b
a


D
o

h
a
p

t
h
u

A
Buoc Song (nm)
Hnh 3.7: Ph hp th ca mu mng ZnS:Mn
1.50 1.75 2.00 2.25 2.50 2.75 3.00 3.25 3.50 3.75 4.00 4.25
0
5
10
15
20
25
30
35
40
45
50
2,82 eV 2,89 eV 3,30 eV 3,79 eV
(4)
(3)
(2)
(1)
(1) M-80
(2) M-200
(3) M-300
(4) M-400


(
A
h

)
2

(
e
V
) 2
h (eV)
Hnh 3.8: th s ph thuc ca
2
) ( Ah vo nng lng h
ca bn dn ZnS i vi cc mu M-80, M-200, M-300 v M-400

49
Hnh 3.8 m t s thay i ca
2
) ( Ah
vo nng lng
h
i vi cc
mu M-80, M-200, M-300 v M-400. T th ta c th xc nh rng vng
cm bng cch ngoi suy s ph thuc ca
2
) ( Ah vo nng lng photon h .
Quy lut s ph thuc ny ph hp vi c ch chuyn mc thng cho php trong
bn dn ZnS:Mn . Kt qu xc nh rng vng cm ca cc mu c cho
trong bng 3.5.
Bng 3.5: rng vng cm ca cc mu mng ZnS:Mn vi nhit x l mu
khc nhau.
Tn mu M-80 M-200 M-300 M-400
E
g
(eV) ~3,79 ~3,30 ~2,89 ~2,82
T bng 3.5 ta thy khi nhit x l mu tng ln th b rng vng cm
ca vt liu nano ZnS:Mn hp li. Kt qu trn hon ton ph hp vi l thuyt
nghin cu .
3.1.3. Kt lun
Qua nghin cu nh hng ca ch x l nhit ln tnh cht cu trc v
hunh quang ca vt liu (bt v mng) ZnS:Mn, chng ti a ra mt s kt
lun sau:
- Khi nhit x l mu cng cao (80400
o
C) th hu nh khng
nh hng n hng s mng ca nano tinh th ZnS:Mn, vt liu
c cu trc sphalerite thuc nhm khng gian
m d
F T
43
2

, kch
thc ht tinh th cng ln (2,55nm). Nguyn nhn l do cc
ht kt m li vi nhau v hnh thnh ht c kch thc ln hn.
ng thi, rng vng cm gim (3,82,8eV).
- Cc mu u pht quang mnh trong vng nh sng nhn thy v
quang st thy c 3 di pht quang quang tng ng vi cc nh
ln lt l D1 (xanh lam), D2 (da cam vng ) v D3 ().
50
Ngun gc ca m pht quang mu xanh lam l do s ti hp
bc x ca cc cp donor acceptor . Ngun gc ca m pht
quang mu da cam vng l do s dch chuyn ca in t t
mc
4
T
1
(
4
G)
6
A
1
(
6
S) . Hnh 3.9 m t s cc mc nng lng
ca ion Mn khi c lp v khi trong trung tinh th ca mng lp
phng . m pht quang mu v tr nh D3 c th lin
quan n tp cht khng mong mun m cha th kim tra c
c trong tinh th ZnS:Mn.

Mang lap phng
Mn
2+
4
T
1
4
T
2
4
A
1
+
4
E
6
S
4
G
Hnh 3.9: S cc mc nng lng ca ion Mn
2+

khi c lp v khi trong trng tinh th ca mng lp phng
- Khi nhit x l mu tng ln, t s cng tng i gia hai
nh pht quang mu da cam v mu xanh tng ln rt nhanh
(bng s liu 3.4). Cng nh pht quang mu xanh lam gim
mnh v hu nh b dp tt khi nhit x l mu l 400
o
C. Nh
vy, ty theo mc ch s dng di pht quang ca vt liu
ZnS:Mn m ta c th chn gi tr nhit nung mu cho thch
hp.
Tuy nhin, l nhng kt qu nghin cu ca tc gi trong phm vi
nhit nung khng ln lm, ng thi bc thay i nhit nung tng i
51
ln nn kt qu thu c c l s cha tht s th hin c tnh quy lut v
tng minh.
3.2. Nghin cu s nh hng ca vic bc ph polymer ln tnh cht
quang ca vt liu ZnS:Mn
3.2.1. Nghin cu mu mng ZnS:Mn bc ph vi hm lng PVA khc
nhau
a. Kt qu chp nh SEM
kho st hnh thi b mt, chng ti tin hnh chp nh SEM ca mu
mng M-PVA4, php o c thc hin trn my JSM-5410LV ti khoa Vt l,
trung i hc Khoa hc T nhin, i hc Quc gia H Ni . Kt qu chp
nh SEM ca mu M-PVA4 c biu din trn hnh 3.10.
T nh SEM ca mu, ta c th a ra cc nhn xt v hnh thi b mt v
kch thc ht ZnS:Mn: mu quan st c dng ht, cc ht phn b cha
ng u trn b mt mng, kch thc ht c 100nm, cc ht ch yu hnh cu,
kch thc tng i ng u. i vi php o t nh SEM, do chm tia qut
trn b mt vt liu, nn nh SEM ch phn nh hnh thi, cu trc b mt v
phn nh tng i kch thc ht.
Tuy nhin nghin cu cu trc bn trong, nhng php o khc cn
c kho st tip theo.
52

