VOLUME 78, NUMBER 13

PHYSICAL REVIEW LETTERS

31 MARCH 1997

Stability of Ordered Phases in Weakly Segregated Diblock Copolymer Systems

Mohamed Laradji,1 An-Chang Shi,2 Rashmi C. Desai,1 and Jaan Noolandi2
2

Department of Physics, University of Toronto, Toronto, Ontario, Canada M5S 1A7 Xerox Research Center of Canada, 2660 Speakman Drive, Mississauga, Ontario, Canada L5K 2L1 (Received 21 October 1996)

Stability of ordered phases in diblock copolymer melts is studied using a theory of anisotropic uctuations, which bears a useful similarity with energy band theory in solids. We calculated stability lines of all ordered phases and found the hexagonally perforated lamellar phase to be unstable around the lamellar-cylindrical ( LC) phase boundaries. We used uctuation analysis to obtain dynamical pathways between ordered phases and argue that the observed modulated layered states along LC boundary regions are due to innitely degenerate uctuation modes of the lamellar phase. [S0031-9007(97)02831-7]
PACS numbers: 61.25.Hq, 64.70. p, 83.70.Hq

In a wide variety of soft materials, an astonishingly rich phase behavior, characterized by periodic ordered structures, is commonly observed as a consequence of competing interactions [1]. Typical examples are surfactant systems and diblock copolymers (DC), which generically exhibit phases of lamellae (L), hexagonal cylinders (H), and body-centered-cubic (bcc) spheres. In particular, DC melts have been the subject of extensive experimental and theoretical studies [27]. Besides the so-called classical phases (L, H, and bcc), a bicontinuous double-gyroid (DG) phase [4,5,8], a hexagonally modulated lamellar phase (HML) and a hexagonally perforated lamellar phase (HPL) have also been identied [6,9,10]. Earlier studies have contributed to the understanding of many aspects of DC phase diagram, and the morphologies of different phases have been well characterized. Nevertheless, stability of these broken-symmetry phases and the processes by which they form have not been explored satisfactorily. Most acute is the existence of the HPL phase, which has never been justied theoretically. This is rooted in the fact that most of the theoretical studies [7] use mean eld approximation; thus they are unable to address questions related to the anisotropic uctuations in ordered phases. In the present Letter, we investigate the stability of the ordered phases through a theory of anisotropic uctuations fully formulated in reciprocal space. The main thrust of our theory is that in order to study the effect of uctuations around an ordered broken-symmetry phase in DC melts, a self-consistent expansion must be performed around its exact mean eld solution. Earlier theories [11 13], accounting for composition uctuations in DC melts, concentrated on the shift of transition lines between various phases, and in particular on the end-critical point. These theories, however, suffer from neglect of an essential ingredient of these systems, namely, the anisotropic nature of ordered phases and their composition uctuations. Recently, Yeung et al. [14] have introduced a novel random phase approximation theory accounting for anisotropic composition uctuations and applied it to the lamellar phase. A description of the theoretical frame0031-9007 97 78(13) 2577(4)$10.00

work and the nature of anisotropic uctuations is given by Shi et al. [15]. The theory is further developed into a particular convenient dimensionless form [16], and implemented in the present work to study the stability of ordered DC phases. Because of the connectivity of polymer chains and the periodicity of ordered phases, the chain conformation is described by a diffusion equation in a periodic potential which is equivalent to the Schrdinger equation of an electron in a periodic potential. Therefore, our theory bears an important analogy to the theory of energy bands in crystalline solids: The origin of anisotropic uctuations is intimately connected to the formation of eigenvalue bands, similar to electronic energy states in solids. As a consequence, just as energy bands in solids are important for their electronic properties, eigenvalue bands in DC systems are crucial for their mechanical properties [17]. Furthermore, this analogy enables us to adapt well known computational methods in solid state physics for calculating spinodal lines and identifying the most unstable modes of the ordered phases. We conclude for the rst time that the HPL phase (space group R 3m) is not a stable equilibrium phase. Moreover, availability of the most unstable mode can be used to infer kinetic pathways as the system undergoes a transition between two ordered phases, and to determine the epitaxial relations between them. We consider a system of incompressible and exible AB-diblock copolymers, with a degree of polymerization N, A-monomer volume fraction f, and Kuhn length b. With the standard formalism of performing the functional integral over chain conformations [18], and introducing the local incompressibility constraint of Hong and Noolandi [19], the system free energy functional is obtained as a functional of the local monomer volume fractions, fa r , and two auxiliary elds, va r , where a A or B [15]. In this formalism, many-chain interactions are described by the uctuating auxiliary elds, va r . The entropic contribution to the free energy functional is described by the propagator Qa r, t j r 0 , which is the statistical weight of an a monomer t at r 1997 The American Physical Society 2577

