letters to nature

8. Eisenberg, H. S., Silberberg, Y., Morandotti, R., Boyd, A. R. & Aitchison, J. S. Discrete spatial optical computers and current-driven organic light-emitting diode dis-
solitons in waveguide arrays. Phys. Rev. Lett. 81, 3383–3386 (1998).
9. Fleischer, J. W., Segev, M., Efremidis, N. K. & Christodoulides, D. N. Observation of two-dimensional
plays. Fabricating high-performance devices is challenging,
discrete solitons in optically induced nonlinear photonic lattices. Nature 422, 147–150 (2003). owing to a trade-off between processing temperature and device
10. Sato, M., Hubbard, B. E., Sievers, A. J., Ilic, B. & Craighead, H. G. Optical manipulation of intrinsic performance. Here, we propose to solve this problem by using
localized vibrational energy in cantilever arrays. Europhys. Lett. 66, 318–323 (2004). a novel semiconducting material—namely, a transparent amor-
11. Swanson, B. I. et al. Observation of intrinsically localized modes in a discrete low dimensional
material. Phys. Rev. Lett. 82, 3288–3291 (1999).
phous oxide semiconductor from the In-Ga-Zn-O system
12. Fehske, H., Kinateder, M., Wellein, G. & Bishop, A. R. Quantum lattice effects in mixed-valence (a-IGZO)—for the active channel in transparent thin-film tran-
transition-metal chain complexes. Phys. Rev. B 63, 245121 (2001). sistors (TTFTs). The a-IGZO is deposited on polyethylene ter-
13. Schwarz, U. T., English, L. Q. & Sievers, A. J. Experimental generation and observation of intrinsic
localized spin wave modes in an antiferromagnet. Phys. Rev. Lett. 83, 223–227 (1999).
ephthalate at room temperature and exhibits Hall effect
14. Xie, A., van der Meer, L., Hoff, W. & Austin, R. H. Long-lived Amide I vibrational modes in mobilities exceeding 10 cm2 V21 s21, which is an order of mag-
myoglobin. Phys. Rev. Lett. 84, 5435–5438 (2000). nitude larger than for hydrogenated amorphous silicon. TTFTs
15. Markovich, T., Polturak, E., Bossy, J. & Farhi, E. Observation of a new excitation in bcc He-4 by fabricated on polyethylene terephthalate sheets exhibit satur-
inelastic neutron scattering. Phys. Rev. Lett. 88, 195301 (2002).
16. Chikamatsu, M., Tanaka, M. & Yamazaki, H. Effect of magnetic dipolar interaction on
ation mobilities of 6–9 cm2 V21 s21, and device characteristics
antiferromagnetic resonance in (C2H5NH3)2CuCl4. J. Phys. Soc. Jpn 50, 2876–2883 (1981). are stable during repetitive bending of the TTFT sheet.
17. de Jongh, L. J. in Physics and Chemistry of Materials with Low-Dimensional Structures (ed. Lévy, F.) Thin-film transistors (TFTs) are fundamental building blocks for
1–51 (Kluwer Academic, Dordrecht, 1990). state-of-the-art microelectronics, such as flat-panel displays and
18. Sato, M., English, L. Q., Hubbard, B. E. & Sievers, A. J. Influence of sample shape on the production of
intrinsic localized modes in an antiferromagnetic lattice. J. Appl. Phys. 91, 8676–8678 (2002).
system-on-glass11,12. Furthermore, the fabrication of low-tempera-
19. English, L. Q. Studies of Intrinsic Localized Spin-Wave Modes in Antiferromagnetic Crystals. Ph.D. ture TFTs will allow flexible large-area electronic devices to be
thesis, Cornell Univ. (2003). developed. These devices are flexible, lightweight, shock resistant
20. Rössler, T. & Page, J. B. Intrinsic localized modes in driven anharmonic lattices with realistic
potentials. Phys. Lett. A 204, 418–426 (1995).
