Ch to cc ht nano ZnS:Mn bc ph cht

hot ha b mt v kho st ph pht quang

ca chng
H. : HKHTN,
2012
S trang 75 tr.

Nguyn Vn Trng

Trng i hc Khoa hc T nhin
Lun vn Thc s ngnh: Quang hc; M s: 60 44 11
Ngi hng dn: PGS.TS Phm Vn Bn
Nm bo v: 2012

Abstract: Tng quan v tnh cht quang ca vt liu ZnS:Mn bc ph cht hot ha
b mt. Trnh by mt s phng php ch to ZnS, ZnS:Mn v thit b thc nghim.
Kt qu thc nghim: Quy trnh ch to cc ht nano ZnS, ZnS:Mn, Cu trc v hnh
thi hc ca cc ht nano ZnS v ZnS:Mn, Tnh cht quang ca cc ht nano ZnS v
ZnS:Mn.

Keywords: Vt l; Quang hc; Ht nano

Content
M U
ZnS, ZnS:Mn l bn dn vng cm rng ( khong 3.68 - 3.9 eV) c chuyn mc thng,
pht quang mnh vng xanh lam v da cam vng nn c ng dng rng ri trong cc
dng c quang in t nh: diode pht quang, n ng, b hin th mu, sensor laser v quang
xc tc [1]. c bit, khi kch thc ht ca ZnS, ZnS:Mn gim xung di bn knh
exciton Bohr (khong 4.5 nm) th cu trc in t v tnh cht quang ca chng thay i ng
k nh s dch b hp th v pha nng lng ln, s tng th tch b mt v s giam cm
phonon [2]. Khi kh nng ng dng ca vt liu ny c tng ln. ch to cc vt liu
nano ZnS:Mn c th s dng cc phng php nh sol - gel, vi nh tng, vi sng, ng kt
ta, thy nhit...[2,5-9], trong phng php thy nhit c th iu chnh kch thc ht
bng cch thay i nhit v thi gian thy nhit. Trong phng php thy nhit c th
dng axit Thioglycolic (TGA), axit ny khng nhng to ra ngun S
2-
m cn to ra cht hot
ha b mt bc ph cc ht nano ZnS, ZnS:Mn lm gim kch thc ht.
Mt khc, cc ht nano thng kt m vi nhau v chu nh hng ca mi trng
xung quanh. cch li cc ht nano ny vi mi trng, trnh hin tng b xy ha, ngn
cn s kt t ca cc ht li vi nhau, ngi ta thng bc ph ht nano bng cc cht
2
polymer v cc cht hot ha b mt khc nh PVA, PVP, TGA ... [5-7].Vic bc ph cc
cht polymer ny khng nhng ngn cn vic kt t tr li lm gim kch thc cc ht nano
m cn tng hiu sut pht quang, cng pht quang ca cc tinh th nano c bc ph
so vi cc tinh th nano cha c bc ph. Khi kh nng ng dng ca vt liu ZnS v
ZnS pha tp Mn ( k hiu l ZnS:Mn ) trong cc dng c quang in t s tng ln. V th
chng ti la chn ti Ch to cc ht nano ZnS:Mn bc ph cht hot ha b mt v
kho st ph pht quang ca chng.
Ngoi li m u, kt lun, ti liu tham kho v ph lc lun vn gm ba chng:
- Chng 1: Tng quan v tnh cht quang ca vt liu ZnS:Mn bc ph cht
hot ha b mt
- Chng 2:Mt s phng php ch to ZnS, ZnS:Mn v thit b thc nghim
- Chng 3 : Kt qu thc nghim v tho lun
CHNG 1
TNG QUAN V TNH CHT QUANG CA VT LIU NANO ZnS:Mn BC
PH CHT HOT HA B MT
1.1. Gii thiu chung v vt liu nano bn dn
1.1.1. Phn loi vt liu nano bn dn.
Vt liu bn dn c phn ra thnh vt liu khi (h ba chiu) v vt liu nano. Vt liu
nano li tip tc c chia nh hn thnh :vt liu nano hai chiu nh mng nano, vt liu nano
mt chiu nh nh ng nano, dy nano (hay thanh nano),vt liu nano khng chiu nh m
nano, ht nano (hay l chm lng t) [1,7] .


