REPORTS

interesting circuit capabilities. The thin polymer sistent with circuit simulation (fig. S7). A re- 10. P. Garrou, Semicond. Int. 28, SP10 (February, 2005).
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16. J. Kong, H. T. Soh, A. M. Cassell, C. F. Quate, H. Dai,
n-channel metal oxide semiconductor inverter in Fig. 3, could be useful for advanced systems Nature 395, 878 (1998).
(logic gate) in which the drive (L = 4 mm, W = such as curved focal plane arrays for wide-angle 17. K. S. Novoselov et al., Science 306, 666 (2004).
200 mm) and load (L = 4 mm, W = 30 mm) Si infrared night vision imagers. 18. Y. Huang, X. Duan, C. M. Lieber, Small 1, 142 (2005).
MOSFETs are on different levels. With a sup- Printed semiconductor nanomaterials provide 19. M. A. Meitl et al., Nat. Mater. 5, 33 (2006).
20. E. Menard, K. J. Lee, D. Y. Khang, R. G. Nuzzo, J. A. Rogers,
ply voltage of 5 V, this double-layer inverter new approaches to 3D heterogeneously integrated Appl. Phys. Lett. 84, 5398 (2004).
exhibits well-defined transfer characteristics systems that could be important in various fields 21. Y. Sun, S. Kim, I. Adesida, J. A. Rogers, Appl. Phys. Lett.
with gains of ~2, comparable to the perform- of application, including not only those suggested 87, 083501 (2005).
ance of conventional planar inverters that use by the systems reported here but also others such 22. S.-H. Hur, D.-Y. Khang, C. Kocabas, J. A. Rogers,
Appl. Phys. Lett. 85, 5730 (2004).
similar transistors. Figure 4B shows an inverter as microfluidic devices with integrated electron-
23. Materials and methods are available as supporting
with a complementary design (CMOS) with the ics, chemical and biological sensor systems that material on Science Online.

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use of integrated n-channel Si MOSFETs and incorporate unusual materials with conventional 24. S. Linder, H. Baltes, F. Gnaedinger, E. Doering, in
p-channel SWNT TFTs, designed to equalize silicon-based electronics, and photonic and Proceedings of the 7th IEEE International Workshop on
the current-driving capability in both pull-up optoelectronic systems that combine light emit- Micro Electro Mechanical Systems, Oiso, Japan, 25 to 28
January 1994 (IEEE, Piscataway, NJ, 1994), pp. 349–354.
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pear in Fig. 4B. The curve shapes and gains ibility of this approach with thin, lightweight 27. The research was supported by the U.S. Department of
Energy, Division of Materials Sciences under award no.
(as high as ~7) are qualitatively consistent plastic substrates may create additional oppor- DEFG02-91ER45439, through the Frederick Seitz Materials
with numerical circuit simulations (fig. S6). tunities for devices that have unusual form Research Laboratory (FS-MRL). We thank T. Banks and
As a third example, we built GaAs metal- factors or mechanical flexibility as key features. K. Colravy for help with cleanroom and other facilities at the
semiconductor-metal (MSM) infrared detectors Frederick Seitz Materials Research Laboratory and H. C. Ko,
Q. Cao, P. Ferreira, J. Dong, and E. Menard for help with
(26), integrated with Si MOSFETs on flexible PI printing and distortion measurements using facilities and
substrates, to demonstrate a capability for fab- References and Notes
1. K. Banerjee, S. J. Souri, P. Kapur, K. C. Saraswat, manufacturing approaches developed at the Center for
ricating unit cells that could be used in active Proc. IEEE 89, 602 (2001). Nanoscale Chemical Electrical Mechanical Manufacturing
infrared imagers. In this case, printed nano- 2. S. F. Al-Sarawi, D. Abbott, P. D. Franzon, IEEE Trans. Systems at the University of Illinois (funded by the NSF under
grant DMI-0328162). All imaging and surface analysis was
ribbons of GaAs (L = 400 mm, W = 100 mm, and Components Packaging Manufacturing Technol. Part B
21, 2 (1998). performed at the FS-MRL Center for Microanalysis of
thickness = 270 nm) transferred onto a substrate Materials at the University of Illinois at Urbana-Champaign,
3. A. S. Brown et al., Mater. Sci. Eng. B 87, 317 (2001).
with a printed array of Si nanoribbon MOSFETs 4. Y.-C. Tseng et al., Nano Lett. 4, 123 (2004). supported by award no. DEFG02-91ER45439.
form the basis of the MSMs. Electrodes (Ti/Au) 5. C. Joachim, J. K. Gimzewski, A. Aviram, Nature 408, 541
Supporting Online Material
deposited on the ends of these GaAs nanoribbons (2000).
www.sciencemag.org/cgi/content/full/314/5806/1754/DC1
form back-to-back Schottky diodes with sepa- 6. G. Roelkens et al., Opt. Express 13, 10102 (2005).
Materials and Methods
7. D. B. Strukov, K. K. Likharev, Nanotechnology 16, 888 (2005).
rations of 10 mm. The resulting detector cells 8. Q. Y. Tong, U. Gosele, Semiconductor Wafer Bonding: Figs. S1 to S15
exhibit current enhancement as the intensity of Science and Technology (John Wiley, New York, 1999). 12 July 2006; accepted 31 October 2006
infrared illumination increases (Fig. 4C), con- 9. M. A. Schmidt, Proc. IEEE 86, 1575 (1998). 10.1126/science.1132394

