Luan Van Thac Si Graphene

3
Lun vn Thc S 2010

----------------------------------------------------------------------------------------------------------------------
Phn A
L THUYT TNG QUAN
Graphene l mt vt liu mi, ch bt u c nghin cu trong nhng nm gn

y, l thuyt cht ch v chng cha c hnh thnh, cho nn trong phn ny chng ti
s gii thiu mt cch tng qut nhng thng tin v l thuyt v thc nghim ca mng
graphene da trn cc bi bo ca cc tp ch c uy tn trn th gii. qua ta c th
thy c v tr v vai tr ca graphene trong th gii vt liu, cng nh xu hng nghin
cu ca th gii hin nay.
Trong phn ny chng ti s trnh by v cc vn sau:
Vt liu carbon.
C s l thuyt v cc tnh cht in in t ca mng graphene.
Mt s ng dng.
Cc phng php sn xut.
---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

HVTH: Hunh Trn M Ha
4
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
I. Vt liu carbon
Carbon l nguyn t ng vai tr quan trng cho s sng v l nguyn t c bn ca
hng triu hp cht ha hc hu c. Trong mt nguyn t carbon, cc electron lp ngoi
cng c th hnh thnh nn nhiu kiu lai ha khc nhau (chi tit phn II.1), do khi cc
nguyn t ny lin kt li vi nhau chng cng c kh nng to nn nhiu dng cu trc
tinh th nh: Cu trc tinh th ba chiu (3D), hai chiu (2D), mt chiu (1D) v khng
chiu (0D). iu ny c th hin thng qua s phong ph v cc dng th hnh ca vt
liu carbon l: Kim cng, graphite, graphene, carbon nanotube, fullerenes.
Kim cng v graphite l hai dng th hnh c cu trc tinh th 3 chiu ca carbon
c bit n nhiu nht. Cu trc ca kim cng c th c m t bng hai mng lp
phng tm mt dch chuyn i vi nhau theo ng cho chnh mt on bng 1/4
ng cho (hnh A.I.1). Mi nguyn t carbon trong kim cng lin kt cng ha tr
vi 4 nguyn t carbon khc to thnh mt khi t din.
Hnh A.I.1- Cu trc tinh th ca kim cng v graphite (3D)

Vi cu trc bn vng ny m kim cng c nhng tnh cht vt l hon ho, n c
cng rt cao, bn nhit, v tn sc cc tt, v th chng c rt nhiu ng dng
trong c cng nghip v ngnh kim hon. Ngnh cng nghip s dng kim cng c t rt
lu v tnh cht cng rn ca chng, kim cng c dng nh bng, ct mi b mt,
HVTH: Hunh Trn M Ha
5
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
ngay c mt vin kim cng khc, dng lm mi khoan, li ca hay bt mi. Kim cng
c kh nng tn sc tt, iu ny gip kim cng bin nhng tia sng trng thnh nhng tia
sng c mu sc khc nhau, to nn sc hp dn ring ca kim cng khi l mt mn trang
sc.
Tri ngc vi kim cng, graphite l cht dn in rt tt, bi v trong graphite
mi nguyn t carbon lin kt cng ha tr vi 3 nguyn t carbon khc hnh thnh nn
mng phng vi cc hnh lc gic, do mi nguyn t carbon trong mng cn d 1
electron, cc electron cn li ny c th chuyn ng t do bn trn v bn di mt mng,
gp phn vo tnh dn in ca graphite. Cc mng carbon ny lin kt vi nhau bng lc
Van der Waals hnh thnh nn cu trc tinh th 3 chiu (hnh A.I.1). Tuy nhin cc electron
t do ch c th chuyn ng dc theo cc b mt, cho nn kh nng dn in ca graphite
c tnh nh hng. Do c im cu trc c s lin kt lng lo gia cc tm (lp) trong
graphite nn n thng c dng trong cng nghip vi vai tr l cht bi trn dng kh.
Cng v c im ny nn graphite thng d v, d tch lp do thng thng trong
cng nghip graphite khng c dng dng nguyn cht nh l cc vt liu c cu trc
n nh, m c s dng di dng graphite nhit phn (pyrolytic graphite) nh l si
carbon, thp, gang xm Cc vt liu ny c c im l rt cng, kh nng chu nhit v
chu lc tt, thng c dng trong ngnh ch to my, c cc bng my ln c phc
tp cao, cc chi tit khng cn chu un ln, nhng cn chu lc nn v chu nhit tt
(nh: cc cng c tin, phay, bo, cc thn my ca ng c t trong) hoc lm cht bao
bc cc u tn la, bn p thng v chi qut cc motor in. Nguyn nhn l do,
di tc dng ca nhit cao cc tm trong cu trc ca graphite s lin kt vi nhau rt
lng lo, v trong qu trnh ng c vi tc tn nhit chm lng graphite ha ln
vo trong cc cht khc c thi gian gii phng thnh cc phin nh c dng tm (
chnh l cc mng graphene), v thnh phn ny c nh hng rt ln n cc hp cht to
thnh lm cho chng c c nhng u im nh trn. Ngoi ra, graphite nguyn cht cn

HVTH: Hunh Trn M Ha
6
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
c s dng nh l v bc v phn iu tit trong cc l phn ng ht nhn, v graphite c

thuc tnh cho ntron i qua rt t theo mt ct ngang.
Fullerenes l mt dng th hnh ca carbon vi cu trc tinh th 0 chiu (0D),
thng c dng hnh cu, cn c gi l buckyball v c ch to u tin vo nm
1985. Cu trc ca fullerenes c xem nh to thnh t vic qun li ca mt lp n
trong cu trc ca graphite (hnh A.I.2) (c gi l graphene trong cc phn trnh by
sau), v khi qun li nh vy th mt s lin kt sp2 trong graphite s bin i thnh lin kt
sp3 trong kim cng, iu ny lm cho cc nguyn t trong fullerenes tr nn n nh hn.
Trong vi thp nin qua, fullerenes c ng dng trong nhiu lnh vc nh: dng lm
lp bc bn ngoi ca o gip, thuc khng sinh khng khun v c bit l ph hy mt
s t bo ung th nh: U melanin, ngoi ra n cng c dng ch to cc cht khng vi
sinh vt nhy sng.
Hnh A.I.2- Cu trc tinh th ca ng nano carbon (1D) v buckyball (0D)
ng nano carbon (Carbon Nanotube CNT) l mt dng th hnh ca carbon vi

cu trc tinh th 1 chiu (1D), v c ch to u tin vo nm 1991. Cu trc ca n
xem nh mt tm graphene c cun trn li thnh hnh tr vi ng knh c nanomet
(hnh A.I.2), t l chiu di vi bn knh ca ng ln n 132.000.000:1, vo nm 2010 th
chiu di ca ng c cng b l 18mm trong khi ng knh ch vi nanomet (xp x
1/50.000 b dy si tc ca con ngi). Cc ng nano carbon c chia lm 2 loi chnh:
HVTH: Hunh Trn M Ha
7
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
n vch v a vch. Mt iu th v l, cc ng nano carbon n vch c nhiu thuc tnh

c bn khc nhau ty thuc vo cch thc chng c cun trn nh th no. Nu cc
nguyn t carbon c cun trn v pha mp, ng s mang tnh cht ca kim loi, cn khi
chng c cun lch (khng ng tm) ng s c tnh cht ca cht bn dn (hnh A.I.3).
Vi nhng c im v cu to nh trn nn CNT c cc c tnh v c, nhit, in, quang
ni bt hn so vi cc vt liu khc nh: dn in ca n gp 1.000 ln dn in ca
ng, mc chu nhit ln n 2.8000C trong mi trng chn khng, cn cng th
vt qua cng ca tinh th kim cng vi cng khi (bulk modulus) ca ng nano
carbon n vch l 462-546GPa, trong khi ca kim cng l 420GPa [15] Cc ng nano
n vch l ng c vin sng gi cho vic thu nh kch thc sn phm ca ngnh c in
t c micro hin nay xung cn nano. S kt hp gia CNT v buckyball c ng
dng trong vic ch to pin mt tri, ngoi ra CNT cn c ng dng trong vic ch to
cc siu t in v cc transistor
a)
b)
Hnh A.I.3- Cu trc cc ng nano carbon c cun trn v pha mp a), v ng nano
carbon c cun lch b)
Mt th thch rt ln i vi vic sn xut CNT l cc nh khoa hc vn cha th
cun trn ng nano theo cch h mun, h cng cha th kim sot c tnh cht nhit
ng hc ca vt cht ny, m li l tnh cht quyt nh khi no ng nano l kim loi
v khi no l bn dn. Ngoi ra chi ph cho vic sn xut CNT cn rt cao.
Graphene l mt mt phng n lp ca nhng nguyn t cacbon c sp xp cht
ch trong mng tinh th hnh t ong 2 chiu (2D). Graphene c cun li s to nn dng
HVTH: Hunh Trn M Ha
8
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
th hnh fullerene 0D, c qun li s to nn dng th hnh cacbon nanotube 1D, hoc
c xp chng ln nhau s to nn dng th hnh graphite 3D (Hnh A.I.4).
V c im trn m nhng l thuyt v graphene bt u c nghin cu t
nhng nm 1940. Nm 1946, P.R. Wallace l ngi u tin vit v cu trc vng nng
lng ca graphene [4], v nu ln nhng c tnh d thng ca loi vt liu ny. Cn
nhng nghin cu v thc nghim th cha c pht trin bi v cc nh khoa hc cho
rng cu trc tinh th 2 chiu vi b dy ch bng 1 nguyn t khng tn ti v cc thit b
k thut lc by gi cng khng th quan st thy cc cu trc ny.
Hnh A.I.4- Graphene - vt liu c cu trc c bn (2D) cho cc vt liu cacbon khc (0D,
1D, v 3D)
n nm 2004, nhng khm ph t thc nghim ca 2 nh khoa hc ngi Lin X
l Kostya Novoselov v Andre Geim thuc trng i hc Manchester Anh chng t
s tn ti ca graphene, t vt liu ny thu ht s quan tm c bit ca cc nh khoa
hc trn th gii bi cc c tnh vt tri ca n. Nhng tm graphene c cu trc phng
v dy mt nguyn t, l vt liu mng nht trong tt c cc vt liu hin c, cu trc