VOLUME 78, NUMBER 13

PHYSICAL REVIEW LETTERS

31 MARCH 1997

provided that the rst a monomer is at r 0 . These propagators are the solution of the modied diffusion equation [18,19], Ha Qa r, t j r 0 2 Qa r, t j r 0 t 2=2 1 va r Qa r, t j r 0 , (1) 0 0 . All with the initial condition Qa r, 0 j r dr2r lengths are rescaled by the radius of gyration Rg p b N 6, and the arclength t along the chain by N. F
2

Within mean eld theory, the saddle-point method on fa and va leads to a set of equations which must be solved self-consistently. Composition uctuations are accounted for by expanding around the mean eld solu0 fa0 r 1 dfa r and va r va r 1 tion; fa r dva r . Since we focus here on the stability of ordered phases around the mean eld solution, only terms up to second order in uctuations are kept in the free energy 0 functional, F F 0 1 F 1 1 F 2 , where F 1 [20] and X #

dfa, dva

dva r dfa r dr xdfA r dfB r 2 yN a ) 1 XZ 0 0 0 dr dr Cab r, r dva r dvb r , 2 2 ab

( 3 Rg Z

"

(2)

where y and x are the segment volume and the FloryHuggins parameter, respectively. Each of the four twopoint cumulants, Cab r, r 0 , is an integral over four mean eld propagators [15,16]. In order to account for the fact that an ordered phase is a broken-symmetry structure, the self-consistent mean eld equations have to be solved in the reciprocal space of its corresponding space group [10,21]. The symmetries of a given phase are completely specied by corresponding reciprocal space vectors, Gn . Since the DC problem requires a solution of the diffusion equation which is nothing but a Schrdinger equation in imaginary time with the Hamiltonian Ha , it is clear that the DC melt bears a useful similarity with an electronic system in a crystalline solid. According to Blochs theorem [22], the eigenmodes of the Hamiltonian can be labeled by a band index n and a wave vector k within the rst Brillouin p zone, and the eigenfunctions have the form a 1 V exp ik ? rP a r , where ua r are unk cnk r nk a periodic functions, ua r nk G unk G exp iG ? r . All that we need for the rest of the calculations are eigenmode a coefcients, ua , and the eigenvalues enk of the nk 0 2 0 operator Ha 2= 1 va r . As a consequence of the broken symmetry, the eigenvalue bands exhibit gaps at the Brillouin zone boundaries [15]. The uctuating elds are then expanded in terms of Blochs functions, and integrated out in the partition function leading to 2 1 3 Rg 3 2 xN 0 C S? I2 , Z e2F det 2pNy 2 (3) T where C C 2 D ? S ? D , C CAA 2 CAB 2 CBA 1 CAA 1 CAB 1 CBA 1 CBB , and D CAA 1 CBB , S CAB 2 CBA 2 CBB . It should be noted that the mean eld solution and the two-point cumulants are functions of xN and f only. The inclusion of uctuations introduces 6 b 6 63 y 2 N, which a third parameter, N Rg yN 2 quanties uctuation effects. This is in accordance with previous studies [11]. The stability of a given phase is investigated by examining, for a given set of xN, f , 2578

the eigenvalues of I 2 xN 2 C (the eigenvalues of S are always positive). If all eigenvalues are positive, the mean eld solution is linearly stable; the phase becomes unstable if at least one of the eigenvalues is negative. In our investigation of DC ordered phases, we rst solved the mean eld equations for the L, H, bcc, HPL, and DG phases, to obtain exact mean eld solutions, fa0 0 and va . The eigenvectors and eigenvalues of Ha0 were then calculated and used to construct the operator I 2 xN 2 C . Finally, the eigenvalues and eigenvectors of I 2 xN 2 C were computed and used to obtain the spinodal lines and the most unstable eigenmodes. Our calculation is restricted to the weak segregation region (10.495 # xN # 11.2). In Fig. 1, we show the eigenvalue of I 2 xN 2 C for the H structure at xN 10.9 and f 0.428. The appearance of gaps and the similarity with electronic energy bands in solids are obvious. In this particular phase, the rst Brillouin zone is a hexagonal prism and the instability occurs at the corners of the hexagon. As we discuss below, this corresponds to an instability against the bcc structure. The spinodal lines of the L, H, bcc, and HPL phases are shown in Fig. 2. The notable aspect of Fig. 2 is that one-phase regions of the so-called classical phases (L, H, and bcc) always lie within their spinodals, indicating their robustness. These three phases are indeed easily observed in experiments. The HPL phase is stable only in the center of the one-phase L region. Because the HPL mean eld free energy is higher than the L free energy in this region [21], the HPL phase is metastable only within its spinodal lines. In particular, the HPL phase is not stable along the L-H phase boundaries where it has been identied in several experiments [6,9]. We believe, as we argue below, that the experimentally observed modulated layered state is simply an intermediate structure. Another interesting feature of the phase diagram in Fig. 2 is that the H and bcc phases have two symmetric unrelated spinodal lines, in contrast to the L and HPL phases.