Hall effect can in principle exist in band in-

Quantum Spin Hall Effect and sulators, where the spin current can flow without
dissipation. Motivated by this suggestion, re-

Topological Phase Transition in searchers have proposed the quantum spin Hall
(QSH) effect for graphene (7) as well as for
semiconductors (8, 9), where the spin current is
HgTe Quantum Wells carried entirely by the helical edge states in two-
dimensional samples.
B. Andrei Bernevig,1,2 Taylor L. Hughes,1 Shou-Cheng Zhang1* Time-reversal symmetry plays an important
role in the dynamics of the helical edge states
We show that the quantum spin Hall (QSH) effect, a state of matter with topological properties (10–12). When there is an even number of pairs
distinct from those of conventional insulators, can be realized in mercury telluride–cadmium of helical states at each edge, impurity scattering
telluride semiconductor quantum wells. When the thickness of the quantum well is varied, the or many-body interactions can open a gap at the
electronic state changes from a normal to an “inverted” type at a critical thickness dc. We show that edge and render the system topologically trivial.
this transition is a topological quantum phase transition between a conventional insulating phase However, when there is an odd number of pairs
and a phase exhibiting the QSH effect with a single pair of helical edge states. We also discuss of helical states at each edge, these effects can-
methods for experimental detection of the QSH effect. not open a gap unless time-reversal symmetry is

he spin Hall effect (1–5) has recently at- tronics. In particular, the intrinsic spin Hall effect

T tracted great attention in condensed mat-

ter physics, not only for its fundamental
scientific importance but also because of its
promises the possibility of designing the intrinsic
electronic properties of materials so that the effect
can be maximized. On the basis of this line of
1
Department of Physics, Stanford University, Stanford, CA
94305, USA. 2Kavli Institute for Theoretical Physics, University
of California, Santa Barbara, CA 93106, USA.
*To whom correspondence should be addressed. E-mail:
potential application in semiconductor spin- reasoning, it was shown (6) that the intrinsic spin [email protected]

www.sciencemag.org SCIENCE VOL 314 15 DECEMBER 2006 1757

 REPORTS
spontaneously broken at the edge. The stability with the following six basic atomic states per where si are the Pauli matrices. The form of
of the helical edge states has been confirmed in unit cell combined into a six-component spinor: H*(−k) in the lower block is determined from
extensive numerical calculations (13, 14). The time-reversal symmetry, and H*(−k) is uni-



time-reversal property leads to the Z2 classifica- Y ¼ jΓ6 , 1 2 〉, jΓ6 , −1 2 〉, jΓ8 , 3=2 〉, tarily equivalent to H*(k) for this system (22).
tion (10) of the QSH state.