Hnh 3.10: Kt qu chp nh SEM ca mu M-PVA4
b. Kt qu o ph hp th
Hnh 3.11 l ph hp th ca cc mu M-PVA2, M-PVA4, M-PVA5 o
300K vi bc sng t 200 n 800nm, ti Vin Khoa hc Vt liu, Vin Khoa
hc v Cng ngh Vit Nam. Kt qu cho thy, ln lt i vi cc mu M-
PVA2, M-PVA4, M-PVA5 th nh ph hp th dch chuyn nh v pha bc
sng ngn hn.
Hnh 3.11: Ph hp th ca cc mu M-PVA2, M-PVA4 v M-PVA5
o nhit 300K
53
Hnh 3.12a m t s thay i ca
2
) ( Ah
vo nng lng
h
i vi cc
mu M-PVA2, M-PVA4 v M-PVA5. T th ta c th xc nh rng vng
cm bng cch ngoi suy s ph thuc ca
2
) ( Ah vo nng lng photon h .
Quy lut s ph thuc ny ph hp vi c ch chuyn mc thng cho php trong
bn dn ZnS:Mn .
Khi vt liu tinh th c cu trc nano th n c nhiu tnh cht khc bit so
vi cc tnh cht ca mu khi tng ng, c bit khi kch thc ca ht tinh
th c th so snh c vi bn knh Bohr (r
B
). Theo nhm tc gi , i vi vt
liu ZnS, bn knh Bohr c xc nh theo cng thc:

1
]
1

+
* * 2
2
2
2
1 1
h e
B
m m e
h
e
h
r

(3.7)
Trong :
76 , 8
l hng s in mi ca vt liu,
o h o e
m m m m 24 , 0 , 34 , 0
* *
ln lt l khi lng hiu dng ca electron v l
trng trong vt liu ZnS,
* *
* *
h e
h e
m m
m m
+

l khi lng rt gn ca cc khi lng
hiu dng
*
e
m v
*
h
m ,
o
m
l khi lng electron t do. T cng thc (3.7) bn
knh Bohr ca vt liu ZnS c tnh khong 2,5nm.
T s dch chuyn ca rng vng cm (E
g
), bn knh ht tinh th c
th c xc nh theo mi quan h nh sau :

r
e
r
h
bulk E film E E
g g g

2
2
2
8 , 1
8
) ( ) ( +
(3.8)
Trong : E
g
(bulk)=3.68 (eV) [Ph lc III].
54
1.50 1.75 2.00 2.25 2.50 2.75 3.00 3.25 3.50 3.75 4.00 4.25 4.50
0
10
20
30
40
50
60
70
80
90
c
b
a
(b)
(a)

1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
K

c
h

t
h

c

h

t

t
i
n
h

t
h

(
n
m
)


1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
3.70
3.72
3.74
3.76
3.78
3.80
3.82
3.84
3.86
3.88