Hnh 1.1: (a) H vt rn khi ba chiu, (b) h hai chiu (mng nano), (c) h mt chiu
(dy nano), (d) h khng chiu (ht nano) [1,7]
1.1.2 Hiu ng giam cm lng t lin quan ti kch thc ht
3
Nh ni trn, khi bn knh ca ht nano tip cn gn ti kch thc ca bn knh
Bohr th s chuyn ng ca in t v l trng b giam hm bn trong ht nano gi l s
giam cm lng t.
Mt trong nhng biu hin r nht ca hiu ng lng t xy ra trong ht nano l s thay
i dng ca cu trc vng nng lng v s phn b li trng thi ln cn nh vng ha tr v
y vng dn, m in hnh l cc vng nng lng s tch thnh cc mc gin on. Mc d cu
trc tinh th v thnh phn cu to nn chng vn khng i, nhng mt trng thi in t v
cc mc nng lng l gin on ging nh nguyn t, nn chng cn c gi l nguyn t
nhn to.
Biu hin r nt th hai l s m rng vng cm ca cht bn dn tng dn khi kch
thc ht gim i v quan st thy s dch chuyn v pha cc bc sng xanh trong ph hp
th. Trong cc nghin cu ca tc gi Kayanuma phn chia thnh cc ch giam gi
lng t theo kch thc sau:
+ Khi bn knh ht r< 2a
B
, ch giam gi mnh vi cc in t v l trng b giam gi
mt cch c lp, tuy nhin tng tc gia in t-l trng vn quan trng.
+ Khi r
>
4a
B
chng ta c ch giam gi yu.
+ Khi 2a
B
s
r
s
4a
B
chng ta c ch giam gi trung gian.
Hiu ng giam gi lng t sinh ra s dch chuyn blue ca rng vng cm, ng
thi c s xut hin ca cc vng con tng ng vi s lng t ho dc theo hng giam
gi. Khi chiu di vng giam gi tng, rng vng cm gim, bi vy cc dch chuyn gia
cc vng dch v pha cc bc sng di hn, cui cng th gn n gi tr ca vt liu khi.
Cc tnh cht quang hc nh pht x hunh quang ph thuc mt cch cht ch vo kch
thc ca cc nano tinh th.
Chnh bi nhng tnh cht khc bit ca mnh m cc vt liu nano c ng dng rng
ri trong cng nghip, y hc, k thut, nghin cu cng nh i sng.
1.1.3 ng dng ca vt liu nano
Cc nh khoa hc cng nghin cu thy rng cc vt liu hp cht c kch thc nano
c tnh cht tt hn so vi cc vt liu hp cht thng thng bi vy c nhiu ng dng c
bit v hiu qu hn. y l loi vt liu m ra nhiu hng nghin cu mi v ha hn nhiu
tim nng ng dng cao. Mt v d in hnh hp cht nano bn dn ZnS.
ZnS c rt nhiu ng dng rng ri trong khoa hc k thut: Bt hunh quang ZnS c
s dng trong cc t in hunh quang, cc mn Rnghen, mn ca cc ng phng in t.
4
Ngi ta ch to c nhiu loi photodiot trn c s lp chuyn tip p-n ca ZnS, sut
quang in ng ca lp chuyn tip p - n trn tinh th ZnS thng t ti 2,5 V. iu ny
cho php hy vng c nhng bc pht trin trong cng ngh ch to thit b ghi c quang
hc laser chng hn nh lm tng mt ghi thng tin trn a, tng tc lm vic ca cc
my in laser, a compact, to kh nng s dng bng mu trn t 3 laser pht mu c bn. Ngoi
ra hp cht ZnS pha vi cc kim loi chuyn tip c s dng rt nhiu trong cc lnh vc in
pht quang, chng hn nh trong cc dng c bc x electron lm vic di tn rng. Vi vic
pha thm tp cht v thay i nng tp cht, c th iu khin c rng vng cm lm cho
cc ng dng ca ZnS cng tr nn phong ph [2].
1.2. Cht hot ha b mt v nh hng ca chng ln s hnh thnh ca cc ht
nano
1.2.1. Cht hot ha b mt v phn loi.
Cht hot ha b mt l cc cht c tc dng lm gim sc cng b mt cht lng. Phn
t hot ha b mt gm 2 phn: u k nc (hydrophopic) v u a nc (hydrophylic).
Tnh cht hot ha b mt ph thuc vo hai phn ny.
- u a nc phi l mt nhm phn cc mnh nh cacboxyl (COO-), hydroxyl (-OH),
amin (-NH
2
), sulfat (-OSO
3
) ...
- u k nc phi di, mch carbon t 8 - 21, ankyl thuc mch ankal, anken mch
thng hay c gn vng cyclo hoc vng benzene ...
1.2.2. nh hng ca cht hot ha b mt ln s hnh thnh cc ht nano.
Vic gim kch thc ca hat nano ti kch thc nh s lm tng tnh cht in, thay
i tnh cht quang, tng kh nng xc tc ca chng do c hiu ng giam cm lng t. ng
thi vic gim kch thc ht ny cng lm thay di hiu ng b mt, y cng l nguyn nhn
dn ti nhiu tnh cht mi l so vi vt liu khi. Cc nguyn t trn b mt c nhiu tnh cht
khc bit so vi tnh cht ca cc nguyn t bn trong vt liu. T s gia s nguyn t bn trn b
mt v tng s nguyn t ca vt liu tng khi vt liu c kch thc nh dn ti hiu ng b mt
gia tng.
1.2.3. Cc cht hot ha b mt
+ Axit thioglycolic (TGA): l hp cht hu c c cng thc ha hc HSCH
2
COOH c
nhm carbonyl C=O.
+ Polyvinyl pyrrolidone (PVP) vi cng thc phn t (C
6
H
9
NO)
n
c nhm carbonyl -
C=O.
5
+ Polyvinyl alcohol (PVA) vi cng thc cu to (C
2
H
3
OH)
n
c nhm hydroxyl, y l
nhm phn cc mnh. Ion O
2-
phn cc
-
trong khi ion Zn
2+
phn cc
+
to thnh cp lin kt.
1.3. Cu trc ca vt liu nano ZnS v nh hng ca Mn ln cu trc, vng nng
lng ca ZnS.
ZnS l hp cht bn dn thuc nhm A
2
B
6
c rng vng cm tng i rng (E
g
=
3.68 eV 300 K) i vi mu khi [1] , 3.7 n 3.9 i vi mu nano, rt thch hp cho vic
a cht kch hot vo to ra bt hunh quang vi bc x trong vng nhn thy v vng
hng ngoi gn. Trong ZnS cc nguyn t Zn v S c th lin kt dng hn hp: ion (77%) v
cng ho tr (23%). Trong lin kt ion th ion Zn
2+
c cu hnh in t lp ngoi cng l
3s
2
p
6
d
10
v S
2-
c cu hnh in t lp ngoi cng l 2s
2
p
6
. Trong lin kt cng ho tr, do
phi ng gp chung in t nn nguyn t Zn tr thnh Zn
2-
c cu hnh in t: 4s
1
p
3
v S
tr thnh S
2+
c cu hnh l : 3s
1
p
3
[2].
1.3.1 Cu trc tinh th lp phng Sphalerite hay Zinblende
Cu trc dng lp phng c xc nh trn c s quy lut xp cu ca hnh lp
phng vi cc nh l nguyn t B (S) c k hiu l . Cc nguyn t A (Zn) c k
hiu l nh hng song song vi nhau [5].
1.3.2. Cu trc mng tinh th lc gic hay wurzite
Khi 2 t din cnh nhau c nh hng sao cho cc y tam gic song song vi nhau
th s to thnh tinh th c cu trc lc gic hay wurtzire (hnh 1.10).
Cu trc dng wurtzire c xy dng trn quy lut xp cu theo hnh 6 cnh ca cc
nguyn t B (S) c k hiu l trong mt na s hng 4 mt cha nguyn t A (Zn)
c k hiu l nh hng song song vi nhau [5].
1.3.3. nh hng ca cc ion Mn
2+
ln cu trc, vng nng lng ca ZnS
1.3.3.1 nh hng ca Mn ln cu trc tinh th v hng s mng ca tinh th ZnS
Bng thc nghim ngi ta thy rng i vi a s cc hp cht bn dn vng cm rng
khi tng nng tp cht trong mt khong no th rng vng cm ca chng tng [1].
1.3.3.2. Cu trc vng nng lng ca tinh th ZnS
ZnS l cht bn dn vng cm rng v thng, y l l do ti sao ZnS c th pht quang
vi bc sng ngn (vng xanh) v c th to ra nhng by bt in t kh su trong vng
cm [1].
6
S vng nng lng ca ZnS
T nhng nghin cu v mt trng thi bng ph phn x in t ch ra rng bn
di ca vng ho tr c to thnh t cc mc nng lng ca cc nguyn t Zn v S vi
cc hm sng i xng s v p tng ng. Do vng ha tr c i xng bi 3.
1.3.3.3. nh hng ca Mn
2+
ln cu trc vng nng lng v rng vng cm
ca ZnS
Bng phng php cng hng spin - in t, spin in t - quay v phng php cng
hng t quang (ODMR) xc nh c cc ion Mn
2+
thay th cc v tr ca Zn
2+
(3d
10
)
trong mng tinh th ca ZnS, to ra cu hnh Mn
2+
(3d
5
). Cc in t 4s
2
ca Mn
2+
ng vai
tr nh cc in t 4s
2
ca Zn
2+
(3d
10
).
CHNG 2