 If inversion symmetry and axial symmetry
States of matter can be classified according jΓ8 , 1 2 〉, jΓ8 , −1 2 〉, jΓ8 , −3=2 〉 ð1Þ around the growth axis are not broken, then
to their topological properties. For example, the interblock matrix elements vanish, as
the integer quantum Hall effect is characterized In quantum wells grown in the [001] direc- presented.
by a topological integer n (15), which deter- tion, the cubic or spherical symmetry is broken We see that, to the lowest order in k, the
mines the quantized value of the Hall con- down to the axial rotation symmetry in the plane. Hamiltonian matrix decomposes into 2 × 2
ductance and the number of chiral edge states. These six bands combine to form the spin-up blocks. From the symmetry arguments given
It is invariant under smooth distortions of the and spin-down (±) states of three quantum well above, we deduce that d3(k) is an even function
Hamiltonian, as long as the energy gap does subbands: E1, H1, and L1 (21). The L1 subband of k, whereas d1(k) and d2(k) are odd functions
not collapse. Similarly, the number of helical is separated from the other two (21), and we of k. Therefore, we can generally expand them
edge states, defined modulo 2, of the QSH state neglect it, leaving an effective four-band model. in the following form:
is also invariant under topologically smooth At the Γ point with in-plane momentum k|| =

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distortions of the Hamiltonian. Therefore, the 0, mJ is still a good quantum number. At this
d1 þ id 2 ¼ Aðk x þ ik y Þ ≡ Ak þ
QSH state is a topologically distinct new state point the |E1, mJ〉 quantum well subband state
of matter, in the same sense as the charge is formed from the linear combination of the
quantum Hall effect. |Γ6, mJ = ±1=2 〉 and |Γ8, mJ = ±1=2 〉 states, while
Unfortunately, the initial proposal of the the |H1, mJ〉 quantum well subband state is d3 ¼ M − Bðk 2x þ k 2y Þ, eðkÞ ¼ C − Dðk 2x þ k 2y Þ
QSH in graphene (7) was later shown to be formed from the |Γ8, mJ = ± 3=2 〉 states. Away ð3Þ
unrealistic (16, 17), as the gap opened by the from the Γ point, the E1 and H1 states can mix.
spin-orbit interaction turns out to be extremely Because the |Γ6, mJ = ±1=2 〉 state has even par- where A, B, C, and D are expansion parameters
small, on the order of 10−3 meV. There are also ity, whereas the |Γ8, mJ = ± 3=2 〉 state has odd that depend on the heterostructure. The
no immediate experimental systems available parity under two-dimensional spatial reflection, Hamiltonian in the 2 × 2 subspace therefore
for the proposals in (8, 18). Here, we present the coupling matrix element between these two takes the form of the (2 + 1)-dimensional Dirac
theoretical investigations of the type III semi- states must be an odd function of the in-plane Hamiltonian, plus an e(k) term that drops out
conductor quantum wells, and we show that the momentum k. From these symmetry consid- in the quantum Hall response. The most im-
QSH state should be realized in the “inverted” erations, we deduce the general form of the ef- portant quantity is the mass or gap parameter
regime where the well thickness d is greater fective Hamiltonian for the E1 and H1 states, M, which is the energy difference between the
than a certain critical thickness dc. On the basis expressed in the basis of |E1, mJ = 1=2 〉, |H1, E1 and H1 levels at the Γ point. The overall
of general symmetry considerations and the mJ = 3=2 〉 and |E1, mJ = – 1=2 〉, |H1, mJ = – 3=2 〉: constant C sets the zero of energy to be the
standard band perturbation theory for semi- top of the valence band of bulk HgTe. In a
conductors, also called k · p theory (19), we   quantum well geometry, the band inversion in
HðkÞ 0
show that the electronic states near the Γ point Heff ðk x , k y Þ ¼ , HgTe necessarily leads to a level crossing at
0 H*ð−kÞ
are described by the relativistic Dirac equation in some critical thickness dc of the HgTe layer.
2 + 1 dimensions. At the quantum phase HðkÞ ¼ eðkÞ þ d i ðkÞsi ð2Þ For thickness d < dc (i.e., for a thin HgTe
transition at d = dc, the mass term in the Dirac
equation changes sign, leading to two distinct U
(1)-spin and Z2 topological numbers on either Fig. 1. (A) Bulk energy
bands of HgTe and CdTe
side of the transition. Generally, knowledge of
near the G point. (B)
electronic states near one point of the Brillouin
The CdTe-HgTe-CdTe
zone is insufficient to determine the topology of quantum well in the
the entire system; however, it does allow robust normal regime E1 > H1
and reliable predictions on the change of with d < dc and in the
topological quantum numbers. The fortunate inverted regime H1 >
presence of a gap-closing transition in the HgTe- E1 with d > dc. In this
CdTe quantum wells therefore makes our theoret- and other figures, G8/H1
ical prediction of the QSH state conclusive. symmetry is indicated in
The potential importance of inverted band- red and G6/E1 symmetry
gap semiconductors such as HgTe for the spin is indicated in blue.
Hall effect was pointed out in (6, 9). The central
feature of the type III quantum wells is band
inversion: The barrier material (e.g., CdTe) has a
normal band progression, with the s-type Γ6
band lying above the p-type Γ8 band, and the
well material (HgTe) having an inverted band
progression whereby the Γ6 band lies below the
Γ8 band. In both of these materials, the gap is
smallest near the Γ point in the Brillouin zone
(Fig. 1). In our discussion we neglect the bulk
split-off Γ7 band, as it has negligible effects on
the band structure (20, 21). Therefore, we re-
strict ourselves to a six-band model, and we start