n
g

v

n
g

c

m

(
e
V
)
Hml ng Polymer d ng trong qu trnh tng h p (g)
a M-PVA2
b M-PVA4
c M-PVA5


(
A
h

)
2

(
e
V
) 2
h (eV)
Hnh 3.12: th s ph thuc ca
2
) ( Ah vo nng lng h ca bn dn ZnS i vi
cc mu M-PVA2, M-PVA4, M-PVA5 (a) v s thay i rng vng cm v kch thc
ht tinh th theo hm lng PVA dng trong qu trnh tng hp mu (b).
Kt qu tnh ton rng vng cm v kch thc ht tinh th (theo cng
thc 3.8) ca cc mu c cho trong bng 3.6.
Bng 3.6: rng vng cm ca bn dn ZnS:Mn v kch thc ht tinh th
tng ng vi cc mu M-PVA2, M-PVA4 v M-PVA5
Tn mu M-PVA2 M-PVA4 M-PVA5
E
g
(eV) ~3,86 ~3,77 ~3,73
r(nm) ~3,9 ~5,5 ~7,4
Hnh 3.12b m t s thay i ca kch thc ht v rng vng cm
ca bn dn ZnS:Mn khi thay i hm lng PVA dng trong qu trnh tng hp
mu. Ta thy b rng di cm gim xung (3,863,73eV) v ln hn b rng
di cm ca mu khi; kch thc ht tinh th tng ln (3.97,4nm) khi hm
lng polymer PVA dng trong qu trnh tng hp mu tng (25g) v ln hn
kch thc ht tinh th ca mu khng bc ph (so vi mu B-80 bng 3.3).
iu ny c th gii thch nh sau: khi tng hm lng Polymer PVA th
nht ca dung dch s tng, ngn cn s ln ln ca cc ht tinh th trong qu
55
trnh kt tinh, ng thi c s kt m ca cc nano tinh th trong qu trnh ch
to mng, v vy kch thc ht tinh th s tng.
Nh vy, t kt qu o nh SEM (hnh 3.10) v kt qu tnh kch thc
ht tinh th (bng 3.6) ca mng ZnS:Mn bc ph vi hm lng PVA khc
nhau ta thy: mt ht trong nh SEM bao gm rt nhiu ht tinh th ZnS:Mn.
Kt hp vi cng ngh ch to mu, chng ti cho rng cc ht tinh th cng
nh cc ht ZnS:Mn c phn tn trong nn polymer PVA.
c. Kt qu o ph pht quang
Ph hunh quang ca h mu M-PVA2, M-PVA4 v M-PVA5 c o
sau thi gian 120 ngy k t ngy ch to mu, nhit 300K khi kch
thch vi bc sng 325nm, thc hin ti Khoa Vt l, Trng i hc
Khoa hc T Nhin - i hc Quc gia H Ni. T ph hunh quang ca
h (hnh 3.13a) ta c nhn xt nh sau:
Ph hunh quang l mt vng ph rng nm trong nh sng kh kin
v gm c ba di pht quang tng i r rt vi cc nh ln lt l
D1 (~442 nm _bc x xanh lam), D2 (~588 nm _bc x da cam) v D3
(~684 nm_bc x ). D1 v D2 l hai nh ph pht x c trng ca
nano tinh th ZnS khi pha tp Mn. nh D3 xut hin do nhng tp
cht cha kim tra c c trong mu.
Hm lng polymer nh hng n lng Mn
2+
thc t i vo trong
mu. Hnh 3.13b ghp vo trong l ph hunh quang ca h mu M-
PVA2, M-PVA4 v M-PVA5 chun ha, mt cch tng i ta thy
t s cng nh pht x mu da cam (D2) v nh pht x mu
xanh lam (D1) ca cc mu l khc nhau v i vi mu M-PVA4 l
mnh nht. iu ny cho thy lng Mn khuch tn vo trong tinh th
56
ZnS l khng ging nhau. Tuy nhin lng Mn
2+
thc t i vo trong
cc mu l bao nhiu th cn phi c nhng php o chnh xc hn.
Polymer PVA khng lm thay i v tr nh hunh quang. Vi hm
lng polymer PVA thch hp s lm tng cng hunh quang
(ngha l hiu sut pht quang s tng), b rng di cm tng ln (kch
thc ht tinh th s gim). Trong phm vi kho st ca ti, vi hm
lng PVA l 2g (ng vi mu M-PVA2) cho thy cng pht
quang l mnh nht. T ph hunh quang (hnh 3.13) v kt qu tnh
ton kch thc ht tinh th (bng 3.6) ta thy hiu ng kch thc
c th hin mt cch r nt.
Qua vic phn tch cc kt qu trn ta thy polymer PVA gip cho vic
phn tn, c lp cc ht nano ZnS:Mn, ngn cn s to thnh m ca cc ht,
lm tng din tch b mt kt qu lm tng hiu sut pht quang.
Hnh 3.13: Ph hunh quang ca h mu mng M-PVA2, M-PVA4, M-PVA5
di bc sng kch thch 325nm vi mt cng sut 0.32W/cm
2
(a)
v th hunh quang chun ha tng ng (b)
57
300 350 400 450 500 550 600 650 700 750 800
0
1000
2000
3000
4000
5000
6000
7000
8000
D3
D2
D1
451


a 0,13 W/cm
2
b 0,19 W/cm
2
c 0,25 W/cm
2
d 0,32 W/cm
2
e 0,38 W/cm
2
f 0,45 W/cm
2
g 0,51 W/cm
2
h 0,57 W/cm
2
i 0,64 W/cm
2
i
h
g
f
e
d
c
b
a C
u
o
n
g

d
o

(
d
.
v
.
t
.
y
)
Buoc song (nm)
Hnh 3.14: Ph pht quang ca mu M-PVA2 nhit 300K khi kch thch
bng bc sng 325nm vi cc mt cng sut kch thch khc nhau
Hnh 3.14 l ph hunh quang ca mu M-PVA2 khi kch thch bng
bc sng 325nm vi cc mt cng sut khc nhau. Ta thy khi mt
cng sut thay i t 0,130,64W/cm
2
, v tr cc i ca cc m pht
quang D1, D2 v D3 hu nh khng thay i v cng ca m mu
xanh lam tng dn theo quy lut:

n
KT HQ
I A I ) .(
vi n0,7 (hnh 3.15) (3.9)
iu ny chng t s tng mt cng sut kch thch trong khong trn
vn cha lm thay i ng k nhit a phng ca tinh th ZnS:Mn, do
rng vng cm ca n vn khng thay i.
7.0 7.2 7.4 7.6 7.8 8.0 8.2 8.4 8.6 8.8 9.0
7.4
7.6
7.8
8.0
8.2
8.4
8.6
8.8
9.0
9.2
9.4
n=0,73
y =A +B*x
Thams gi tr sai s
------------------------------------------------------
A 2,5616 0,1153
B 0,7273 0,0142
------------------------------------------------------