HVTH: Hunh Trn M Ha
9
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
bn vng ca graphene c xem l vt liu cng nht hin nay vi sut Young ~ 0,51,0TPa, bn vt liu ~125GPa [34], v dng tinh khit th graphene dn in nhanh
hn bt c cht no khc (ngay c nhit bnh thng). Hn na, cc electron i qua
graphene hu nh khng gp in tr nn t sinh nhit (in tr ca graphene ~ 10-6 .cm
[15], thp hn in tr ca Ag v l in tr thp nht hin nay nhit phng), linh
ng ca cc ht ti in trong graphene ~ 200.000 cm2V-1s-1 [15], [34], y l gi tr ln
nht c cng b t trc n nay cho c bn dn v bn kim loi. c bit l nhng o
lng thc nghim v dn cng cho thy rng linh ng ca in t v l trng l
gn bng nhau. Bn thn graphene cng l cht dn nhit, cho php nhit i qua v pht tn
rt nhanh ngay nhit phng ( dn nhit ca graphene t (4,840,44) 103 n
(5,300,48) 103 Wm1K1) [3]. Ngoi ra graphene cn l mt cht trong sut, mt s
nghin cu cho thy truyn qua l hn 70% vng bc sng 1000-3000 nm [39].
Ni bt hn c l nhng kt qu thc nghim cng cho thy rng t mng
graphene thun c to thnh bng phng php epitaxy trn silic cacbua (SiC), ta c
th chuyn n thnh bn dn loi n hoc bn dn loi p ty thuc vo vic pha tp bitmut
(Bi), antimon (Sb) hay nguyn t vng (Au). iu ny em li nhng ha hn cho vic
ng dng vt liu graphene vo nhng thit b khc nhau [16].

HVTH: Hunh Trn M Ha
10
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
II. C s l thuyt ca graphene

II.1- Nguyn t carbon v cc trng thi lai ho ca carbon
S a dng v cc dng th hnh ca carbon bt ngun t kh nng hnh thnh nn
nhng dng lin kt c tnh linh hot ca nguyn t ny. Trong graphene c xem l
dng th hnh ng vai tr quan trng, bi v nhng c tnh in t ca dng vt liu ny
l kin thc c bn cho vic tm hiu nhng tnh cht ca cc dng th hnh khc. tm
hiu v mng graphene, ta bt u t vic tm hiu nguyn t carbon v cu hnh electron
v cc trng thi lai ha ca n.
Carbon l nguyn t v tr th 6 trong bng h thng tun hon cc nguyn t ho
hc. Trong t nhin, carbon tn ti cc ng v C12, C13v C14 , trong ng v C12 chim
s lng ch yu (khong 99%) c spin ht nhn bng 1, trong khi spin ca ng v C13 l
1/2. trng thi c bn, mi nguyn t carbon c 6 electron vi cu hnh 1s2 2s2 2p2, trong
cc electron chim gi vn o 1s c nng lng lin kt ln nht v hu nh khng
tham gia vo cc phn ng ho hc. Lp v ngoi, cha 4 electron chim gi cc vn o s
v p, cha c in y nn c xu hng d dng hnh thnh lin kt cng ho tr to
thnh cu trc bn vng [1], [18], [30].
Trng thi kch thch
Trng thi c bn
2s
1s
2px
2py
2pz
2s
2px
2py
2pz
1s
Hnh A.II.1- Cu hnh in t ca carbon trng thi c bn v trng thi

kch thch

HVTH: Hunh Trn M Ha
11
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
Do s khc bit gia cc mc nng lng ca cc vn o 2s v 2p (bao gm p x, py

v pz) trong nguyn t carbon l rt nh so vi nng lng lin kt ho hc, hm sng ca
cc vn o ny d dng xen ph ln nhau lm thay i trng thi chim gi in t ca
chng v tng cng lin kt gia nguyn t carbon vi cc nguyn t ln cn.
Trong lin kt ha hc, thut ng lai ha ch s chng chp ln nhau gia cc vn
o ca electron hay l s chng chp ca cc hm sng vi nhau, n gip m t cc i
lng v gii thch cc lin kt trong phn t. trng thi kch thch, mt vn o trng
thi lng t 2s c th xen ph vi n vn o 2p j (j = x, y, z) hnh thnh cc trng
thi lai ho spn, trong quan trng nht l lai ho sp, sp2 v sp3. Cc lai ho bc >=3 u
c quy v mt trong ba trng thi lai ho ph bin k trn [18], [30] (hnh A.II.1).
Trng thi lai ho sp
Lai ho sp c hnh thnh khi c s kt hp ca mt vn o s v mt trong ba vn
o p, chng hn px, trong khi khng lm thay i hai vn o p cn li. trng thi ny,
cc vn o lai ho sp xp trn cng mt ng thng. Trng thi lng t tng ng
c xc nh thng qua s lin kt i xng hoc phn i xng, theo cc biu thc sau :
sp
1
2s 2px
2
v sp
1
2s 2px
2
(II.1.1)
Mt in t ca vn o lai c dng nh hnh A.II.2 v c ko di theo

phng ca vn o p ban u, ph thuc vo cch lin kt.

HVTH: Hunh Trn M Ha
12
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
sp+
sp-_
Hnh A.II.2- Lai ho sp. Trng thi 2s 2p x c ko di theo chiu dng ca trc
Ox, trong khi trng thi 2s 2p x m rng theo hng ngc li
in hnh cho trng thi lai ho sp l s hnh thnh lin kt trong phn t Acetylen
CH CH, trong vn o s kt hp vi mt vn o p ca nguyn t carbon hnh
thnh trng thi lai ho sp. S chng chp ca hai vn o lai sp-sp to thnh lin kt ,
ng thi cc vn o p cn li ca hai nguyn t carbon k cn kt hp vi nhau hnh
thnh nn hai lin kt , t to ra lin kt 3 gia hai nguyn t carbon trong phn t,
hnh A.II.3.
Lin kt hnh thnh

do xen ph sp-s
Lin kt hnh thnh

do xen ph sp-sp
Lin kt
Lin kt
Hnh A.II.3-. Minh ho trng thi lai ho v cc lin kt hnh thnh trong phn t
acetylene

HVTH: Hunh Trn M Ha
13
Lun vn Thc S 2010
---------------------------------------------------------------------------------------------------------------------
Trng thi lai ho sp2

Trong trng thi lai ho ny, mt vn o s s lin kt vi hai vn o p, to thnh
ba nhnh s-p nm trong cng mt mt phng v mi nhnh to vi nhnh k cn mt gc

120o (hnh A.II.4), vn o p cn li nm vung gc vi mt phng ca cc vn o lai s-p.
Hnh A.II.4- Cc vn o lai ha sp2 trong nguyn t carbon

Cc trng thi lng t ca vn o lai c xc nh thng qua biu thc :
sp12
1
2
2s
2p y
3
3
sp22
1
2 3
1
2s
2p x 2p y
3 2
2
3
sp32
(II.1.2)
1
2
3
1
2s
2p x 2p y
3 2
2
3
Tng t vi lai ho sp, dng ny, mt carbon lai ho sp2 cn lin kt vi mt

carbon lai ho sp2 khc to thnh phn t, chng hn nh phn t ethylene. Mt trong ba
nhnh ca vn o lai sp2 s kt hp vi mt vn o lai sp2 ca carbon khc hnh thnh
lin kt , trong khi hai nhnh cn li s lin kt vi nguyn t hydro. Ngoi ra, vn o p
khng lai ho s hnh thnh lin kt , dn n hnh thnh ni i (gm 1 lin kt v mt
lin kt ) trong phn t ny, hnh A.II.5.
HVTH: Hunh Trn M Ha
14
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
Lin kt hnh thnh

bi lai ha sp2-s
Lin kt hnh
thnh bi sp2-sp2
Lin kt
Lin kt
Lin kt
Lin kt
Hnh A.II.5- Minh ho s hnh thnh cc vn o lai v cc lin kt trong phn t ethylene,
trong cc lin kt c hnh thnh t s chng chp cc vn o lai sp2, trong khi
lin kt l kt qu ca s kt hp gia cc vn o pz khng tham gia lai ho
Trng thi lai ho sp3
Hnh A.II.6- Cc vn o lai ha sp3 trong nguyn t carbon

L trng thi lai ho xy ra khi mt vn o s lin kt vi ba vn o p, to thnh
bn nhnh tng ng vi bn nh ca mt t din. Cc nhnh ny hp vi nhau mt gc
bng 109,5o (hnh A.II.6). trng thi kch thch, mi vn o p s b chim gi bi 1 in
t, do to thnh cu hnh bn, nguyn t carbon ny cn phi lin kt vi cc nguyn
t khc, chng hn dng chung in t lp s ca nguyn t hydro to thnh phn t CH4
(methane) hoc vi mt carbon lai ho sp3 khc to thnh H3C CH3 (ethane). Khi