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 REPORTS
layer), the quantum well is in the “normal” in their spin quantum number—are far away in Figure 2A shows the energies of both the E1
regime, where the CdTe is predominant and energy from any other bands (21), hence and H1 bands at k|| = 0 as a function of quantum
hence the band energies at the Γ point satisfy making an effective Hamiltonian description well thickness d obtained from our analytical
E(Γ6) > E(Γ8). For d > dc, the HgTe layer is possible. Indeed, the form of the effective Dirac solutions. At d = dc ~ 64 Å, these bands cross.
thick and the well is in the inverted regime, Hamiltonian and the sign change of M at d = dc Our analytic results are in excellent qualitative
where HgTe dominates and E(Γ6) < E(Γ8). As for the HgTe-CdTe quantum wells deduced and quantitative agreement with previous nu-
we vary the thickness of the well, the E1 and above from general arguments is already merical calculations for the band structure of
H1 bands must therefore cross at some dc, and completely sufficient to conclude the existence Hg1−xCdxTe-HgTe-Hg1−xCdxTe quantum wells
M changes sign between the two sides of the of the QSH state in this system. For the sake of (20, 21). We also observe that for quantum
transition (Fig. 2, A and B). Detailed cal- completeness, we also provide the microscopic wells of thickness 40 Å < d < 70 Å, close to
culations show that, close to transition point, derivation directly from the Kane model using dc, the E1± and H1± bands are separated from
the E1 and H1 bands—both doubly degenerate realistic material parameters (22). all other bands by more than 30 meV (21).
Let us now define an ordered set of four
six-component basis vectors y1, ..., 4 = (|E1, +〉,
|H1, +〉, |E1, −〉, |H1, −〉) and obtain the
Hamiltonian at nonzero in-plane momentum

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in perturbation theory. We can write the
effective 4 × 4 Hamiltonian for the E1±, H1±
bands as
Z∞
ij ðk x ,
H eff kyÞ ¼ dz〈yj jHðk x , k y , −i∂z Þjyi 〉
−∞
ð4Þ

where H(kx, ky, −i∂z) is the six-band Kane model

(19). The form of the effective Hamiltonian is
severely constrained by symmetry with respect
to z. Each band has a definite z symmetry or
antisymmetry, and vanishing matrix elements
between them can be easily identified. For
example,
Z∞
1