MT S PHNG PHP CH TO, BC PH CHT HOT HA B MT VT
LIU NANO ZnS:Mn V THIT B THC NGHIM

2.1. Mt s phng php ch to vt liu nano ZnS:Mn.
2.1.1. Phng php thy nhit.
Phng php thy nhit l phng php trong ngnh ha vt liu dng thu cc vt
liu v c c cu trc nano tinh th. Tng hp thy nhit l qu trnh tng hp c nc tham
gia vi vai tr ca cht xc tc, xy ra nhit cao (ln hn 100
0
C) v p sut ln (ln hn
vi atm). Trong phng php ny ngi ta s dng kh nng ha tan trong nc ca hu ht
cc cht v c nhit cao, p sut ln v s tinh th ha ca cht lng vt liu ha tan.
Da vo cc kt qu thc nghim, ta thy khong nhit c dng trong qu
trnh thy nhit t 100
0
C n 1800
0
C, p sut khong 15 atm n 10
4
atm. Cc th nghim
dng phng php thy nhit c gi n nh, trnh rung ng nhit v p sut khng
i.
u im:
+ C kh nng iu chnh kch thc ht bng nhit thy nhit.
+ C kh nng iu chnh hnh dng cc ht bng cc vt liu ban u.
+ Thu c sn phm cht lng cao t cc vt liu khng tinh khit ban u.
+ C th dng cc nguyn liu r tin to cc sn phm c gi tr.
+ C th s dng nhiu nguyn liu vo khc nhau.
+ L phng php n gin ch to tinh th di nhit v p sut cao.
7
2.1.2. Phng php ng kt ta
C s ca phng php ng kt ta: S kt ta ng thi ca cht nn v cht kch
hot
u im: Dng phng php ha hc tng mc tip xc gia cc cht tham gia
phn ng v h nhit phn ng. Phng php ny cho sn phm di dng bt mn hn
sn phm thu c theo phng php gm truyn thng.
phng php ng kt ta, hin tng khuch tn ca cc cht tham gia phn ng
mc phn t .
Quy trnh ch to:
+ Pha hn hp dung dch cha hai mui ca cht nn v cht kch hot sao cho sn
phm kt ta thu c, ng vi t l cht nn cht kch hot nh trong sn phm mong mun.
+ To kt a
+ Lc kt ta
+ Sy kh kt ta trn ta thu c mu di dng bt
+ Tin hnh mu vi trm to nn cu trc hon ho ca mng tinh th.
Trong phng php ng kt ta c hai vn cn lu :
+ m bo ng quy trinh ng kt ta ngha l ng thi kt ta c hai kim loi .
+ Phi m bo trong hn hp pha rn cha hai ion kim loi theo ng t l nh trong
sn phm gm mong mun: Chng ta bit tch s tan ca cc cht khc nhau l rt khc
nhau. Do trong hn hp hai cht kt ta c th cha hai kim loi khng ng nh hai kim
loi trong dung dch chun ban u.
2.1.3. Phng php bc ph cc cht hot ha b mt vt liu ZnS:Mn
Nh ni trn, cc ht nano c nhiu u im v tnh ng dng cao hn cc vt liu
khi cng loi.Vic gim kch thc ca ht nano ti kch thc nh s lm tng tnh cht
in, thay i tnh cht quang, tng kh nng xc tcca chng do c hiu ng giam cm
lng t. ng thi vic gim kch thc ht ny cng lm thay i hiu ng b mt, y l
cng l nguyn nhn dn ti nhiu tnh cht mi l so vi vt liu khi .Hi u

ng b mt la

hi u

ng lin quan n ca

c nguyn t

b m t cu

a v t li u . Cc nguyn t trn b mt c nhiu

tnh cht khc bit so vi tnh cht ca cc nguyn t bn trong lng vt liu. T s gia s
nguyn t trn b mt v tng s nguyn t ca vt liu gia tng khi vt liu c kch thc
nh d n n hi u

ng b m t tng . V d, xt vt liu to thnh t cc ht nano hnh cu . Nu

8
coi s nguyn t

trn b mt la

n
s
v tng s nguyn t l n th ta co

phng tri

nh lin h
gi

a chu

ng l n
s
= 4n
2/3
. T rt ra c t s gia s nguyn t trn b mt v tng s
nguyn t s l
f = n
s
/n = 4n
2/3
/n = 4/n
1/3
= 4r
0
/r, v

i r
0
l bn knh ca nguyn t v r l bn knh ca
ht nano. Nh vy, khi kch thc ca vt liu gim t

c r gim th t s f tng ln. Khi kch

thc vt liu gim i th hiu ng c lin quan n cc nguyn t b mt - hiu ng b mt
tng ln do t s f tng. Khi kch thc ca vt liu gim n nm th gi trf ny se