L
n
(
I H
Q
)
Ln (I
KT
)
58
Hnh 3.15: S ph thuc cng m xanh lam ca mu M-PVA2
vo mt cng sut kch thch 300K khi kch thch bng bc sng 325nm
Hnh 3.16 l kt qu o ph hunh quang phn gii theo thi gian ca
m xanh lam ca mu M-PVA2 300K khi kch thch bng bc sng
337nm. Ta thy khi tng thi gian tr t 60ns n 114ns, cc i ca m
ny dch chuyn v pha nng lng thp v cng ca n cng gim
i (~5.7 ln). y l c trng in hnh ca ti hp bc x cc cp
donor-acceptor.
350 375 400 425 450 475 500 525 550 575
0
50
100
150
200
250
300
350
400
e
d
c
b
a
M-PVA2

ex
= 337 nm


C
u
o
n
g

d
o

(
d
.
v
.
t
.
y
)
Buoc song (nm)
a 60 ns
b 68 ns
c 76 ns
d 89 ns
e 114 ns
Hnh 3.16: Ph pht quang phn gii theo thi gian m xanh lam
ca mu M-PVA2 300K khi kch thch bng bc sng 337nm
iu ny c th gii thch nh sau: khi thi gian tr nh, cc cp donor-
acceptor gn vi thi gian sng nh ti hp trc, khi tng thi gian tr cc
cp donor-acceptor xa vi thi gian sng ln ti hp sau v xc sut ti hp
gim dn, v th nh ca m ny b dch chuyn v pha nng lng thp v
cng tng ng ca m b gim.
Vi c im trn cng vi s bt i xng ca th chng ti cho rng
m pht quang mu xanh lam l do s chng chp ca nhiu nh hunh
quang v l do s ti hp bc x ca cc cp donor-acceptor, trong cc nt
59
khuyt ca S
2-
ng vai tr l tm donor cn cc nt khuyt ca Zn
2+
ng vai
tr l cc tm acceptor.
Hnh 3.17a l th m t hunh quang tt dn ca mu M-PVA2 ti
bc sng 450nm. T th trn ta c th tnh c thi gian sng hunh
quang tng ng l 22ns (hnh 3.7b).
0 10 20 30 40 50 60 70 80 90 100 110 120
0
50
100
150
200
250
300
350
400


C
u
o
n
g

d
o

(
d
.
v
.
t
.
y
)
Thoi gian (ns)
M-PVA2

ra
= 450 nm

ex
= 337 nm
0 10 20 30 40 50 60 70 80 90 100 110
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
(2)
(1)
M-PVA2

ra
= 450 nm
= 22 ns


L
n

[
I
(
t
)
/
I
(
0
)
]
Thoi gian (ns)
(1) Data
(2) FitLinear
Y =A +B *X
---------------------------------------
Thngs gi tr sai s
A 1,47 0,01
B -0,045 2,19E-4
---------------------------------------
Hnh 3.17a: ng cong tt pht quang ti bc
x 450nm ca mu M-PVA2 300K khi kch
thch bng bc sng 337nm ca laser Nit
Hnh 3.17b: th xc nh thi gian sng
hunh quang ca bc x 450nm.
3.2.2. Nghin cu mu mng ZnS:Mn bc ph cc loi polymer khc nhau
Trong phn ny chng ti trnh by mt s kt qu bc u nghin cu
tnh cht quang ca mng nano tinh th ZnS:Mn bc ph mt s loi polymer
khc nhau ch to bng phng php nhng ph, nhm mc ch so snh tnh
cht pht quang ca chng.
a. Kt qu chp nh SEM
kho st hnh thi b mt, chng ti tin hnh chp nh SEM ca mu
mng M-PA(1:1), php o c thc hin trn my JSM-5410LV ti khoa Vt
60
l, trung i hc Khoa hc T nhin, i hc Quc gia H Ni. Kt qu chp
nh SEM ca mu M-PA(1:1) c biu din trn hnh 3.18.
T nh SEM ca mu, ta nhn xt thy khng phi mt ht m l mt
m ht ZnS:Mn kt t trong nn polymer, b mt mng khng ng u, c
nhiu k nt. Polymer lin kt thnh mng ln v cc ht nano ZnS:Mn c
khuch tn trong nn polymer.