H eff
23 ¼ pffiffiffi Pkþ dz〈Γ6 , þ1 2 ðzÞjΓ8 , − 1=2 ðzÞ〉
6
−∞
ð5Þ

where P is the Kane matrix element (19),

vanishes because |Γ6, +1=2 〉(z) is even in z, where-
as |Γ8, − 1=2 〉(z) is odd. The procedure yields
exactly the form of the effective Hamiltonian
(Eq. 2), as we anticipated from the general
symmetry arguments, with the coupling func-
tions taking exactly the form of Eq. 3. The dis-
persion relations (22) have been checked to be in
agreement with prior numerical results (20, 21).
We note that for k ∈ [0, 0.01 Å−1] the dispersion
relation is dominated by the Dirac linear terms.
The numerical values for the coefficients depend
on the thickness, and values at d = 58 Å and d =
Fig. 2. (A) Energy of E1 (blue) and H1 (red) bands at k|| = 0 versus quantum well thickness d. (B) 70 Å are given in (22).
Energy dispersion relations E(kx,ky) of the E1 and H1 subbands at d = 40, 63.5, and 70 Å (from left
Having presented the realistic k · p calcula-
to right). Colored shading indicates the symmetry type of the band at that k point. Places where the
tion starting from the microscopic six-band
cones are more red indicate that the dominant state is H1 at that point; places where they are more
blue indicate that the dominant state is E1. Purple shading is a region where the states are more Kane model, we now introduce a simplified
evenly mixed. At 40 Å, the lower band is dominantly H1 and the upper band is dominantly E1. At tight-binding model for the E1 and H1 states
63.5 Å, the bands are evenly mixed near the band crossing and retain their d < dc behavior moving based on their symmetry properties. We con-
farther out in k-space. At 70 Å, the regions near k|| = 0 have flipped their character but eventually sider a square lattice with four states per unit
revert back to the d < dc farther out in k-space. Only this dispersion shows the meron structure (red cell. The E1 states are described by the s-orbital
and blue in the same band). (C) Schematic meron configurations representing the di(k) vector near states y1,3 = |s,a = ± 1=2 〉, and the H1 states are
the G point. The shading of the merons has the same meaning as the dispersion relations above. described by thepffiffispin-orbit
ffi coupled p-orbital
The change in meron number across the transition is exactly equal to 1, leading to a quantum jump states y2,4 = ±(1/ 2)|px ± ipy , a = ± 1=2 〉, where
of the spin Hall conductance s(s) 2
xy = 2e /h. We measure all Hall conductances in electrical units. All a denotes the electron spin. Nearest-neighbor
of these plots are for Hg0.32Cd0.68Te-HgTe quantum wells. coupling between these states gives the tight-

www.sciencemag.org SCIENCE VOL 314 15 DECEMBER 2006 1759

 REPORTS
binding Hamiltonian of the form of Eq. 2, with yield a precise determination of the Hall gapless Dirac point per 2 × 2 block. This
the matrix elements given by conductance for the whole system. However, as behavior is qualitatively different from the
one changes the quantum well thickness d across Haldane model of graphene (27), which has
d 1 þ id 2 ¼ A½sinðk x Þ þ i sinðk y Þ
dc, M changes sign and the gap closes at the Γ two gapless Dirac points in the Brillouin zone.
point, leading to a vanishing di (k = 0) vector at For M/2B < 0, sxy = 0; for 0 < M/2B < 2, sxy = 1.
d 3 ¼ −2B½2 − ðM =2BÞ − cosðk x Þ − cosðk y Þ
the transition point d = dc. The sign change of M Because this condition is satisfied in the in-
leads to a well-defined change of the Hall verted gap regime where M/2B = 2.02 ×10−4 at
eðkÞ ¼ C − 2D½2 − cosðk x Þ − cosðk y Þ
ð6Þ conductance Dsxy = 1 across the transition. As 70 Å (22) and not in the normal regime where
the di(k) vector is regular at the other parts of the M/2B < 0, we believe that the inverted case is
The tight-binding lattice model simply reduces Brillouin zone, these parts cannot lead to any the topologically nontrivial regime supporting a
to the continuum model Eq. 2 when expanded discontinuous changes across the transition point QSH state.
around the Γ point. The tight-binding calcula- at d = dc. We now discuss the experimental detection of
tion serves dual purposes. For readers un- So far, we have only discussed one 2 × 2 the QSH state. A series of purely electrical
initiated in the Kane model and k · p theory, block of the effective Hamiltonian H. General measurements can be used to detect the basic
this gives a simple and intuitive derivation of time-reversal symmetry dictates that sxy(H) = signature of the QSH state. By sweeping the gate
our effective Hamiltonian that captures all the −sxy(H*); therefore, the total charge Hall voltage, one can measure the two-terminal