tn g ln
ng k. c th gim kch thc ca ht lm tng hiu ng b mt ngi ta nghin cu
nhiu phng php, trong c phng php s dng cc cht hot ha b mt nh l cc
cht polymer
C hai phng php thng thy khi bc ph cc ht nano bng cc cht hot ha b
mt (TGA, PVA, PVP) nh sau:
+ Phng php bc ph trc : Cc cht hot ha b mt c trn chung cng vi dung
dch tin cht v khuy u trong nhiu gi trc qu trnh to ht nano
+ Phng php bc ph sau : Sau khi c to thnh, cc ht nano c cho vo cc
dung dch c cha cht hot ha b mt v khuy u trong vng nhiu gi
T thc nghim cho thy vic bc ph trc t c hiu qu cao hn, cc ht c
bc ph u hn so vi vic bc ph sau. Bi vy cc nghin cu ca chng ti ch yu s
dng phng php bc ph trc.
Khi cc ht nano c bc ph cc cht hot ha b mt s trnh c vic cc ht kt
t tr li vi nhau to thnh mu khi khin cho din tch kch thc b mt tng ln. iu
ny dn ti cng pht quang v hiu sut pht quang ca ht nano cng tng. Chnh bi
vy, vic bc ph cc ht nano bng cc cht nh TGA, PVA, PVP, PVC thu ht c rt
nhiu s quan tm. Trong bi bo nghin cu s tng hp v pht quang ca cc ht nano
ZnS:Mn bc ph PVA G.Murugadoss, B. Rajamannan v V. Ramasamy[11] ch ra rng
cc ht nano c bc ph PVA nng cao tnh pht quang so vi cc ht m khng c bc
ph.Trong nghin cu ca Subhendu K. Panda v ng nghip[19], sau khi bc ph PVP th
kch thc trung bnh ca ht nano ZnS c 2.8 nm, PVP lm n nh cc ht nano v cng
cho thy nh hng khng gian ca PVP bc ph cc ht nano ZnS qua lin kt vt l v ha
hc hn ch mi lin h gia cc ht v ngn chn s kt t ca cc ht bn trong s kt t
hnh cu.
2.2 H ch to mu
2.2.1 My rung siu m
My rung siu m c s dng lm sch cc dng c th nghim. My c cc thang
iu chnh nhit ca dung dch bn trong v iu chnh thi gian lm sch ti a l 15
pht, s dng ngun in 220V.
9
2.2.2 My khuy t gia nhit
ha tan cc cht vo trong dung mi v trn u cc cht vi nhau chng ti tin
hnh pha trn chng trong cc thy tinh t trn my khuy t c gia nhit ca hng VELP
.
2.2.3 My quay ly tm
Qu trnh lc kt ta c thc hin nh my quay ly tm. Chng ti s dng my
Hettich EBA 8S.
2.2.4 H l sy v mu
a) Cu to:
- Ngun nui :L hot ng di in p 220V, dng cc i trn 9A, cng sut cc i
2000W. Nhit ti a cho php l 350
o
C.
- V l :Vt liu dng lm v l l thp dy 2 mm. V l c gia cng c dng hnh
tr ng knh trong 36 cm, ng knh ngoi 53 cm, di 50 cm, c t trn mt gi cao
10 cm. mt u l c thit k mt np y c th ng m d dng. Trong qu trnh sy,
np l c c nh bi 4 chic vt xoy t 4 gc ca np. Tc dng ca v l l to khung
gi c nh v bo v cc b phn bn trong thn l (dy in tr, bng cch nhit).
- Bng cch nhit :Vt liu c s dng lm b phn cch nhit l bng thy tinh,
c kh nng cch nhit v chu nhit vo loi tt nht. H s dn nhit bng thy tinh: 0.035
0.081 (W/mK).
- Dy in tr :Dy in tr c s dng y l Constantan chu c nhit ti a
l 1200 1300
o
C. Nhit tt nht c th chu c l 800
o
C.
- Bm chn khng :Bm chn khng c cu to gm 1 m t in 3 pha c ni
vi mt my quay li tm lch trc thng qua h thng dy curoa. hn ch ma st v
lm cho h bm c kn ngi ta du vo thn bm. Khi hot ng, bm s c hai
ca mt ca lm nhim v ht kh trong thn l v mt ca x kh ra bn ngoi.
B phn ht kh ca bm chn khng c ni vi b phn lc l mt bnh thy tinh
trnh hin tng du trn vo l sy. ng ht kh sau c ni vo mt sau ca l. Trn
ng c gn mt ng h o p sut v mt van chn khng ngn khng cho kh trn vo l.
b) Hot ng ca h l sy : Hot ng ca h l sy s dng b iu khin nhit , thi
gian c ch ra hnh 2.6
10


Hnh 2.6: Hot ng ca h l sy s dng b iu khin nhit , thi gian
in p a vo dng t nng dy in tr trong l sy. Cp nhit in trong thn l
sinh ra sut in ng nhit in (ph thuc vo nhit trong l). Sut in ng nhit in
c a vo b iu khin t l P, thng qua sut in ng nhit in b iu khin s xc
nh v hin th cho ta bit nhit chnh xc nhit trong l. ng thi, b iu khin P
cng iu chnh dng qua tr ti sao cho ph hp vi nhit v thi gian ngi s dng
t trc.
2.3 H xc nh cu trc, hnh thi b mt ca mu
2.3.1 H o ph nhiu x tia X (ph X-ray)
Nguyn tc chung ca phng php phn tch cu trc tinh th v thnh phn pha bng
nhiu x tia X (XRD) da trn hin tng nhiu x tia X ca mng tinh th khi tha mn iu
kin Bragg :
2dsinu = n
2.3.2 H o ph tn sc nng lng
2.4. H o ph pht quang, ph kch thch pht quang, ph hp th
2.4.1 H o ph pht quang MS-257 dng k thut CCD
S khi ca h thu ph pht quang bng my quang ph cch t a knh MS-257
dng k thut CCD c dn ra hnh 2.9. Cu to ca h gm ba b phn chnh: Ngun
kch thch, my quang ph cch t MS-257.
2.4.2 H o ph kch thch pht quang FL3 22
H thu ph kch thch v ph pht quang Fluorolog FL3-22 ca Trung tm Khoa hc
Vt liu Khoa Vt l Trng i hc Khoa hc T nhin.
11
2.4.3 H o ph hp th
Quan h gia cng ca chm sng truyn qua mt mi trng c b dy x tnh t
b mt, vi s hp th quang hc ca mi trng lan truyn nh sng, c cho t nh lut
Lambert.
CHNG 3
KT QU THC NGHIM V BIN LUN