HVTH: Hunh Trn M Ha
15
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
lin kt gia carbon v carbon trong phn t l lin kt . dng cc tinh th cht rn, lai
ho sp3 ng vai tr l ngun gc ca s hnh thnh tinh th kim cng, khi cc nguyn t
carbon trng thi lng ho rn di iu kin p sut v nhit cao.
II.2- Cu trc ca graphene
Hnh A.II.7- Cc lin kt ca mi nguyn t carbon trong mng graphene

V mt cu trc mng graphene c to thnh t cc nguyn t carbon sp xp
theo cu trc lc gic trn cng mt mt phng, hay cn c gi l cu trc t ong. Trong
, mi nguyn t carbon lin kt vi ba nguyn t carbon gn nht bng lin kt to
thnh bi s xen ph ca cc vn o lai s-p, tng ng vi trng thi lai ho sp2. Khong
cch gia cc nguyn t carbon gn nht l a = 0,142 nm. Theo nguyn l Pauli, cc mc
nng lng trong lin kt c lp y, do cc vn o lai ha sp2 s c trng cho
mc bn vng trong cu trc phng ca mng graphene. Vn o p cn li ca cc
nguyn t carbon, nm vung gc vi cu trc phng ca mng, xen ph bn vi nhau hnh
thnh nn lin kt , v mc nng lng ca lin kt ny cha c lp y nn n cn
c gi l cc vn o khng nh x, cc vn o ny s ng vai tr quan trng trong
vic hnh thnh nn cc tnh cht in khc thng ca graphene [33] (hnh A.II.7).
Mc d c s i xng cao trong cu trc, lc gic trong graphene khng c
chn lm n v, do cc nguyn t carbon lin k khng c vai tr tng ng nhau.
iu ny c th hin trong hnh A.II.8, cc nguyn t v tr A v v tr B l khng
tng ng trong h to Dercates, mi nguyn t trong mng graphene u c 3

HVTH: Hunh Trn M Ha
16
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
nguyn t gn nht to thnh mt tam gic u, nhng khi so snh 2 tam gic u ca ln
lt 1 nguyn t v tr A v 1 nguyn t v tr B th ta thy chng lch nhau mt gc
600. Tuy nhin, mt cch tng qut, c th xem mng graphene l s t hp ca 2 mng
con gm ton cc nguyn t carbon v tr A v ton cc nguyn t v tr B, trong cng
mng con cc nguyn t ln cn hon ton tng ng nhau v mt cu trc v tnh cht.
y
Vng Brillouin th nht
b1
a1
R1
R2
a2
R3
K
M
b2
Nguyn t C v tr A
Nguyn t C v tr B
Hnh A.II.8- Cu trc mng graphene, trong cc nguyn t carbon c sp xp u

n trn cc lc gic vi cc vector n v mng thc a1 v a 2 , khong cch gia hai
nguyn t carbon ln cn l 0,142 nm (hnh tri). Hnh bn phi th hin cc vector mng
o b1 , b 2 v vng Brillouin th nht (mu ) cha hai im i xng c bit K v K
C ngha l cu trc mng tinh th ca graphene c th c m t bng cc vector
nguyn t ca cc mng con ny, hay cu trc lc gic ca mng graphene c th c xc
a 3 a
;
2
2
nh thng qua cc vector nguyn t a1 v a2 nh hnh A.II.8 [18], trong a1 =
a 3 a
; (vi a l chiu di ca vector nguyn t). Vi cch chn vector
v a 2 =
2
2

HVTH: Hunh Trn M Ha
17
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
nguyn t nh vy, mi nguyn t trong mng thc ca graphene s c xem nh to

thnh bi hai vector a1 v a2 nhng cha 2 nguyn t carbon (A v B). ng thi, v tr
gia nguyn t carbon trong mng A v B c lin h vi nhau thng qua cc vector R 1
a
a
a a
a
, v R 3 =
, , R2 =
,0 . Khong cch gia cc nguyn t
=
2 3 2
2 3 2
3
carbon ln cn l dC-C = 0,142 nm (tng t khong cch gia cc nguyn t carbon trong
vng benzel). Khi , ln ca cc vector nguyn t a1 a 2 a = dC-C 3 = 0, 246nm.
Din tch ca nguyn t AC =
3 a2/2 = 0,051 nm2 v mt nguyn t tng ng l nC
=2/AC = 39 nm-2 = 39.1015 cm-2. Mt khc, trong mng graphene, cc vn o pz khng

tham gia vo qu trnh lai ho cng kt hp vi nhau hnh thnh nn cc lin kt v s
lng lin kt ny bng s nguyn t carbon trong mt nguyn t ca mng, do mt
cc lin kt trong mng graphene l n = nC = 39.1015 cm-2 [18].
Trong khng gian mng o Brillouin tng ng, cc vector mng o c xc
0 khi i j
2 2
, v b 2 =
nh bi iu kin a i .b j = 2.ij, vi ij =
. Khi b1 =
1 khi i = j
a 3 a
2
2
, , tc l cc vector mng o b quay mt gc 90o so vi vector n v mng
a
a 3
thun v vng Brillouin th nht c dng hnh lc gic c th hin trong hnh A.II.8.
Bn cnh cc vector n v, to ca cc nguyn t carbon gn nht cng c xc nh
thng qua cc vector R 1 , R 2 , v R 3
Trong khng gian mng o, v tr ca cc im gc K v K ca vng Brillouin
2
2 2
2
,
,
, K'
. Cc im
a 3 3a
a 3 3a
th nht c xc nh thng qua cc vector K
ny c gi l cc im Dirac, ng vai tr quan trng trong qu trnh truyn in t

trong mng graphene, tng t nh im trong cu trc vng nng lng ca cc cht
bn dn trc tip (bn dn chuyn mc thng) nh GaAs. Vai tr c th ca cc im K v
HVTH: Hunh Trn M Ha
18
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
K s c tho lun k hn khi kho st tnh cht in ca mng graphene trong phn
II.3.1.
II.3. Tnh cht in in t ca graphene
Nh gii thiu, graphene l loi vt liu c nhng tnh cht in in t tng
i c bit hn so vi cc loi vt liu khc. Do gii hn ca mt lun vn, phn ny
chng ti s gii thiu mt vi trong s nhng tnh cht c lin quan n ti, v gii
thch s xut hin cc tnh cht ny da trn c s cu trc vng nng lng v mt
trng thi ca mng graphene.
II.3.1. Cu trc vng nng lng ca Graphene
i vi graphene v dng th hnh khc ca carbon (ngoi tr kim cng), cc in
t chnh l cc in t ho tr v ng vai tr quan trng trong cc hin tng lin quan
n qu trnh truyn in t cng nh cc tnh cht vt l khc. xc nh cu trc vng
nng lng ca graphene v cc vt liu lin quan, php gn ng lin kt mnh thng
c cc nh khoa hc s dng v chng l cng c n gin nhng c bit hu hiu.
Trong php gn ng lin kt mnh, tr ring nng lng Ei (k) c xc nh
thng qua phng trnh det[H ES] = 0, trong H l ma trn Hamiltonian th hin tng
tc truyn, S l ma trn th hin tng tc xen ph v E tng ng vi nng lng ca
trng thi th i. Ei (k) l mt hm tun hon trong khng gian o v c th c m t chi
tit trong vng Brillouin th nht. Trong cc mng cht rn 2 hoc 3 chiu, vic xc nh
h thc tn sc cho nng lng tr nn c bit phc tp, do Ei (k) ch c m t trn
mt s phng nht nh c tnh i xng cao trong vng Brillouin [30]. Nh vy, xc
nh ph nng lng E(k) (hay cu trc vng nng lng) trong mng graphene, ta cn xc
nh: to cc vector n v, cc im i xng c bit trong khng gian mng thun v
mng o; vi mi gi tr cho trc ca vector sng k , xc nh cc ma trn truyn (H) v

HVTH: Hunh Trn M Ha
19
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
ma trn che ph (S), t gii phng trnh lin quan n cc i lng trn, ta thu c
cc gi tr nng lng tng ng E(k) .
Da trn nguyn tc ny, nh trnh by trn, s khng tng ng gia cc
nguyn t carbon ln cn dn n mng graphene c xem l s kt hp gia hai mng
tinh th ch gm cc nguyn t carbon v tr A v cc nguyn t v tr B. Do , hm
sng ton phn m t trng thi ca graphene c th xem l s t hp tuyn tnh gia cc
trng thi ca mng nguyn t A v nguyn t B [4], [30]:
(k, r) CAA (k, r) CBB (k, r)

Vi A (k, r)
(II.3.1)
1
1
eikR A (r R A ) v B (k, r)
eikR B (r R B )
N RA
N RB
Trong N l tng s n v trong mng graphene, R l vector nh v nguyn

t v (r R ) (vi = A, B) l hm sng m t trng thi ca cc nguyn t carbon
trong mng A hoc B. Ph nng lng c xc nh thng qua vic gii phng trnh
H AB
H E
Schrodinger c quy v ma trn cho 22 c dng AA
vi HAA, HBB,
H
H
E
BA
BB
HAB l cc Hamiltonian tng tc gia cc nguyn t carbon trong ni mng A hoc B v

gia cc nguyn t ca hai mng ny vi nhau, E l tr ring nng lng
H AA (r)
1
eik(R R ') A (r R) H A (r R ')
'
N R,R
H AB (r)
1
eik(R R ') A (r R) H B (r R ')
N R,R '
(II.3.2)
Trong cc mng ch gm cc nguyn t A hoc B, khi ch xt tng tc gia cc

nguyn t carbon gn nht vi nhau, ta c HAA = H BB = E2p, vi E2p l nng lng tng
ng vi trng thi c bn ca cc vn o pz (vn o tham gia to lin kt ). ng thi,