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essential symmetries and topology. On the other conductance vanishes, and the spin Hall con- conductance GLR from the p-doped to bulk-
hand, it also introduces a short-distance cutoff ductance (given by the difference between the insulating to n-doped regime (Fig. 3). In the bulk
so that the topological quantities can be well two blocks) is finite and given by DsðsÞ xy = 2 in insulating regime, GLR should vanish at low
defined. units of e2/h. From the general relationship temperatures for a normal insulator at d < dc,
Within each 2 × 2 subblock, the Hamiltonian between the quantized Hall conductance and the whereas GLR should approach a value close to
is of the general form studied in (9), in the number of edge states (25), we conclude that the 2e2/h for d > dc. Strikingly, in a six-terminal
context of the quantum anomalous Hall effect, two sides of the phase transition at d = dc must measurement, the QSH state would exhibit van-
where the Hall conductance is given by differ in the number of pairs of helical edge ishing electric voltage drop between the termi-
ZZ states by 1, thus concluding our proof that one nals m1 and m2 and between m3 and m4, in the zero
1
sxy ¼ − 2 dk x dk y ^
d ˙ ∂x ^
d  ∂y ^
d ð7Þ side of the transition must be Z2 odd and temperature limit and in the presence of a finite
8p topologically distinct from a fully gapped electric current between the L and R terminals. In
conventional insulator. other words, longitudinal resistance should vanish
in units of e2/h (the square of the charge on the It is desirable to establish which side of the in the zero temperature limit, with a power-law
electron divided by the Planck constant), where transition is topologically nontrivial. For this dependence, over distances larger than the mean
^
d denotes the unit di(k) vector introduced in the purpose, we return to the tight-binding model free path. Because of the absence of back-
Hamiltonian Eq. 2. When integrated over the Eq. 6. The Hall conductance of this model has scattering, and before spontaneous breaking of
full Brillouin zone, sxy is quantized to take been calculated (25) in the context of the time reversal sets in, the helical edge currents flow
integer values that measure the skyrmion num- quantum anomalous Hall effect, and previously without dissipation, and the voltage drop occurs
ber, or the number of times the unit ^ d winds in the context of lattice fermion simulation (26). only at the drain side of the contact (11). The
around the unit sphere over the Brillouin zone Besides the Γ point, which becomes gapless at vanishing of the longitudinal resistance is one of
torus. The topological structure can be best M/2B = 0, there are three other high-symmetry the most remarkable manifestations of the QSH
visualized by plotting ^d as a function of k. In a points in the Brillouin zone. The (0,p) and (p,0) state. Finally, a spin-filtered measurement can be
skyrmion with a unit of topological charge, the points become gapless at M/2B = 2, whereas the used to determine the spin Hall conductance sðsÞ xy .
^
d vector points to the north (or the south) pole (p,p) point becomes gapless at M/2B = 4. Numerical calculations (13) show that it should
at the origin, points to the south (or the north) Therefore, at M/2B = 0, there is only one take a value close to sðsÞ 2
xy = 2e /h.
pole at the zone boundary, and winds around the
equatorial plane in the middle region. Fig. 3. (A) Experimental µ1 µ2
Substituting the continuum expression for
A
setup on a six-terminal
the di(k) vector as given in Eq. 3, and cutting off Hall bar showing pairs of
the integral at some finite point in momentum edge states, with spin-up
X
space, one obtains sxy = 1=2 sign (M), which is a states in green and spin-
well-known result in field theory (23). In the down states in purple. (B) µL µR
continuum model, the ^ d vector takes the con- A two-terminal measure- X
figuration of a meron, or half of a skyrmion, ment on a Hall bar would
where it points to the north (or the south) pole at give GLR close to 2e2/h
the origin and winds around the equator at the contact conductance on µ3 µ4
boundary. As the meron is half of a skyrmion, the QSH side of the B
the integral Eq. 7 gives ±1=2 . The meron transition and zero on 2 2
the insulating side. In a GLR ( e ) GLR ( e )
configuration of di(k) is depicted in Fig. 2, B h h
six-terminal measure-
and C. In a noninteracting system, half-integral ment, the longitudinal 4 4
Hall conductance is not possible, which means voltage drops m2 − Egap
that other points from the Brillouin zone must m1 and m4 − m3 vanish
either cancel or add to this contribution so that 2 2
on the QSH side with a Egap
the total Hall conductance becomes an integer. power law as the zero
The fermion-doubled partner (24) of our low- temperature limit is 0 0
µFermi µFermi
energy fermion near the Γ point lies in the approached. The spin
d<dc normal regime
higher-energy spectrum of the lattice and Hall conductance s(s) xy d>dc inverted regime
contributes to the total sxy . Therefore, our has a plateau with the
effective Hamiltonian near the Γ point cannot 2
value close to 2e /h.