Hnh 3.18: nh SEM ca mu M-PA(1:1)
b. Kt qu o ph pht quang
Hnh 3.20 l ph hunh quang ca h mu M-PVA(1:1), M-PA(1:1), M-
PS(1:1) c o bng bc sng kch thch 325nm ca laser He Cd vi
mt cng sut 0,13W/cm
2
ti khoa Vt l, Trng i hc Khoa hc
T Nhin i hc Quc gia H Ni. T ph hunh quang, mt cch
tng i ta c nhn xt nh sau:
Cc mu u pht quang mnh trong vng nh sng kh kin v xut
hin kh r ba di pht quang ln lt ng vi cc nh hunh quang
D1 (~452nm), D2 (~593nm) v D3 (~682nm).
Mc d o hai thi im khc nhau kh xa (cch nhau khong 120
ngy), v o trn hai h o khc nhau nhng chng ta thy c hai ln
o hnh dng ph, cc m pht quang trong ph hunh quang, cng
61
tng i gia cc nh trong cng mt ph cng nh gia cc ph
hunh quang vi nhau th hon ton ging nhau. Tuy nhin, v tr nh
ph pht x mu xanh ca cc mu trn hai h o khng trng nhau.
iu ny chng ti d on nguyn nhn l do hai h o s dng
ngun laser kch thch c bc sng ging nhau (325nm) nhng cng
nh sng (hay mt cng sut) l khng ging nhau, iu ny dn
n cng hunh quang cng nh v tr nh pht x mu xanh
khc nhau.
350 400 450 500 550 600 650 700 750 800 850 900 950 1000
0
4000
8000
12000
16000
20000
24000
28000
32000
(b)
(a)

300 400 500 600 700 800 900 1000
0.0
0.2
0.4
0.6
0.8
1.0
a
b
c
d


I(
d
.
v
.t
.y
)
Buoc song(nm)
d Bot
e Kinh
D3
D1
D2
576
e
d
c
b
a
a M_PVA(1:1)
b M_PA(1:1)
c M_PS(1:1)


C
u
o
n
g

d
o

h
u
y
n
h

q
u
a
n
g

(
d
.
v
.
t
.
y
)
Buoc song (nm)
Hnh 3.19: Ph pht quang ca h mu M-PVA(1:1), M-PA(1:1) v M-PS(1:1) nhit 300K
bng bc sng 325nm (a) v th chun ha tng ng (b)
{o ngy 5/6/2008-Vin Vt Liu-Vin Khoa hc v Cng ngh Vit Nam}
Cng m pht quang mu xanh lam (D1) ca cc mu khng
ging nhau, c th i vi mu M-PVA(1:1) l mnh nht, cn i vi
mu M-PS(1:1) l yu nht v thm ch cn yu hn c cng pht
quang ca mu bt ZnS:Mn khi cha tin hnh bc ph (hnh 3.19).
Kt qu ny hon ton trng hp vi kt qu m nhm tc gi
nghin cu. iu ny theo nhm tc gi gii thch nguyn nhn l do
khi cc vinyl polymer nh PVA v PA c chiu bng tia t ngoi,
62
cc phn ng to lin kt ngang c th xut hin (s lu ha tia t
ngoi). Polymer PVA v PA c kh nng polymer ha (trng hp) cao
hn v hnh thnh lin kt ngang, trong khi kh nng polymer ha
ca PP xut hin khng cao. Xa hn na, s polymer ha c th dn
n s kt t trn b mt ca cc ht tt hn v c th lm gim s cc
lin kt tha (dangling bonds) trn b mt ca cc ht. Cc lin kt
tha cung cp cc trng thi by b mt dn n s ti hp khng
bc x.
Tuy nhin, nu gii thch ch da vo lin kt ngang v s polymer ha
cao ca cc phn t th ng ha b mt ca cc ht th s khng th p dng
gii thch tnh cht quang ca mu khng bc ph v bc ph polymer PP.
Bi t hnh 3.19a v cc kt qu m nhm tc gi nghin cu, ta thy mu
bc ph PP v mu khng bc ph cng rt nhy vi s chiu x tia t ngoi.
Theo nhm tc gi hnh nh c mt nguyn nhn khc dn n s tng cng
pht quang ca mu bc ph PVA v PA.
Nh vy, s tng hay gim cng pht quang ca cc ht tinh th
ZnS:Mn khi bc ph polymer cn l mt vn i hi cn phi c gii thch
c th hn.
Cng m pht quang mu da cam (D2) ca cc mu cng hon
ton khc nhau (hnh 3.19b v 3.20b), iu ny cho thy hm lng
Mn khuch tn vo trong mng tinh th ZnS l khng ging nhau.
iu ny c th gii thch l do trong qu trnh phn tn cc ht nano
ZnS:Mn vo dung mi tin hnh ch to mng, do nh hng ca
nhit cng nh iu kin ch to mng c th lm cho lng
Mn
2+
phn no thot khi nn tinh th bn dn ch ZnS.
63
nh hunh quang mu xanh lam ca hai mu M-PA(1:1) v M-
PS(1:1) c s dch nh v pha bc sng ngn (pha nng lng cao)
so vi ca mu M-PVA(1:1). Trng hp trn chng ti d on l do
trong qu trnh phn tn cc ht nano ZnS:Mn v ha tan polymer PVA
vo trong dung mi H
2
O, chng ti gia nhit h n khong 80
o
C
(PVA tan rt chm trong H
2
O 300K). Ngc li khi phn tn cc ht
nano v ha tan PA hoc PS vo trong xylen ch to mng M-PA v
M-PS chng ti khng gia nhit (xylen bay hi tng i nhanh ngay
c nhit phng). Chnh v l do c th nh hng n s
dch nh hunh quang nh trn.
350 400 450 500 550 600 650 700 750 800 850
0
1000
2000
3000
4000
5000
6000