3.1. Cc quy trnh ch to cc ht nano ZnS, ZnS:Mn
3.1.1. Quy trnh ch to cc ht nano ZnS, ZnS:Mn bc ph TGA bng phng
php thy nhit.
Bng phng php thy nhit cc ht nano ZnS, ZnS:Mn c ch to t cc tin cht
Zn(CH
3
COO)
2
.2H
2
O, C
2
H
4
O
2
S (TGA), Mn(CH
3
COO)
2
.4H
2
O. Quy trnh ch to bt nano
ZnS:Mn c thc hin qua 4 bc sau:
Bc 1: Pha dung dch
+ Tnh ton ha cht
Do Zn
2+
kt hp vi S
2-
theo t l 1:2 nn cc tin cht trn c to thnh cc dung
dch Zn(CH
3
COO)
2
.0.1M (A), Mn(CH
3
COO)
2
0.25 M (B) (vi dung mi nc ct hai ln) v
TGA 0.2M (C) (dung mi: nc ct hai ln).
Bc 2: To kt ta
Hn hp cui cng c a vo ng thy tinh, bnh teflon v bnh inox cha teflon,
vn cht np bnh inox to p sut. Ton b bnh inox c a vo thy nhit 220
0
C
trong 20h. Trong qu trnh thy nhit mi mt loi phc cht c ln ln hnh thnh cc ht
nano ZnS:Mn, trong cc ht nano vn c bc ph bi axit TGA. V th kch thc cc
ht nano ZnS:Mn ch to bng phng php thy nhit vi s hin din ca axit TGA nh.
Cng qu trnh thy nhit mt phn gc hu c SCH
2
COOH
-
ca TGA c tch ra khi cc
ht nano ZnS:Mn.
Bc 3: Lc ra kt ta
Sau khi thy nhit ngui t nhin ta thu c kt ta. Lc ra kt ta t 4 n 5 ln
bng nc ct 2 ln loi cc tp bn v cc ion cn d trong kt ta. loi tr lng S
cn d bm trn b mt ca cc ht nano ZnS:Mn trong kt ta, chng ti dng dung mi
CS
2
ra kt ta khong 3 ln sau li lc ra bng nc ct hai ln.
Bc 4: Sy kt ta
12
Sau khi lc ra kt ta c sy kh 80
0
trong 12h ta thu c bt nano ZnS:Mn.
Cc bt pht quang ZnS v ZnS:Mn vi nng cht kch hot: 0 mol % C 20 mol
% cng vi nhit thy nhit v thi gian thy nhit khc nhau c kho st:
+ V cu trc v hnh thi b mt, thng qua: Ph nhiu x tia X (XRD) v nh TEM.
+ V tnh cht quang, thng qua: Ph pht quang, ph kch thch hunh quang v ph
hp th.
3.1.2. Quy trnh ch to cc ht nano ZnS:Mn (C
Mn
= 8 mol%) bc ph PVA bng
phng php ng kt ta
Bng phng php ng kt ta, bt nano ZnS:Mn bc ph PVA c ch to t cc
tin cht: Zn(CH
3
COO)
2
.2H
2
O, Na
2
S, Mn(CH
3
COO).4H
2
O, PVA. Quy trnh ch to cc bt
nano ZnS:Mn c thc hin qua nhng bc sau:
Bc 1: Pha dung dch
+Tnh ton ha cht:
Do Zn
2+
kt hp vi S
2-
theo t l 1:1 nn cc tin cht trn c to thnh cc dung
dch Zn(CH
3
COO)
2
.0.1M (A), Mn(CH
3
COO)
2
0.1 M (B) (vi dung mi nc ct hai ln) v
Na
2
S.0.1M (C) (dung mi: nc ct hai ln).
Bc 2: To kt ta
Ngay sau khi nh dung dch C vo dung dch F lp tc xut hin kt ta ng thi ca
ZnS v MnS theo phng trnh phn ng (3.14) v (3.15) Dung dch huyn ph to thnh
c khuy u trong 30 pht to s ng nht trong kt ta.
Bc 3: Lc ra kt ta
Kt ta c lc bng my quay li tm vi tc 2500 vng/ pht, trong 10 pht. Tip
tc lc ra kt ta ba ln bng nc ct hai ln loi cc ion Na
+
v cc tp bn trong kt
ta.
Bc 4: Sy kt ta
Sau khi lc ra, kt ta c sy kh 80
0
C trong 8h, ta c cc tinh th rn, kh.
Tip nghin nh kt ta kh bng ci m no ta c bt pht quang nano ZnS:Mn bc
ph PVA
3.2. Cu trc v hnh thi hc ca cc ht nano ZnS v ZnS:Mn
13
3.2.1. Cu trc v hnh thi hc ca cc ht nano ZnS
Hnh 3.1 l ph XRD ca cc ht nano ZnS c ch to bng phng php thy nhit
trong 20h vi cc nhit thy nhit khc nhau. Khi thy nhit 130
0
C, 150
0
C trong ph
XRD ca n ch xut hin cc m rng (hnh 3.1-a,b).
20 40 60
0
2000
4000
C
u
o
n
g

d
o

(
a
.
u
)
2u (deg)
f. 240
0
e. 220
0
d. 200
0
c. 180
0
b. 150
0
a. 130
0
a
b
c
d
e
f
(010)
(002)
(011)
(110)
(013)
(112)