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 REPORTS
Constant experimental progress on HgTe 5. J. Wunderlich, B. Kaestner, J. Sinova, T. Jungwirth, 22. See supporting material on Science Online.
over the past two decades makes the experimen- Phys. Rev. Lett. 94, 047204 (2005). 23. A. N. Redlich, Phys. Rev. D 29, 2366 (1984).
6. S. Murakami, N. Nagaosa, S. C. Zhang, Phys. Rev. Lett. 24. H. B. Nielsen, M. Ninomiya, Nucl. Phys. B 185, 20 (1981).
tal realization of our proposal possible. The 93, 156804 (2004). 25. X. L. Qi, Y. S. Wu, S. C. Zhang, Phys. Rev. B 74, 045125
mobility of the HgTe-CdTe quantum wells has 7. C. L. Kane, E. J. Mele, Phys. Rev. Lett. 95, 226801 (2006).
reached m ~ 6 × 105 cm2 V–1 s–1 (28). Experi- (2005). 26. M. F. L. Golterman, K. Jansen, D. B. Kaplan, Phys. Lett. B
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Supporting Online Material

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4. Y. Kato et al., Science 306, 1910 (2004). (2000). 10.1126/science.1133734

well-defined nanotubular objects, whose walls

Photoconductive Coaxial Nanotubes consist of a graphitic layer of p-stacked HBC
and whose inner and outer surfaces are covered