350 400 450 500 550 600 650 700 750
0.0
0.2
0.4
0.6
0.8
1.0
c
b
a


C
u
o
n
g
d
o

h
u
y
n
h
q
u
a
n
g
c
h
u
a
n
h
o
a

Buoc song(nm)
D3
D1
D2
(b)
(a)
445
682
593
452
c
b
a
a M-PVA(1:1)
b M-PA(1:1)
c M-PS(1:1)


C
u
o
n
g

d
o

h
u
y
n
h

q
u
a
n
g

(
d
.
v
.
t
.
y
)
Buoc song (nm)
Hnh 3.20: Ph pht quang ca h mu M-PVA(1:1), M-PA(1:1) v M-PS(1:1) nhit 300K
bng bc sng 325nm vi mt cng sut 0,13W/cm
2
(a) v th chun ha tng ng (b)
{o ngy 29/9/2008-Trng HKH T Nhin}
Hnh 3.21 l ph hunh quang ca mu M-PVA(1:1) khi kch thch bng
bc sng 325nm vi cc mt cng sut khc nhau. T ph hunh
quang ta thy khi mt cng sut thay i t 0,13W/cm
2
n
0,64W/cm
2
, v tr cc i ca cc m pht quang D1, D2 v D3 hu nh
64
khng thay i v cng ca nh mu xanh lam tng dn theo quy
lut:

n
KT HQ
I A I ) .(
vi n1,3 (hnh 3.24). (3.9)
iu ny chng t s tng mt cng sut kch thch trong khong trn
vn cha lm thay i ng k nhit a phng ca tinh th ZnS:Mn, do
rng vng cm ca n vn khng thay i.
300 350 400 450 500 550 600 650 700 750 800
0
10000
20000
30000
40000
50000
60000
D3
D2
D1

452
i
h
b
c
d
e
f
g
a

C
u
o
n
g

d
o

(
d
.
v
.
t
.
y
)
Buoc song (nm)
a 0,13 W/cm
2
b 0,19 W/cm
2
c 0,25 W/cm
2
d 0,32 W/cm
2
e 0,38 W/cm
2
f 0,45 W/cm
2
g 0,51 W/cm
2
h 0,57 W/cm
2
i 0,64 W/cm
2
Hnh 3.21: Ph pht quang ca mu M-PVA(1:1) nhit 300K khi kch thch
bng bc sng 325nm vi cc mt cng sut kch thch khc nhau
7.0 7.2 7.4 7.6 7.8 8.0 8.2 8.4 8.6 8.8 9.0
8.0
8.5
9.0
9.5
10.0
10.5
11.0
11.5
y =A +B*x
Thams Gi tr Sai s
--------------------------------------------------
A -0,8436 0,5117
B 1,3134 0,0628
--------------------------------------------------


L
n
(
I H
Q
)
Ln(I
KT
)
Hnh 3.22: S ph thuc cng m xanh lam 450nm ca mu M-PVA(1:1)
vo mt cng sut kch thch 300K khi kch thch bng bc sng 325nm
65
Hnh 3.23 l kt qu o ph pht quang phn gii theo thi gian ca m
xanh lam ca mu M-PVA(1:1) 300K khi kch thch bng bc sng
325nm. Khi tng thi gian tr t 72ns n 160ns cc i ca m ny
dch chuyn v pha nng lng thp v cng ca n cng gim i
(~3,2 ln). y l c trng in hnh ca ti hp bc x cc cp donor-
acceptor. Kt qu hon ton tng t nh i vi khi kho st mu M-
PVA2 trn.
350 400 450 500 550 600
0
50
100
150
200
250
300
350
400
450


e
d
c
b
a
C
u
o
n
g

d
o

(
d
.
v
.
t
.
y
)
Buoc song (nm)
a 72ns
b 88ns
c 104ns
d 130ns
e 160ns
Hnh 3.23: Ph pht quang phn gii theo thi gian m xanh lam
ca mu M-PVA(1:1) 300K khi kch thch bng bc sng 325nm
T cc kt qu trn cng vi s bt i xng ca th chng ti cho
rng m pht quang mu xanh lam l do s chng chp ca nhiu nh hunh
quang v l do s ti hp bc x ca cc cp donor-acceptor, trong cc nt
khuyt ca S
2-
ng vai tr l tm donor cn cc nt khuyt ca Zn
2+
ng vai
tr l cc tm acceptor.
Hnh 3.24a l th m t hunh quang tt dn ca mu M-PVA(1:1) ti
bc sng bc x l 450nm vi bc sng kch thch 337nm ca laser
nit. T th trn ta c th tnh c thi gian sng hunh quang tng
ng vi bc x c bc sng 450nm l 83ns (hnh 3.24b).
66
0 50 100 150 200 250 300 350 400 450 500 550
0
50
100
150
200
250
300
350
400
450
500
550
600