iu ny chng t cc nhit ny ZnS cha c cu trc tinh th. Khi tng nhit
thy nhit n 180
0
C cc ht nano ZnS bt u kt tinh thnh dng tinh th. Trong ph XRD
ca n xut hin cc vch nhiu x ng vi cc mt phn x chnh (010), (002), (011), (110),
(013) v (112) trong vch (002) c cng ln nht, vch (013) c cng nh nht
(hnh 3-c). Khi tng nhit t 200
0
C n 240
0
C cc vch nhiu x c cng tng v cng
th hin r nt thnh nh nhng v tr ca n hu nh khng thay i. iu ny chng t s
tng nhit trong khong trn lm cho cu trc tinh th ca ZnS tr ln hon ho hn. T
ph XRD cho thy cc ZnS l n pha kt tinh dng a tinh th thuc nhm i xng khng
gian C
6v
4
P6
3
mc. T ph XRD chng ti xc nh c cc hng s mng a,b,c ca tinh
th ZnS. Khi tng nhit t 180
0
C n 240
0
C th hng s mng a = b hu nh khng thay
i trong khong 3.8360 A
0
, cn hng s mng c tng nh t 6.2285 A
0
n 6.2648 A
0
.
T gin XRD v cng thc Debye Scherrer:

u |

cos
9 . 0
= D


Hnh 3.1: Ph XRD ca cc ht nano ZnS ch to bng phng php thy nhit
trong 20h vi cc nhit thy nhit vi nhau
14
trong :
D (A
o
) l kch thc ht
= 1.54056 A
o
l bc sng tia X
(rad) l bn rng ca vch nhiu x
(rad) l gc nhiu x
Chng ti xc nh c kch thc trung bnh ca ht khong 10.4 13.4nm.
nh TEM ca cc ht nano ZnS ch to bng phng php thy nhit trong 20h cc
nhit thy nhit 130
0
C, 180
0
C, 220
0
C. Khi thy nhit 130
0
C cc ht nano kt t vi nhau
thnh cc m (hnh 3.2 - a,d). Khi tng nhit thy nhit n 180
0
C cc ht nano bt u
tch ri nhau. Khi tng nhit thy nhit n 220
0
C cc ht nano tch ri nhau hn na
vi kch thc ht trung bnh khong t 10-15 nm. Kt qu ny c th xem nh ph hp vi
kt qu thu c t ph XRD.
3.2.2. Cu trc hnh thi hc ca cc ht nano ZnS:Mn ch tao bng phng php
thy nhit
Gin XRD ca cc ht nano ZnS:Mn thy nhit trong 15h 220
0
C vi cc nng
Mn tng t 1mol% n 20mol%. Trong ph XRD ta thy xut hin cc vch nhiu c ng vi
mt phn x chnh (010), (002), (011), (110), (013), (112) trong vch (002) c cng
ln nht, vch (013) c cng nh nht. T ph XRD cho thy ZnS:Mn l n pha, kt
tinh dng a tinh th c cu trc lc gic thuc nhm khng gian C
6v
4
P6
3
mc.
3.2.3. Cu trc v hnh thi hc ca cc ht nano ZnS:Mn bc ph PVA
Gin XRD ca cc ht nano ZnS:Mn (C
Mn
= 8mol%) khng bc ph PVA v bc
ph PVA vi cc khi lng PVA khc nhau. Trong ph XRD ca ZnS:Mn khng bc ph
PVA xut hin cc vch nhiu x ng vi cc mt phn x chnh (111), (202), (113) trong
vch (111) c cng ln nht v vch (113) c cng nh nht. T gin XRD cho
thy cc ht nano ZnS:Mn kt tinh dng a tinh th c cu trc cubic thuc nhm i xng
khng gian Khi cc ht nano ZnS:Mn c bc ph PVA vi khi lng PVA tng t
vi hng s mng a = b = c = 5.318 A
0
. Khi cc ht ZnS:Mn c bc ph
PVA vi cc khi lng t 0.2g n 1.5g v tr cc vch nhiu x v cc hng s mng hu
nh khng thay i. iu ny chng t s bc ph PVA khng lm thay i tnh cht cu trc
ca ZnS:Mn.
15
T gin XRD v s dng cng thc Debye Scherrer chng ti xc nh c kch
thc trung bnh ca ht khong t 2.81 n 4.42nm.
3.3 Tnh cht quang ca cc ht nano ZnS
3.3.1 Ph pht quang ca ht nano ZnS theo nhit thy nhit
Ph pht quang ca cc ht nano ZnS 300K c thy nhit trong 20h vi cc nhit
thy nhit khc nhau t 130
0
n 240
0
khi kch thch bng bc x bc sng 325nm ca
laser He-Cd. Trong ph pht quang ca cc ht nano ZnS thy nhit 130
0
C xut hin 1 m
xanh lam khong 433 nm c cng kh ln. m ny c trng cho cc nt khuyt ca
Zn (V
Zn
), S (V
S
) v cc nguyn t in k ca chng v cc trng thi b mt [12]. Khi nhit
tng t 150
0
C n 200
0
C th cng ca m ny gim v rng ph tng. Khi nhit
tng n 220
0
v 240
0
th m xanh lam ny (433 nm) hu nh b dp tt. iu ny chng
t rng m ny phi c trng cho cc nt khuyt ca Zn, S v cc nguyn t in k ca
chng. Khi nhit thy nhit tng th tinh th ca ZnS c cu trc hon ho hn nn cc nt
khuyt b gim i.
3.3.2 Ph hp th v ph kch thch pht quang ca cc ht nano ZnS theo nhit
thy nhit
lm sng t thm bn cht bc x ca m xanh lam, chng ti kho st ph hp
th v ph kch thch pht quang ca m ny.
Ph hp th ca cc ht ZnS 300K c thy nhit trong thi gian 20h vi cc nhit
tng t 130
0
n 240
0
trong vng bc sng t 200nm n 800nm ca n hydro halogen
3.4 Tnh cht quang ca cc ht nano ZnS:Mn
3.4 Tnh cht quang ca cc ht nano ZnS:Mn
3.4.1 Ph pht quang ca cc ht nano ZnS:Mn
Ph pht quang ca cc ht nano ZnS:Mn 300K thy nhit 220
0
trong thi gian 15h
vi nng C
Mn
khc nhau. Trong ph pht quang ca ZnS:Mn vi C
Mn
= 1mol% xut hin m
xanh lam c cng yu khong 440nm v m da cam vng c cng ln hn khong