VOLUME 78, NUMBER 13

PHYSICAL REVIEW LETTERS

31 MARCH 1997

FIG. 1. The eigenvalues of the matrix I 2 xN 2 C for the H phase at xN 10.9 and f 0.428 (shown by a solid circle in the phase diagram of Fig. 2). The rst Brillouin zone of this phase is shown in the inset. The paths GM, ML, and LZ are shown in the Brillouin zone. The arrow indicates where the smallest eigenvalue occurs, indicating that the H phase is unstable.

This is because in either the L or the HPL structure, the minority and majority domains are topologically equivalent under the transformation f ! 1 2 f (the HPL structure being bicontinuous). We now discuss the nature of the least stable mode cor responding to the smallest eigenvalue of I 2 xN 2 C , and infer the kinetic pathway between ordered phases.

FIG. 2(color). Phase diagram with the spinodal lines. The shaded regions correspond to the one-phase regions of the L ( blue), H (red), and bcc (green) phases. The spinodal lines of the ordered phases are shown by their corresponding colors. The spinodal line of the HPL phase is shown in yellow. The white region corresponds to the homogeneous phase. The eigenmodes of Fig. 3 are calculated at the point shown by the square and circle. The outer spinodal line of the bcc phase is not obtained due to numerical difculties in nding unstable bcc mean eld solutions in the homogeneous phase.

The kinetics of the L ! H and H ! L transitions have been recently investigated in the experiments of Hajduk et al. [23] and Sakurai et al. [24], respectively. When the L phase is driven into the H phase, the phase transition proceeds through the formation of an intermediate modulated layered state which converts into the H phase upon prolonged annealing [23]. On the other hand, when the H phase is driven into the L phase, no intermediate state is observed [24]. In our calculations, we nd that the most unstable mode of the L phase is specied by the amplitude, but not the direction, of the wave vector parallel to the lamellae and is therefore innitely degenerate. This mode corresponds to alternate pinching and bulging of the minority domains [14]. If a single orientation is selected, this mode leads to hexagonally packed cylinders with a periodicity corresponding to the stable H phase. However, if different orientations are simultaneously selected, a situation most likely encountered in an experiment, the most unstable eigenmode leads to a modulated layered (ML) structure. Because the relaxation of this ML intermediate structure into the H phase occurs through rearrangements of material which is inherently slow, we believe that the experimentally observed HPL phase is not thermodynamically stable but corresponds instead to this long-lived ML intermediate structure. Such a scenario is indeed in agreement with the recent theoretical work of Qi and Wang [25] and a recent experiment of Hajduk et al. [26]. The information on kinetic pathways away from the H phase is obtained from the least stable modes of the H phase shown in Fig. 3. When the H phase is brought into the L phase, the effect of the most unstable eigenmode with small amplitudes leads to elongation of the cylinders in the [01] or equivalent directions. For larger amplitudes, the elongated cylinders merge in order to form a lamellar structure (Fig. 3). Therefore, there is no intermediate state encountered in the H ! L transition. The kinetic pathways between the L and H phases emerging from our calculations are consistent with the available experiments [23,24]. When the H phase is driven into the bcc phase, the effect of the most unstable mode with small amplitudes leads to undulation of the cylinders as shown in Fig. 3. For larger amplitudes, the undulated cylinders break up in order to form ellipsoids centered on a bcc lattice with a lattice constant corresponding to the equilibrium bcc phase (Fig. 3). Therefore, the instability of the hexagonal phase leads to a bcc phase whose [111] direction is along the original cylinders. This kinetic pathway of the H ! bcc transition is indeed in agreement with a recent study using a time-dependent Ginzburg-Landau model by Qi and Wang [25]. We now turn our attention to the DG phase, which is found to be stable within mean eld approximation along the L-H phase boundary for xN $ 11.14 [21]. We have carried out the stability analysis of this phase in the weak segregation region up to xN 12, but found surprisingly 2579