HVTH: Hunh Trn M Ha
20
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
Hamiltonian tng tc gia cc nguyn t A v B ln cn (xc nh thng qua cc vector
R1 , R 2 v R 3 ), ta c : HAB = t(eikR1 eikR 2 eikR3 ) = tf(k). Trong h to Decartes,

f(k) eik x a /
k a
2eik x a /2 3 cos y
2
(II.3.3)
(t : l nng lng cn thit electron dch chuyn gia cc nguyn t ln cn)

Do f(k) l hm phc nn HAB l ton t Hermit, dn n HBA = H*AB . i vi cc
ma trn tch phn che ph S, ta cng c SAA = SBB = 1, SAB = sf(k) = S*BA (s c trng cho
s che ph nng lng gia cc nguyn t A B ln cn). Thay cc gi tr ca H v S vo
E 2p
phng trnh det[H ES] = 0, vi H =
*
tf (k)
tf (k)
sf (k)
1
, ta c
v S =
*
E 2p
1
sf (k)
biu thc tn sc nng lng theo vector sng k :
E(k)
E 2p t(k)
1 s(k)
(II.3.4)
Cc gi tr E+ v E th hin nng lng cc trng thi lin kt (trng thi c

bn) v trng thi phn lin kt * (trng thi kch thch), vi hm:
(k)
3k x a
ka
k ya
2
2 y
f (k) 1 4cos
cos
4cos
2
2
2
(II.3.5)
Hnh A.II.9 m t h thc tn sc nng lng ca mng graphene trong vng

Brillouin th nht theo cc phng c tnh i xng cao, trong E 2p = 0, t = 3,033 eV
v s = 0,129 eV.
Trong hu ht cc trng hp ca graphene, ta thng chn s = 0 n gin trong
vic tnh ton cu trc vng nng lng. Khi , theo phng trnh (II.3.4), cc vng , *
tr nn i xng quanh gi tr E = E2p v h thc tn sc c dng :
3k x a
k a
k ya
2 y
E(k x , k y ) t 1 4cos
cos
4cos
2
2
2
(II.3.6)

HVTH: Hunh Trn M Ha
21
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
Theo cc phng c tnh i xng cao, E ln lt nhn cc gi tr 3t, t v 0,

tng ng vi cc im , M v K.
T h thc tn sc, c th thy c ti cc v tr i xng K (im Dirac), khong
cch gia cc mc nng lng ti cc trng thi lin kt v phn lin kt * ca graphene
l bng 0, ngha l graphene c th c xem nh cht bn dn c rng vng cm bng
0. Ln cn cc im ny, s tn sc nng lng l tuyn tnh, ngha l E ph thuc bc 1
theo k, thay v bc hai nh trong cc h cht rn thng thng. Tuy nhin, s tn ti ca
vng cm bng 0 ny ti cc im i xng K v K yu cu tnh i xng cao trong cu
trc, ngha l mng cc nguyn t A v B phi ng vai tr tng ng nhau. Trong
trng hp A v B l cc nguyn t khc loi (chng hn B l Nit), gia cc mc v *
s xut hin vng cm nh cc bn dn thng thng. Hin tng ny ng vai tr quan
trng trong vic gii thch kh nng truyn dn in t cao v cc hiu ng lng t c
bit khc nh: hiu ng Hall lng t, ca mng graphene cng nh ng nano carbon.
Hnh A.II.9- Minh ho cu trc vng nng lng ca graphene trong vng Brillouin th nht da trn h
thc tn sc thu c t php gn ng lin kt mnh. Ti cc im K v K, khong cch gia trng thi
phn lin kt * (ng vi cc mc nng lng vng dn) v trng thi lin kt (tng ng vi cc mc
nng lng vng ho tr) l bng 0. Hnh bn phi, th hin s thay i ca h thc tn sc dc theo trc
i qua cc im c tnh i xng cao K M (im chnh gia cnh ni cc im K v K) K.
Nng lng c biu din theo n v t (nng lng cn thit electron dch chuyn gia cc nguyn t
ln cn) v vector sng k theo n v 1/a [18].

HVTH: Hunh Trn M Ha
22
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
Tng t cc mc v *, khi cc nguyn t carbon lin kt vi nhau s t hp

ca cc vn o lai ho sp2 ca 2s, 2px v 2py hnh thnh nn cc mc nng lng lin kt
v phn lin kt *. S dng php gn ng lin kt mnh tng t nh trn, vi mi
gi tr xc nh ca vector sng k, ta c th thu c h thc tn sc nng lng t phng
trnh det[H ES] = 0, c th hin trong hnh A.II.10. Kt qu cho thy c s giao nhau
gia cc mc nng lng v , cng nh * v *, ngha l khng c s ngn cch gia
cc vng v ti cc v tr ny. iu ny ng vai tr quan trng trong vic nghin cu
cc hin tng lin quan n dch chuyn quang hc gia vng v * v ngc li da
trn c s ca nguyn tc lc la, cng nh cc nghin cu v qu trnh truyn in tch
gia cc ion kim loi kim v graphene trong cc mng graphene pha tp.
Hnh A.II.10- H thc tn sc th hin s ph thuc gia nng lng v vector sng k
cho cc vng , *, , * trong mng graphene hai chiu dc theo phng cha nhiu yu
t i xng.

HVTH: Hunh Trn M Ha
23
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
Hin nay, trong thc nghim, k thut ARPES (Angle Resolved Photoemission
Spectroscopy Ph pht quang phn gii gc) thng c s dng rng ri nghin cu
hin tng tn sc nng lng. Cc kt qu t k thut ny cng cho thy hin tng tn
sc nng lng ca mng graphene ch to c trong thc nghim c s trng khp vi
cc nghin cu l thuyt. Kt qu cng cho thy mc nng lng Fermi EF c gi tr xp x
khong 0,45 eV ti ln cn cc im K v K [18].
II.3.2. Mt trng thi
Bn cnh h thc tn sc, s khc bit v hm mt trng thi ca graphene so
vi cc h cht rn hai chiu khc cng l mt i tng nghin cu th v, nh hng n
tnh cht c bit ca graphene. Hm mt trng thi cho bit s trng thi lng t ln
cn mt nng lng xc nh v c bit hu ch trong vic nghin cu cc dch chuyn
lng t trong cc h thp chiu.
i vi graphene, hm mt trng thi c xc nh bng biu thc [4]:
(E)
Z1
4 E 1
K
,
2 t 2 Zo 2 Zo
(II.3.7)
2
2
1
2
t E t
1 E / t E / t 1
4
Trong , Zo
4 E / t
3t E t t E 3t
4 E / t
v Z1
2
2
1
2
E
/
t
E
/
t
(II.3.8)
t E t
3t E t t E 3t
(II.3.9)

vi K , x l hm tch phn eliptic loi 1.
2
Ln cn cc im Dirac, h thc tn sc nng lng cho thy s t l thun gia
nng lng v vector sng k, ng thi hm mt trng thi quy v dng (vi iu kin
E
t) [18]:

HVTH: Hunh Trn M Ha
24
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
(E)
gE
2 2 v F2
(II.3.10)
Vi g l bc suy bin khi xt n tng tc spin (g = 4 trong mng graphene). T h thc

(II.3.10) trn c th thy c hm mt trng thi b trit tiu ti cc im Dirac (c
nng lng E = 0) v l h qu trc tip khi h thc tn sc c dng tuyn tnh
E (k ) vF k ti ln cn cc im ny.
Kt qu ny hon ton ngc li vi cc mng cht rn hai chiu khc, c h thc

2
k2
gm*
tn sc v hm mt trng thi xc nh theo th t l: E
v (E)
.
2m*
2 2
Hnh A.II.11- Minh ha s ph thuc ca mt trng thi theo nng lng trong
mng graphene. ng cho t nt th hin hm mt trng thi c dng tuyn tnh
ng vi gi tr nng lng ti cc im cc tr K, K
Hm mt trng thi c th hin trong hnh A.II.11. Trong vng E
t, hm
(E) c dng tuyn tnh v bng 0 khi E = 0. Ngoi ra, (E) b phn k ti cc im nng
lng c gi tr E = t, gi l im d thng Van-Hove, tng ng vi cc im M nm
tai bin vng Brillouin th nht.

HVTH: Hunh Trn M Ha
25
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
II.3.3. Khi lng cyclotron

Nh trnh by trn, mt trong nhng tnh cht c bit nht ca graphene l
cc ht ti ca vt liu ny khng tun theo h thc tn sc thng thng, vi nng lng
t l thun vi bnh phng ca vector sng k nh trong cc kim loi v bn dn thng
thng. Thay vo , ti v tr ln cn cc im K v K, h thc tn sc c dng : E =
kvF (vF 106 m/s l vn tc Fermi). S ph thuc bc nht ca nng lng vo vector
sng k nh vy c th c m t bng phng trnh Dirac [25]:
(r) E(r)
H
0
v
trong H
F
k x ik y
(II.3.11)
k x ik y
v F .k l Hamiltonian Dirac
0
l ma trn Pauli trong mng 2 chiu

Nh vy, do electron trong graphene tun theo phng trnh Dirac nn c th xem
chng nh cc fermion Dirac v tho mn cc tnh cht ca loi ht ny.
Ngoi ra, cc im gc (K) trong vng Brillouin th nht cng c gi l cc im
Dirac v ti cc im ny, khi lng hiu dng ca ht ti trong mng graphene c th
xem l bng 0. Tht vy, khi lng hiu dng ca in t c tnh theo cng thc :
m
*
2E
2
k
(II.3.12)
M ti cc im Dirac E = kv F , nn khi lng hiu dng b trit tiu ti cc

im ny.
Kt qu tng t cng thu c khi kho st cc ht Dirac, c nng lng tng
i tnh E = p2c2 mo2c4 . Khi thay ng lng ca ht p =
k v c = vF vo phng
trnh (II.3.12), khi lng ngh ca ht Dirac bng 0. Hin tng khi lng hiu dng ca
ht ti trit tiu cho thy trong vng nng lng thp (E < 1 eV), electron v l trng c
th xem nh khng tng tc vi mng tinh th.