586nm. m xanh lam c trng cho cc nt khuyt ca Zn, S v cc nguyn t ca chng nm
l lng gia cc nt mng [17,19]. m da cam vng c trng cho dch chuyn bc x ca cc
electron trong lp v cha lp y 3d
5
ca cc ion Mn
2+
[
4
T
1
(
4
G)
6
A
1
(
6
S)] trong tinh th ZnS
[17]. Khi tng nng Mn t 5mol% n 20mol%, cng ca m xanh lam gim cn cng
ca m da cam vng tng v t cc i C
Mn
= 20mol% nhng v tr ca chng hu nh
16
khng thay i, iu ny chng t m xanh l cy phi c trng cho cc nt khuyt Zn, S ... cn
m da cam vng phi c trng cho cc ion Mn
2+
. Khi tng nng Mn cc ion Mn
2+
(3d
5
) thay
th v tr ca cc ion Zn
2+
(3d
10
) v cc nt khuyt ca chng tng, v th cng m xanh lam
gim cn cng m da cam vng tng. Kt qu ny ph hp vi mt s ti liu tham kho
[16-19]
3.4.2. Ph hp th v ph kch thch pht quang ca cc ht ZnS:Mn
Hnh 3.18 l ph hp th ca cc ht nano ZnS, ZnS:Mn 300K thy nhit 220
0
C trong
15h vi nng Mn khc nhau. Trong ph hp th ca ZnS xut hin 2 m vi cc i khong
241nm (5.1452 eV) v 324nm (3.8272 eV), trong m 324nm c hp th ln hn. m
241nm c trng cho dch chuyn hp th vng vng ca tinh th ZnS v nng lng photon
ng vi dch chuyn ny ln hn nhiu so vi rng vng cm ca n. m 324nm c trng
cho dch chuyn hp th gn b vng ca tinh th ZnS v nng lng photon ng vi dch chuyn
ny rt gn vi rng vng cm [12]. Khi cc ht nano ZnS pha tp Mn vi nng Mn tng t
1mol% n 20mol% v tr ca cc m v cng ca chng hu nh khng thay i. iu ny
chng t rng khi pha tp Mn vo ZnS trong khong nng trn vn khng lm thay i ng k
n cu trc tinh th ZnS. Cc m c trng cho hp th ca cc ion Mn
2+
trong cc tinh th ZnS
vng bc sng di t 380nm n 575nm vn cha xut hin thnh nh.
.4.3. Ph pht quang ca PVA v ZnS:Mn bc ph PVA
Ph pht quang ca PVA 300K khi kch thch bng bc x 325nm ca laser He-Cd.
Trong ph ny ch xut hin 1 m pht quang rng c cng ln khoang 395 nm. m
ny c trng cho s dch chuyn bc x ca cc electron t trng thi in t kch thch
LUMO xung trng thi in t c bn HOMO ca phn t PVA [8]. m ny c bc sng
rt gn vi bc sng 387nm trong ph kch thch pht quang ca cc ht nano ZnS:Mn v th
bc x ca phn t PVA c kh nng kch thch trc tip cc ion Mn
2+
trong tinh th ZnS.
3.4.4. Ph hp th v ph kch thch pht quang ca ZnS:Mn bc ph PVA
Ph hp th ca cc ht nano ZnS:Mn (C
M
= 8mol%) 300K bc ph PVA vi cc
khi lng PVA khc nhau ch to bng phng php ng kt ta. Trong ph hp th ca
ZnS:Mn xut hin 2 m vi cc i khong 245nm (5.0612 eV) v 306nm (4.052 eV),
trong m 306nm c hp th ln hn. m 245nm c trng cho dch chuyn hp th
vng vng ca tinh th ZnS v nng lng photon ng vi dch chuyn ny ln hn nhiu so
vi rng vng cm ca n. m 306nm c trng cho dch chuyn hp th gn b vng
ca tinh th ZnS v nng lng photon ng vi dch chuyn ny rt gn vi rng vng cm
17
[12]. Khi cc ht nano ZnS pha tp Mn vi nng Mn l 8mol% bc ph PVA vi khi
lng PVA tng ln t 0g n 1.5g th v tr ca cc m v cng ca chng hu nh
khng thay i. iu ny chng t rng khi thay i khi lng PVA th vn khng lm thay
i ng k n cu trc tinh th ZnS.
3.5 Tho lun kt qu
T cc kt qu thu c v gin XRD, nh TEM, ph pht quang, ph kch thch
pht quang, ph hp th ca cc ht nano ZnS, ZnS:Mn ch to bng phng php thy nhit
t axit TGA, axit nay va to nn ngun S
2-
va to l cht hot ha b mt cho cc ht nano
chng ti nhn thy:
+ i vi cc ht nano ZnS ch to bng phng php thy nhit trong 20h, khi tng
nhit thy nhit t 130
0
C n 240
0
C th:
- 130
0
C, 150
0
C cc mu vn cha c cu trc tinh th
- T 180
0
C cc ht nano bt u c cu trc tinh th, cc nhit 200
0
C, 220
0
C,
240
0
C th cu trc lc gic ca tinh th cng tr nn hon ho hn. S hon ho ny nh
hng nh hng ln n tnh cht quang ca n nh ph pht quang, ph kch thch pht
quang v ph hp th. m xanh lam khong 433nm c trng cho cc nt khuyt ca
Zn, S v cc nguyn t in k ca chng c cng gim dn khi tng nhit thy
nhit. iu ny chng t nhit thy nhit l mt thng s nh hng ln n qu trnh
hnh thnh cu trc ca cc ht nano.
+ i vi cc ht nano ZnS:Mn c ch to bng phng php thy nhit 220
0
C
trong 15h, khi tng nng Mn t 1 mol% n 20mol% th tnh cht cu trc ca n hu nh
khng thay i, t nh hng n ph hp th nhng li nh hng nhiu n ph pht quang:
cng m xanh lam gim cn cng m da cam vng tng v v tr ca n hu nh
khng thay i. iu ny chng t m xanh lam phi c trng cho cc nt khuyt ca Zn,
S, cc nguyn t in k ca chng, cn m da cam vng c trng cho cc ion Mn
2+
,
l s dch chuyn ca cc electron trong lp v in t cha lp y 3d
5
ca cc ion Mn
2+