and potentially affordable—properties that are necessary for large,
21. Sato, M. et al. Observation of locked intrinsic localized vibrational modes in a micromechanical economic, high-resolution displays, wearable computers and paper
oscillator array. Phys. Rev. Lett. 90, 044102 (2003). displays1. Further, when combined with ‘transparent circuit tech-
22. Shen, Y. R. The Principles of Nonlinear Optics (John Wiley & Sons, New York, 1984). nology’13–17, TFTs can integrate display functions even on the
23. Almeida, N. S. & Mills, D. L. Nonlinear infrared response of antiferromagnets. Phys. Rev. B 36,
2015–2023 (1987).
windscreens of cars.
24. Lim, S.-C., Osman, J. & Tilley, D. R. Calculation of nonlinear magnetic susceptibility tensors for a Organic semiconductors and hydrogenated amorphous silicon
uniaxial antiferromagnet. J. Phys. D 33, 2899–2910 (2000). (a-Si:H) have been extensively investigated for flexible electronics,
25. Lai, R. & Sievers, A. J. Identification of an intrinsic localized spin wave resonance in antiferromagnetic and have demonstrated the ability to be fabricated into flexible solar
chains with single-ion easy-plane anisotropy. Phys. Rev. B 55, 11937–11940 (1997).
cells and TFTs2–10. However, device performance is limited by the
Acknowledgements We acknowledge conversations with P. Brouwer, L. English, B. Hubbard, low mobilities of the channel materials (field effect mobilities, m FE,
D. Mills, J. Page, J. Parpia, J. Sethna and R. Silsbee. This work was supported by NSF-DMR and by are ,1 cm2 V21 s21 for a-Si:H, ,2.7 cm2 V21 s21 for a pentacene
the Cornell Center for Materials Research. single crystal, and ,1.5 cm2 V21 s21 for a pentacene thin film10). In
addition, Si-based devices are of less interest for transparent circuits
Competing interests statement The authors declare that they have no competing financial because they are not transparent, owing to the small bandgap18.
interests.
Amorphous semiconductors are preferred over polycrystalline
Correspondence and requests for materials should be addressed to A.J.S. ones for active layers from the viewpoints of processing temperature
([email protected]). and uniformity of device characteristics. However, the carrier
mobility of a-Si:H is lower by two or three orders of magnitude
than that of single-crystalline Si (,200 cm2 V21 s21 for carrier
concentration ,1019 cm23). The mobility of a-Si:H is limited to
.............................................................. ,1 cm2 V21 s21, as carrier transport is controlled by hopping
between localized tail-states and band conduction is not achieved.
Room-temperature fabrication The low mobility is associated with the intrinsic nature of the
chemical bonding (Fig. 1a): average carrier transport paths in
of transparent flexible thin-film covalent semiconductors such as a-Si:H consist of sp 3 orbitals
with strong directivity and, therefore, the bond angle fluctuation
transistors using amorphous significantly alters the electronic levels, leading to somewhat high-
density deep tail-states.
oxide semiconductors In contrast, degenerate band conduction and large mobility
(.10 cm2 V21 s21) are possible in amorphous oxide semiconduc-
Kenji Nomura1, Hiromichi Ohta1, Akihiro Takagi2, Toshio Kamiya1,2, tors (AOSs) containing post-transition-metal cations19,20. These
Masahiro Hirano1 & Hideo Hosono1,2,3 features are completely different from those of the covalent semi-
1
conductors. Figure 1b illustrates the carrier transport paths (that is,
ERATO-SORST, JST, in Frontier Collaborative Research Center, Mail Box the wavefunction of the conduction band bottom) in AOSs. The
S2-13, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, bottom of the conduction band in the oxide semiconductors that
226-8503, Japan
2 has high ionicity is primarily composed of spatially spread metal ns
Materials and Structures Laboratory, Mail Box R3-1, Tokyo Institute of
Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan orbitals with isotropic shape (here n is the principal quantum
3
Frontier Collaborative Research Center, Mail Box S2-13, Tokyo Institute of number), and direct overlap among the neighbouring metal ns
Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan orbitals is possible. The magnitude of this overlap is insensitive to
............................................................................................................................................................................. distorted metal–oxygen–metal (M–O–M) chemical bonds that
Transparent electronic devices formed on flexible substrates are intrinsically exist in amorphous materials21,22. Therefore, AOSs
expected to meet emerging technological demands where silicon- exhibit Hall-effect mobilities similar to those of the corresponding
based electronics cannot provide a solution. Examples of active crystalline phase, even if they are formed at room temperature.