HVTH: Hunh Trn M Ha
26
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
Hnh A.II.12- S ph thuc khi lng cyclotron ca in t v l trng vo nng

ht ti theo hm m . Kt qu ny gp phn khng nh s ph hp ca gi thuyt gii
thch kh nng dn in ca graphene khi xem ht ti trong vt liu ny c bn cht tng
t vi cc gi ht fermion Dirac.
Tnh cht ny c kim chng bng thc nghim (hnh A.II.12) thng qua th
nghim ca Geim [4]. Trong , cc electron v l trng trong graphene tun theo phng
trnh Dirac v c biu hin tng t nh cc fermion Dirac, c khi lng hiu dng t l
vi cn bc hai ca mt in t. H thc ny thu c t nh ngha ca khi lng
hiu dng theo Aschroft v Mermin:
m*
1 A(E)
2 E E EF
(II.3.14)
E2
k
vi A l tit din ng trn Fermi A(E) = k = 2 m* F
EF
vF
2

HVTH: Hunh Trn M Ha
27
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
k 2F
n , do
Mt khc gia mt in tch n v kF lin h vi nhau theo biu thc
m*
n . Trong khi , cc h cht rn thng thng, gi tr ny khng thay i

vF
khi mt in tch thay i v bng
gm
, vi g l bc suy bin.
2 2
Nh vy, kt qu thc nghim cho thy c s ph hp hon ton gia l thuyt v

thc nghim khi kho st s ph thuc ca khi lng hiu dng v mt in tch
chng t s tn ti ca cc ht fermion Dirac khng c khi lng trong mng graphene.
II.3.4. dn cc tiu
Do s c bit trong cu trc mng tinh th, graphene c xem l vt liu khng
c vng cm, hay khong cch gia vng dn v vng ho tr l bng 0. Loi ht ti trong
mng c xc nh bi v tr ca mc nng lng Fermi EF v c th c thay i theo
in th p vo l m hay dng, tc l c s ph thuc cht ch gia dn v in th
cung cp. iu ny c th hin trn hnh A.II.13. dn t gi tr cc tiu khi EF = 0
v nm chnh gia vng dn v vng ho tr. Khi in th thay i t 100 V n 100V,
mc Fermi dch chuyn t vng ho tr, n im chnh gia ng vi in th bng 0 v
sang vng dn, dn n s thay i mt ht ti in v dn cng nh loi ht ti
in. dn gim khi in th thay i t 100V n 0V, t cc tr v tng li khi in
th tng t 0 n +100V. Ti im Dirac (EF = 0) c th xem nh c s trung ho v mt
in tch. V mt l thuyt, s trung ho in tch ti v tr ny dn n dn b trit tiu
(gim v 0). Tuy nhin trn thc t, t cc tiu vi gi tr xc nh min exp
thc nghim v min theo
4e2
theo
h
4e2
da trn cc nghin cu l thuyt. Hin nay hin tng ny
h
vn cha c gii thch r rng v ang c tip tc nghin cu.

HVTH: Hunh Trn M Ha
28
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
Hnh A.II.13- dn cc tiu ca mng graphene. Mi lin gia dn ca mng

graphene v in th
II.3.5. Hiu ng Hall lng t trong graphene
Hiu ng Hall c in do Edwin H. Hall pht hin vo nm 1879, hiu ng ny xy
ra khi c dng in chy qua vt dn t trong t trng. Trong h ta Dercartes, ta xt
dng in chy qua vt dn dc theo trc Oy, vt dn c t trong t trng c vector
cm ng t B hng theo trc Ox. Khi di tc dng ca lc Lorentz, trn hai b mt
vt dn vung gc vi trc Oz s xut hin cc in tch tri du, v khi t n trng thi
n nh th gi tr hiu in th gia hai mt ny c gi l hiu in th Hall, c tnh
theo cng thc:
U H E.L Z
vB
LZ
c
(II.3.15)
vi: v l vn tc ht ti, B l cm ng t ca t trng, v Lz l khong cch gia hai

mt ang xt.
T c th xc nh c in tr v in tr sut (hoc dn in) theo cc h
thc sau:
RH =
UH
B
v H =
I
nqc
(II.3.16)
vi: I l cng dng in qua vt dn , c l vn tc nh sng, n v q ln lt

l nng v in tch ca ht ti.

HVTH: Hunh Trn M Ha
29
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
Nh vy, khi o c hiu in th Hall ta c th xc nh mt ht ti v loi ht

ti (in tch m hay dng). ng thi in tr sut Hall t l vi cng ca cm ng
t B v t l nghch vi nng ht ti n.
Hiu ng Hall lng t c pht hin ln u tin bi K. Von Klitzing, G.Dorda,
v M. Pepper vo thp nin 80 [41] v c xem l mt trong nhng pht minh quan trng
nht trong vt l cht rn do n th hin cc tnh cht c bn ca vt liu m khng b nh
hng bi cc yu t khc (nh s pha tp, cc hiu ng to bi cc lp tip gip ),
phn nh bn cht ca h kh in t hai chiu di tc dng ca in t trng mnh.
Trong ng cong th hin s ph thuc ca in tr Hall vo t trng B hoc mt
ht ti n c dng bc thang.
Xt trn quan im ca c lng t, t vic gii phng trnh Schrodinger m t
chuyn ng ca cc electron:
2
1
eB
H
y p 2y p z2 s z B E
p x
2m
c
(II.3.17)
Ta thu c biu thc tr ring nng lng ca in t:
1
p2
E N N c s z B z
2
2m
vi c
(II.3.18)
eB
, sz l i lng c trng cho spin in t theo trc z.
mc
l mmen t ca electron.
Trong trng hp cc h kh in t hai chiu (hnh A.II.14), thnh phn cui c
cha pz trong phng trnh trn b trit tiu, ng thi di tc dng ca in trng
mnh, spin in t b phn cc hon ton v h s lin quan n spin electron c th xem
l hng s. Nh vy, nng lng ca in t c xc nh bi phng trnh (II.3.18) nhn
cc gi tr gin on xc nh, v cc mc nng lng ny c gi l cc mc Landau
[41], ng thi c s xut hin cc mc suy bin vi mt c xc nh bi biu thc :

HVTH: Hunh Trn M Ha
30
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
nB =
eB
hc
(II.3.19)
Bn cnh , do s xut hin ca cc sai hng trong cu trc vt liu dn n s

xut hin ca cc trng thi nh x gia cc mc Landau. Khi t trng suy gim,
khong cch gia cc mc Landau ( C ) v mt cc mc suy bin nB cng gim theo.
Khi mc Landau th N khng cung cp trng thi cc electron chim gi v
lng in t d ny c xu hng chim gi cc trng thi ca mc N + 1, tng ng vi
s thay i lin tc ca in tr Hall theo t trng. Tuy nhin, do s c mt ca cc trng
thi nh x gia cc mc Landau, cc electron d s b gi ti cc mc nh x ny v
khng tham gia vo qu trnh dn in. iu c ngha l in tr Hall c gi tr khng
i trong khi t trng thay i mt lng xc nh v gi tr RH ca n lc ny ng vi
mc th N b chim y cho n khi t trng B gim n gi tr thch hp v mc Fermi
EF dch chuyn n gn mc Landau k tip cc in t c th chim gi c mc
ny. Kt qu l in tr suy gim lin tc v dng li gi gi tr khng i khi mt mc
th N no b lp y.
Hnh A.II.14- Hnh minh ha s m rng mt trng thi ca kh lng t 2 chiu

di tc dng ca t trng mnh
Cc php o kho st in tr sut hoc dn ca cc h hai chiu trong iu kin t
trng mnh v nhit thp cho thy in tr sut Hall khng cn t l nghch vi nng
ht ti hoc t l vi cm ng t B, m thay vo ng cong in tr sut c s xut

HVTH: Hunh Trn M Ha
31
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
hin cc bc thang (Hnh A.II.15). Khi , in tr Hall RH = xy b lng t ho v nhn

cc gi tr gin on :
RH
h
vi N = 1, 2, 3
Ne 2
(II.3.20)
Hnh A.II.15- S ph thuc ca in tr sut vo t trng trong hiu ng Hall lng t