C
u
o
n
g

d
o

(
d
.
v
.
t
.
y
)
Thoi gian (ns)
M-PVA(1:1)

ra
= 450 nm

ex
= 337 nm
0 25 50 75 100 125 150 175 200 225
-4.5
-4.0
-3.5
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
M-PVA(1:1)

ra
= 450 nm
= 83 ns


L
n

[
I
(
t
)
/
I
(
0
)
]
Thoi gian (ns)
Data
Fitlinear
Y =A +B *X
---------------------------------------------
Thngs gi tr sai s
---------------------------------------------
A 0,56 0,006
B -0,012 4,8E-5
---------------------------------------------
Hnh 3.24a: ng cong tt pht quang ti bc
x 450nm ca mu M-PVA(1:1) 300K khi
kch thch bng bc sng 337nm.
Hnh 3.24b: th xc nh thi gian sng
hunh quang ti bc x 450nm ca mu M-
PVA(1:1) 300K khi kch thch bng bc
sng 337nm.
3.2.3. Kt lun
Qua nghin cu s nh hng ca vic bc ph polymer ln tnh cht
hunh quang ca vt liu ZnS:Mn, chng ti c cc kt lun nh sau:
- T kt qu o nh SEM v ph hunh quang cho thy mu
ZnS:Mn bc ph polymer ch to c cht lng kh tt.
- Cc mu u pht quang mnh trong vng nh sng nhn thy,
quan st thy c 3 di pht quang tng i r rt vi cc nh
hunh quang tng ng l mu xanh lam, da cam v . Ngun
gc ca cc di bc x ny uc gii thch nh trong phn 3.1.3.
- chng minh c ngun gc ca di pht x da xanh lam l do
s ti hp bc x ca cc cp donor acceptor. Trong cc nt
khuyt S
2-
ng vai tr l tm donor v cc nt khuyt Zn
2+
ng
vai tr l tm acceptor.
67
- Kt qu cho thy polymer nh hng trc tip n tnh cht pht
quang ca mu cng nh nng Mn
2+
khuch tn vo trong
mu.
- i vi mu M-PVA2, kch tht ht xc nh t nh SEM
khong 100nm. Kch thc ht tinh th suy ra t rng vng
cm c gi tr khong t 3,97,4nm. Kt hp vi cng ngh ch
to mu, chng ti cho rng ch to c vt liu nano
ZnS:Mn bc ph lp v polymer bn ngoi.
- Cng pht quang nh xanh lam ca mu M-PVA2 v M-
PVA(1:1) tun theo quy lut:
n
KT HQ
I A I ) .(
.
- Cc mu bc ph vi hm lng PVA tng ln (25g), b rng
di cm gim xung (3,863,73eV) v ln hn b rng di cm
ca mu khi, kch thc ht tinh th tng ln (3,9 7,4nm).
Hiu ng kch thc th hin tng i r rt.
- Mu mng ZnS:Mn bc ph PVA vi hm lng s dng l 2g
PVA ha tan trong 100ml hn hp dung dch 1 v 2 c cng
pht quang tt nht. B rng di cm ca mu l 3,86eV v kch
thc ht tinh th l 3,9nm. Thi gian sng trung bnh ca in t
nm trng thi kch thch trc khi tr v trng thi c nng
lng thp ng vi bc x c bc sng 450nm l 22ns.
- Mu mng bc ph PVA v PA c cng pht quang mnh.
Mu mng bc ph PS c cng pht quang yu hn c mu
khi cha bc ph. Tuy nhin vic gii thch ti sao vn cn l mt
vn cn nhiu nghin cu tip theo. i vi mu mng bc
68
ph PVA theo t l 1:1, thi gian sng hunh quang tng ng vi
bc x c bc sng 450nm l 83ns.
----- -----
KT LUN CHUNG
I- Cc kt qu t c
1. tin hnh ch to thnh cng v c cht lng tng i tt:
H mu bt ZnS:Mn bng phng php ha t.
H mu mng ZnS:Mn khng bc ph polymer PVA v h mu mng
ZnS:Mn bc ph Polymer PVA bng phng php quay ph.
Mu mng ZnS:Mn bc ph cc loi Polymer PVA, PA v PS bng
phng php nhng ph.
2. tin hnh nghin cu nh hng ca nhit nung n tnh cht cu
trc v tnh cht pht quang ca vt liu nano ZnS:Mn. Khi nhit x l
mu tng (80400
o
C), kch thc ht tinh th ca mu bt cng ln (2,5
5nm), rng vng cm kho st mu mng gim (3,82,8eV) v cng
hunh quang gim dn.
3. nghin cu nh hng ca vic bc ph polymer ln tnh cht quang
ca vt liu nano ZnS:Mn di dng mng mng. Kt qu cho thy
polymer nh hng rt ln n tnh cht pht quang cng nh hm lng
Mn c trong mu. chng minh ngun gc ca bc x xanh lam l do s
ti hp cc cp donor acceptor. Ngun gc ca bc x cam l do s dch
69
chuyn ca in t t mc
4
T
1