flexible applications include paper displays and wearable com- These carrier transport properties are unique to oxide semiconduc-
puters1. So far, mainly flexible devices based on hydrogenated tors, and are not seen in covalent amorphous semiconductors such
amorphous silicon (a-Si:H)2–5 and organic semiconductors2,6–10 as a-Si:H.
have been investigated. However, the performance of these Here we report room-temperature fabrication and performance
devices has been insufficient for use as transistors in practical of flexible TTFTs fabricated using a-IGZO as an active n-channel
488 ©2004 Nature Publishing Group NATURE | VOL 432 | 25 NOVEMBER 2004 | www.nature.com/nature
 letters to nature
layer. Films of a-IGZO were prepared by pulsed laser deposition band edge; these potential barriers are formed owing to random
with a KrF excimer laser, using a polycrystalline InGaZnO4 target at distribution of Ga3þ and Zn2þ ions in the crystal structure. The
room temperature in an oxygen atmosphere (oxygen pressure PO2 ). potential barriers are overcome when carrier concentration exceeds
The chemical composition of the obtained films measured by X-ray 3 £ 1018 cm23, and therefore the Hall mobility increases as the
fluorescence spectroscopy was In:Ga:Zn ¼ 1.1:1.1:0.9 (in atomic carrier concentration increases, and larger Hall mobilities
ratio). (.10 cm2 V 21 s 21 ) are obtained at carrier concentrations
Figure 2a shows an X-ray diffraction pattern of an a-IGZO film .1018 cm23. Similar behaviours are also observed in a-IGZO,
deposited on a glass substrate. The film is amorphous and optically which would result from a similar mechanism associated with the
transparent in the entire visible and near-infrared regions (wave- random amorphous structure.
length l ¼ 390–3,200 nm), as shown in Fig. 2a inset. The optical The amorphous phase is thermally stable up to ,500 8C in air.
transmittance is greater than 80%, including the reflection associ- Other AOSs such as a-ITO, and also crystalline ZnO (an amorphous
ated with the film and glass substrate. The optical bandgap (E g) phase of ZnO has yet been reported), have high-density carriers
estimated from the Tauc’ plot is ,3.0 eV, which is similar to that of even in as-deposited states, and are difficult to make into devices
the crystalline phase (,3.4 eV). The electrical conductivities at with controlled characteristics. Thus it is vital to choose a material
room temperature are ,1025 S cm21 when the films are deposited in which carrier concentration can be controlled at a low level, for
at PO2 . 6 Pa. The values correspond to carrier concentrations example, ,1014 cm23, in order to achieve a low off current and large
of ,1014 cm23 if an electron mobility of 1 cm22 V21 s21 is assumed. on-to-off current ratios24. Incorporating Ga ions would be import-
The sign of the Seebeck coefficients obtained from thermopower ant in a-IGZO for suppressing carrier generation via oxygen vacancy
measurements is negative, indicating that a-IGZO is an n-type formation, because the Ga ion forms stronger chemical bonds with
semiconductor. oxygen than Zn and In ions.