Bn cnh in tr, ta cng c th kho st s thay i dn ca cc h lng t hai
chiu v cng thu c kt qu tng t, vi dn in thay i theo h thc:
xy N
ge2
h
(II.3.21)
trong N = 1, 2, 3 l mc Landau th N v g l h s c trng cho nh hng cc

trng thi suy bin do tng tc spin.
Th nghim kho st Hiu ng Hall lng t trn graphene c thc hin ln u tin
vo nm 2005 [17], [25], [41] cho thy c s khc bit ng k so vi hiu ng Hall lng
t quan st c trn cc h hai chiu ca cc vt liu khc. Trong , dn Hall c
xc nh theo h thc :
1 4e2
xy N
2 h
(II.3.22)
vi N l cc mc Landau (trong mng graphene gi tr g = 4). iu ny c ngha l s suy

gim ca dn Hall c dng bc thang vi cc bc bng nhau, v thay i nhn cc
HVTH: Hunh Trn M Ha
32
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
4e 2
gi tr bn nguyn ca
thay v cc gi tr nguyn, v hiu ng ny khng thay i khi
h
ht ti c bn thay chuyn t electron sang l trng (hnh A.II.16). Nguyn nhn ca hin
tng ny c gii thch l do s khc bit v nng lng ca ht ti khi chim gi cc
mc Landau. Biu thc ca s ph thuc nng lng E N vo cm ng t B v N khng c
dng nh h thc (II.3.18) c s dng cho cc vt liu khc, m thay vo c m t
bng cng thc c xy dng da trn c s xem ht ti trong graphene biu hin cc
thuc tnh ging fermion Dirac vi cc c tnh trnh by trong phn trn :
1 1
E = v F 2e B N
2 2
(II.3.23)
Trong , du dng xc nh ht ti c bn l in t hay l trng, vF l vn tc

Fermi c gi tr bng 106 m/s v N c trng cho cc mc Landau.
Hnh A.II.16- Hiu ng Hall lng t trong graphene. (Hnh gc trn bn tri : Hiu
ng Hall lng t thng thng)
T nhng th nghim cho thy c s khc bit ca hiu ng Hall lng t trong
graphene so vi hiu ng Hall lng t trong cc vt liu khc, mt ln na chng t
rng c s c bit trong cu trc vng nng lng ca graphene, s xut hin ca cc
im Dirac v cc ht ti in c bn cht ging vi cc fermion Dirac.

HVTH: Hunh Trn M Ha
33
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
III. Mt s ng dng
Mc d ch mi bt u pht trin t nm 2004, nhng vi nhng c tnh xut sc
nh nu trn, vt liu graphene tr thnh tm im cho nhng nghin cu khoa hc
trn th gii v c ng dng bc u vo trong cc thit b ca nhng lnh vc khc
nhau, sau y l mt s ng dng in hnh:
Nh vo cu trc in t khc thng nn graphene c kh nng dn in tt vi
mc truyn qua cao, v vt liu ny c s dng lm in cc trong sut thay th
cho ITO, mt b phn thit yu trong cc thit b nh: mn hnh cm ng, mn hnh tinh
th lng, t bo quang in, pin mt tri hu c Nm 2009, mng graphene thu c t
phng php kh graphite oxide nhit cao ( vi dy mng ~7nm) c s dng
trong vic ch to OLED bi mt nhm nghin cu ngi M v Trung Quc (hnh
A.III.1), nhng c tnh quang in ca sn phm thu c c th so snh vi cc OLED
ch to t ITO [21].
Hnh A.III.1- Cu to ca OLED c s dng graphene lm lp in cc trong sut

Ngoi nhng yu cu v tnh dn in v truyn qua cao, cc in cc oxide kim
loi trong mn hnh tinh th lng v cc thit b quang hc cn cn phi c bn ha hc
cao, nhm hn ch s khuch tn ca oxi v cc ion kim loi vo trong cc lp vt liu
khc. Bi v s khuch tn ca oxi vo trong cc lp in mi c th gy ra hin tng oxi

HVTH: Hunh Trn M Ha
34
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
ha, iu ny s dn n vic nh thng in mi ch vi in th thp, hoc trong mn

hnh tinh th lng khi cc ion kim loi khuch tn vo trong cc lp hiu chnh s to nn
cc by in tch to nn in trng trn mn hnh (hnh A.III.2), iu ny s dn n hin
tng lu nh (hay con gi l hin tng bng ma) trn mn hnh. Cc vn ny s c
khc phc khi s dng graphene lm in cc v graphene c to thnh t cc nguyn t
carbon nn l vt liu c bn ha hc cao. c bit hn, graphene cn c bn c hc
v tnh do vt tri so vi ITO nn n cn c tip tc nghin cu ch to cc mn
hnh c kh nng un do [27].
Hnh A.III.2- Hnh minh ha ca thit b tinh th lng vi cc lp c bn. 1) thy

tinh; 2) graphene; 3) Cr/Au; 4) lp hiu chnh (polyvinyl alcohol); 5) lp tinh th lng;
6) lp hiu chnh; 7) ITO; 8) thy tinh.
Trong vic ch to sensor nhy kh th graphene c xem l loi vt liu tt hn
ht, bi v graphene l vt liu c cu trc phng 2 chiu nn n c din tch b mt rt ln,
(ln n 2630m2/g [10], [31]) kt hp vi kh nng dn in cao v nhiu thp.
Hnh A.III.3- Phn t nitrogen dioxide bm trn b mt ca mng graphene

HVTH: Hunh Trn M Ha
35
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
Khi cc phn t kh bm vo b mt graphene s lm thay i in tr cc b ti v

tr , v da trn c ch ny m cc phn t kh s c pht hin. Cc sensor nhy kh
c ch to vi kch thc micromet (hnh A.III.3), c nhy cao cho php pht hin
cc cht kh vi nng 10-6 [10].
Bn cnh nhng ng dng thc tin i hi lp graphene c cu trc cng hon ho
cng tt nh trn, th cng c nhng ng dng khng km phn quan trng khc nhng li
khng yu cu cao v cu trc ng u ca mng, in hnh nh: s dng graphene trong
vic ch to pin LIBs (thit b dng d tr nng lng cho cc thit b s dng lu
ng). Graphene oxide c tng hp t phng php ha hc (chi tit phn A - IV.3), s
c kh bng ha cht hydrazine, nhit phn nhit thp hoc chiu x bng chm
in t thch hp s to nn sn phm c gi l graphene paper. Qu trnh oxi ha v
kh to nn nhiu im khuyt v mt trt t trn b mt ca mng, ng thi lm cho
khong cch gia cc lp trong graphene paper ~ 0,4nm. Nhng khuyt tt ny cng vi s
gia tng khong cch gia cc lp ph hp cho vic by v g b nhng ion Li nhanh
chng trong qu trnh np v phng in ca pin. Thc nghim ch to c cc pin vi
in dung t 1013 1054 mA h/g, cao hn so vi cc pin truyn thng s dng graphite
lm in cc vi dung lng lu tr <372 mA h/g [8].
Ngoi ra, mng graphene cn c s dng ch to cc siu t in vi cc u
im so vi t in truyn thng l: in dung ln, thi gian sng di, t phi bo dng v
trng lng nh. Cc transistor kch thc nano, transistor hiu ng trng c ch to t
cht liu graphene cho thy cc electron c kh nng di chuyn m khng b tn x t in
cc ngun n in cc thu nhit phng. y l transistor c hai nh nghin cu
l Andre Geim v Kostya Novoselov thuc trng i hc Manchester ch to.

HVTH: Hunh Trn M Ha
36
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
IV. Cc phng php ch to graphene

C nhiu phng php khc nhau ch to mng graphene, cc nhm phng
php c tin hnh nhiu nht l: phng php tch lp vi c hc ca graphite
(micromechanical exfoliation of graphite), phng php epitaxy (epitaxial growth) v
phng php ch to graphene t dung dch.
IV.1. Phng php tch lp vi c hc
Phng php ny s dng cc lc c hc tc ng t bn ngoi tch vt liu
graphite dng khi ban u thnh cc lp graphene. Vi nng lng tng tc Van der
Waals gia cc lp khong 2eV/nm2, ln lc cn thit tch lp graphite l khong
300nN/m2 [5], y l lc kh yu v d dng t c bng cch c xt mt mu graphite
trn b mt ca SiO2 hoc Si, hoc dng bng keo dnh.
Nm 2004, Andre K. Geim v Kostya Novoselov ti i hc Manchester Anh tnh
c tm ra c mt cch to ra graphene, h dn nhng mnh vn graphite trn mt
ming bng keo, gp dnh n li, ri ko git ra, tch ming graphite lm i. H c lm
nh vy nhiu ln cho n khi ming graphite tr nn tht mng, sau dn ming bng
keo ln silicon xp v ma st n, khi c vi mnh graphite dnh trn ming silicon xp,
v nhng mnh c th c b dy l 1 nguyn t, chnh l graphene (hnh A.IV.1).
Trong nhng nm gn y, s pht trin ca cc knh hin vi u d qut SPM
(Scanning Prodes Microscope) vi phn gii cao cho php cc nh nghin cu c th
xc nh c n lp graphene, tin s Geim quan st c mt mnh graphite dy 1
nguyn t khi t n trn Si/SiO2 (b dy ca lp oxide l 300nm hoc 90nm)[5]. n
nay, khi quan st bng knh hin vi v qua mu sc nhn thy, cc nh nghin cu c th d
on c dy ca mnh graphite: mt mnh graphite dy hn 100 lp (mu vng), dy
40 n 30 lp (mu xanh dng), dy khong 10 lp (mu hng) hoc ch l 1 lp n
chnh l graphene (mu hng nht, gn nh khng thy c). Tin s Geim ni ng ngh

HVTH: Hunh Trn M Ha
37
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
rng cc nh nghin cu trc y sn xut ra c graphene nhng n gin l h

khng nhn thy c graphene m thi.
y l phng php n gin to ra nhng mu gaphene nh, ph hp cho
nhng nghin cu c bn, ngoi ra khm ph ny cn c ngha quan trng l n m ra
bc ngot mi cho nhng nghin cu thc nghim v graphene, l tin cho s thnh
cng ca nhng phng php khc trong vic ch to mng graphene, mt vt liu c
cho l b lng qun trong 40 nm qua.
Hnh A.IV.1- Phng php tch lp graphite bng bng dnh

u im: y l phng php t tn km, d thc hin v khng cn nhng thit b
c bit.
Khuyt im: Kt qu ca phng php khng nht nh m ch mang tch cht cu
may, mng to nn khng phng v y l phng php i hi tnh t m khng ph hp
cho vic ch to graphene vi s lng ln ng dng cho sn xut cng nghip. Ngoi
ra, khi s dng bng dnh hoc cc in cc tch lp graphite, lng tp cht nh c th
bm li trn b mt ca grphene, lm nh hng n linh ng ca cc ht ti in.
hn ch lng keo tha trong lp graphene, ngi ta thay th cc lp bng keo dnh ny
bng vic s dng lc tnh in ca cc in cc (cn gi l phng php gn kt dng
cc).