VOLUME 78, NUMBER 13

PHYSICAL REVIEW LETTERS

31 MARCH 1997

R. C. D. and M. L. thank the Natural Sciences and Engineering Research Council of Canada for support.

FIG. 3. Contour plot of the hexagonal phase including the least stable uctuating mode. The contour is dened by 0 fA r 1 acA r 0.5, where cA r is the least fA r unstable eigenfunction of I 2 xN 2 C . The right column corresponds to xN 10.9 and f 0.476 and the three congurations, from top to bottom, correspond to a 0, 0.06, and 0.08, respectively. The left column corresponds to xN 10.9 and f 0.43, and the congurations from top to bottom correspond to a 0, 0.02, and 0.075, respectively.

that it is always unstable. We should emphasize that this result is obtained with a limited number of plane waves which can be handled (#783). Although we cannot exclude the possibility of not using large enough number of plane waves, our result does lead to an interesting speculation that the DG phase within mean eld theory is indeed a saddle-point solution which might be stabilized by higher order uctuations. Inclusion of higher order uctuations is possible within our theoretical framework, but this is beyond the scope of the present work. Our conclusions concerning the stability of the DG phase are consistent with experiments [6] where the DG phase is observed only for DC melts with strong uctuations, i.e., for short diblock chains in the weak segregation region [27]. We also note that in our calculation the most unstable eigenmode of the DG phase leads to hexagonally packed cylinders oriented along the [111] direction of its cubic unit cell. This epitaxial relation between the DG and H phases is consistent with the conclusion of Schultz et al. based on their experiment [28]. We acknowledge helpful discussions with Professor C. Yeung, Dr. D. A. Hajduk, and Dr. M. W. Matsen.

[1] M. Seul and D. Andelman, Science 267, 476 (1995). [2] F. S. Bates and G. H. Fredrickson, Annu. Rev. Phys. Chem. 41, 525 (1990). [3] T. Hashimoto, in Thermoplastic Elastomers, edited by N. R. Legge et al. (Carl Hanser Verlag, Vienna, 1987). [4] H. Hasegawa et al., Macromolecules 20, 1651 (1987). [5] E. L. Thomas et al., Macromolecules 19, 2197 (1986). [6] A recent review of the experimental phase diagram of DC melts is found in F. S. Bates et al., Faraday Discuss. 98, 7 (1994). [7] A recent review of theories of DC melts is given by M. W. Matsen and F. S. Bates, Macromolecules 29, 1091 (1996). [8] D. A. Hajduk et al., Macromolecules 27, 4063 (1994). [9] I. W. Hamley et al., Macromolecules 26, 5959 (1993). [10] The ordered phases are characterized by their symmetries. The assignment of the space groups used in our analysis is H (p6m), bcc (Im3m), HML HPL (R 3m), and DG (Ia3d). Note that the HML and HPL phases have identical symmetries. At the mean eld level, the HML phase does not occur. [11] G. H. Fredrickson and E. Helfand, Macromolecules 87, 697 (1987). [12] M. Olvera de la Cruz, Phys. Rev. Lett. 67, 85 (1991). [13] M. Muthukumar, Macromolecules 26, 5259 (1993). [14] C. Yeung, A.-C. Shi, J. Noolandi, and R. C. Desai, Macromol. Theory Simul. 5, 291 (1996). [15] A.-C. Shi, J. Noolandi, and R. C. Desai, Macromolecules 29, 6487 (1996). [16] M. Laradji, A.-C. Shi, J. Noolandi, and R. C. Desai, Macromolecules (to be published). [17] The anisotropic density-density correlation function, characterized by the eigenvalue bands, describes the uctuation modes of the ordered structure. The elastic moduli of the system can be extracted from the correlation functions (see Ref. [14]). [18] E. Helfand, J. Chem. Phys. 87, 697 (1975). [19] K. M. Hong and J. Noolandi, Macromolecules 14, 727 (1981). [20] The rst order correction vanishes since the mean eld solution extremizes F 0 . [21] M. W. Matsen and M. Schick, Phys. Rev. Lett. 72, 2041 (1994). [22] N. W. Ashcroft and N. D. Mermin, Solid State Physics (Saunders, Philadelphia, 1976). [23] D. A. Hajduk et al., Macromolecules 27, 490 (1994). [24] S. Sakurai et al., Macromolecules 26, 485 (1993). [25] S. Qi and Z.-G. Wang, Phys. Rev. Lett. 76, 1679 (1996); Phys. Rev. E 55, 1682 (1997). [26] D. A. Hajduk (private communication). [27] There is, however, evidences for the DG structure in intermediate to strong segregated copolymer melts [3,5], indicating that further studies are needed. [28] M. F. Schultz et al., Phys. Rev. Lett. 73, 86 (1994).

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