Figure 2b shows the room-temperature Hall mobility of a-IGZO We fabricated top-gate flexible TTFTs using the a-IGZO film as
films as a function of carrier concentration. This carrier concen- an n-channel active layer on 200-mm-thick polyethylene terephthal-
tration varies from ,1014 to 1020 cm23 when PO2 is varied from ,7 ate (PET) films (Fig. 3a). Source, drain, gate contacts and a gate
to 0.1 Pa. The data obtained on single-crystalline InGaO3(ZnO)5 insulator were defined by standard photolithography and lift-off
(c-IGZO) films are shown for comparison. We have reported23 that techniques. A ,140-nm-thick Y2O3 layer was chosen for the gate
carrier transport in c-IGZO is governed by percolation conduction insulator and ITO (Sn:10%) was used for source, drain and gate
over the distribution of potential barriers around the conduction transparent electrodes. These layers were deposited by pulsed laser

Figure 1 Schematic orbital drawings for the carrier transport paths (that is, conduction b, Amorphous oxide semiconductors composed of post-transition-metal cations. Spheres
band bottoms) in crystalline and amorphous semiconductors. a, Covalent semiconductors denote metal s orbitals. The contribution of oxygen 2p orbitals is small. Direct overlap
have carrier transport paths composed of strongly directive sp 3 orbitals, so structural between neighbouring metal s orbitals is rather large, and is not significantly affected even
randomness greatly degrades the magnitude of bond overlap, that is, carrier mobility. in an amorphous structure.
Note that the orbitals shown are illustrative, and do not show exact wavefunctions.
NATURE | VOL 432 | 25 NOVEMBER 2004 | www.nature.com/nature
©2004 Nature Publishing Group 489
letters to nature
deposition at room temperature using Y2O3 and ITO ceramic the devices measured). Similarly, a field-effect mobility (m FE)
targets. The measured dielectric constant of the Y2O3 gate insulator estimated from the linear region in the I DS–V DS curve (using
was ,161 0 (where 1 0 is the dielectric constant of vacuum), which is I DS ¼ (C i mW/L)(V GS 2 V T )V DS ) is ,5.6 cm2 V 21 s 21 at
close to that reported for crystalline Y2O3 (,181 0)25. The channel V DS ¼ 2.4 V, which agrees roughly with the m sat value.
length and width were 50 mm and 200 mm, respectively (Fig. 3c). The transfer characteristic (Fig. 4b) shows that a low off-current,
The performances of the flexible TTFTs were measured in air at of the order of 1027 A, and an on-to-off current ratio ,103 are
room temperature. Figure 4a shows typical source-to-drain current obtained. The threshold gate voltage is positive (V T < þ1.6 V),
(I DS)–voltage (V DS) characteristics of a virgin device. The current showing that the TTFT operates in the enhancement mode (nor-
I DS markedly increases as V DS increases at a positive gate bias (V GS), mally-off characteristics). The gate leak current is lower by several
indicating that the channel is n-type. The I DS reaches ,0.02 mA at a orders of magnitude than the source-to-drain current, which
V GS of 5 V. The I DS–V DS characteristics exhibit a clear pinch-off and guarantees that the TFT characteristics are unaffected by the gate
current saturation, confirming that the TTFT operation follows the leak current. Small hystereses were observed in the I DS–V GS curves
standard field-effect transistor theory. The saturation mobility with negative shifts in gate bias of 0.1–0.5 V at a scan speed of
(m sat) is obtained from the I DS–V DS curves in the saturation region 0.5 V s21, which would be due to interface states.
using the equation I DS,sat ¼ (C im satW/2L)(V GS 2 V T)2, where C i, Next, bending effects on the TTFT characteristics were examined.
V T, W and L denote the gate capacitance, threshold gate voltage,
channel width and length, respectively. The estimated m sat value is
,8.3 cm2 V21 s21, much larger than those obtained in organic and
a-Si:H TFTs (the m sat value ranges from ,6 to ,9 cm2 V21 s21 in

Figure 2 Amorphous IGZO films. a, Glance angle X-ray diffraction pattern of the a-IGZO
film deposited on a silica glass substrate at room temperature. No sharp peak is observed.