HVTH: Hunh Trn M Ha
38
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
IV.2. Phng php epitaxy

Epitaxy l phng php to mng n tinh th trn mt ca mt tinh th. C hai
c ch c nghin cu: th nht l c ch phn hy nhit ca mt s cacbua kim loi, th
hai l c ch mc mng n tinh th ca graphene trn kim loi hoc cacbua kim loi
bi s lng ng hi ha hc (Chemical Vapor Deposition) ca cc hydrocarbon.
C ch phn hy nhit thng c tin hnh vi silic cacbua (SiC) 13000C
trong mi trng chn khng cao hoc 16500C trong mi trng kh Argon, bi v s
thng hoa ca Si xy ra 11500C trong mi trng chn khng v 15000C trong mi
trng kh Argon. Khi c nng nhit n nhit cao cc nguyn t Si s thng hoa,
cc nguyn t cacbon cn li trn b mt s c sp xp v lin kt li trong qu trnh
graphite ha nhit cao, nu vic kim sot qu trnh thng hoa ca Si ph hp th s
hnh thnh nn mng graphene rt mng ph ton b b mt ca SiC (hnh A.IV.2).
Phng php ny to nn cc mng graphene n lp vi linh ng ca ht ti ln
n 2000cm2/Vs 27K, mt ht ti tng ng l ~1013cm-2 [5].
Si
Hnh A.IV.2 C ch to mng graphene bng phng php nung nhit SiC
C ch mc mng graphene trn cc kim loi (Ni, Cu,) v cacbua kim loi
c tm tt nh sau: u tin cc c nung n nhit cao (~10000C) trong mi
trng kh H2 v Ar loi b nhng oxide trn b mt, sau dng kh long ca
hydrocarbon c a vo, nhit cao cc hydrrocacbon s b phn hy v lng ng

HVTH: Hunh Trn M Ha
39
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
li trn b mt , cui cng nhit ca h thng c lm lnh nhanh cc nguyn t

carbon phn tch (segregation) trn b mt v hnh thnh mng graphene (hnh A.IV.3).
Khi s dng kim loi Ni v hydrocacbon l metan to ra c mng graphene vi
linh ng ca ht ti t n 4000cm2/Vs. Mt s kt qu khc cng cho thy mng
graphene ch to t phng php ny t c truyn qua l 80% vi in tr ca
mng 280/ [29].
Kh
Hydrocarbon
hydrocacbon
gas
Kim
loi
Metal
(Ni, Cu)
S ha tan
Carbon
ca
cacbon
dissolving
Lm lnhfast
cccooling
nhanh
Extremely
Lm
nhanh
Fastlnh
cooling
Slowlnh
cooling
Lm
chm
Hnh A.IV.3- C ch to mng graphene bng phng php CVD

u im: u im ni tri ca phng php ny l ch to c cc mng graphene
din tch ln (~1cm2), ng u mng cao hn so vi cc phng php khc. T cc
mng graphene cht lng tt ny c th pha tp thch hp to nn cc bn dn loi n,
loi p. Mng graphene to t vic nung nng silic cacbua c tin s Walter de Heer s
dng ch to cc computer chip.

HVTH: Hunh Trn M Ha
40
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
Khuyt im: Th thch ca phng php ny l kh nng kim sot hnh thi hc
v nng lng bm dnh iu kin nhit cao. Tn s plasma (plasma-enhanced CVD),
s nhit phn ca kh v s ng u ca mng l cc yu t rt kh kim sot. Bn cnh
, phng php ny cn c nhng thit b v cht lng cao, cho nn sn phm to
thnh s c gi thnh cao v ch c th p ng cho mt s ng dng tiu biu, khng thch
hp cho vic sn xut vi s lng ln phc v cho nhng ng dng cng nghip.
Ngoi ra qu trnh chuyn ca mng cng cn nhiu kh khn.
IV.3. Phng php ch to graphene t dung dch
Phng php ny c hai qui trnh ch to:
Qui trnh 1: Qui trnh ch to c oxi ha
y l qui trnh ch to mng graphene bng phng php ha hc thng qua vic
tng hp cht trung gian l graphite oxide. Qu trnh thc hin c chia lm hai phn:
Tng hp graphite oxide v chuyn ha graphite oxide thnh graphene.
Hnh A.IV.4- Hnh nh minh ha mng graphene oxide

Gii thiu v graphite oxide. Graphite oxide (GO) l vt liu c to ra t qu
trnh oxi ha graphite, hnh thnh nn cc nhm chc c cha oxi, trong c 4 nhm
chc ch yu l : Hydroxyl, epoxide nh trn b mt, v carboxyl, carbonyl nh mp
ca cc n lp (hnh A.IV.4), nhng GO vn gi nguyn dng cu trc lp ban u ca

HVTH: Hunh Trn M Ha
41
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
graphite [22], [31], [34]. V s hnh thnh ca cc nhm chc c cha oxi m mt phn
lin kt sp2 trong mng tinh th b suy thoi v tr thnh lin kt sp3, v chnh cc in
tch m ca cc nhm chc ny lm xut hin lc y tnh in lm cho GO d dng
phn tn vo trong cc dung mi phn cc, nht l trong dung mi nc to nn cc n
lp graphene oxide. Cng v l do ny m tnh dn in ca graphite gim dn theo qu
trnh oxi ha, thm ch graphene oxide l mt cht cch in, bi v khi ny phn ln
carbon trong graphite ban u b chuyn i t trng thi lai ha sp 2 thnh lai ha sp3,
lm gim ng k s lng lin kt cng nh cc in t t do trn b mt ca n. C
nhiu cch khc nhau m t cu trc ca GO, nhng n nay th cu trc chnh xc vn
cha c xc nh r rng.
Vi cu trc c trng nh trnh by, GO c ng dng trong nhiu lnh vc
khc nhau. Do s c mt ca cc nhm chc, graphene oxide c th c iu chnh thnh
phn ha hc thng qua cc phn ng vi cc nhm chc ny, sau s c kh to
nn sn phm l graphene c bin i ha hc (chemically modified graphene), cc
hp cht ny thng c s dng lu tr nng lng trong cc siu t in, cc pin lu
ng nh pin LIBs vi cht lng cao. c bit, trong cc dung mi phn cc GO c
phn tn thnh cc n lp graphene oxide, nu sau chng c kh b cc nhm chc
c cha oxi th kh nng thu c graphene l rt kh quan. Khi vi b dy mc
nguyn t, graphene s tr thnh vt liu c truyn qua cao i vi cc nh sng nhn
thy, v kt hp vi dn in cao th n hon ton c kh nng c s dng nh cc
in cc trong sut, ng dng lm ca s quang hc trong cc thit b in t.
Vic oxi ha graphite c tin hnh bng cch s dng cc cht oxi ha v cc axit
mnh. Cng vic ny c bit n t nhng nm 1958 vi cc phng php ph bin
nh: Hummers, Brodie v Staudenmaier, trong phng php Hummmers c p dng
ph bin hn c [28]. Nhng qu trnh ny c nhng khuyt im l: mt nhiu thi gian
v hiu sut oxi ha cha cao. ci tin, cc nh nghin cu c nhng iu chnh

HVTH: Hunh Trn M Ha
42
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
trong qu trnh thc hin, nhng vn da trn qu trnh oxi ha c bn ca Hummers, v

cc phng php ny c gi l Hummers bin tnh (Modified Hummers).
Ngy nay, qu trnh tng hp graphite oxit bng phng php Modified Hummers
c tin hnh t vic lm yu lc lin kt Van der Waals gia cc lp graphite. Bng cch
lng cc thnh phn d bay hi vo trong khong khng gian gia cc lp ny, sau cc
cht chen vo ny s c phn hy bi cc phn ng ha hc hoc vic tng nhit ln cao
t ngt, to ra lng kh ln gy ra p sut cao lm cho lc lin kt gia cc lp tr nn
lng lo, qu trnh ny c gi l s tch lp graphite. Sau sn phm ny s c oxi
ha bi mt trong cc cch c in, v thy rng hiu sut tng ng k. Nh vy, chnh
vic lm yu lc lin kt Van der Waals gia cc lp graphite to iu kin thun li
cho cc phn ng oxi ha d dng din ra trn b mt ca cc lp. Ty thuc vo cc cht
oxi ha s dng v phng php tin hnh m loi nhm chc c cha oxi v s lng
ca mi loi nhm to thnh s khc nhau, do m GO khng c cng thc ha hc c
th.
Hnh A.IV.5- (1) Oxi ha graphite thnh graphite oxide, (2) Phn tn graphite oxide
trong dung mi phn cc
Vic chuyn ha graphite oxide thnh graphene c tin hnh nh sau: GO s
c ha tan vo cc dung mi thch hp to thnh dung dch (hnh A.IV.5), sau mng
mng GO c to thnh trn cc khc nhau (ty vo mc ch s dng) bng phng
php ph quay (spin coating) hoc phun nhit phn (spray pyrolysis). Cui cng, cc mng
mng ny s c kh ct b cc nhm chc c cha oxi trn b mt, khi phc li lin