of Molecularly Connected Electron by hydrophilic triethylene glycol (TEG) chains

(22, 23). Upon doping with oxidants, the HBC
graphitic nanotubes become electrically conduc-
Donor and Acceptor Layers tive (22, 24). In the present work, we prepared
HBC-TNF 1 and 2, which bear an electron-
Yohei Yamamoto,1 Takanori Fukushima,1,2* Yuki Suna,1 Noriyuki Ishii,3 Akinori Saeki,4 accepting 4,5,7-trinitro-9-fluorenone functionali-
Shu Seki,4 Seiichi Tagawa,4 Masateru Taniguchi,4 Tomoji Kawai,4 Takuzo Aida1,2* ty (25) at each terminus of either (1) and both (2)
of the TEG chains (Fig. 1A). The energy levels of
Controlled self-assembly of a trinitrofluorenone-appended gemini-shaped amphiphilic the highest occupied molecular orbital (HOMO)
hexabenzocoronene selectively formed nanotubes or microfibers with different photochemical and the lowest unoccupied molecular orbital
properties. In these nanotubes, which are 16 nanometers in diameter and several micrometers (LUMO) of HBC 3 (22) and TNF 4 (26) (Fig.
long, a molecular layer of electron-accepting trinitrofluorenone laminates an electron-donating 1B) were determined by means of square-wave
graphitic layer of p-stacked hexabenzocoronene. The coaxial nanotubular structure allows voltammetry and electronic absorption spectros-
photochemical generation of spatially separated charge carriers and a quick photoconductive copy (fig. S1) (27). Apparently, photoinduced
response with a large on/off ratio greater than 104. In sharp contrast, the microfibers consist of a electron transfer is energetically possible between
charge-transfer complex between the hexabenzocoronene and trinitrofluorenone parts and exhibit the HBC and TNF functionalities of 1 and 2.
almost no photocurrent generation. Compounds 1 and 2 were synthesized by
oxidative cyclization of the corresponding hexa-
s exemplified by organic photovoltaic TNF laminates an electron-donating graphitic phenylbenzene precursors with FeCl3 in CH2Cl2/

A devices (1–3), heterojunction of electron

donor and acceptor layers at a macro-
scopic level allows for the conversion of light
layer of p-stacked HBC (Fig. 2) (12). This
structure creates an extremely wide interface for
the spatially segregated redox couple so that,
MeNO2 (27). Both compounds in tetrahydrofuran
(THF) were colored brown, indicating a CT
interaction between the HBC and TNF parts in
energy into electrical energy (4, 5). If one can upon photoirradiation, the electrical conduction
1
elaborate a nano-object composed of molecularly has a large on/off ratio (>104) that is difficult to Aida Nanospace Project, Exploratory Research for Ad-
vanced Technology–Solution Oriented Research for Science
conjugated domains of such a redox couple, the attain with other carbon-based materials (13–15). and Technology (ERATO-SORST), Japan Science and Tech-
resultant material is expected to serve as a Such molecularly engineered photoconductive nology Agency, National Museum of Emerging Science and
nanoscopic energy converter. However, donor materials with a tubular morphology are unusual Innovation, 2-41 Aomi, Koto-ku, Tokyo 135–0064, Japan.
2
and acceptor molecules tend to stack on one and join the few examples of photoconductive Department of Chemistry and Biotechnology, School of
Engineering, and Center for NanoBio Integration, The
another, rather than segregate (6–8), giving rise to nanostructured assemblies that have been University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113–
charge-transfer (CT) assemblies (9–11), in which reported (7, 16). 8656, Japan. 3Biological Information Research Center,
photochemically generated charge carriers are HBC derivatives with symmetrically substi- National Institute of Advanced Industrial Science and
trapped and readily annihilated through a rapid tuted paraffinic side chains form discotic liquid- Technology, Tsukuba Central-6, 1-1-1 Higashi, Tsukuba,
recombination. Here we report a coaxial nano- crystalline materials that exhibit a hole-transport Ibaraki 305–8566, Japan. 4Institute of Scientific and In-
dustrial Research, Osaka University, 8-1 Mihogaoka,
tubular object formed by controlled self-assembly capability through their one-dimensional columnar Ibaraki, Osaka 567–0047, Japan.
of trinitrofluorenone (TNF)–appended hexaben- HBC stacks (5, 17–21). Recently, we have *To whom correspondence should be addressed. E-mail:
zocoronene (HBC) amphiphile 1 (Fig. 1A), in discovered that gemini-shaped amphiphilic HBCs [email protected] (T.F.); aida@
which a molecular layer of electron-accepting (structure 3, Fig. 1A) can self-assemble to form macro.t.u-tokyo.ac.jp (T.A.)

www.sciencemag.org SCIENCE VOL 314 15 DECEMBER 2006 1761

 Quantum Spin Hall Effect and Topological Phase Transition in HgTe Quantum
Wells
B. Andrei Bernevig, Taylor L. Hughes, and Shou-Cheng Zhang

Science 314 (5806), . DOI: 10.1126/science.1133734

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