CuKa1 radiation was used. Inset is the optical transmission spectrum of the film. The
measured bandgap (E g) is ,3.0 eV. b, Relationship between room-temperature Hall
mobility and carrier concentration for a-IGZO films. Data on single-crystalline
InGaO3(ZnO)5 films are shown for comparison. Electron mobility strongly depends on Figure 3 Flexible TTFTs. a, Structure of TTFT fabricated on a plastic sheet. b, A
carrier concentration, and exceeds 10 cm2 V21 s21 at carrier concentrations greater than photograph of the flexible TTFT sheet bent at R ¼ 30 mm. The TTFT sheet is fully
1018 cm23, owing to potential distribution in the vicinity of the conduction band bottom transparent in the visible light region. c, A photograph of the flexible TTFT sheet. The
(see ref. 23 for details). transparent TFT devices are made visible by adjusting the angle of the illumination.
490 ©2004 Nature Publishing Group NATURE | VOL 432 | 25 NOVEMBER 2004 | www.nature.com/nature
 letters to nature

Figure 4 Typical TTFT characteristics before and after bending. a, I DS–V DS and current ratio is ,103. c, I DS–V DS and d, I DS–V GS characteristics after bending. The
b, I DS–V GS characteristics before bending. The TTFT operates in the enhanced mode with device was bent at R ¼ 30 mm.
a threshold voltage of ,þ1.6 V. The saturation mobility is ,8.3 cm2 V21 s21. On-to-off

The TTFT sheet was bent into a curve with a surface curvature tor and p–n junction diodes fabricated at room temperature26; this
radius (R) of 30 mm (corresponding to a tensile strain of ,0.3% in would extend the possibilities of flexible transparent electronic
the TTFTs), as shown in Fig. 3b. The TTFTafter bending maintained circuits. A
good characteristics, such as m sat < 7 cm2 V21 s21 and an on-to-off Received 4 July; accepted 5 October 2004; doi:10.1038/nature03090.
current ratio of ,103 (Fig. 4c, d). We stress that the TTFT
1. Huitema, H. E. A. et al. Plastic transistors in active-matrix displays. Nature 414, 599 (2001).
performance is almost unaffected by bending, although a slight 2. Kagan, C. R. & Andry, P. (eds) Thin Film Transistors (Marcel Dekker, New York, 2003).
decrease is observed in the saturation current. After the initial 3. Yang, C.-S., Smith, L. L., Arthur, C. B. & Parsons, G. N. Stability of low-temperature amorphous
bending, the TFT characteristics are stable and reproducible during silicon thin film transistors formed on glass and transparent plastic substrates. J. Vac. Sci. Technol. B
18, 683–689 (2000).
and after repetitive bending. The TTFT is stable at temperatures up 4. Carey, P. G., Smith, P. M., Theiss, S. D. & Wickboldt, P. Polysilicon thin film transistors fabricated on
to 120 8C, but becomes inoperative at higher temperatures, prob- low temperature plastic substrates. J. Vac. Sci. Technol. A 17, 1946–1949 (2000).
ably owing to the softening of the PET substrate. 5. Wang, S. C. et al. Device transfer technology by backside etching for poly-Si thin-film transistors on
glass/plastic substrate. Jpn. J. Appl. Phys. 42, 1044–1046 (2003).
The present study demonstrates the room-temperature fabrica- 6. Shaw, J. M. & Seidler, P. F. Organic electronics: Introduction. IBM J. Res. Dev. 45, 3–9 (2001).
tion and operation of flexible TTFTs based on an amorphous oxide 7. Dimitrakopoulos, C. D. & Malenfant, P. R. L. Organic thin film transistors for large area electronics.
semiconductor, a-IGZO. TTFTs were fabricated on inexpensive Adv. Mater. 14, 99–117 (2002).