6
A
1
(ca ion Mn
2+
). Ngun gc bc x
l do tp cht. Cng hunh quang nh xanh lam tng tun theo quy
lut
n
KT HQ
I A I ) .(
.
rng vng cm ca cc mu bc ph PVA vi hm lng khc nhau
t trong khong 3,733,86eV, kch thc ht tinh th c gi tr t 3,9
7,4nm. Mu M-PVA2 c cng pht quang mnh nht, rng vng
cm ln nht (3,86), kch thc ht nh nht (3,9nm). Kt qu th hin r
hiu ng kch thc ca ht nano. Thi gian sng hunh quang ca bc
x 450nm khong 22ns.
Mu mng bc ph PVA v PA c cng pht quang mnh. Mu mng
bc ph PS c cng pht quang yu hn c mu khi cha bc ph.
i vi mu mng bc ph PVA theo t l 1:1, thi gian sng hunh
quang tng ng vi bc x c bc sng 450nm l 83ns.
II- Phng hng nghin cu tip theo
1. Kho st tnh cht in hunh quang ca cc mu ch to.
2. Nghin cu ng dng mu ch to vo trong i sng thc tin.
----- -----
70
MT S CNG TRNH NGHIN CU LIN QUAN N LUN VN
1. Nguyen Minh Vuong, Tran Minh Thi, Le Thi Thu Huyen, Influence of
annealed temperature on the photoluminescence spectra and the band gap
of ZnS:Mn
2+
nano powder and thin films. Bo co ti Hi ngh Quang hc
Quang ph ton quc ln th V, thng 9-2008.
2. Tran Minh Thi, Nguyen Minh Vuong, Le Thi Thu Huyen, Investigation on
some optical properties of polymer capped Mn doped ZnS
nanocrystalline thin films synthesised by chemical process. Bo co ti Hi
ngh Quang hc Quang ph ton quc ln th V, thng 9-2008.
3. Tran Minh Thi, Pham Van Ben, Nguyen Minh Vuong, The optical
properties of the polymer capped ZnS:Mn nano thin films. VNU. Joural of
Science, Mathematics Physics 2008.
71
PH LC
Ph lc I: Quan h gia tng bnh phng (h
2
+k
2
+l
2
) v ch s nhiu x
h
2
+k
2
+l
2
Lp phng
n gin
Lp phng
tm khi
Lp phng
tm mt
T gic Lc gic Kim cng
1 100 100 100
2 110 110 110
3 111 111 111 111
4 200 200 200 200 200 200
5 210 210
6 211 211
8 220 220 220
9 221, 300 221, 300 221, 300
10 310 310 310
11 311 311 311 311
12 222 222 222 222
13 320 320 320
14 321 321
16 400 400 400 400 400 400
17 410, 322
18 330, 411 330, 411
19 331 331
20 420 420 420 420
21 421 421
72
Ph lc II: Mi lin h gia sin
2
vi cc thng s mng cc cc h tinh th
H
TINH TH
C TRNG
HNH HC

2
sin
Tam t
(Triclinic)
a b c
90
o
[ ]
hl
S kl S hk S l S k S h S
V
13 23 12
2
33
2
22
2
11
2
2
4
+ + + + +

n t
(Monoclinic)
a b c
= = 90
o

1
]
1

+ +

2 2 2
2
2
2
2 2
2 2
sin . .
cos 2
sin sin 4 c a
hl
c
l
b
k
a
h
Tam gic
(Rhombohedr
al)
a = b = c
= = 90
o
) cos 2 cos 3 1 (
) cos )(cos ( 2 sin ) (
3 2 2
2 2 2 2 2


+
+ + + + +
a
kl hl hk l k h
T gic
(Tetragonal)
a = b c
= = = 90
o
1
]
1

+
+
2
2
2
2 2 2
4 c
l
a
k h
Lc gic
(Hexagonal)
a = b c
= = 90
o
, =
120
o
1
]
1

,
_

+ +
2
2
2
2 2 2
3
4
4 c
l
a
k hk h
Trc thoi
(Orthorhombic)
a b c
= = = 90
o
1
]
1

+ +
2
2
2
2
2
2 2
4 c
l
b
k
a
h
Lp phng
(Cubic)
a = b = c
= = = 90
o
1
]
1

+ +
2
2 2 2 2
4 a
l k h
Trong : S
11
=(b.c.sin)
2
S
12
=abc
2
(cos.cos-cos)
S
22
=(a.c.sin)
2
S
23
=a
2
bc(cos.cos-cos)
S
33
=(a.b.sin) S
31
=ab
2
c(cos.cos-cos)
V=abc(1-cos
2
- cos
2
- cos
2
- cos
2
- 2cos.cos.cos)
73
Ph Lc III: Cc tnh cht ca cc bn dn thng dng nhit 300K
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