[
4
T
1
(
4
G)
6
A
1
(
6
S)] trong tinh th ZnS [17].
T cc kt qu thu c v gin XRD, nh TEM, ph pht quang ca cc ht nano
ZnS:Mn (C
Mn
= 8mol%) khng bc ph v c bc ph PVA ch to bng phng php ng
kt ta chng ti nhn thy:
18
+ S bc ph cc ht nano ZnS:Mn bi PVA hu nh khng lm thay i cu trc cubic
ca tinh th m ch lm gim kch thc ht, lm tng cng ca m da cam vng v
dch chuyn m ny v pha bc sng di khong 7nm so vi m pht quang da cam
vng ca cc ht nano ZnS:Mn ch to bng phng php thy nhit.
+ S tng cng ca m da cam vng ca cc ht nano ZnS:Mn bc ph PVA c
th c gii thch nh sau:
Di tc dng ca laser He-Cd hoc ca n Xe, ngoi vic to ra cc cp in t - l
trng tham gia vo qu trnh truyn nng lng kch thch cho cc ion Mn
2+
trong tinh th
ZnS, cn xy ra s kch thch cc phn t PVA bao quanh cc ht nano ZnS. Cc phn t
PVA hp th photon ca bc x kch thch chuyn t trng thi in t c bn (HOMO) ln
trng thi in t kch thch (LUMO), sau chuyn v trng thi in t c bn pht ra bc
x 603 nm. Bc x ny c th kch thch cc in t 3d
5
ca ion Mn
2+
v th cng m
da cam - vng tng ln khi tng khi lng bc ph PVA. Khi khi lng ca PVA ln c th
xy ra s dp tt pht quang do tng tc gia cc phn t PVA vi nhau v vi cc ht nano
ZnS:Mn. S cc mc nng lng, vng nng lng v s dch chuyn bc x trong PVA,
ZnS:Mn.
KT LUN
Thc hin ti Ch to cc ht nano ZnS:Mn bc ph cht hot ha b mt v kho
st ph pht quang ca chng chng ti thu c mt s kt qu ch yu sau:
+ Thu thp c cc ti liu tng quan v mt s tnh cht cu trc, tnh cht quang ca
cc ht nano ZnS, ZnS:Mn ch to bng phng php thy nhit v ZnS:Mn bc ph PVA
ch to bng phng php ng kt ta.
+ Nghin cu ch to c cc ht nano ZnS theo nhit thy nhit t 130
0
C n
240
0
C trong 20h v ZnS:Mn 220
0
C trong 15h t axit Thioglycolic (TGA), axit ny va to
nn ngun S
2-
va to nn cht hot ha b mt cho cc ht nano.
+ Nghin cu ch to c cc ht nano ZnS:Mn (C
Mn
= 8mol%) bc ph PVA vi
khi lng PVA t 0g n 1.5g bng phng php ng kt ta.
+ Kho st c tnh cht cu trc, hnh thi b mt v mt s tnh cht quang ca cc
ht nano ch to c. Kt qu cho thy:
- i vi cc ht nano ZnS ch to bng phng php thy nhit trong 20h, khi tng
nhit thy nhit t 130
0
C n 240
0
C th:
19
- 130
0
C, 150
0
C cc mu vn cha c cu trc tinh th
- T 180
0
C cc ht nano bt u c cu trc tinh th, cc nhit 200
0
C, 220
0
C,
240
0
C th cu trc lc gic ca tinh th cng tr nn hon ho hn. S hon ho ny nh
hng nh hng ln n tnh cht quang ca n nh ph pht quang, ph kch thch pht
quang v ph hp th. m xanh lam khong 433nm c trng cho cc nt khuyt ca
Zn, S v cc nguyn t in k ca chng c cng gim dn khi tng nhit thy nhit.
- i vi cc ht nano ZnS:Mn c ch to bng phng php thy nhit 220
0
C
trong 15h, khi tng nng Mn t 1 mol% n 20mol% th tnh cht cu trc ca n hu nh
khng thay i, t nh hng n ph hp th nhng li nh hng nhiu n ph pht quang:
cng m xanh lam gim cn cng m da cam vng tng v v tr ca n hu nh
khng thay i. m xanh lam phi c trng cho cc nt khuyt ca Zn, S, cc nguyn t in
k ca chng, cn m da cam vng c trng cho cc ion Mn
2+
, l s dch chuyn ca cc
electron trong lp v in t cha lp y 3d
5
ca cc ion Mn
2+
[
4
T
1
(
4
G)
6
A
1
(
6
S)] trong tinh
th ZnS.
- i vi cc ht nano ZnS:Mn (C
Mn
= 8mol%) bc ph PVA ch to bng phng
php ng kt ta th: s bc ph cc ht nano ZnS:Mn bi PVA hu nh khng lm thay i
cu trc cubic ca tinh th m ch lm gim kch thc ht, lm tng cng ca m da
cam - vng v dch chuyn m ny v pha bc sng di khong 7nm so vi m pht
quang da cam - vng ca cc ht nano ZnS:Mn ch to bng phng php thy nhit.
+ Bc u a ra c ch bc ph v truyn nng lng t PVA sang cc tm Mn
2+
dn
n lm gim kch thc ht v tng cng pht quang ca m da cam vng.

References
Ting Vit:
[1]. Phm Vn Bn (2008), Quang ph phn t nghiu nguyn t, NXB HQGHN, H ni.
[2]. Nguyn Quang Lim (1995), Chuyn di in t trong cc tm pht t hp ca bn dn
A
II
B
VI
, LA.PTS.
[3]. Nguyn Ngc Long (2007), Vt l cht rn, NXB HQGHN, H ni
[4]. Trng Th Luyn (2011), Nghin cu, ch to ZnS:Mn t axit thioglycolic, axetat Zn,
Mn bng phng php thy nhit v kho st ph pht quang ca chng, lun vn thc
s khoa hc vt l, HKHTN HQGHN, H Ni.
20
[5]. Nguyn c Ngha (2007), Ha hc Nano, Cng ngh nn v vt liu ngunNXB Vin
Khoa hc Vit nam, H ni.
[6]. Phan Trng Tu, 2007, Ch to v nghin cu mt s tnh cht quang ca vt liu hunh
quang ZnS:Mn:Ba, lun vn thc s khoa hc vt l, HKHTN - HQGHN, H Ni
Ting Anh
[7]. Ageeth A. Bol, et. Al.( 2002), Journal of Luminescence 99, p 325- 334
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