8. Choi, H. Y., Kim, S. H. & Jang, J. Self-organized organic thin-film transistors on plastic. Adv. Mater.
polymer films and displayed good performance—such as saturation
16, 732–736 (2004).
mobilities of ,6–9 cm2 V21 s21, a low leak current of ,10210 A, 9. Lee, J. H. et al. Pentacene thin film transistors fabricated on plastic substrates. Synth. Metals 139,
and an on-to-off ratio of ,103 —even during and after bending. We 445–451 (2003).
used pulsed laser deposition to form the active a-IGZO layer in this 10. Dimitrakopoulos, C. D. & Mascaro, D. J. Organic thin-film transistors: A review of recent advances.
IBM J. Res. Dev. 45, 11–27 (2001).
study, but a sputtering or metal-organic chemical vapour depo- 11. Taur, Y. & Ning, H. T. Fundamentals of Modern VLSI Devices (Cambridge Univ. Press, New York,
sition (MOCVD) method can be used for large-area uniform 1988).
deposition and mass production, as demonstrated for window 12. Kuo, Y. (ed.) Thin Film Transistors: Materials and Processes (Kluwer Academic, Dordrecht, 2004).
13. Thomas, G. Invisible circuits. Nature 389, 907–908 (1997).
electrodes of solar cells and flat-panel displays. 14. Kawazoe, H. et al. P-type electrical conduction in transparent thin films of CuAlO2. Nature 389,
These achievements imply that transparent amorphous oxide 939–942 (1997).
semiconductors have the potential to overtake a-Si:H, and are 15. Ohta, H. & Hosono, H. Transparent oxide electronics. Mater. Today 7, 42–51 (2004).
16. Wager, J. F. Transparent electronics. Science 300, 1245–1246 (2003).
promising materials for transparent flexible electronics. Further-
17. Hosono, H. Built-in nanostructures in transparent oxides for novel photonic and electronic functions
more, flexible TTFTs may be integrated with other already- materials. Int. J. Appl. Ceram.Technol 1, 106–118 (2004).
developed devices that use a p-type amorphous oxide semiconduc- 18. Madelung, O. (ed.) Technology and Application of Amorphous Silicon (Springer, Berlin, 2000).

NATURE | VOL 432 | 25 NOVEMBER 2004 | www.nature.com/nature

©2004 Nature Publishing Group 491
letters to nature
19. Hosono, H. et al. Working hypothesis to explore novel wide band gap electrically conducting In agreement with predictions from mode-coupling theory9, there is
amorphous oxides and examples. J. Non-Cryst. Solids 198–200, 165–169 (1996).
20. Orita, M. et al. Amorphous transparent conductive oxide InGaO3(ZnO)m (m # 4): a Zn 4s
also evidence for a glass or gel transition at low particle volume
conductor. Phil. Mag. B 81, 501–515 (2001). fractions and high interparticle attractions. Such a scenario
21. Mott, N. F. Silicon dioxide and the chalcogenide semiconductors; similarities and differences. Adv. obviously affects the ability to form the high quality crystals
Phys. 26, 363–391 (1977). required for protein crystallography15. Using two apparently quite
22. Narushima, S. et al. Electronic structure and transport properties in the transparent amorphous oxide
semiconductor 2CdO·GeO2. Phys. Rev. B 66, 35203 (2002).
different model systems, we demonstrate the generality of this
23. Nomura, K. et al. Carrier transport in transparent oxide semiconductor with intrinsic structural emerging description of the effect of a short-range attraction
randomness probed using single-crystalline InGaO3(ZnO)5 films. Appl. Phys. Lett. 85, 1993–1995 combined with either a hard or soft repulsion on the phase
(2004).
behaviour of a wide range of colloidal suspensions.