HVTH: Hunh Trn M Ha
43
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
kt sp2 ca cu trc graphene. Cc phng php thng c s dng kh l: kh ha

hc v x l nhit. Trong phng php ha hc, ta s dng cc cht phn ng nh:
Hydrazine, dimethylhydrazine, sodium borohydride, cc cht ny s phn ng vi cc
nhm chc trn b mt ca lp graphene oxide loi b oxi. Cn trong phng php x
l nhit, cc mng GO sau khi ph trn s c nhit (ln n 11000C) trong mi
trng chn khng cao hoc trong mi trng kh Ar, H2, N2 vi nhit c th thp
hn (~8000C). Ngoi ra, cn c cc phng php kh khc nh: chiu x tia t ngoi, nhit
phn nhit thp.
u im ca c ch to mng graphene bng phng php ha hc thng qua qu
trnh tng hp cht trung gian GO l: qu trnh ny khng phc tp, mt t thi gian, khng
tn km v c th kim sot linh hot th vn (suspension) graphene oxide trong dung dch
to nn cc mng graphene mng vi din tch rng. Ngoi ra, graphite oxide vi s c
mt ca cc nhm chc c cha oxi d phn ng hoc gn kt vi cc cht khc, to nn
nhng sn phm c c tnh in ha khc bit so vi graphite v c dng thay th
cho graphite trong cc ng dng vi mc ch khc nhau, v d: hp cht graphene-Cu2O
c s dng lm vt liu anode trong pin Lithium ion [6] .
Bn cnh phng php ny vn cn tn ti nhng khuyt im nh: cc mng
graphene oxit phn tn trong dung dch d b v vn, kt qu ca qu trnh kh graphene
oxit thnh graphene c bo co cho n nay l cha hon ton, vn cn li mt lng
cc nhm chc cha oxi trong mng, v trong qu trnh kh cng gy ra mt s sai hng.
iu ny s lm gim dn ca mng graphene trong vic ch to mng trong sut dn
in v cn phi c nhng bin php khc phc. Mc d kt qu thu c t cch lm
ny cha cao, cc mng graphene to thnh ch t c truyn qua l 80% vi in tr
b mt l 1k/ [29]. Tuy nhin, mt hng gii quyt c a ra ci thin dn
in ca n m khng lm nh hng nhiu n truyn qua ca mng l chn thm vo
mng graphene thun cc vt liu c kh nng dn in cao nh: silic v cacbon nanotube.
Kt qu thu c tht ng k, in tr ca mng thu c l 240/ vi truyn qua l

HVTH: Hunh Trn M Ha
44
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
86% [37], nhng mng ny bc u c ng dng ch to pin mt tri [39].

Nhng kt qu ny cho thy y l 1 phng php rt kh quan, c th to ra c 1 loi
vt liu ha hn trong cc ng dng quan trng ca mng trong sut dn in.
Qui trnh 2: Qui trnh tch lp graphite khng oxi ha
Qui trnh ny da trn qu trnh sonvat ha, ngha l to ra s n nh enthalpy ca
nhng mng graphene phn tn bi s hp th dung mi [5]. Cc tc gi tin hnh cch ny
phn tn v x l siu m vt liu graphite tch lp trong cc dung mi hu c nh:
N-methyl-pyrrolidone
(NMP),
dimethylformamide
(DMF),
dimethylacetamide
(DMA)[34]. Qui trnh ny din ra tng t nh qui trnh 1, ch khc ch l khng c

qu trnh oxi ha. Kt qu thu c cng rt kh quan, mt s nhm tch ra c mt
n lp trong dung mi DMF hoc benzene (hnh A.IV.6). Cch ny c u im l c
tin hnh n gin, tuy nhin vn cn mt s hn ch nh: tnh c hi ca cc dung mi
s dng nh hng nhiu n mi trng, gi thnh ca dung mi cao, v vic loi b
nhng lng dung mi d tha trong sn phm l khng hon ton.
Hnh A.IV.6- nh minh ha qui trnh tch lp graphite trong dung dch,
khng oxi ha.

HVTH: Hunh Trn M Ha
45
Lun vn Thc S 2010
----------------------------------------------------------------------------------------------------------------------
Nhn xt: T vic phn tch cc u v khuyt im ca mt s phng php ang

c s dng hin nay ch to mng graphene cho thy: mc d phng php epitaxy
v CVD tng hp nn cc lp graphene cht lng cao nhng khng c tin hnh ph
bin v hiu sut thp, nhit ca qu trnh kh cao (>10000C), mi trng s dng l
mi trng ca kh him, v c bit l cn phi s dng cc thit b hin i vi gi thnh
cao. Trong khi phng php ha hc ch to mng graphene thng qua s to thnh
cht trung gian l graphite oxide c cho l kh thi nht khi cn i gia cc yu t c
lin quan, v ang c quan tm tin hnh rng ri trn th gii. Phng php ny c th
to ra lng graphene ln, cht lng tng i cao v c bit l gi thnh sn xut thp
d dng chp nhn c cho phn ln cc ng dng hin nay. Theo mt s tnh ton, vi
lng graphite t nhin hin nay l ~800.000.000 tn chng ta c th to ra mt lng
graphene khng l. y cng l phng php m ti nghin cu ca ti hng n.

HVTH: Hunh Trn M Ha

Luan Van Thac Si Graphene

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Luan Van Thac Si Graphene

Uploaded by

Copyright:

Available Formats

3

Lun vn Thc S 2010

L THUYT TNG QUAN

Graphene l mt vt liu mi, ch bt u c nghin cu trong nhng nm gn

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

Hnh A.I.1- Cu trc tinh th ca kim cng v graphite (3D)

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

c s dng nh l v bc v phn iu tit trong cc l phn ng ht nhn, v graphite c

Hnh A.I.2- Cu trc tinh th ca ng nano carbon (1D) v buckyball (0D)

ng nano carbon (Carbon Nanotube CNT) l mt dng th hnh ca carbon vi

n vch v a vch. Mt iu th v l, cc ng nano carbon n vch c nhiu thuc tnh

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

II. C s l thuyt ca graphene

Hnh A.II.1- Cu hnh in t ca carbon trng thi c bn v trng thi

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

Do s khc bit gia cc mc nng lng ca cc vn o 2s v 2p (bao gm p x, py

Mt in t ca vn o lai c dng nh hnh A.II.2 v c ko di theo

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

Lin kt hnh thnh

Lin kt hnh thnh

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

Trng thi lai ho sp2

ba nhnh s-p nm trong cng mt mt phng v mi nhnh to vi nhnh k cn mt gc

Hnh A.II.4- Cc vn o lai ha sp2 trong nguyn t carbon

Tng t vi lai ho sp, dng ny, mt carbon lai ho sp2 cn lin kt vi mt

Lin kt hnh thnh

Hnh A.II.6- Cc vn o lai ha sp3 trong nguyn t carbon

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

Hnh A.II.7- Cc lin kt ca mi nguyn t carbon trong mng graphene

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

Vng Brillouin th nht

Hnh A.II.8- Cu trc mng graphene, trong cc nguyn t carbon c sp xp u

nh thng qua cc vector nguyn t a1 v a2 nh hnh A.II.8 [18], trong a1 =

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

nguyn t nh vy, mi nguyn t trong mng thc ca graphene s c xem nh to

3 a2/2 = 0,051 nm2 v mt nguyn t tng ng l nC

=2/AC = 39 nm-2 = 39.1015 cm-2. Mt khc, trong mng graphene, cc vn o pz khng

th nht c xc nh thng qua cc vector K

ny c gi l cc im Dirac, ng vai tr quan trng trong qu trnh truyn in t

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

(k, r) CAA (k, r) CBB (k, r)

Trong N l tng s n v trong mng graphene, R l vector nh v nguyn

HAB l cc Hamiltonian tng tc gia cc nguyn t carbon trong ni mng A hoc B v

Trong cc mng ch gm cc nguyn t A hoc B, khi ch xt tng tc gia cc

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

Hamiltonian tng tc gia cc nguyn t A v B ln cn (xc nh thng qua cc vector

R1 , R 2 v R 3 ), ta c : HAB = t(eikR1 eikR 2 eikR3 ) = tf(k). Trong h to Decartes,

(t : l nng lng cn thit electron dch chuyn gia cc nguyn t ln cn)

biu thc tn sc nng lng theo vector sng k :

Cc gi tr E+ v E th hin nng lng cc trng thi lin kt (trng thi c

Hnh A.II.9 m t h thc tn sc nng lng ca mng graphene trong vng

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

Theo cc phng c tnh i xng cao, E ln lt nhn cc gi tr 3t, t v 0,

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

Tng t cc mc v *, khi cc nguyn t carbon lin kt vi nhau s t hp

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

Vi g l bc suy bin khi xt n tng tc spin (g = 4 trong mng graphene). T h thc

Kt qu ny hon ton ngc li vi cc mng cht rn hai chiu khc, c h thc

---------------------------------------------------------------------------------------------------------------------GVHD: TS Trn Quang Trung

II.3.3. Khi lng cyclotron

l ma trn Pauli trong mng 2 chiu

M ti cc im Dirac E = kv F , nn khi lng hiu dng b trit tiu ti cc