24. Nomura, K. et al. Thin film transistor fabricated in single-crystalline transparent oxide
semiconductor. Science 300, 1269–1272 (2003). We first investigated solutions of the globular protein lysozyme
25. Kwo, J. et al. Properties of high k gate dielectrics Gd2O3 and Y2O3 for Si. J. Appl. Phys. 89, 3920–3927 (molecular mass 14.4 kDa, radius R m < 1.7 nm)17–19. Using small-
(2001). angle X-ray (SAXS) and neutron (SANS) scattering, we studied
26. Narushima, S. et al. P-type amorphous oxide semiconductor, ZnRh2O4, and room temperature
fabrication of amorphous oxide P-N hetero-junction diodes. Adv. Mater. 15, 1409–1413 (2003).
spatial correlations in concentrated solutions at low ionic strength,
where the long-range repulsive electrostatic potential is only weakly
Competing interests statement The authors declare that they have no competing financial screened. We then compared these findings with confocal
interests. microscopy results using colloid–polymer mixtures, a popular
Correspondence and requests for materials should be addressed to H.H.
model system with easily tunable interactions. Here we used
([email protected]). spherical colloidal particles interacting with a long-range repulsion
resulting from a modest charge21 and a short-range attraction
induced by a polymer-mediated ‘depletion effect’22.
Figure 1 presents SAXS measurements on a lysozyme concen-
tration series at 5 8C. The normalized scattering intensities I(q)/c,
.............................................................. where I(q) is the scattering intensity at scattering vector q, and c is
Equilibrium cluster formation in the protein concentration, show a forward intensity I(q ! 0)/c that

concentrated protein solutions

and colloids
Anna Stradner1, Helen Sedgwick2, Frédéric Cardinaux1,
Wilson C. K. Poon2, Stefan U. Egelhaaf2,3 & Peter Schurtenberger1
1
Department of Physics, University of Fribourg, Chemin du Musée 3, CH-1700
Fribourg, Switzerland
2
School of Physics and COSMIC, The University of Edinburgh, Mayfield Road,
Edinburgh EH9 3JZ, UK
3
School of Chemistry, The University of Edinburgh, West Mains Road, Edinburgh
EH9 3JJ, UK
.............................................................................................................................................................................
Controlling interparticle interactions, aggregation and cluster
formation is of central importance in a number of areas, ranging
from cluster formation in various disease processes to protein
crystallography and the production of photonic crystals. Recent
developments in the description of the interaction of colloidal
particles with short-range attractive potentials have led to
interesting findings including metastable liquid–liquid phase
separation and the formation of dynamically arrested states
(such as the existence of attractive and repulsive glasses, and
transient gels)1–7. The emerging glass paradigm has been success-
fully applied to complex soft-matter systems, such as colloid–
polymer systems8 and concentrated protein solutions9. However,
intriguing problems like the frequent occurrence of cluster
phases remain10–13. Here we report small-angle scattering and
confocal microscopy investigations of two model systems: pro-
tein solutions and colloid–polymer mixtures. We demonstrate
that in both systems, a combination of short-range attraction and
long-range repulsion results in the formation of small equili-
brium clusters. We discuss the relevance of this finding for
nucleation processes during protein crystallization, protein or
DNA self-assembly and the previously observed formation of
cluster and gel phases in colloidal suspensions12–17.
A number of globular proteins have been shown to exhibit the Figure 1 Normalized scattered intensity I (q )/c and corresponding effective structure
major characteristics of colloids that interact via a short-range factors S eff(q), as obtained by SAXS from lysozyme solutions of different concentrations c.
attractive potential. At high ionic strength, where the salt screens a, I (q )/c of a dilution series (3 mg ml21 to 273 mg ml21) at 5 8C. Large open circles
electrostatic repulsions, these short-range attractions increasingly represent the I (q )/c values extrapolated to q ¼ 0.1 nm21 and stars show the projection
dominate with decreasing temperature. This leads to a metastable of the peak maximum onto the q–c plane. b, S eff(q) of the concentrated samples in a.
liquid–liquid phase separation and related critical phenomena18–20. Concentration ranges from 36 mg ml21 (open squares) to 273 mg ml21 (filled circles).
492 ©2004 Nature Publishing Group NATURE | VOL 432 | 25 NOVEMBER 2004 | www.nature.com/nature